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[Display omitted] • Paper mill sludge ash (pm SA) was used as catalysts to activate PMS. • Aerobic calcination was conducive to the exposure/formation of octahedral FeIII. • The O O bond fracture was the root pathway for FeIV O production. • The release of solid calcium in pm SA could inhibit the active decay of FeIV O. • The pm SA could effectively degrade similar pollutants in near-neutral water. The excellent performance of high-valent iron-oxo species (FeIV O) in the degradation of pollutants by activating peroxymonosulfate (PMS) had attracted much attention. However, the generation and reaction mechanisms were still unclear. In this study, iron-rich paper mill sludge was used as a raw material for the first time to prepare iron-based catalysts with abundant octahedral FeIII sites (Fe oct III). The results showed that the highest content of Fe oct III was found in the paper mill sludge ash obtained by aerobic calcination at 800 °C (pm SA800), and the pm SA800 could exhibit excellent catalytic activity (0.4785 min−1) and stability during the oxytetracycline (OTC) degradation process. The characterization and density functional theory (DFT) calculations further indicated that the Fe oct III was the dominant active site for FeIV O production. PMS tended to be adsorbed on two adjacent Fe oct III sites to form a [Fe oct III-OSO 2 OO(H)-Fe oct III] complex with a two-site adsorption configuration. Subsequently, the O O and O H bonds in [Fe oct III-OSO 2 OO(H)-Fe oct III] broken by absorbing energy, generating FeIV O. It's worth noting that the Ca species of pm SA800 effectively stabilized the pH of the reaction solution, which ensured the stable and continuous production of FeIV O. This work provides a new idea and insight for preparing catalysts that could produce FeIV O active species. [ABSTRACT FROM AUTHOR]

Given its superior structure, the abundance of surface functional groups, and low cost, cotton fiber filtration paper can be used as the support for hydrogen evolution reaction (HER) and oxygen evolution reaction catalysts (OER) instead of copper foam (CF), nickel foam (NF), or carbon cloth (CC). Herein, the chemical plating method was used to create thin self-supporting electrodes based on cotton fiber filtration paper (FP). The Co-Ni-P amorphous nanospheres can be uniformly dispersed on the self-supporting FP due to its porous structure and oxygen functional groups. The Co-Ni-P/FP electrode has an overpotential as low as 125 mV for HER and 320 mV for OER at the current density of 10 mA cm−2. Additionally, according to density functional theory (DFT) calculations, the Co atom added to the Ni-P nanosphere can lead to considerably more charge accumulation around the Co and Ni active sites, which greatly encourages the HER and OER processes. The novel porous support, FP, provides a fresh way the preparation of self-supporting electrodes. [Display omitted] • Filter paper is used to prepare the self-supporting electrode as the substrate. • The preparation method is simple and the properties are stable. • Rich oxygen-containing functional groups of FP promote deposition and dispersion. • Explore the excellent electrochemical performance of amorphous Co-Ni-P/FP by DFT. [ABSTRACT FROM AUTHOR]

[Display omitted] • Catalytic properties of MoS 2 in presence of glucose has been studied using DFT. • Molecular level substrate-analyte interaction has been studied through NCI plot. • Mos 2 functionalized paper based electrochemical sensor for glucose has been developed. • The paper based electrochemical sensor shows good accuracy and selectivity. • The ML-driven smart app, GluQuantify, shows enhanced accuracy and resolution. A paper-based electrochemical sensor utilizing MoS 2 as sensing material is developed to quantitatively estimate glucose in a complex extracellular fluid matrix. The contribution of MoS 2 as sensing material is substantiated in the context of density functional theory formalism. The molecular modelling of MoS 2 and glucose interaction is elucidated through the theoretical estimation of non-covalent interactions and charge density difference plots. The charge transfer phenomenon during the oxidation of glucose molecule in electrochemical experiments is verified through electronic band structure analysis and frontier orbital theory. The electrochemical responses indicate that the sensor exhibits an average accuracy of nearly 96%, with a quantification limit of 100 nM. Furthermore, the chronoamperometric measurements highlight the superior sensitivity of the device in presence of various perturbing molecules. The obtained DPV responses were integrated with a robust machine learning-driven standalone app GluQuantify. This app precisely predicts the glucose concentrations in serum samples. The utilization of GluQuantify substantially elevates the overall accuracy of the sensing platform to 99% and automates the detection process. The application also enhances the resolution of the sensor to 0.01 µM, which mitigates the sensor resolution-related issues in manual estimation. [ABSTRACT FROM AUTHOR]

[Display omitted] • N-BPQD was synthesized through a solvothermal method using formamide as N source and solvent. • The N-BPQD exhibit a bright blue fluorescence with high quantum yield of 73.7%. • N-BPQD on fPAD was used as a visual fluorescent sensing platform for detection of bilirubin. • The fluorescent sensor shows high sensitivity and selectivity to bilirubin. • N-BPQD was a good fluorescent probe for cellular imaging. A facile top down producing approach for synthesis and doping of a nitrogen doped black phosphorus quantum dots (N-BPQD) in one-pot was developed by solvothermal method with formamide as a nitrogen source and solvent. The nitrogen atoms had introduced into BPQD structure and exhibit a bright blue photoluminescent with a high quantum yield of 73.7 %. The morphology and chemical structure of N-BPQD was characterized by transmission electron microscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. A fluorescent paper analysis device (fPAD) was applied in rapid and cost-effective detection of biomarker bilirubin with naked eyes. The fPAD sensor present a high selectivity, stability and sensitive response to bilirubin in a wide linear range of 10 to 150 µM with a limit of detection limit as 26 nM (S/N = 3) and limit of quantitation as 86 nM (S/N = 10). The principles-based density functional theory, calculations on doping and binding energy of N-BPQD were analyzed via the density functional theory (DFT) simulations. Moreover, N-BPQD showed extremely low cytotoxicity, which is a promising as a good fluorescent probe for stem cell imaging application. This work provide a new platform for diagnosis of jaundice disease. [ABSTRACT FROM AUTHOR]

Introducing defects into Pd-based metallene has been shown to significantly enhance its electrocatalytic performance. In this study, we embedded a new type of atomic-scale cavities into the basal plane of PdMo bimetallene (c-PdMo) through precise etching. These cavities introduced tensile strain and increased the generalized coordination number (CN ̅), resulting in superior performance in formate oxidation reaction (FOR) and methanol oxidation reaction (MOR), with mass activities of 5.01 mA μ g NM − 1 and 5.38 mA μ g NM − 1 , respectively. Notably, a two-electrode system comprising commercial Pt/C and c-PdMo coated on carbon paper achieved cell voltages of only 0.517 V and 0.362 V at 10 mA cm−2 for FOR and MOR, respectively. Additionally, density functional theory calculations revealed that the deliberate lattice tensile strain and enhanced coordination numbers reduced the D-band center of defective PdMo, which improved OH adsorption and reduced CO adsorption, thus optimizing FOR and MOR catalysis on the surface of c-PdMo bimetallene. [Display omitted] • PdMo bimetallene with atomic-scale cavities (c-PdMo) was prepared via etching. • Atomic-scale cavities can regulate coordination number and strain of bimetallene. • Atomic-scale cavities can modulate the surface adsorption energies of CO and OH. • c-PdMo exhibited highly-efficient mass activity for FOR and MOR. [ABSTRACT FROM AUTHOR]

Vacancy engineering has repeatedly proven to be a powerful strategy for manipulating material properties. The important influence of selenium vacancies (V Se) on the physicochemical properties of rhenium diselenide (ReSe 2), exciting applications can be opened in areas such as catalysis and photoelectric devices. However, the effects of V Se on electronic structure, carrier lifetime, and electrochemical activity of ReSe 2 have remained inadequately explored and poorly elucidated. Herein, hydrothermal controlled growth of ReSe 2 with vacancy (V Se -ReSe 2) is used by different synthesis strategies, revealing its growth mechanism. An ethanol-assisted hydrothermal method based on carbon paper was used to adjust the V Se concentration by changing the time parameters. Mediated excitonic effects in the transient absorption (TA) spectroscopy and photoluminescence response of ReSe 2 regulated by V Se were characterized. The defect level (DL) leads V Se -ReSe 2 to produce a unique defect emission peak, and the V Se -mediated exciton dynamics problem was discussed. Moreover, the TA result of V Se -ReSe 2 shows that high V Se concentration prolongs carrier lifetime and causes high carrier separation efficiency and electron utilization. The electrocatalytic hydrogen evolution reaction of ReSe 2 catalyst revealed the ability of V Se concentration to regulate the electrochemical activity, which provides ideas for vacancy management catalyst performance. The presence of DL and the reduction of band gap are indicated by density functional theory, which confirms the regulatory effect of V Se concentration on the electronic structure of ReSe 2. This work proffers an optimal solution strategy for hydrothermal preparation of ReSe 2 , which demonstrates the feasibility of regulating electrochemical activity by vacancy engineering, and the excellent performance of V Se -ReSe 2 makes it show great potential in many fields such as water cracking and physical devices. [Display omitted] • A regulation strategy for the successful construction of V Se rich ReSe 2 nanoflowers was developed. • DFT investigated the reduction of the band gap and orbital contribution of ReSe 2 regulated by V Se. • Mediated excitonic effects in the TA and PL response of ReSe 2 regulated by V Se were analyzed. • The effectively regulate the HER activity of V Se -ReSe 2 were analyzed. Vacancy engineering is powerful for manipulating material properties. Selenium vacancies (V Se) exert significantly impact on the physicochemical properties of rhenium diselenide (ReSe 2), triggering applications in catalysis and photoelectric devices. However, the effects on electronic structure, carrier lifetime, and electrochemical activity are inadequately explored and poorly elucidated. Herein, hydrothermal-controlled growth of ReSe 2 with V Se is synthesized by different strategies. The ethanol-assisted hydrothermal method can adjust V Se concentration of ReSe 2 on carbon paper by time parameters. Mediated excitonic effects were characterized in the transient absorption spectroscopy and photoluminescence of V Se -regulated ReSe 2. The defect level produces unique defect emission peak, and the V Se -mediated exciton dynamics problem was discussed. The transient absorption result shows that high V Se concentration can optimize carrier lifetime, carrier separation efficiency, and electron utilization. The electrocatalytic hydrogen evolution reaction of ReSe 2 catalyst revealed the electrochemical activity regulation by V Se concentration, which provides ideas for enhancing catalyst performance. Density functional theory result confirms the role of selenium vacancies in the regulation of the electronic structure of ReSe 2. This work proffers an optimal solution strategy for hydrothermal preparation of ReSe 2 , and demonstrates the feasibility of regulating electrochemical activity by vacancy engineering. The excellent performance is beneficial for water cracking and physical devices. [ABSTRACT FROM AUTHOR]

Lead-free halide double perovskites (DPs) with superior photoelectric performance are of great importance in perovskites materials family. In this paper, a series of rare-earth (RE) based Cs 2 NaRECl 6 (RE = Y, Ce–Nd, Sm–Gd, Dy–Lu) DPs microcrystals (MCs) were prepared by convenient hydrothermal method. Cs 2 NaCeCl 6 and Cs 2 NaEuCl 6 MCs exhibit typical UV emission from the 5d→4f transition of Ce3+ and orange-red emission from characteristic 5D 1 → 7F 0 , 5D 0 → 7F 1 , 5D 0 → 7F 2 , 5D 0 → 7F 3 , 5D 0 → 7F 4 transitions of Eu3+, respectively. The blue light emissions of Cs 2 NaYCl 6 (300–650 nm) and Cs 2 NaLuCl 6 (300–550 nm) are from the respective self-trapped exciton states (STEs). In addition, the bandgap and partial density of state (PDOS) of Cs 2 NaRECl 6 (RE = Ce, Eu, Y, Lu) were calculated based on density functional theory (DFT) to have a further insight into the optical properties of the RE-DPs. The as-prepared RE based DPs have potential applications in advanced lighting, displaying and anti-counterfeiting, etc. [ABSTRACT FROM AUTHOR]

To alleviate the environmental pressure caused by SF 6 emissions, SF 6 /N 2 has been widely used in power systems as a replacement gas. In case of abnormal equipment failure, SF 6 /N 2 will decompose and produce many kinds of toxic and harmful gases, so it is necessary to place molecular sieves to safeguard the insulation performance of the equipment. Since γ-Al 2 O 3 is the main component of molecular sieves, the adsorption of N 2 O and NF 3 on the surface of γ-Al 2 O 3 (110) is systematically calculated in this paper using density functional theory to investigate the adsorption energy, charge transfer, density of states (DOS), electrons density difference (EDD), electron localization function (ELF) and frontier molecular orbital theory for their stable configurations. The calculated results show that although N 2 O adsorption on γ-Al 2 O 3 (110) is slightly stronger than NF 3 , both gases have weak interactions with γ-Al 2 O 3 (110) and thus may both be physisorbed. This paper deepens the basic understanding of adsorbent adsorption of SF 6 /N 2 decomposition gases in power equipment, and provides a theoretical basis for the optimisation study of adsorbents required for equipment with SF 6 /N 2 as the insulating medium. [Display omitted] [ABSTRACT FROM AUTHOR]

In the advent of the digital revolution, Artificial Intelligence (AI) has emerged as a pivotal tool in various domains, including materials design and discovery. This paper provides a comprehensive review of the AI methodologies integrated within this context, encompassing materials informatics, density functional theory, molecular dynamics, and finite elements analysis. We further delve into the transformative role of AI within process engineering, manufacturing, and industry 4.0, with a focus on manufacturing process optimization techniques. Highlighting the importance of active learning, self-correcting processing, and digital twins in the era of smart manufacturing, this review underscores the impact of big data and data quality. The paper provides an insight into the challenges and future prospects, pointing towards the tremendous potential AI holds for revolutionizing the field of materials science. • Comprehensive exploration of AI methods in Materials Design and Discovery. • Review of the transformative role of AI within process engineering. • Discussion on the importance of data quality and quantity in the era of Big Data. • Insight into challenges and potential of AI in the field of Materials Science. [ABSTRACT FROM AUTHOR]

The Dirac cone in the single-layer graphene limits its application in electronic devices such as Schottky barrier diodes and field-effect transistors. Thus, we make the novel heterostructures based on graphene to solve this problem. The electronic and optical properties of pristine and Ag/Au/Cu-doped graphene/MoS 2 heterostructures are investigated by using the density functional theory. For the Ag/Au/Cu-doped MoS 2 monolayer, the results show that they are magnetic. Their bands across the Fermi level, which indicates these systems are metallic. For the Ag/Au/Cu-doped graphene/MoS 2 heterostructures, they are metallic and nonmagnetic. Especially in the Au-doped graphene/MoS 2 , the Dirac cone opens about 66 meV. It means that Au-doped graphene/MoS 2 has the potential to be a candidate material for high speed electronic devices. Compared with pristine heterostructure, the probability of electron transition in the low energy region is the enhanced in Ag/Au/Cu-doped systems. The optical absorption coefficient of doped heterostructure is enhanced in the range of 0–0.4 eV and 1.7–2.7 eV. This work indicates that these heterostructures have a certain potential in the application of nanodevices. [Display omitted] • This paper confirms that the graphene can adsorb on Ag/Au/Cu-doped MoS 2 monolayer stably. • This paper finds that the Dirac cone in the Au-doped graphene/MoS 2 heterostructure opens about 66 meV. • The introduction of Ag/Au/Cu atoms in graphene/MoS 2 heterostructure can make the electron transfer at low energy. • The optical absorption coefficient is improved in these doped heterostructures. [ABSTRACT FROM AUTHOR]

• Solubility of β-HMX in three binary mixed solvent systems was measured by the laser dynamic method. • Six thermodynamic models were used to correlate the solubility of β-HMX. • The thermodynamic properties' microscopic mechanisms of β-HMX were revealed by DFT calculations and MD simulations. Octogen (HMX) is the most powerful military explosive in current use. However, the unclear thermodynamic molecular mechanisms severely limit the development of its production process. In this paper, the solubility of β-HMX in three binary mixed solvent systems (acetone + ethanol, acetone + dichloromethane, acetone + toluene) was measured via a dynamic method at temperature ranging from 283.15 to 313.15 K under atmospheric pressure. The experimental results reveal that the solubility of β-HMX in these binary mixed solvent systems is positively correlated with acetone molar fraction and temperature, and the solvent composition has a greater impact on its solubility compared with the temperature. Moreover, the solubility of β-HMX is further correlated with the Van't Hoff equation, modified Apelblat equation, CNIBS/R-K model, Jouyban-Acree-Van't Hoff model, Jouyban-Acree-Apelblat model and NRTL model, and the modified Apelblat equation can give better fitting result (ARD = 8.101 × 10−3, RMSD = 1.065 × 10−5). Finally, the microscopic mechanism of the thermodynamic properties of β-HMX in binary mixed solvents is revealed by investigating the types, intensity and interaction sites of interactions based on density functional theory (DFT) and molecular dynamic (MD) simulation. The results demonstrate that both acetone molecules and ethanol molecules can form certain intermolecular interactions with β-HMX molecules, which are the main driving force of solubilization. In contrast, solvent–solvent interactions have an antagonistic effect on the solubility of β-HMX in mixed solvents. This work can further be informative for researchers in the field of energetic material for the solubility evaluations and provide a reference for the industrial production and performance enhancement of HMX in the future. [ABSTRACT FROM AUTHOR]

Efficient detection and timely resolution of internal faults within synthetic ester oil transformers are imperative for ensuring the stability of power systems. This paper proposes the utilization of MoSTe monolayer modified with Cu n and Pd n (n=1–3) clusters for detecting internal fault gases (C 2 H 2 , C 2 H 4 , and CH 4) in transformers. The adsorption mechanism and electronic properties of target gases on the modified substrate surface are systematically studied through density functional theory analysis of adsorption energy, density of states, and deformation charge density. The results indicate that TM n clusters possess the capability to enhance the reactivity of the MoSTe surface, leading to varying degrees of improvement in conductivity and adsorption capacity. Different target gases exhibit distinct adsorption characteristics, with the modified monolayer showing strong adsorption capabilities for C 2 H 2 and C 2 H 4. The calculation of work function and recovery time further reveal the promising potential of Pd n -MoSTe monolayer as resistive gas sensing materials for detecting C 2 H 2 and C 2 H 4 , while Cu n -MoSTe monolayer are also identified as high-quality candidates for C 2 H 4 sensing materials. This study is expected to facilitate the practical application of MoSTe monolayer in the field of transformer operational state monitoring, providing new insights for exploring novel gas sensing materials. • The conductivity of the TM n clusters modified MoSTe monolayers is consequently improved to different extents compared with the initial MoSTe substrate. • Combined adsorption parameters, DOS and DCD analysis reveal that the adsorption of C 2 H 2 and C 2 H 4 on TM n -MoSTe monolayers is chemisorption, while the adsorption of CH 4 is weak physisorption. The adsorption capability ranking is: C 2 H 2 > C 2 H 4 > CH 4. • The variation of work function and band gap demonstrate that the adsorption of target gases can improve the surface properties of substrate. This effect is particularly pronounced in the TMn-MoSTe/C 2 H 2 and TM n -MoSTe/C 2 H 4 systems. • The recovery time reveals the promising potential of Pd n -MoSTe monolayer as sensing materials for detecting C 2 H 2 and C 2 H 4 , while Cu n -MoSTe monolayer is suitable for rapid recovery of C 2 H 4 under ambient conditions. [ABSTRACT FROM AUTHOR]

Synergistic effects of mixed oxides have the potential to improve sensing performances of environmental, domestic and industrial monitoring devices. However, mixed oxides often come in the form of separate particles and are thus addressed separately by the environment, instead of capitalizing on the interface between the metal oxides. This paper describes a new core@shell gas sensing material of tetrapodal zinc oxide with a surface coating of crystalline copper oxide(t-ZnO@CuO). The special surface conversion strategy yields a unique, self-assembled and pinhole-free coating of CuO nanoplatelets. The morphologies, structural, chemical and gas sensing properties of the heterostructure were investigated. To evaluate the sensing properties of the heterostructure, t-ZnO@CuO was fabricated as nanosensors, consisting of one core-shell rod of CuO-coated crystalline ZnO. The single core@shell rod showed high selectivity towards hydrogen already at comparatively low operation temperatures of 150 °C. Computational calculations based on the density functional theory (DFT) have been carried out to understand the interaction of the H 2 gas molecule with the surface of the CuO nanostructures. The surface conversion was done wet chemically and is a novel method for generating heterostructures that can be potentially transferred to heterojunctions with unique properties for chemosensors. [Display omitted] • A perfect coating of amorphized nanoplatelets of CuO with t-ZnO rods were obtained. • Absolute selectivity for H 2 was obtained from single microrod t-ZnO@CuO sensors. • The selectivity for H 2 over VOCs is due to complete coverage of CuO on t-ZnO arm. • Hetero2 structure (two substitutional Cu atoms) exhibits stronger interaction of H 2. • Bader charge analysis confirms Hetero2 structure as a favourable interaction site. [ABSTRACT FROM AUTHOR]

The problems of poor Faraday efficiency and high overpotential usually limit electrochemical nitrogen reduction (NRR) catalysts. In this paper, 28 different transition metal single-atoms (TM-SAs) supported on W 2 N 3 (TM@W 2 N 3) were designed by density functional theory (DFT) for catalytic N 2 reduction. The stability, N 2 activation capacity, selectivity and NRR mechanism of TM@W 2 N 3 were analyzed. Following the screening process, only 9 TM@W 2 N 3 (TM=Sc, Ti, V, Co, Cu, Y, Mo, Ag, W) structures were identified as exhibiting high stability, strong activation capacity and high NRR selectivity. And then N 2 activation mechanism of V@W 2 N 3 , Mo@W 2 N 3 and W@W 2 N 3 , as well as the Gibbs free energies of its four NRR reaction pathways were further discussed. The overpotentials (η) of Mo@W 2 N 3 and V@W 2 N 3 to NRR are 0.129 V and 0.470 V, respectively. The overpotential (η) of W@W 2 N 3 is the lowest at 0.059 V, while its catalytic activity is the highest. V@W 2 N 3 and W@W 2 N 3 are more likely to follow the distal pathway for NRR, while Mo@W 2 N 3 is more likely to follow the enzymatic pathway. This study offers some theoretical foundation and reference for the design of new and efficient electrocatalytic NRR catalysts. [Display omitted] • 28 transition metal supported on W 2 N 3 (TM@W 2 N 3) were designed by DFT for NRR. • Analyzed TM@W 2 N 3 : stability, N 2 activation capacity, selectivity and NRR mechanism. • N 2 activation mechanism of V@W 2 N 3 , Mo@W 2 N 3 and W@W 2 N 3 for NRR pathways were discussed. • V@W 2 N 3 and W@W 2 N 3 follow the distal pathway, Mo@W 2 N 3 follows the enzymatic pathway. • W@W 2 N 3 exhibits the lowest overpotential (η=0.059 V) and the highest catalytic activity. [ABSTRACT FROM AUTHOR]

Photocatalysis is an ideal method for the removal of tetracycline hydrochloride (THC) in water, but it remains challenging, mainly due to the rapid recombination of electron-hole pairs in the catalyst. In this paper, BiVO 4 is prepared by in-situ piezoelectric assisted method (BVO-U) for the first time and applied to the piezo-photocatalytic degradation of THC. It is found that the two catalysts (BVO prepared by stirring assisted method and BVO-U) have similar structures and chemical states, but they exhibit different piezoelectric properties. It is worth mentioning that the degradation efficiency of BVO-U (90 %) is higher than that of BVO (83 %) under ultrasonic coupled light irradiation. In addition, the mechanism is revealed through density functional theory (DFT) calculations, which suggests that the dipole moment of BVO-U increased, promoting the separation of photo-generated carriers, thereby improving the catalytic activity. These findings highlight the great potential of in-situ piezoelectric-assisted synthesis of BVO in piezo-photocatalytic degradation and provide an idea for designing efficient catalysts in the future. [Display omitted] • BVO-U is firstly prepared by in-situ piezoelectric assisted method. • The polarization of BVO-U significantly inhibits carrier recombination. • The piezo-photocatalytic activity of BVO-U is explored. • The non-radiative transition may effect piezo-photocatalytic performance. [ABSTRACT FROM AUTHOR]

Fluoride pollution is a problem of increasing concern to global public health, and it is important to reduce the concentration of fluoride ions in water. In this paper, the composite adsorbent (Al 2 O 3 -COF) of Al 2 O 3 and melamine polymer network (MPN) was prepared by the solvothermal method, and the physicochemical properties of the material were characterized. The characterizations showed that Al 2 O 3 -COF had a porous and loosely packed morphology, and the adsorption behavior conformed to the pseudo-first-order kinetic and the Langmuir isotherm model. This study showed that Al 2 O 3 -COF exerted the synergistic effect of Al 2 O 3 and COFs to adsorb fluoride, with an adsorption capacity superior to that of a single alumina at 66.2 mg/g. The adsorption performance test showed that the interfering anions (PO 4 3-, Cl-, Br-, NO 3 -, SO 4 2-) had little effect on the adsorption performance of Al 2 O 3 -COF while maintaining a fluoride removal rate of over 83 %. After 5 cycles of recycling, more than 75 % of fluoride ions could also be removed. In addition, insights into the adsorption mechanism of Al 2 O 3 -COF, mainly through ion exchange and chemisorption, were calculated by density functional theory. This experiment is to apply COFs in the field of F- adsorption, which can provide ideas and guidance for future research. [Display omitted] • Al 2 O 3 -COF adsorbent in the form of yellowish powder was prepared by solvothermal method. • For the first time, COF materials were applied to the field of adsorption and fluorine removal. • The maximum adsorption capacity of the Al2O3-COF adsorbent was 66.2 mg/g. • Al 2 O 3 -COF possesses excellent adsorption regeneration capacity and has good economic benefits. • The adsorption mechanism was found to be mainly chemisorption and ion exchange after DFT calculations. [ABSTRACT FROM AUTHOR]

• A Ni-doped Fe 2 O 3 electrocatalyst is prepared by a solvent-free method. • Ni enables the crystalline phase of Fe 2 O 3 to transform γ-Fe 2 O 3 into α-Fe 2 O 3. • α-Fe 2 O 3 leads to the more thermodynamically favourable NO 3 RR process. • α-Fe 2 O 3 -Ni-CB shows the high electrocatalytic NO 3 RR activity and selectivity. Electrocatalytic nitrate reduction reaction (NO 3 RR) provides an alternative to the conventional Haber-Bosch process for ammonia synthesis and is an effective method for removal of nitrate ions from polluted waters, which is highly significant from both energy and environmental perspectives. However, NO 3 RR involves the complex eight-electron process alongside various nitrogen-containing intermediates and is also in competition with hydrogen evolution reaction, thus demanding highly active and selective electrocatalysts. In this work we prepare a Ni-doped Fe 2 O 3 electrocatalyst via a solvent-free route. It is found that the addition of Ni induces the crystalline-phase transformation of Fe 2 O 3 from γ-Fe 2 O 3 to α-Fe 2 O 3. The density functional theory (DFT) results reveal that compared to γ-Fe 2 O 3 , α-Fe 2 O 3 gives rise to a lower potential-determining step (PDS) energy barrier, leading to the more thermodynamically favourable reaction. By modulating the crystalline phase, the optimal catalyst achieves high ammonia yield rates of > 5000 μg h−1 cm−2 and faradaic efficiencies of > 90 %, showcasing its high electrocatalytic activity and selectivity. From this perspective, this paper provides new insights and strategies for the green nitrate-to-ammonia conversion. [ABSTRACT FROM AUTHOR]

• Different crystalline forms of Nb 2 O 5 were prepared by simple ball milling and preparative methods. • The material structure was calculated based on density functional theory. • The material obtains very excellent electrochemical properties. Lithium-ion batteries (LIBs), extensively utilized today, encounter challenges with anode materials, such as capacity degradation and shortened cycle life during prolonged cyclic charging and discharging. These issues significantly hinder further advancements and applications of LIBs. Among various innovative anode materials, niobium pentoxide (Nb 2 O 5) has garnered considerable interest due to its high specific capacity and exceptional cycling stability. However, different crystal types of Nb 2 O 5 have different structures and properties, so they need to be studied in depth to find better anode materials for LIBs. In this paper, pseudo-hexagonal (TT-Nb 2 O 5), orthorhombic (T-Nb 2 O 5), and monoclinic (H-Nb 2 O 5) crystalline forms of Nb 2 O 5 have been prepared by simple ball milling and calcination methods. We have calculated the structural model of the material based on the density flooding theory (DFT), and the results have demonstrated that the T-Nb 2 O 5 has a large structural advantage, which is characterized by a very low diffusion energy barrier, a low internal resistance, and a higher conductivity. The electrochemical properties of the material were also analyzed, and T-Nb 2 O 5 has excellent cycling stability and rate performance. After 200 cycles (at 0.1A/g), the specific capacity of T-Nb 2 O 5 was maintained at 440.8mAh/g. 3000 cycles at high current (at 5A/g) maintained a specific capacity of 95mAh/g. T-Nb 2 O 5 has great potential, which has already been proved. With the continuous pursuit and development of energy storage technology, we believe that the research of different crystalline types of Nb 2 O 5 will provide us with more efficient and reliable energy storage solutions. [ABSTRACT FROM AUTHOR]

• The bipolar COF-GZU1 structure was successfully designed. • The prepared COF-GZU1 films exhibited high specific surface area, crystallinity and porosity. • The ordered porous structure facilitates electron conduction and ion mass transfer. • Great electrochromic properties and regulation. Because of the ordered and loose structure, covalent organic framework (COF) holds broad promise in the field of electrochromism, but the simple color change limits its application and development. A bipolar and polychromatic COF-GZU1 was successfully designed and prepared in this paper. The structure, electrostatic potential and orbital structure of the COF-GZU1 were predicted and calculated using density functional theory, and the calculation results confirmed the feasibility of bipolar construction strategy. XRD, SEM, BET and GIWAXS further mutually established the successful synthesis of COF-GZU1, which exhibited high specific surface area, crystallinity and porosity. Results from electrochemical impedance spectroscopy, density of states analysis, and ion diffusion coefficient measurements verified that the ordered porous structure facilitates electron conduction and ion mass transfer, leading to a significant improvement in electrochromic performance. Moreover, the COF-GZU1 film displayed excellent electrochromic performance, providing polychromatic switching with a rapid response time (7.8/14.5 s and 1.0/12.6 s for coloring/bleaching process) and high coloring efficiency (112.8 and 127.8 cm2∙C-1 at 799 and 570 nm). These results collectively demonstrate the superiority of the COF-GZU1 film and suggest that the bipolar COF design strategy could pave the way for new and high-performance polychromatic electrochromic materials. [ABSTRACT FROM AUTHOR]

Nanosheet materials have larger specific surface area and more active sites than bulk materials. In this paper, ultrathin graphite carbon nitride (UCN) nanosheets were first prepared by a multi-step calcination method, and then Bi 2 WO 6 nanoflowers were grown in-situ on the surface of UCN by a simple hydrothermal method to synthesize ultrathin graphite carbon nitride and bismuth tungstate composite (UCN/BWO). The synthesized catalyst was applied to the photocatalytic oxidative coupling of benzylamine (BA). After reacted 5 h under light in air atmosphere, BA was almost completely converted into N -benzylidenebenzylamine, which was 3.8 times higher than that of bulk graphite carbon nitride (BCN). The enhanced photocatalytic activity was not only attributed to the thin nanosheet structure of UCN which shortened the migration distance of photogenerated electrons, but also because the construction of Z -scheme heterojunction that inhibited the recombination of photogenerated carriers and improved the oxidation ability of the catalyst. Based on density functional theory (DFT) calculation and photoelectric performance test, the existence of Z -scheme heterojunction was proved. Combined with the active species capture experiments, the pathway of electron transfer in the reaction process and the possible reaction mechanism were proposed. [Display omitted] • Ultrathin graphite carbon nitride (UCN) obtained by multi-step calcination. • Flower-like Bi 2 WO 6 grow in-situ on UCN and constructed the Z -scheme heterojunction. • UCN/BWO-50 can selectively oxidize benzylamine under mild conditions. • Band structure and electron transfer pathway of the materials are revealed. • Reaction mechanism is proposed by photoelectric properties and DFT calculation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ultrathin defect-rich nickel phyllosilicate was prepared by a ball milling trio strategy. • Active sites of nickel phyllosilicate were quantitatively and qualitatively regulated. • Metal utilization ratio was significantly improved owing to the ultrathin defect-rich structure. • This method possessed in situ regeneration property of the deactivated Ni/SiO 2 catalyst. • The optimum catalyst exhibited both high activity and stability for CO 2 methanation. This paper proposes a ball milling trio strategy that integrates mechanical exfoliation, liquid-phase exfoliation, and hydrogen peroxide modification to synthesize ultrathin defect-rich Ni-phyllosilicate for CO 2 methanation. The obtained catalyst exhibits a unique layered structure with a thickness of only 0.86–1.37 nm and numerous holes, which results in weakened metal-support interaction, enhanced metal utilization ratio, and an appropriate coordination environment for Ni species. Consequently, it displays competitive catalytic activity with a turnover efficiency of CO 2 (TOF CO2) of 8.0 × 10–2 s−1 and a low active energy (E a) of 41.49 KJ·mol−1 for CO 2 methanation; importantly, it maintains high stability without Ni sintering and coking in a 100 h-long term test. In-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) results confirms the coexistence of *HCOO and *CO intermediates, and density functional theory (DFT) calculations indicate the formate pathway is thermodynamically more feasible, with the rate-determining step of *CO+*OH+*H→*CHO+*OH (ΔE =0.73 eV). Moreover, this method demonstrates high universality in preparing various metal (Fe, Co, Ni, Cu) phyllosilicates and possesses the in-situ regeneration capacity for the deactivated Ni/SiO 2 catalyst. [ABSTRACT FROM AUTHOR]

[Display omitted] • A NF/Mn 2 CoO 4 @MoO 2 electrode was prepared for Pb2+-targeted removal via CDI technology. • SCR of the electrode relies on preferential adsorption and sluggish desorption for Pb2+. • Synergistic effects of Mn 2 CoO 4 and MoO 2 are beneficial for Pb2+ capacitive removal. • Theoretical calculations confirm SCR is due to stronger bonding between Pb2+ and MoO 2. • Electrodepositing loaded MoO 2 onto NF/Mn 2 CoO 4 for 60 min achieved optimum capacitance. To achieve targeted removal of Pb2+ from industrial wastewater, a NF/Mn 2 CoO 4 @MoO 2 composite electrode, synthesised using the hydrothermal method combined with electrodeposition technology, was employed to construct an asymmetric capacitive deionization (CDI) system to selectively electro-adsorb and desorb Pb2+ ions. The electrode exhibited pseudocapacitive characteristics in solutions containing Pb2+, facilitating rapid and reversible redox reactions. The asymmetric CDI system, utilising graphite paper as the positive electrode and NF/Mn 2 CoO 4 @MoO 2 as the negative electrode, displayed exceptional adsorption performance at 1.4 V for 1 h, decreasing the Pb2+ concentration from 50 ppm to 4 ppb, achieving an adsorption capacity of 156.24 mg g−1, and displaying outstanding cyclic stability. Moreover, the electrode demonstrated preferential adsorption of Pb2+ in mixed solutions containing multiple heavy metal ions, with relative removal coefficients of 4.48 − 19.86 compared with other ions. Analysis of the adsorption mechanism indicated that during the adsorption process, Pb2+ was embedded between MoO 2 layers, disrupting the electron cloud symmetry and triggering an oxidation reaction. Octahedral MoO 2 then lost electrons and transformed into tetrahedral [MoO 4 ]2-, forming PbMoO 4 with embedded Pb2+ between the layers, and achieving effective removal of Pb2+ with high selectivity. Molecular dynamics simulations and density functional theory (DFT) calculations confirmed the high selectivity of the prepared electrode for Pb2+ ions based on stronger binding of Pb2+ to MoO 2 than other ions. The electrode has application potential for the capacitive removal of Pb2+ from industrial effluent through CDI technology. [ABSTRACT FROM AUTHOR]

[Display omitted] • Global reactive parameters, structural and topological studies provides the clear insight of the compound. • Chemical reactivity of the 2-(Carboxymethyl)benzoic acid is analyzed by MEP study in different solvent phases. • Enhanced NLO parameters provide favourable nonlinear optical applications. • Molecular docking studies verify the title compound's potent anticancer activity and its bioactive characteristics. Nowadays density functional theory (DFT) is one of the best methods to explore the vibrational modes and structure of the biological system. Quantum mechanical calculations are performed using gas phase and different solvents (DMSO, methanol and water). The derived global reactive parameters, structural and topological study provides the clear insight of the 2-(Carboxymethyl) benzoic acid. Depth studies of DFT proves the existence of hydrogen bonds between donor and acceptor in the compound, which is supportive for the biological applications. In this paper, different experimental and computational simulated FT-IR, FT-Raman, UV–Vis spectral studies are used to explicate vibration assignments of the 2-(Carboxymethyl) benzoic acid. Experimentally observed vibrational frequency is compared with theoretically simulated spectrum. B3LYP method with 6–311++G (d, p) basis set is used in DFT to optimize the 2-(Carboxymethyl)benzoic acid structure. The most stable lower energy conformer is identified using potential energy surface (PES) analysis using Gaussian 16 W software. ESP, HOMO-LUMO, NBO, and QTAIM calculations have evinced an adequate electronic characterization of 2-(Carboxymethyl) benzoic acid. Further, van der Waals and steric interactions among 2-(Carboxymethyl) benzoic acid have been discussed with the help of RDG study. Hirshfeld surface studies establish the existing various interaction among molecules and total packing arrangement of the crystal structure. Due to the high biological activity score, 2-(Carboxymethyl) benzoic acid is a good therapeutic candidate. Lipophilicity analysis of 2-(Carboxymethyl)benzoic acid clearly explicates the bioactivity properties and its effective drug applications. Further, molecular docking investigates that the compound can be used as anticancer medication. The detailed DFT study of the 2-(Carboxymethyl) benzoic acid justified its biological applications of the present communication. The calculated NLO parameters of 2-(Carboxymethyl)benzoic acid evidenced for good efficacy in diverse filed application has been discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • For the Cu 7 M, Cu 8 M, and Cu 9 M atomic clusters, the M metal atoms tend to be centered. • We found that the addition of transition metals enhanced the stability of clusters. • The addition of transition metals increased the adsorption energy of CO 2 clusters. • In the reaction of catalytic CO 2 reduction, CunNi was found to be the preferred catalyst. The efficient and selective electroreduction of CO 2 in chemical fuels can be environment-energy friendly; however, it highly relies on catalysts with controllable selectivity and reaction paths. At present, copper-based catalysts are a good option for CO 2 reduction, and the formation of C 1 + products is presented in this paper. First, we systematically studied the three-dimensional structures of the Cu 4-12 M clusters (a total of nine types). The M atoms were sequentially replaced by first-row transition metals (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), which enhanced the stability of the clusters and their CO 2 adsorption energy. Second, studies on the catalytic reduction of CO 2 indicated that these clusters tend to produce methane through pathways mediated by CHO*. Finally, we summarized the lowest rate-determining steps of all clusters and identified the most suitable catalyst candidates. This work advances the theoretical study of nanoclusters for catalytic CO 2 reduction. [ABSTRACT FROM AUTHOR]

[Display omitted] • The machine-learned potential for aluminum was developed as based on Behler-Parrinello neural network scheme. • The potential demonstrates an excellent agreement with experimental data and DFT calculations concerning thermodynamic, elastic, liquid phase and generalized stacking fault energy properties. • High accuracy was achieved due to the optimal training set and configuration parameters used to generate the machine learning potential. Aluminum and its alloys are most often used as structural materials due to their specific properties, such as low weight, low energy consumption for remelting and the possibility of almost complete processing. This paper utilizes machine learning, specifically the Behler-Parrinello neural network scheme, to develop a powerful potential for studying the underlying mechanisms of deformation, fracture, and defect formation. By surpassing the limitations of first principles calculations, the application of machine-learned potentials (MLP) becomes highly advantageous for describing pure aluminum (Al) in its solid and liquid phases. Specifically, from the generated potential equilibrium, thermodynamic, elastic, and vibrational properties of face-centered cubic (fcc) Al are obtained in very good agreement especially with density functional theory (DFT) results as well as with previous calculations using existing semi-empirical potentials, such as EAM and MEAM, recent machine-learned potentials, and experimental data. Furthermore, our potential proves to accurately reproduce defect formation energies such as previously computed and measured stacking-fault energy curves. Finally, stacking fault profiles as well as key quantities of the liquid phase such as the melting point at ambient pressure, temperature-dependent densities, and radial distribution functions are also calculated in very good agreement with the results from previous theoretical and experimental investigations. Nevertheless, our investigation goes beyond previous studies in proving excellent agreement with experimental data especially of the specific heat and the melting point at very high pressures. The competitive analysis performed in this work thus clearly demonstrates the validity and accuracy of the generated machine-learned potential to describe a wide range of properties of Al at various temperatures and pressures and thereby lays ground for future applications. [ABSTRACT FROM AUTHOR]

In the density functional theory (DFT), it is well-known that the generalized gradient approximation (GGA) underestimates the energy gap. One of the commonly used GGA functionals is the Perdew–Burke–Ernzerhof (PBE) functional. This paper presents a machine learning approach to correct the energy gap estimated by PBE, using a minimal set of five features, to the accuracy level of the many-body perturbation theory G 0 W 0 band gap, which is known for its precision but high computational cost. These features are identified by seeking those which can be obtained directly from PBE-DFT calculations or from the standard atomic tables and directly connected to Coulombic interaction, and by minimizing feature correlations. The utilized features are the PBE band gap and the average atomic distance (obtained directly from PBE-DFT calculations) and the average oxidation states, electronegativity, and the minimum difference of electronegativity between constituents (obtained from the standard atomic tables). These features do not require any further atomistic calculations. The developed models are trained and validated using 265 inorganic semiconductors and insulators with energy gaps ranging from 0.75 to 14.55 eV. Several regression techniques have been applied, all of which have produced highly accurate and comparable results. This suggests that the five features employed in the analysis effectively capture the underlying physics. The most accurate model is based on Gaussian process regression (GPR), achieving a validation accuracy of 0.252 eV root-mean-square error (RMSE) and an R 2 value of 0.9932. The best bootstrapped model achieves an RMSE of 0.232 eV. The developed GPR model is then applied successfully to completely independent data sets. The developed model should allow calculating gaps with G 0 W 0 accuracy using the relatively much faster DFT-PBE. This is especially useful in materials discovery where computational efficiency is crucial. Furthermore, the model should allow empirical investigation of the influences of different compositional and structural characteristics on the gap. • Bandgap underestimation problem in DFT-PBE is corrected using machine learning with a minimal set of five features. • A Gaussian process regression achieved a validation RMSE of 0.252 eV and an R 2 of 0.9932. • Features are obtained directly from PBE-DFT calculations or from standard atomic tables. [ABSTRACT FROM AUTHOR]

Catalysts derived from Metal-Organic Frameworks (MOF) present a compelling blend of cost-effectiveness and superior performance in reduction reactions. In this study, polymer-decorated MOF-Cobalt (MOF-Co) was deposited onto porous magnesium oxide (MgO) layers, acquired through surface modification of AZ31 Mg alloy via plasma-assisted oxidation, with the aim of fabricating novel catalysts for reduction reactions. Herein, this synthesis involved the utilization of Cobalt-benzene dicarboxylic acid (Co-BDC), where cobalt ions served as metal nodes and 1,4-benzene dicarboxylic acid (H 2 BDC) functioned as an organic linker, with and without the presence of polyvinylpyrrolidone (PVP) as an active site enhancer. The morphology of the prepared catalysts was affected by several factors such as pH, hydrothermal treatment duration, PVP content, and the presence of a MgO layer. The optimal catalyst, designated as metal-organic frameworks-cobalt at 80 °C temperature and 1 h of hydrothermal treatment at pH 4 (MOF-Co 1.4), was synthesized on the MgO layer using a solution containing 1.7 g of PVP, H 2 BDC, and Co(NO₃)₂.6H₂O. The paper-like morphology of the MOF-Co 1.4 catalyst facilitated exceptional performance, efficiently degrading p-nitrophenol (p-NP) under visible light irradiation with an impressive 99.74 % efficiency within just 5 min of exposure, while also demonstrating stability over five successive cycles. ·O 2 − species was found to drive the reduction reaction to p-aminophenol, with harmless compounds as byproducts, while GC-MS analysis identified intermediates in the reduction of p-NP. Density functional theory (DFT) calculations suggested that H 2 BDC and PVP jointly provided multi-active sites, enabling effective contact with reactants and rapid electron transfer, thus playing a synergistic role in the catalytic reduction process. This study pioneers a novel method for designing efficient bulk catalysts, achieving high efficiency and stability in pollutant degradation with fast, low-energy fabrication. [ABSTRACT FROM AUTHOR]

The paper presents the theoretical calculation results of exploratory research relating to the leaching of cobalt-containing pyrite using sodium thiosulfate as a lixiviant. It is well known that density functional theory (DFT) calculations can qualitatively evaluate the exchange of matter and energy between the mineral system and the surroundings, which greatly expands the breadth and depth of leaching process. Thus, DFT method was used to determine the effectiveness of sodium thiosulfate (Na 2 S 2 O 3) as a lixiviant for the leaching of cobalt-containing pyrite in this study. The analyses of DFT calculations illustrated that thiosulfate can be well adsorbed on the surface of cobalt-containing pyrite due to the formation of S-Fe and O-Co bonds between the S 3p orbital and O 2p orbital in sodium thiosulfate and the Fe 3d orbital and Co 3d orbital in cobalt-containing pyrite. Analysis of crystal orbital Hamilton population (COHP) indicated that Fe-S and S-Co bonds became longer when the thiosulfate adsorbed on the surface of the cobalt-containing pyrite, resulting in the weakening of interactions between S and Fe or Co atoms. Overall, the findings suggested that sodium thiosulfate was a promising lixiviant，favored the dissolution of Fe and Co. [Display omitted] • Thiosulfate can be well adsorbed on the surface of cobalt-containing pyrite. • The adsorption of thiosulfate favored the dissolution of Fe and Co. • Sodium thiosulfate was a promising lixiviant for recovery cobalt. [ABSTRACT FROM AUTHOR]

[Display omitted] • The in-situ conversion of hydrogen bonds into static electricity on the simulated biomembrane surface was investigated using SECM. • The number of hydrogen bonds at different pH was characterized by voltammetry and Approaching curves. • The intensity of in-situ conversion can be controlled by changing applied potential. • The key sites of weak interactions were visualized based on theoretical calculations. • Explored the influence of ion pairs on conversion intensity. In order to deeply understand the mechanism of biological function, it is significance to study conversion of weak interactions at the biomembrane surface. In this paper, the 3-mercaptopropionic acid self-assembled monolayer (3-MPA SAM) was constructed as a simplified model to simulate biomembrane, in which ferrocene carboxylic acid (FcCOOH) is adsorbed on the membrane surface through hydrogen bonds. Under positive potential induction, the in-situ conversion of hydrogen bonds into static electricity was investigated using scanning electrochemical microscopy (SECM). The conversion mechanism was the positive potential promoting the dissociation of carboxylic acids (COO−) on the membrane surface, followed by electrostatic attraction with the oxidation products (Fc+COOH). The study also found a positive correlation between conversion rate and potential value. Based on density functional theory (DFT), relevant information such as molecular structure, electrostatic potential and binding energy were obtained, and key sites of weak interactions were visualized using a reduced density gradient (RDG). The universality and competitiveness of conversion have been confirmed in different environments. This work provided some reference for revealing the properties and variations of weak interaction conversion at the biomembrane surface. [ABSTRACT FROM AUTHOR]

[Display omitted] • BCN/PMS/Vis system completely degraded 4-Chlorophenol in 60 min. • Revealed the mechanism of carbon doping affecting the photocatalytic effect of BCN. • Carbon doping induces peroxymonosulfate to lose electrons for 1O 2 production. • Non-free radical pathway played a dominant role in pollutant removal. In order to improve the photocatalytic activity of pristine carbon nitride while maintaining its metal-free property to achieve the activation of peroxymonosulfate (PMS), a series of carbon-doped g-C 3 N 4 (BCN) with different carbon contents were synthesized in this paper by adding benzotriazole to urea. The catalyst obtained by this approach significantly promoted PMS activation and enhanced the degradation efficiency of 4-chlorophenol (4-CP). Experiments and theoretical calculations showed that the introduction of carbon not only narrowed the band gap, but also accelerated the separation of photoinduced electron-hole pairs, which greatly improved the photocatalytic activity of g-C 3 N 4. In the degradation of pollutants, free radicals and non-free radicals acted simultaneously, with non-free radicals playing a dominant role. This study explained the origin of 1O 2 by Density functional theory (DFT) calculations, visible light excited photocatalysts to form holes, while carbon introduction decreased the valence-electron density around the area, inducing electron transfer from PMS toward g-C 3 N 4 directed to generate 1O 2. The 1O 2 -dominated degradation process improved the application of the catalysts in complex aqueous matrices. In addition, we proposed 4-CP degradation pathways, and the toxicity of intermediates derived from 4-CP degradation process reduced. [ABSTRACT FROM AUTHOR]

• A biochar gel was designed by combining alginate with biochar. • DFT calculation predicted that alginate can improve the adsorption performance of biochar. • MD simulation predicts that biochar can improve the reusability of alginate gel. • Biochar/alginate composite gel was synthesized by compounding activated platanus acerifolia leaf charcoal with alginate, and the experimental results achieved the expectations of the simulation. In this paper, activated biochar and alginate are combined to form gel for the removal of Pb(II) in water. This composite not only improves the adsorption performance of biochar for Pb(II), avoiding the drawback of difficult recovery of biochar but also enhances the structural stability of alginate gel in the recycling process by utilizing biochar. The adsorption mechanism of Pb(II) on functional group-modified carbon and alginate structures, as well as the structural stability of the adsorbent, were observed using density functional theory (DFT) and molecular dynamics (MD) simulations. The results indicate that the adsorption of carboxyl groups to Pb(II) is stronger than that of hydroxyl groups, and the adsorption performance of alginate is stronger than that of carbon. Carbon improves the stability of the composite adsorbent. The biochar/alginate composite gel was synthesized by compounding activated platanus acerifolia leaf charcoal with alginate and was used in the experiment of removing Pb(II) from water. The experimental results achieved the expectations of the simulation. The adsorption isotherms and kinetic data were analyzed and fitted. The results indicate that the adsorption isotherms conform to the Langmuir model, and the adsorption kinetics follow pseudo-second-order adsorption. [ABSTRACT FROM AUTHOR]

It is highly important to develop low-cost hydrogen evolution cathode materials. In this paper, Ni(OH) 2 /NF electrode was prepared by a hydrothermal method using nickel foam (NF) as a substrate, and NiTe-Ni(OH) 2 /NF cathode with high efficiency and low cost was prepared by secondary hydrothermal method. The material was characterized by physical characterization and electrochemical performance tests. Ni(OH) 2 /NF electrode materials prepared by a one-step hydrothermal method had a three-dimensional petal-like pore space structure. This special structure provided abundant active points for the two-step hydrothermal preparation of NiTe-Ni(OH) 2 /NF, which helps to improve the efficiency of HER. Compared with NF and Ni(OH) 2 /NF, NiTe-Ni(OH) 2 /NF cathode exhibited better HER catalytic performance. The results shown that NiTe-Ni(OH) 2 /NF is possesed excellent hydrogen evolution performance, and density functional theory can confirm this. At a current density of 10 mV∙cm−2, the NiTe-Ni(OH) 2 /NF electrode has an overpotential of only 129 mV, long-term stability, and an electrochemically active specific surface area (ECSA) of 91.75 cm−2. The Tafel slope was 31.5 mV∙dec−1, and the charge transfer resistance obtained by electrochemical impedance analysis was 9.81 Ω. This article provided valuable insights into the rational regulation of crystal phases on nickel telluride to improve HER properties. • The synergistic effect of porous petal-like Ni(OH) 2 /NF and uniform nanorod-like NiTe effectively maintained the stable structure of NiTe-Ni(OH) 2 /NF. • NiTe-Ni(OH) 2 /NF nanobars could provide excellent conductive networks and abundant H+ transfer active sites. • The NiTe-Ni(OH) 2 /NF composite had a low overpotential, abundant electrocatalytically active sites, and ultralong stability. • Density functional theory confirmed that NiTe-Ni(OH) 2 /NF had a low hydrogen adsorption energy and excellent kinetic properties. [ABSTRACT FROM AUTHOR]

• Thermal decomposition characteristics of [Pmim]NO 3 and [Amim]NO 3 were explored. • The thermal pyrolysis mechanism of [Pmim]NO 3 and [Amim]NO 3 were evaluated. • Effect of alkyl side chain structure on thermal hazard of imidazole ILs was studied. Imidazole ionic liquid, as a green solvent, is one of the most widely used ionic liquids. Understanding its thermal safety characteristics and mechanism is the essential basis for its safe application. In this paper, the thermal hazard characteristics of two ionic liquids with typical structural characteristics are systematically studied, which were 1-allyl-3-methylimidazole nitrate and 1-propyl-3-methylimidazole nitrate ionic liquids. The thermal decomposition peculiarities of two ionic liquids were systematically analyzed by thermogravimetric analyzer, differential scanning calorimetry and accelerating rate calorimeter techniques, and the risk of thermal runaway is also evaluated. In addition, the pyrolysis products and microscopic pyrolysis mechanism of ionic liquids were studied via thermogravimetry-Fourier transform infrared spectroscopy, thermogravimetric mass spectrometry and density functional theory calculation, and the essential mechanism of thermal hazard were determined. The influence of substituent structure on the thermal hazard characteristics of imidazole nitrate ionic liquid was preliminarily analyzed from macroscopic experiment and microscopic mechanism two aspects. This study provides a theoretical basis for the safe application, design and development of imidazole nitrate ionic liquids. [ABSTRACT FROM AUTHOR]

[Display omitted] • Molar diamagnetic susceptibility values for some amino acids are reported for the first time. • The results obtained are evaluated in terms of electronic structure principles. • Molar diamagnetic susceptibility can be used in the introducing new chemical hardness, polarizability and entropy scales. One of the main aims of the theoretical chemists is to introduce new and useful approaches for the estimation of chemical reactivity descriptors of Conceptual Density Functional Theory (CDFT) like absolute hardness, polarizability and magnetizability. In addition to providing results close to experimental results, the methods developed for this purpose must also be easily applicable to many molecular systems and easy to learn. "Property Prediction from Structural Differences" method proposed by one of the authors of this article is based on the idea that various properties of molecules can be easily calculated by taking the sum of the functional group contributions in the structure of the molecule. The most important thing in the applying of the method is the reliable determination of functional group contributions. In the present paper, using "Property Prediction from Structural Differences" method, we predicted the molar diamagnetic susceptibilities of amino acids with reasonably good accuracy. The computed values are in good agreement with experimental data and the results of previously introduced theoretical models. The reason why amino acids were especially preferred in the study is the lack of the molar diamagnetic susceptibility data of some amino acids in the literature. Additionally, to test whether a molar diamagnetic susceptibility based scale can be proposed for the calculation of any CDFT based reactivity descriptor, DFT computations were also performed for amino acid molecules. The relationships between parameters were evaluated in terms of the electronic structure rules like Maximum Hardness, Minimum Polarizability, Minimum Magnetizability and Minimum Electrophilicity Principles. [ABSTRACT FROM AUTHOR]

• The material exhibits an exceptionally high PLQY of 90.7% at room temperature. • The material exhibits NTQ effects at 90–300 K and achieve pink to orange emission. • The material has good color stability and can reach a color rendering index of 95.2. • The influence of defect states on the negative quenching effect is explained by density functional theory. Low-dimensional organic–inorganic metal halides, which have exceptional host–guest structures and high radiative recombination have emerged as a primary focus in the exploration of multifaceted optoelectronic materials. Nevertheless, the employment feasibility of these materials in optoelectronic field is significantly hindered by the unavoidable thermal quenching effect. In this paper, zero-dimensional (0D) hybrid metal halide (Ph 3 S) 2 SbCl 5 exhibited a negative thermal quenching effect (NTQ) between 90 K and 300 K, and the color of the powder gradually changed from pink (670 nm) to orange (645 nm). The origin of the negative thermal quenching effect in (Ph 3 S) 2 SbCl 5 is attributed to trap states induced by structural defects, as supported by experimental characterization and first-principles calculations. The potential application of this material in light-emitting diodes (LEDs) is explored, showing good color rendering index (95.2) and thermal stability. By uncovering the impact of defects on the photophysical characteristics of materials, this research paves the way for exploring novel approaches to enhance the performance of LEDs based on NTQ mechanism. [ABSTRACT FROM AUTHOR]

In this paper, the diffusive migration behaviour of alloy atoms in aluminium matrix and different types of graphene/aluminium interfaces is systematically investigated by using a machine learning accelerated density functional theory. A small sample dataset is established by first principles calculation, the types of input and output eigenvalues are determined by feature engineering, and the number of input features for perfect interfaces, defective interfaces, and aluminium matrix are finally determined to be 6, 5, and 4 by taking into account the effects of model complexity and prediction accuracy. With a five-fold crossover and by comparing more than a dozen machine learning models, the CatBoost algorithm possesses the lowest error as well as a better coefficient of determination. We further optimized the CatBoost algorithm with further parameters and adjusted the regularization term coefficients to avoid the risk of overfitting. The impact of each feature on the model prediction results was quantitatively described by constructing a matrix of SHAP values. The best performing Catboost model was used to predict the full periodic table data, which in turn was used to screen out the elemental species that are easy to move towards the graphene/aluminium composite interface. Those alloying elements are beneficial for modifying the defective graphene in the composite by comparing the results of elemental diffusive migration in the aluminium matrix as well as at different graphene/aluminium interfaces. The results of machine learning accelerated first principles calculations can provide a theoretical basis for further development of new aluminium alloy composite. • A database was created by first-principles calculations. • The number of input features and descriptors for different targets was determined using recursive feature elimination. • Machine learning accelerated first-principles computation can provide a theoretical basis for further development of novel aluminium alloys. [ABSTRACT FROM AUTHOR]

Ruthenium(II) polypyridine compounds often luminesce, with ligand-dependant lifetimes. This is the third in a series of papers devoted to finding orbital-based luminescence indices (LI) for predicting luminescence lifetimes. The third attempt (LI3) was based upon a frontier molecular orbital (FMO) like estimate of the height of the barrier to conversion from an initial phosophorescent triplet metal-ligand charge transfer ( 3 MLCT) state to a nonluminescent triplet metal-centered ( 3 MC) state which decays nonradiatively. A linear correlation was found between LI3 and extracted empirical average 3 MLCT → 3 MC transition state (TS) barrier heights (E a v e s) which were not believed to be quantitative but which were believed to capture the trends in the true barrier heights correctly. As it is known that E a v e is a large underestimate of the true 3 MLCT → 3 MC TS barrier height in the case of the tris bipyridine ruthenium(II) cation { [Ru(bpy) 3 ] 2 + }, but accurate TS barrier heights are difficult to obtain experimentally, it was judged useful to verify the ideas used to derive the LI3 index in the present work by calculating the energetics of the gas-phase 3MLCT → 3MC reaction for a series of ruthenium(II) tris bipyridine complexes using the same density functional and basis sets used in calculating LI3. Specifically, four closely-related bipyridine complexes { [Ru(N ∧ N) 3 ] 2 + with N ∧ N = bpy (6), 4,4'-dm-bpy (70), 4,4'-dph-bpy (73), and 4,4'-DTB-bpy (74) } were used for these calculations. In the process, we examined the gas-phase trans dissociation mechanism in greater detail than has been previously done and uncovered a two part mechanism. In the first part, the electron is transferred to a single ligand rather than symmetrically to all three ligands. It is the two Ru-N bonds to this ligand which are equally elongated in the transition state. The intrinsic reaction coordinate then continues down a ridge in hyperspace and bifurcates into one of two symmetry-equivalent 3 MC structures with elongated trans bonds. Interestingly, no significant difference is found for the TS barriers for the four complexes treated here. Instead, LI3 is linearly correlated with the energy difference Δ E = E ( 3 MLCT) − E ( 3 MC) , different from what was originally intended but still consistent with the FMO arguments underlying the derivation of LI3. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Probe NPAMQ was used for quantitative and qualitative analysis of Cu2+ ions in foodstuff and water samples. • The LOD was calculated to be 81.49 nM for Cu2+ ions. • The density functional theory (DFT) calculations were performed for NPAMQ and NPAMQ-Cu2+. A novel molecular chemosensor (E)-5-(2-(4-nitrophenyl) azo)-2-methylquinolin-8-ol (NPAMQ) was synthesized and characterized by FT-IR, UV–Vis, 1H NMR, 13C NMR, and TGA. The sensing ability of NPAMQ towards several cations and anions was evaluated by UV–Vis absorption spectroscopy and naked-eye detection. The chemosensor NPAMQ displayed a distinct color change (from yellow to red) towards Cu2+ ions in less than a hundredth of a second, which is easily recognized by the naked eye. UV–Vis spectroscopic studies also proved a bathochromic shift (lower energy) in absorption spectra of NPAMQ in the presence of Cu2+ ions due to the formation of the stable complex NPAMQ-Cu2+. The NPAMQ showed a linear response toward Cu2+ ions (0–50 μM) with detection limits (LOD) of 81.7 nM (0.0197 mg/L). Job's plot showed formation of a complex between Cu2+ ions and chemosensor NPAMQ (NPAMQ-Cu2+ complex) which reveals presence of a stoichiometric ratio of 1:1. Moreover, the binding constant of the NPAMQ-Cu2+ complex was measured to be 3.07 × 104 M−1. NPAMQ can be easily recycled using EDTA and reused for over 5 times preserving a high level of detection efficiency. For better understanding the optical characteristics of the sensor, density functional theory (DFT) calculations were performed for NPAMQ and NPAMQ-Cu2+. Furthermore, the chemosensor NPAMQ was applied for the quantitative and qualitative analysis of Cu2+ ions in foodstuff and water samples. The paper test strips containing NPAMQ chemosensor were also fabricated and applied for detection of Cu2+ ions in aqueous solutions. This designed sensor with great features like cost-effective, short response times, excellent selectivity and sensitively can be used at different pH for detection of copper ions in industrial and biological samples. [ABSTRACT FROM AUTHOR]

Photosensitizer systems play a crucial role in light absorption and charge transfer processes. Designing and selecting dye molecules with exceptional photoelectric features remains a significant scientific challenge in the realm of solar cell research. The paper explores the photovoltaic properties of two D-A'-π-A dyes (CS-70 and CS-72) both individually and after co-sensitization with chlorophyll derivatives, utilizing density functional theory (DFT) and time-dependent density-functional theory (TD-DFT) methods. The monomeric dye molecules share the same donor and conjugated bridge but differ in their auxiliary receptors (benzothiadiazole and naphthobisthiadiazole). Firstly, the study investigates the impact of various auxiliary acceptors on the properties of the dye molecules by analyzing their geometrical structure, frontier molecular orbitals, spectral properties, chemical reaction parameters, intramolecular charge transfer, electron injection, density of projected states, and dye regeneration. A detailed explanation for the superior performance of CS-72 is provided. Furthermore, a solar cell evaluation model was developed for the short circuit current density (Jsc), open circuit voltage (Voc), and photoelectric conversion efficiency (PCE) of the single dye molecule. Subsequently, simulations of the co-sensitized molecules with chlorophyll are performed, focusing on structure, excited state properties and charge transfer, suggesting that co-sensitization enhances spectral properties, light-trapping, and regeneration abilities, and long-range charge transfer between the dye molecules and chlorophyll can be found. The results also demonstrate that the Jsc of the co-sensitized molecules were improved, which facilitates the realization of a higher PCE. This study provides theoretical support for the potential of co-sensitizing dye molecules with chlorophyll to enhance solar cell efficiency, offering valuable insights for the future development of green, cost-effective, and efficient solar cells. [ABSTRACT FROM AUTHOR]

In this paper, the molecular adsorption behavior and photoelectric properties of tungsten trioxide monohydrate (WO 3 ·H 2 O) (002) crystal plane into tungsten trioxide (WO 3) (002) crystal plane were studied by Density Functional Theory (DFT) and Electrochemical Impedance Spectrum (EIS). DFT simulation shows that the adsorption active sites change from two to one after the transformation of WO 3 ·H 2 O (002) crystal plane to WO 3 (002) crystal plane, which further affects the molecular adsorption behavior of the crystal plane. The crystal plane conversion leads to the decrease of the adsorption energy of water (H 2 O) molecules and the increase of the adsorption energy of oxygen (O 2) molecules, which reduces the adverse effect of water molecules on the gas sensing performance of the material and enhances the adsorption of O 2 molecules. Like O 2 molecules and H 2 O molecules, the adsorption of four kinds of organic molecules on two crystal planes will lead to an increase in the conductivity of the crystal plane. The competitive adsorption of organic molecules with O 2 molecules leads to the decrease of the conductivity of both crystal planes. However, acetone (C 2 H 6 CO) molecules are combined in the form of hydrogen bond on the WO 3 ·H 2 O (002) crystal plane, and the contribution to the increase of the conductivity of the crystal plane is significantly higher than that of O 2 molecules. After the conversion to the WO 3 (002) crystal plane, this hydrogen bond disappears. These results were confirmed by EIS test experiments. The UV-Vis diffuse reflectance absorption spectra and photocurrent spectra show that the band gap increases after the WO 3 ·H 2 O (002) crystal plane is converted into the WO 3 (002) crystal plane. Understanding the influence of crystal plane transformation on molecular adsorption behavior and photoelectric properties is of great significance for optimizing the gas sensing properties and regulating the photoelectric properties of materials. • Crystal transformation affects the surface adsorption and photoelectric properties. • Density functional theory is used to simulate the crystal plane molecular adsorption. • The change of the active sites affects the molecular adsorption behavior. • Different molecules have competitive adsorption at the same adsorption active site. • The adsorption of molecules will change the crystal surface conductivity. [ABSTRACT FROM AUTHOR]

[Display omitted] • The main N 2 O removal methods and their catalysts are elucidated. • The previous mechanism studies using DFT are revealed. • The characteristics and improvement strategies of various catalysts are summarized. • The future development of more efficient N 2 O removal catalyst is proposed. • It furnishes theoretical basis and data support for exploring N 2 O removal catalysts. With the increasing global warming, the control of nitrous oxide (N 2 O) emissions in various fields has become urgent. Direct catalytic decomposition is currently the most widely used technology to reduce N 2 O emissions from the nitric acid industry. Selective catalytic reduction (SCR), which can utilize unburned NH 3 from engine exhaust as a reductant, is the most promising technology for reducing N 2 O emissions from ammonia-fueled engines. Increasing demands on the operating temperature window, O 2 /H 2 O/NO resistance, and hydrothermal stability of catalysts have stimulated the development of novel catalytic N 2 O removal catalysts. This review first summarizes the N 2 O generation mechanism, comprehensive N 2 O catalytic removal reaction mechanism and O 2 /H 2 O/NO inhibition mechanism, and then provides a comprehensive overview of the related catalysts, including Ru- and Rh-based precious metal catalysts, Cu- and Co-based non-precious metal catalysts, and Fe- and Cu-based molecular sieve catalysts, focusing on direct catalytic decomposition of N 2 O and N 2 O-SCR. Effective strategies for various catalysts to improve the acidity, redox cycling, and toxicity resistance of the catalysts through modification, creation of novel nanostructures, and exposure of specific crystalline surfaces are summarized, and the challenges and opportunities they face are presented. In addition, this paper summarizes some other methods for catalytic removal of N 2 O and develops a detailed description for the synergistic removal of N 2 O and NO x. Finally, this review provides some suggestions for future research directions. It is hoped that this review will provide a theoretical basis for the optimal preparation of catalysts to bridge the gap between catalyst performance and practical needs, and help to realize the commercial application of efficient catalysts in the near future. [ABSTRACT FROM AUTHOR]

Oxygen evolution reaction (OER) is reconciled with the bottleneck in hydrogen production via photo- or electrocatalytic water splitting. One of the remedies to overcome this shortcoming is to develop catalytically efficient anode materials. Strontium titanate (STO) is a potential candidate for the OER by referring to recent experimental reports on enhanced photocatalytic activity of faceted nanoparticles. In this paper, we perform electronic structure calculations in the density functional theory approximation to study the OER on flat and stepped surfaces, such as encountered in nano-sized STO. We demonstrate that stepped surfaces reveal higher OER activity than flat surfaces, which is consistent with experimental data. We also observe partial breaking of OER scaling relation on stepped surfaces, albeit this does not necessarily cause higher catalytic activity. Finally, we propose recommendations for thorough implementation of zero-point energy calculations as the calculation method may impact the free-energy landscape of the OER. Demonstrating enhanced catalytic properties of a stepped strontium titanate surface toward oxygen evolution reaction. [Display omitted] • Stepped strontium titanate surfaces show increased OER catalytic activity. • The ridge of the step is the main contributor to the increased catalytic activity. • Different configurations of *O and *OOH adsorbates are possible. • The breaking of Δ G 2 + Δ G 3 scaling relation is observed. • The way of approximating the zero-point energy impacts conclusions in selected cases. [ABSTRACT FROM AUTHOR]

Due to the serious consequences of the accumulation of heavy metals in organisms throughout the aqueous phase, the treatment of heavy metal pollution has received extensive attention. Porous geopolymer adsorbent (PGA) has been proposed as a promising remover of heavy metal ions due to its production convenience, low cost, and large surface area. However, it is easy to be broken under water impact. Besides, compared to some other adsorbents, the heavy metal ions capacity of PGA needs to be enhanced. In this paper, PGA with 1000 kg/m3 density was directly prepared based on solid waste including fly ash and slag at room temperature. Nano-silica (NS) was added to improve material strength. The compressive strength of PGA with 2 % NS addition increases up to 63.5 % compared with the material without NS addition, and the removal rate of Cu2+ goes to 78.4 % under this condition. Although the filling effect caused by NS addition is not beneficial for the adsorption ability improvement, the molecular dynamics simulation results confirm that the physical adsorption ability upward is mainly caused by the more Natrium-Aluminate-Silicate-Hydrate formation due to the decreasing Ca/Si ratio. Compared with Calcium-Aluminate-Silicate-Hydrate, Natrium-Aluminate-Silicate-Hydrate has a higher physical adsorption ability due to the evenly distributed electropositive region known from the density functional theory analysis, which contributes to PGA adsorption capacity from the outside environment. [Display omitted] • Porous geopolymer adsorbent is a promising remover of heavy metal ions. • NS addition improves adsorbent strength by 63.5% avoiding the adsorbent from being broken. • NS addition leads to more NASH formation contributing to adsorption ability improvement. • The rate of Cu2+ removed by porous geopolymer adsorbent in this study reaches 78.4%. • The evenly distributed electropositive region of NASH contributes to a stronger adsorption ability. [ABSTRACT FROM AUTHOR]

The chemical mechanical polishing (CMP) process of Through Silicon Via (TSV) tantalum (Ta) base barrier layer is essential for 3D packaging and 2.5D packaging of IC chips. However, achieving high tantalum layer removal rates and an adjustable selection ratio of tantalum to copper (Cu) remains a major challenge. The effect of ethylenediamine etramethylenephosphonic acid (EDTMPA) as a complexing agent on the chemical-mechanical polishing of tantalum base barrier layer of TSV was studied in this paper. When the concentration of EDTMPA is 2 wt%, the removal rates of Cu and Ta are 561 Å/min and 1533 Å/min, respectively, and the rate selection ratio of Ta and Cu reaches 2.73:1. Through electrochemical experiments, X-ray photoelectron spectrometer (XPS), Scanning electron microscope (SEM) and Density Functional Theory (DFT) simulation, the mechanism of EDTMPA promoting the removal of Cu and Ta was revealed. It was found that EDTMPA molecules reacted with Cu and Ta and oxides to form mass complexes, which promoted the corrosion of Cu and Ta. By comparing the surface quality before and after polishing with atomic force microscopy, it is found that the surface roughness of Cu decreases from 1.4 nm before polishing to 0.164 nm after polishing, and the surface roughness of Ta decreases from 1.74 nm before polishing to 0.142 nm after polishing. The results show that EDTMPA can effectively improve the surface quality of TSV tantalum barrier layer after polishing. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Multi-level optimization of BCLG achieve biomass utilization by obtaining high-purity syngas. • Comparing the DOS, d-dond and adsorption properties, CuFe 2 O 4 is the best composite oxygen carrier for BCLG. • Research BCLG reaction mechanism by ReaxFF MD simulation for obtaining the gasification temperature. • Based on CuFe 2 O 4 and reaction mechanism, process optimization of BCLG is achieved. Biomass chemical looping gasification (BCLG) is one of the essential technology to utilize renewable resources, but the current lack of in-depth research on BCLG makes it difficult for practical industrial applications. In this paper, the combination of quantum chemical calculation, ReaxFF molecular dynamic (ReaxFF MD) simulation, and process simulation is used to conduct an in-depth study of BCLG process. Firstly, three composite oxygen carriers (CuFe 2 O 4 , CoFe 2 O 4 , and Fe 3 O 4) are selected by density functional theory (DFT), which finally indicates that CuFe 2 O 4 is the best composite oxygen carrier for BCLG. Then, the reaction mechanism between syngas and oxygen carrier surface is studied at the microscopic level, which validates the high performance of CuFe 2 O 4. After determining the oxygen carrier, the reaction mechanism of BCLG and the effect of temperature on the product distribution are studied by ReaxFF MD simulation. Finally, the process simulation of BCLG is constructed based on the results discussed above. [ABSTRACT FROM AUTHOR]

Silicon-based composite anodes continue to raise interest for their high theoretical specific capacity, but the complexity of their behaviour during battery operation presents an obstacle to both their characterization and their practical application. In this paper we present a comprehensive multiscale model of a Si-based composite anode, based on a detailed characterization and encompassing nano-, micro-, and meso-scale details. The model is used to explore the relationship between the chemo-mechanical changes in the anode components and the electrode stability during battery operation, through the prediction of the morphological evolution of the material during the lithiation process. Through the combined analysis of DFT, FEM, and DEM models we highlight the influence of Si and SiO 2 lithiation on electrode swelling and damage, and the predominant influence of particle-level morphology on electrochemical behaviour. [Display omitted] • Multiscale model of a SiO x /C composite anode for lithium-ion batteries. • Direct correlation of nano- and micro-scale morphology with electrode stability. • Ab initio theoretical volumetric expansion value for Li 3.75 Si validated at +244%. • Morphology-specific SiO x /C particle volumetric expansion in the range 60%–100%. • Low-swelling SiO x /C particles preserve up to 90% binder upon lithiation at 875 mAh/g. [ABSTRACT FROM AUTHOR]

[Display omitted] • High-mass loading CoO@NiCo-LDH was prepared from ZIF-67 self-sacrificing template. • Irregular electrode surfaces of 3D nanochannels enable rapid reaction kinetics. • Core-shell structure enhances LDH's conductivity and Faradaic activity. • A simple one-step hydrothermal method to prepare the High-mass loading FeNi-S anode. The rapidly growing market of portable and wearable smart electronics has created strong interest in flexible electrode materials with high specific capacitance and fast charging/discharging properties. However, high mass-specific capacitance active materials are often limited by the low areal mass-loading required. High areal capacity electrodes can make more efficient use of the limited internal space of these miniature devices by minimizing the volume and weight taken by current collectors and separators. Herein, a method is proposed to prepare a nickel–cobalt layered double hydroxide binder-free cathode on flexible carbon cloth with a mass loading of 20 mg cm−2. This core–shell hybrid structure prepared using a MOF self-sacrificing template, achieves a high energy density using thick electrodes while improving their slow kinetics by enhancing both the ion diffusion process and charge transfer dynamics. The areal capacitance reaches a staggering 4.42 mAh cm−2 (31.79 F cm−2) at a current density of 8 mA cm−2. Furthermore, a one-step hydrothermal method to prepare the FeNi-S anode (1.67 mAh cm−2, 2 mA cm−2) is proposed. Upon assembling with the gel electrolyte, this flexible device possesses an impressive energy density of 3.29 mW h cm−2 (3 mW cm−2). It can readily supply energy to watches, wireless e-paper, LEDs, and can be anticipated to be widely used in next-generation high-performance portable and wearable devices. [ABSTRACT FROM AUTHOR]

[Display omitted] • Carbon foam loaded Co and Ni single atoms are directly used as HER working electrode. • Co and Ni atoms produce synergistic effect to accelerate H* adsorption and desorption. • CoNi-N/CMF with non-bonding configuration shows excellent HER performance in both acidic and alkaline media. Developing a new type of high-loaded single atom catalysts to further improve the performance of electrocatalytic hydrogen evolution reaction (HER) is still a major challenge. However, multiple single atom sites with synergistic effect between different atoms can promote catalytic activity. In this work, we develop a strategy based on inkjet printing-pyrolysis to anchor Co and Ni single atom sites on carbon foam substrate to form CoNi-N/CMF self-supporting electrode, which shows outstanding electrocatalytic hydrogen evolution performance. Aberration-corrected transmission electron microscopy revealed the coexistence of well dispersed Co and Ni single atoms with atomic distance of 5.3 Å, indicating part of Co and Ni single atoms are indirect bonding between the two atoms. CoNi-N/CMF showed impressive overpotential of 32.6 and 36.6 mV to reach a current density of 10 mA cm−2 under acidic and alkaline conditions, respectively, which is lower than that of Co or Ni single atoms. Density functional theory calculations revealed that the non-bonding configuration between the two metal atoms forms a synergistic effect to accelerate H* adsorption and desorption, thus optimizing the HER process. This paper provides a new method for the development of single atom catalysts. [ABSTRACT FROM AUTHOR]

Mechanistic modeling of chalcopyrite separation from talc by HDP. [Display omitted] • Using a new reagent HDP as an inhibitor for flotation of chalcopyrite and talc. • Analyzed the selective adsorption mechanism of HDP. • The phase diagram of HDP adsorption on talc surface was analyzed through AFM. • The adsorption energy of HDP with different minerals was calculated through DFT. • The interaction form between HDP and talc was simulated through DFT calculations. Chalcopyrite and talc exhibit strong natural hydrophobicity, making it challenging for conventional inhibitors to effectively separate the two through flotation. This paper proposes a novel starch-modified reagent, Hydroxypropyl distarch phosphate (HDP), for the separation of chalcopyrite and talc. Micro-flotation test results indicate that HDP has a significant inhibitory effect on talc, while the flotation recovery of chalcopyrite is almost unaffected. Effective separation of chalcopyrite and talc can be achieved with the addition of only 5 mg/L of HDP. Zeta potential, adsorption amount, and FTIR tests reveal that HDP can selectively adsorb onto the surface of talc, with minimal adsorption on chalcopyrite. Further analysis through XPS and AFM indicates that HDP acts on the talc surface through physical adsorption, generating a larger phase angle to inhibit talc flotation. Concurrently, Density functional theory (DFT) simulation calculations suggest the presence of hydrogen bonding during the adsorption process between HDP and talc. [ABSTRACT FROM AUTHOR]

In spite of being commercialized for well over a century, hydrogenation is still a subject of intensive research and development. A patent landscape analysis showed high growth rates for topics related to climate change, bio-renewables, low waste and recyclability. The current paper describes trends, providing examples on the effect of structure sensitivity, on novel intermetallic active phases and on discoveries initiated by modelling. Due to increased processing costs and a negative environmental impact of undesirable by-products, the present focus favours high selectivity over activity. A relatively new class of materials showing an exponential growth in publications, these are the so-called intermetallics. These materials are defined as compounds formed by at least two metals, with – at least partly – ordered crystal structures which are different from the ones of the constituting elements. Non-metallic active phases formed by interaction of a metal ion and a (reducible) support may have a superior hydrogenation performance compared to the corresponding zero-valent metals. Aided by Density Functional Theory modelling (DFT) new, often intermetallic catalysts like Ni 5 Ga 3 were identified which sparked a great number of follow-up studies. • An exponential growth in hydrogenation patents in the last decade is observed. • For many reactions the rate of reaction declines when nanoparticle size decreases. • Non-metallic active phases may have a superior performance. • Aided by DFT, new catalysts like Ni 5 Ga 3 for CO 2 hydrogenation, were identified. [ABSTRACT FROM AUTHOR]