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Graphitic carbon nitride (g-CN), composed of heptazines, holds promise as a photocatalyst for hydrogen evolution. But its suboptimal visible light absorption and poor electrical conductivity limit photocurrent density and catalytic activity. Carbon atom doping, specifically carbon-modified g-CN (C/g-CN), enhances photocatalytic performance. This study investigates the impact of carbon dopants at the three-coordinated nitrogen atom (N3C) and the two-coordinated nitrogen atom (N2C) sites on the reaction mechanism of water-splitting in the ground and excited states. Nonadiabatic dynamics simulations are employed on water hydrogen-bonded to C-doped heptazines (H 2 O⋯C/heptazine) to unveil the molecular-level decomposition mechanism in the excited states. The simulations reveal that the C dopants at N2C improve the activity for water-splitting in the ground state. The C dopants at N3C improve the H atom detachment from H 2 O via the electron-driven proton transfer (EDPT) process. The synergistic effect of carbon dopants on enhanced catalytic activity of C/g-CN is elucidated. [Display omitted] • The reaction mechanism for water-splitting is studied on the C-doped g-CN. • The C dopants at the N2C site improve the activity in the ground state. • The C dopants at the N3C site improve light adsorption and photoinduced reactions. • The synergistic effect of carbon dopants on enhanced catalytic activity is reported. [ABSTRACT FROM AUTHOR]

Advancing the development of economical, high-performance, and durable non-precious metal electrocatalysts for oxygen evolution reaction (OER) holds critical significance. This study presents a self-supporting ternary metal phosphide (NiCoFe–P/NF) electrode developed by direct phosphating metal-organic frameworks (MOFs) precursor. Benefiting from a three-dimensional hierarchical porous structure, optimized electronic configuration, high electrical conductivity, and synergistic effect of multiple elements, the synthesized NiCoFe–P/NF electrocatalyst exhibits exceptional catalytic performance compared to the monometallic or bimetallic phosphides, achieving a low overpotential of 209 mV and a Tafel slope of 29 mV dec−1 at 10 mA cm−2 in 1 M KOH solution. In addition, the prepared catalyst exhibits superior stability and durability, as evidenced by its well-preserved morphology after 48 h of stability test. Furthermore, at a high current density of 100 mA cm−2, the long-term efficiency remains >90% even after 96 h. Density functional theory (DFT) calculations reveal that the high catalytic performance of the NiCoFe–P/NF catalyst is ascribed to modified electronic states and lower adsorption energy to the related species. This study not only presents the synthesis of extremely stable and active OER catalysts but also offers a novel and practical method for the development of new catalysts. [Display omitted] • Self-supporting trimetallic phosphide was investigated for OER. • NiCoFe–P/NF electrode provides superior OER activity and stability. • DFT calculations explain the origin of the high catalytic activity. • A chemically uniform trimetallic two-dimensional MOF served as the precursor. [ABSTRACT FROM AUTHOR]

Studying the excited‐state decay process is crucial for materials research because what happens to the excited states determines how effective the materials are for many applications, such as photoluminescence and photocatalysis. The high computational cost, however, limits the use of high‐accuracy theoretical approaches for analyzing research systems containing a significant number of atoms. Time‐dependent density functional theory is a practical approach to investigate the photorelaxation processes in these systems, as demonstrated in the studies of the excited‐state decays of heptazine‐water clusters and adenine in water described in this review. Here, we highlight the importance of conical intersections in the excited‐state decay processes of these systems using the aforementioned examples. In the heptazine‐water and adenine‐water systems, these intersections are associated with the photocatalytic water splitting reaction, caused by a barrierless reaction called water to adenine electron‐driven proton transfer. We expect the result would be helpful for researching the excited‐state decays of graphitic carbon nitride materials and DNA nucleotides. [ABSTRACT FROM AUTHOR]

Molecular photothermal conversion materials are recently attracting increasing attention for phototherapy applications. Herein we investigate the excitation and de-excitation processes of a photothermal molecule (C1TI) that is among the recently developed class of small-molecule-based photothermal imines with superb photothermal conversion efficiencies (PTCEs) up to 90% and a molecule (M2) that is constructed by replacing the amino group of C1TI with an H atom, via excited-state dynamics simulations based on the time-dependent density functional theory (TD-DFT). The simulations reveal fast (<150 fs of average time) nonradiative decays of the lowest excited singlet (S1) state to a conical intersection (CI) with the ground (S0) state in high yields (C1TI: 93.9% and M2: 87.1%). The fast decays, driven by C=N bond rotation to a perpendicular structural configuration, are found to be barrierless. The slight structural difference between C1TI and M2 leads to drastically different S0-S1 energy surfaces, especially M2 features a relatively much lower CI (0.8 eV in energy) and much more decay energy (1.0 eV) to approach the CI. This work provides insights into the de-excitation mechanisms and the performance tuning of C=N enabled photothermal materials. [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride (CN) materials have drawn remarkable research attention due to their extraordinary optical properties, which are especially promising for metal-free photocatalysis and photoluminescence. Herein we theoretically study the light absorption, electronic, and excitonic characteristics of covalently hybrid structures of CN quantum dots (CNQDs) and graphene quantum dots (GQDs). Density functional theory (DFT) and time-dependent DFT (TD-DFT) reveal that the relative size of CNQDs and GQDs and chemical modification to GQDs or CNQDs surface are critical determining the absorption and photocatalytic/photoluminescent performances of the as-studied structures. Importantly, the distribution position of the photoexcited electron–hole pair is found to depend on the relative size of CNQDs and GQDs, and chemical groups such as epoxy group may lead to distinct exciton distributions in the CNQD–GQD hybrid structures after attaching them to GQD or CNQD surface as compared to the case of pristine GQD and CNQD, indicating a non-negligible influence of unintended chemical reactions to CNQDs and/or GQDs under working conditions on the efficiencies of the materials for photocatalytic and photoluminescent applications. [ABSTRACT FROM AUTHOR]

Enhancing the photoconversion efficiency of graphene-based nanomaterials, especially graphene quantum dots (GQDs) and graphene nanoribbons (GNRs), has been a long pursued interest in diverse optical applications. Though chemical modification has shown its effectiveness to enhance the photoluminescence efficiencies of these materials, an accurate, comprehensive fundamental understanding of this enhancement is demanded for further development. Herein, density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations reveal that chemical species on the graphene nanostructure surface perturb the intrinsic electronic structures of the graphene moiety, with the perturbation manner and extent crucially depending on the binding positions of the species. In several configurations studied, the surface species lead to significantly enlarged oscillator strengths for the lowest optical transition (S 1 →S 0) and localized excitons (bounded electron and hole) compared to those of the pristine nanographene structures, indicative of their role in enhancing the photoluminescence as emission centers. By contrast, the surface species in the other configurations show trivial influence on the emission efficiency, as indicated by the only slightly altered electronic/excitonic structures and oscillator strengths. These results provide a fundamental understanding of the trap emission mechanism and also the tuning/engineering of photoluminescence efficiencies in relevant materials. Image 1 [ABSTRACT FROM AUTHOR]

The exploration of inexpensive, facile, and large-scale methods to prepare carbon scaffolds for high sulfur loadings is crucial for the advancement of Li-S batteries (LSBs). Herein, the authors report a new nitrogen and oxygen in situ dual-doped nonporous carbonaceous material (NONPCM) that is composed of a myriad of graphene-analogous particles. Importantly, NONPCM could be fabricated on a kilogram scale via inexpensive and green hydrothermal-carbonization-combined methods. Many active sites on the NONPCM surface are accessible for the efficient surface-chemistry confinement of guest sulfur and its discharge product; this confinement is exclusive of physical entrapment, considering the low surface area. Electrochemical examination demonstrates excellent cycle stability and rate performance of the NONPCM (K)/S composite, even with a sulfur loading of 80 or 90 wt%. Hence, the scaffolds for LSBs exhibit potential for industrialization through further optimization and expansion of the present synthesis. [ABSTRACT FROM AUTHOR]

Abstract: Dyeing wastewater removal is important for the water treatment, and adsorption is an efficient treatment process. In this study, three modified bentonites, chitosan modified bentonite (CTS-Bent), hexadecyl trimethyl ammonium bromide (CTAB) modified bentonite (CTAB-Bent), and both chitosan and hexadecyl trimethyl ammonium bromide modified bentonite (CTS–CTAB-Bent) were prepared and characterized by FTIR and XRD analysis. Batch experiments were conducted to evaluate the adsorptive removal of weak acid scarlet from aqueous phase using modified bentonites under different conditions. The results show that the adsorption capacity of weak acid scarlet onto natural bentonite was low (4.9%), but higher for 1CTS-Bent and 1CTS–10CTAB-Bent. The optimal conditions for weak acid scarlet adsorption were 1% chitosan, 10% CTAB, at 80°C and reaction time 2.5h. The best removal efficiency was ∼85%, and the adsorption capacity of weak acid scarlet was around 102.0mgg−1, much higher than that of commercial activated carbon (27.2mgg−1). These results suggest that 1CTS–10CTAB-Bent is an excellent adsorbent for effective weak acid scarlet removal from water. The adsorption isotherms of weak acid scarlet were investigated. It was found that Langmuir and Temkin models fitted the data very well (R 2 >0.99). [Copyright &y& Elsevier]

Heteroatom doping, especially with elements of lower electronegativity and smaller atomic radius, can effectively modulate the electronic structure and surface properties of electron materials, facilitating the electrochemical performance of supercapacitors. Herein, we have designed boron-doped NiCoP nanoarrays grown on carbon cloth (B-NCP-CC) for supercapacitor cathode materials using a simple process method combining hydrothermal, calcined phosphating and boronation processes. The introduction of boron, with lower electronegativity (2.04) and smaller atomic radius (0.85 Å) than phosphorus (2.19 and 1.00 Å), induces electron redistribution and shortens the Ni/Co–B bonds, enhancing their redox activity and charge transfer kinetics. The boron doping greatly enables the B-NiCoP-CC-18 (NiCoP-CC borated for 18 h) cathode material to provide a high capacity of 801 C g−1. The assembled B-NiCoP-CC-18‖‖AC hybrid supercapacitor achieves a high energy density of 73.22 W h kg−1 at a power density of 963.8 W kg−1 and retains 90% capacity after 5000 cycles, significantly improving the stability of nickel-based materials. Besides, density functional theory (DFT) calculations further elucidate that the introduction of boron increases the d-band centers of Ni and Co in NiCoP, promoting the conductivity and enhancing the electrochemical properties. [ABSTRACT FROM AUTHOR]

[Display omitted] • 1D MWO 4 (M = Mn, Co, Cd) nanomaterials were synthesized by electrospinning method. • CoWO 4 nanotubes exhibited superior efficiency in degrading BPA under UV–Vis–NIR light. • The wide-spectrum responses mechanism for MWO 4 (M = Mn, Co, Cd) were explained by DFT. Broadening the absorption region to near-infrared (NIR) light is critical for the photocatalysis due to the larger proportion and stronger penetration of NIR light in solar energy. In the present paper, one-dimensional (1D) MWO 4 (M = Mn, Co, and Cd) materials synthesized by electrospinning technique, were studied by combining the density functional theory (DFT) with experiment results, which possessed the enhanced light absorption capability within the range of 200–2000 nm. It was proved that in the ultraviolet–visible (UV–Vis) region, the absorption bands of CoWO 4 and MnWO 4 samples were attributed to the metal-to-metal charge transfer mechanism, while the absorption of CdWO 4 sample may be referable to the ligand-to-metal charge transfer mechanism. In the near-infrared (NIR) region, the absorption of CoWO 4 and MnWO 4 primarily originated from the d-d orbital transitions of Mn2+ and Co2+. The photocatalytic experimental results showed that the degradation rates for bisphenol A (BPA) over CoWO 4 , MnWO 4 , and CdWO 4 photocatalysts under UV–Vis/NIR light irradiation for 140 min/12 h were 78.8 %/75.9 %, 23.8 %/21.3 %, 12.8 %/8.7 %, respectively. This research offers the novel insights into the precise construction of tungstate catalytic systems and contributes to the advancement of UV–Vis–NIR full spectrum photocatalytic technology, and lays a foundation for a cleaner and more environmental-friendly future. [ABSTRACT FROM AUTHOR]

Developing new soft magnetic amorphous alloys with a low cost and high saturation magnetization (Bs) in a simple alloy system has attracted substantial attention for industrialization and commercialization. Herein, the glass-forming ability (GFA), thermodynamic properties, soft magnetic properties, and atomic structures of Fe80+xSi5−xB15 (x = 0–4) amorphous soft magnetic alloys were investigated by ab initio molecular dynamics (AIMD) simulations and experiments. The pair distribution function (PDF), Voronoi polyhedron (VP), coordination number (CN), and chemical short- range order (CSRO) were analyzed based on the AIMD simulations for elucidating the correlations between the atomic structures with the glass-forming ability and magnetic properties. For the studied compositions, the Fe82Si3B15 amorphous alloy was found to exhibit the strongest solute–solute avoidance effect, the longest Fe-Fe bond, a relatively high partial CN for the Fe-Fe pair, and the most pronounced tendency to form more stable clusters. The simulation results indicated that Fe82Si3B15 was the optimum composition balancing the saturation magnetization and the GFA. This prediction was confirmed by experimental observations. The presented work provides a reference for synthesizing new Fe-Si-B magnetic amorphous alloys. [ABSTRACT FROM AUTHOR]

Although molecular self‐assembled porous materials capable of ratiometric fluorescence probing and recycling of metal ions are both economically and environmentally attractive, very few current efforts have been devoted. Herein, we demonstrated a three‐dimensional pure organic cage, namely 4‐cage, which can serve as a fluorescent probe for simultaneous ratiometric detection and recycling of Ag+ ion. Taking advantage of the promising emission behavior of its rigidified tetraphenylethylene scaffolds and the chelating ability of its dynamically reversible imine moieties, on one hand, upon the addition of Ag+, 4‐cage undergoes coordination to form a stable but poorly soluble fluorescent complex, Ag+@4‐cage, accompanied by a fluorescence color change from bluish‐green to yellowish‐green. This allows us to differentiate Ag+ from other cations with high selectivity. On the other hand, upon the addition of Cl− anion, Ag+@4‐cage can be effectively converted into free 4‐cage due to the competitive coordination of Cl− with Ag+. Through this process, secondary usage of 4‐cage and the recycling of Ag+ ion can be achieved. [ABSTRACT FROM AUTHOR]

Whispering‐gallery‐mode (WGM) microcavities featuring distinguishable sharp peaks in a broadband exhibit enormous advantages in the field of miniaturized photonic barcodes. However, such kind of barcodes developed hitherto are primarily based on microcavities wherein multiple gain medias were blended into a single matrix, thus resulting in the limited and indistinguishable coding elements. Here, a surface tension assisted heterogeneous assembly strategy is proposed to construct the spatially resolved WGM hetero‐microrings with multiple spatial colors along its circular direction. Through precisely regulating the charge‐transfer (CT) strength, full‐color microrings covering the entire visible range were effectively acquired, which exhibit a series of sharp and recognizable peaks and allow for the effective construction of high‐quality photonic barcodes. Notably, the spatially resolved WGM hetero‐microrings with multiple coding elements were finally acquired through heterogeneous nucleation and growth controlled by the directional diffusion between the hetero‐emulsion droplets, thus remarkably promoting the security strength and coding capacity of the barcodes. The results would be useful to fabricate new types of organic hierarchical hybrid WGM heterostructures for optical information recording and security labels. [ABSTRACT FROM AUTHOR]

Whispering‐gallery‐mode (WGM) microcavities featuring distinguishable sharp peaks in a broadband exhibit enormous advantages in the field of miniaturized photonic barcodes. However, such kind of barcodes developed hitherto are primarily based on microcavities wherein multiple gain medias were blended into a single matrix, thus resulting in the limited and indistinguishable coding elements. Here, a surface tension assisted heterogeneous assembly strategy is proposed to construct the spatially resolved WGM hetero‐microrings with multiple spatial colors along its circular direction. Through precisely regulating the charge‐transfer (CT) strength, full‐color microrings covering the entire visible range were effectively acquired, which exhibit a series of sharp and recognizable peaks and allow for the effective construction of high‐quality photonic barcodes. Notably, the spatially resolved WGM hetero‐microrings with multiple coding elements were finally acquired through heterogeneous nucleation and growth controlled by the directional diffusion between the hetero‐emulsion droplets, thus remarkably promoting the security strength and coding capacity of the barcodes. The results would be useful to fabricate new types of organic hierarchical hybrid WGM heterostructures for optical information recording and security labels. [ABSTRACT FROM AUTHOR]

Liquid–liquid phase transition (LLPT) is a transition from one liquid state to another with the same composition but distinct structural change, which provides an opportunity to explore the relationships between structural transformation and thermodynamic/kinetic anomalies. Herein the abnormal endothermic LLPT in Pd43Ni20Cu27P10 glass-forming liquid was verified and studied by flash differential scanning calorimetry (FDSC) and ab initio molecular dynamics (AIMD) simulations. The results show that the change of the atomic local structure of the atoms around the Cu-P bond leads to the change in the number of specific clusters <0 2 8 0> and <1 2 5 3>, which leads to the change in the liquid structure. Our findings reveal the structural mechanisms that induce unusual heat-trapping phenomena in liquids and advance the understanding of LLPT. [ABSTRACT FROM AUTHOR]

[Display omitted] • The effect of atomic structures on GFA was studied by AIMD. • The average degree of LFFS is critical factor for enhancing GFA. • The effect of electronic structures on M s was studied by DFT. The poor glass forming ability (GFA) and magnetic properties of Co-based metallic glasses limit their applications. Herein the effects of similar element substitution of Co by Fe on the GFA and magnetic properties of Co 72.5-x Fe x Si 12.5 B 15 (x = 0, 4.5, 20, and 36) amorphous alloys were studied by experiments and density functional theory (DFT) calculations. The experimental results indicate that Fe substitution for Co improves the GFA of the studied metallic glasses, but in a concentration dependent manner, where Co 52.5 Fe 20 Si 12.5 B 15 shows the best GFA. Meanwhile, the saturated mass magnetization (M s) enhances with increasing Fe content. The atomic structures were analyzed by pair distribution function, coordination number, chemical short-range order, Voronoi polyhedron, and locally five-fold symmetry, and it was found that the highest average degree of the locally five-fold symmetry in Co 52.5 Fe 20 Si 12.5 B 15 is a critical factor for enhancing GFA, which improves the stability of the local atomic structures by increasing the packing density and reducing the potential energy. Density of states and magnetic moments calculated for the four metallic glasses manifest that the larger magnetic moment of Fe atoms and gradual increase in the contribution of the Fe 3d state are responsible for the increase in the M s with Fe content. This work links the GFA and magnetic properties of Co–Fe–Si–B metallic glasses with their atomic/electronic structures, providing reference for designing Co-based metallic glasses with good GFA and enhanced magnetism. [ABSTRACT FROM AUTHOR]

Polymeric carbon nitride (PCN) is a promising candidate for photocatalytic hydrogen evolution reaction (HER). However, the fast recombination of photogenerated charge carriers often gives an overall poor photocatalytic activity. Herein, we report anchoring of a donor-acceptor structure into the C–N skeleton, made in one-pot synthesis, where thiophene and cyano groups are introduced as the donor and acceptor, respectively, to modulate the electronic structure of pristine PCN. The separation and migration of the photogenerated charge-carriers in the PCN with donor-acceptor structure (CN-Cy-Th) were significantly promoted due to the enlarged π-conjugated system and much strengthened electron-redistribution effect, as confirmed by a series of experimental characterizations and density functional theory calculations. As such, the CN-Cy-Th exhibited a remarkable visible-light photocatalytic hydrogen evolution rate of 2.448 mmol g−1h−1, which was 9.0-fold rise as compared with that of pristine PCN (Bulk CN). This work provides a facile and effective new pathway for accelerating the transfer of photogenerated charge carriers in semiconducting materials and constructing high performance photocatalysts. To solve the problem of fast recombination of photogenerated charge carriers and poor photocatalytic activity of pristine polymeric carbon nitride (PCN), we anchored a donor-acceptor structure into the C–N skeleton, where thiophene and cyano groups were introduced as the donor and acceptor, respectively, to modulate the electronic structure of pristine PCN. The separation and migration of the photogenerated charge-carriers in the PCN with donor-acceptor structure (CN-Cy-Th) were significantly promoted due to the enlarged π-conjugated system and much strengthened electron-redistribution effect, as confirmed by a series of experimental characterizations and density functional theory calculations. As such, the CN-Cy-Th exhibited a remarkable visible-light photocatalytic hydrogen evolution rate of 2.448 mmol g−1h−1, which was 9.0-fold rise as compared with that of pristine PCN (Bulk CN). This work provides a facile and effective new pathway for accelerating the transfer of photogenerated charge carriers in semiconducting materials and constructing high performance photocatalysts. [Display omitted] [ABSTRACT FROM AUTHOR]

In this study, four polycarbazole derivatives (PCMB-Ds) with different alkyl side chains were designed and synthesized via Wittig–Horner reaction. A novel solid-phase electrochemiluminescence (ECL) system was prepared by immobilizing PCMB-D on an indium tin oxide (ITO) electrode with polyvinylidene fluoride (PVDF) in the presence of tripropylamine (TPrA). It could be found that the increase in alkyl side chain length had little effect on the ECL signal of PCMB-D, while the increase in the degree of polymerization (DP) greatly enhanced the ECL signal. Furthermore, the P-3/ITO ECL sensor based on the polyoctylcarbazole derivative (P-3) with the best ECL performance was successfully constructed and detected Fe3+ under the optimal experimental conditions. The ECL signal steadily diminished with the increased concentration of Fe3+ because of the competition and complexation between Fe3+ and P-3 under the condition of pH 7.4. This P-3/ITO platform could realize a highly sensitive and selective detection of Fe3+ with a wide detection range (from 6 × 10−8 mol/L to 1 × 10−5 mol/L) and low detection limit of 2 × 10−8 mol/L, which could allow the detection of Fe3+ in multiple scenarios, and would have a great application prospect. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ru-doped SrFe 1-x Ru x O 3-δ perovskite oxides were successfully fabricated through a modified sol–gel method. • The SrFe 0.7 Ru 0.3 O 3-δ exhibits significantly enhanced bifunctional electrocatalytic activities for HER and OER in alkaline electrolytes. • The DFT studies demonstrate Ru doping optimizes the electronic structure of SrFe 0.7 Ru 0.3 O 3-δ and thus improves the charge transfer efficiency. • An electrolyzer with SFR30 as both the anode and cathode catalysts requires only a cell voltage of 1.58 V vs. RHE to drive a current density of 10 mA cm−2 in an alkaline medium. Recently, perovskite oxides have acquired a rapidly growing research interest in energy storage and conversion systems, especially the electrolysis of water. Rational doping is an extremely effective strategy to enhance the hydrogen evolution reaction/oxygen evolution reaction (HER/OER) of the perovskite oxides. Herein, a series of novel bi-functional electrocatalysts were synthesized by doping Ru in SrFeO 3-δ perovskite oxide (SrFe 1-x Ru x O 3-δ , x = 0, 0.15, 0.30, 0.45) which exhibit remarkable enhancements of HER/OER activities and long-term stabilities in the alkaline solution (1.0 M KOH). Among them, SrFe 0.7 Ru 0.3 O 3-δ (SFR30) shows the best electrocatalytic activities for overall water splitting, exhibiting low overpotentials for HER (∼41 mV) and OER (∼334 mV) at −10 and 10 mA cm−2, respectively, generating current densities of 10 mA cm−2 in alkaline electrolytic cell using the potential of 1.58 V. In addition, the SFR30 electrocatalyst exhibits remarkable stability which can be operated continuously for 96 h without significant delay. Density functional theory (DFT) calculations indicate that Ru doping can effectively modulate the adsorption of intermediates on the active sites to achieve excellent electrocatalytic performance. Many new prospects have been opened for the development of bi-functional electrocatalysts for overall water splitting. [ABSTRACT FROM AUTHOR]

• Mo is successfully doped into SrCo 0.5 Fe 0.5 O 3-δ perovskite oxides using a modified sol-gel method. • SrCo 0.5 Fe 0.4 Mo 0.1 O 3-δ requires ∼200 and ∼310 mV overpotentials to reach 10 mA cm−2 for HER and OER. • A current density of 10 mA cm−2 could be achieved by applying a potential of 1.68 V vs. RHE in the SCFM10||SCFM10 electrolyzer. • SrCo 0.5 Fe 0.4 Mo 0.1 O 3-δ exhibits remarkable stability for HER and OER in alkaline electrolyte. Perovskite oxides with high electrocatalytic activities and cost-effectiveness can be developed by rational doping. Here, we fabricate a series of perovskite oxides comprising SrCo 0.5 Fe 0.5-x Mo x O 3-δ (x = 0, 0.05, 0.10, 0.15) doped with different proportions of Fe and Mo elements to enhance the long-term stabilities and electrocatalytic activities for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Among them, SrCo 0.5 Fe 0.4 Mo 0.1 O 3-δ (SCFM10) exhibits the optimum electrocatalytic activity for water splitting, exhibiting overpotentials at −10 mA cm−2 and 10 mA cm−2 of ∼200 mV for HER and ∼310 mV for OER, respectively, generating a current density of 10 mA cm−2 using only 1.68 V in a two-electrode electrolytic cell. Additionally, SCFM10 demonstrates outstanding stability, maintaining continuous operation for 100 h without visible decay. These results give some new points of view into the development of bifunctional catalysts for the purpose of efficient water splitting in a sensible way. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • The semi-ionic C-F (SIF) bonds could weaken Li-O coordination in PEO electrolyte. • The SIF bonds modified electrolytes facilitate the formation of LiF-rich SEI. • The SIF-PEO/LiTFSI exhibits good cycling stability toward high-voltage cathode. Poly(ethylene oxide) (PEO) based electrolytes are of special potential for solving the safety problem of lithium metal batteries due to their high processability and outstanding solvation ability of lithium salts. Unfortunately, their insufficient ionic conductivity and limited electrochemical stability greatly hinder their applications. Herein, we propose a strategy based on regulating the Li-O coordination for high-voltage solid lithium-metal batteries, by generating a fluorinated PEO with C-F bonds in a semi-ionic state (SIF-PEO) as the electrolyte. The Li+ solvation structure in SIF-PEO/LiTFSI electrolyte can be modulated by SIF bonds, and the Li-O coordination is weakened which effectively boosts the Li+ ion transport ability. The density functional theory (DFT) calculation reveals that the introduction of SIF bonds into PEO depresses the highest occupied molecular orbital (HOMO) energy level which contributes to a higher oxidative decomposition potential of the electrolyte. As a consequence, the ionic conductivity and cathodic oxidation potential of SIF-PEO are significantly elevated as compared to pristine PEO. The SIF-PEO electrolyte shows highly stable cycling performance of Li symmetric cells at a current density of 0.1 mA cm−2 (up to 550 h) with a low overpotential of 136 mV. Remarkably, the assembled lithium metal batteries with high-voltage cathode deliver outstanding capacity retention and cycling stability (Coulombic efficiency, 99.79 %, 500 cycles at 0.5C with LiNi 0.5 Co 0.2 Mn 0.3 O 2) at 40 °C. This work provides a powerful engineering avenue to regulate polymer electrolytes for high-voltage all-solid-state lithium metal batteries. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) heterostructures with domain‐controlled emissive colors have shown great potential for achieving high‐throughput sensing, anti‐counterfeit and information security. Here, a strategy based on steric‐hindrance effect is proposed to construct lateral lanthanide‐MOFs (Ln‐MOFs) epitaxial heterostructures, where the channel‐directed guest molecules are introduced to rebalance in‐plane and out‐of‐plane growth rates of the Ln‐MOFs microrods and eventually generate lateral MOF epitaxial heterostructures with controllable aspect ratios. A library of lateral Ln‐MOFs heterostructures are acquired through a stepwise epitaxial growth procedure, from which rational modulation of each domain with specific lanthanide doping species allows for definition of photonic barcodes in a two‐dimensional (2D) domain with remarkably enlarged encoding capacity. The results provide molecular‐level insight into the use of modulators in governing crystallite morphology for spatially assembling multifunctional heterostructures. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) heterostructures with domain‐controlled emissive colors have shown great potential for achieving high‐throughput sensing, anti‐counterfeit and information security. Here, a strategy based on steric‐hindrance effect is proposed to construct lateral lanthanide‐MOFs (Ln‐MOFs) epitaxial heterostructures, where the channel‐directed guest molecules are introduced to rebalance in‐plane and out‐of‐plane growth rates of the Ln‐MOFs microrods and eventually generate lateral MOF epitaxial heterostructures with controllable aspect ratios. A library of lateral Ln‐MOFs heterostructures are acquired through a stepwise epitaxial growth procedure, from which rational modulation of each domain with specific lanthanide doping species allows for definition of photonic barcodes in a two‐dimensional (2D) domain with remarkably enlarged encoding capacity. The results provide molecular‐level insight into the use of modulators in governing crystallite morphology for spatially assembling multifunctional heterostructures. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) have recently emerged as appealing platforms to construct microlasers owing to their compelling characters combining the excellent stability of inorganic materials and processable characters of organic materials. However, MOF microstructures developed thus far are generally composed of multiple edge boundaries due to their crystalline nature, which consequently raises significant scattering losses that are detrimental to lasing performance. In this work, we propose a strategy to overcome the above drawback by designing spherically shaped MOFs microcavities. Such spherical MOF microstructures are constructed by amorphizing MOFs with a topological distortion network through introducing flexible building blocks into the growth environment. With an ultra‐smooth surface and excellent circular boundaries, the acquired spherical microcavities possess a Q factor as high as ≈104 and can provide sufficient feedback for high‐quality single‐mode lasing oscillations. We hope that these results will pave an avenue for the construction of new types of flexible MOF‐based photonic components. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) have recently emerged as appealing platforms to construct microlasers owing to their compelling characters combining the excellent stability of inorganic materials and processable characters of organic materials. However, MOF microstructures developed thus far are generally composed of multiple edge boundaries due to their crystalline nature, which consequently raises significant scattering losses that are detrimental to lasing performance. In this work, we propose a strategy to overcome the above drawback by designing spherically shaped MOFs microcavities. Such spherical MOF microstructures are constructed by amorphizing MOFs with a topological distortion network through introducing flexible building blocks into the growth environment. With an ultra‐smooth surface and excellent circular boundaries, the acquired spherical microcavities possess a Q factor as high as ≈104 and can provide sufficient feedback for high‐quality single‐mode lasing oscillations. We hope that these results will pave an avenue for the construction of new types of flexible MOF‐based photonic components. [ABSTRACT FROM AUTHOR]

In their Research Article (e202310263), Zhenhua Gao, Yong Sheng Zhao et al. have developed a surface tension assisted heterogeneous assembly strategy to construct WGM hetero-microrings through regulating the charge-transfer (CT) interactions along circular boundaries, which remarkably promotes the security level and encoding capacity of the barcodes. Keywords: Anti-Counterfeiting Applications; Heterogeneous Assembly; Organic Hetero-Microring; Photonic Barcodes; Whispering-Gallery-Mode EN Anti-Counterfeiting Applications Heterogeneous Assembly Organic Hetero-Microring Photonic Barcodes Whispering-Gallery-Mode 1 1 1 11/09/23 20231113 NES 231113 B Whispering-gallery-mode b (WGM) microcavities featuring distinguishable sharp peaks in a broadband exhibit enormous advantages in the field of miniaturized photonic barcodes. Anti-Counterfeiting Applications, Heterogeneous Assembly, Organic Hetero-Microring, Photonic Barcodes, Whispering-Gallery-Mode. [Extracted from the article]

In their Research Article (e202310263), Zhenhua Gao, Yong Sheng Zhao et al. have developed a surface tension assisted heterogeneous assembly strategy to construct WGM hetero-microrings through regulating the charge-transfer (CT) interactions along circular boundaries, which remarkably promotes the security level and encoding capacity of the barcodes. Anti-Counterfeiting Applications, Heterogeneous Assembly, Organic Hetero-Microring, Photonic Barcodes, Whispering-Gallery-Mode Back Cover: Spatially Resolved Organic Whispering-Gallery-Mode Hetero-Microrings for High-Security Photonic Barcodes (Angew. [Extracted from the article]

• 1D MWO 4 (M = Zn, Ni, Cu) nanomaterials were synthesized by electrospinning method. • CuWO 4 nanotubes exhibited superior degradation performances under UV–Vis-NIR light. • NIR responses of CuWO 4 and NiWO 4 were explained by metal ion d-d orbital transition. Photocatalysis is a promising technology for addressing environmental pollution and energy shortages in a carbon neutral way, and highly effective utilization of solar light is very important for water treatment via photocatalysis. In this study, we synthesized one-dimensional wolframite-structured MWO 4 (M = Zn, Ni, and Cu) nanomaterials as UV–Vis–NIR broad spectrum-driven photocatalysts via the electrospinning method, and observed the excellent performances in the photocatalytic degradation of tetracycline (TC) and bisphenol A (BPA) under the UV–Vis–NIR light illumination. The degradation experiments showed that CuWO 4 nanotubes exhibited the highest degradation capability, and achieved the TC removal rates of 91.8% and 94.2% after 140 min and 12 h under UV–Vis and NIR light irradiation, respectively. The UV–Vis–NIR responsive photocatalytic activities and mechanisms could be explained by the charge transfer mechanism and metal ion d-d orbital transition based on the experimental results and density functional theory modulations. Our findings demonstrate that the MWO 4 (M = Zn, Ni, and Cu) photocatalysts could be responsive to the UV–Vis–NIR broad-spectrum lights, representing a major step forward in the development of photocatalytic technology. [ABSTRACT FROM AUTHOR]

At present, most common catalysts are faced with the problem of high cost and only visible light response. Graphitic carbon nitride (g-C 3 N 4) consists of elements C and N that are sufficiently abundant in the world and has visible light responses, but the electron-hole recombination rate of this photocatalyst is high. In this work, we directly prepare a series of g-C 3 N 4 -bismuth oxyhalides composites via facile in-situ deposition. Bismuth oxides with different chloro-iodine ratios (BiOCl x I 1-x) are prepared, followed by g-C 3 N 4 deposition, setting up interfaces and improving photogenic charge carriers transfer. By testing the compositions, Cl:I = 8:2 in BiOCl x I 1-x and 10% of g-C 3 N 4 doping amount enable the best photocatalytic performance of the samples. Under visible light irradiation, the degradation rate of rhodamine B (RhB) reaches 99% within 40 min. Through a variety of tests, the photogenerated hole (h+) and superoxide radical (•O 2 −) are found to play key roles in the degradation process. Cl element doping and heterojunction building improve the photocatalysis capacity of g-C 3 N 4 and broaden the visible-light response of pure BiOI. [ABSTRACT FROM AUTHOR]

Mineralizers can efficiently promote the transition of barium aluminosilicate (BaAl 2 Si 2 O 8 , BAS) from hexacelsian to celsian (H-M). However, the detailed mechanism regarding the phase transformation of BAS is still unclear, especially in different glass systems. Herein we systematically studied the crystallization behaviors of SiO 2 -Al 2 O 3 -BaF 2 glass in supercooled oxyfluoride aluminosilicate liquids with increasing Na 2 O concentration, and the influence of crystal phases precipitated from the precursor glass on the dielectric properties of oxyfluoride aluminosilicate glass ceramics was analyzed. We observed that the high addition of Na 2 O promoted no transformation of H-M, but resulted in the precipitation of second phases (e.g., NaAlSi 2 O 6 , Ba 3 AlF 9). Our results provide guidance for designing glass ceramics containing celsian (Monoclinic BAS) nanocrystals with superior thermodynamically stable and dielectric characters. [ABSTRACT FROM AUTHOR]

[Display omitted] • A universal, facile and ultrafast precipitation polymerization method is developed. • Dual-aldehyde monomers are adopted to prepare hierarchical polymer particles. • Without using templates, hydrothermal devices, surfactants and catalysts. • The preparation process just cost 10 minutes. • Representative WBL carbon microsphere anodes exhibit high performance for LIBs. Hierarchical polymer architectures have attracted considerable attention owing to their crucial roles in catalysis, drug delivery, biology, electronics and energy storage fields. Unfortunately, the current synthesis of polymer particles with hierarchical structures mainly relies on templates, hydrothermal devices, surfactants, and catalysts approaches that have the disadvantages of time-consuming procedures, complex manufacturing processes, high cost, the use of toxic agents (e.g. HF acid for templates removal) and potential risk of explosion (hydrothermal methods). Herein, for the first time, we have developed an ultrafast template-free, hydrothermal-free, surfactant-free, and catalyst-free precipitation polymerization method to synthesize a diversity of polymer particles with multi-dimensional (0D, 1D, 2D and 3D) hierarchical structures simply from polymerization of common dual-aldehyde and amino monomers at room temperature, and the fabrication process only took 10 min. After carbonizing one typical polymer particles (wool-ball-like structure) as an application example, we further tested the electrochemical performance of the as-obtained typical structures and the results show a reversible lithium-ion storage capacity of 226.5 mAh g−1 after 3200 cycles at the current density of 5 A g−1. Our technique provides a cost-effective, rapid, scalable, and green approach to prepare multi-dimensional hierarchical polymer structures and paves the way towards their application in a diversity of emerging fields. [ABSTRACT FROM AUTHOR]

Keywords: 2D photonic barcodes; anti-counterfeiting applications; dimensional modulation; lanthanides; MOF heterostructures EN 2D photonic barcodes anti-counterfeiting applications dimensional modulation lanthanides MOF heterostructures 24931 24931 1 11/02/21 20211108 NES 211108 B Mehrfarbige Heterostrukturen b auf der Basis von Lanthanoid-basierten metallorganischen Gerüsten (Ln-MOFs) haben großes Potenzial für fälschungssichere Anwendungen gezeigt. Innenrücktitelbild: Laterally Engineering Lanthanide-MOFs Epitaxial Heterostructures for Spatially Resolved Planar 2D Photonic Barcoding (Angew. In ihrem Forschungsartikel auf S. 24724 präsentieren Zhenhua Gao, Xiangeng Meng, Yong Sheng Zhao et al. eine Strategie, um laterale 2D-Ln-MOFs zu konstruieren. [Extracted from the article]

Keywords: 2D photonic barcodes; anti-counterfeiting applications; dimensional modulation; lanthanides; MOF heterostructures EN 2D photonic barcodes anti-counterfeiting applications dimensional modulation lanthanides MOF heterostructures 24727 24727 1 11/02/21 20211108 NES 211108 B Lanthanide-based metal-organic frameworks b (Ln-MOFs) multicolor heterostructures have shown great potential for achieving anti-counterfeiting applications. The domain-controlled emissive colors in these 2D lateral Ln-MOFs epitaxial heterostructures allow for definition of 2D photonic barcodes, which could be used for advanced anti-counterfeiting applications. 2D photonic barcodes, anti-counterfeiting applications, dimensional modulation, lanthanides, MOF heterostructures. [Extracted from the article]

The biologically and medicinally interesting heterocyclic scaffolds are formed in a regioselective manner and generally good to excellent yields under mild conditions. [ABSTRACT FROM AUTHOR]