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High entropy materials (HEM) have been attracting much attention as emerging catalysts for electrochemical water splitting. HEM catalysts have unique properties such as an interesting cocktail effect, broad design space, customizable electronic structure, and excellent entropy stabilization effect compared with single-digit catalysts. This paper provides a comprehensive overview of the use of HEM as a catalyst for hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and water splitting. HEM design strategies including phase structure modulation, defect engineering, electrode configuration engineering, and computational aids are discussed to develop HEM catalysts with high performance and stability. In particular, the importance of density functional theory, high-throughput screening techniques, and machine learning for the discovery and design of HEM catalysts is emphasized. Finally, the challenges and imminent difficulties are prospected, and the corresponding strategies to deal with these challenges are put forward to promote the development of HEM catalysts in the field of electrochemical water splitting. [ABSTRACT FROM AUTHOR]

The development of efficient non-noble metal electrocatalysts for the oxygen evolution reaction (OER) under acidic conditions remains a critical challenge. Herein, we report a N-doped carbonaceous component-engineered Co3O4 (NCEC) catalyst synthesized via the sol-gel method. Dopamine hydrochloride (DA)-derived nitrogen-doped carbonaceous components were found to boost the OER performance of Co3O4. The optimized catalyst can reach an overpotential as low as 330 mV in 1 M H2SO4 at a current density of 10 mA cm-2 and maintains a good long-term stability of 60 hours. In particular, we found that the thermodynamic overpotential was inversely proportional to the content of oxidized N and pyridinic N, whereas it was directly proportional to the pyrrolic-N content. Our experiments and density functional theory (DFT) calculations confirm that the optimized catalyst exhibits enhanced charge transfer and the oxidized N species on Co3O4 is responsible for the high catalytic activity. Our study suggests that the performance of NCEC in acidic media can be further optimized by enhancing the content of oxidized N species. [ABSTRACT FROM AUTHOR]

This study employs density functional theory at the SMD/B3LYP-D3/6-311+G(2d,p),def2-TZVPP//SMD/B3LYP-D3/6-31G(d),SDD level of theory to explore the mechanistic details of O2 generation from tBuOOH, using H218O as the solvent, in the presence of the Mn(II) catalyst [Mn2(mcbpen)2(H2O)2]2+. Since this chemistry was reported to occur through the reaction of Mn(III)(μ-O)Mn(IV)–O˙ with water, we first revaluated this proposal and found that it occurs with an activation barrier greater than 36 kcal mol−1, ruling out the functioning of such a dimer as the active catalyst. Experimental evidence has shown that the oxidation of [Mn2(mcbpen)2(H2O)2]2+ by tBuOOH in H218O produces the Mn(IV) species [Mn(18O)(mcbpen)]+. Our investigations revealed a plausible mechanism for this observation in which [Mn (18O)(mcbpen)]+ acts as the active catalyst, generating the tert-butyl peroxyl radical (tBuOO˙) through its reaction with tBuOOH. In this proposed mechanism, the O–O bond is formed through the interaction of tBuOO˙ with another [Mn(18O)(mcbpen)]+, finally leading to the formation of the 16O＝18O product. Our findings underscore the pivotal role of [Mn(18O)(mcbpen)]+ in both generating the active species tBuOO˙ and consuming it to produce 16O＝18O. With activation barriers as low as about 9 kcal mol−1, these elementary steps highlight the feasibility of our proposed mechanism. Moreover, this mechanism elucidates why, experimentally, one of the oxygen atoms in the released O2 comes from water, while the other originates from tBuOOH. This research broadens our understanding of high oxidation state manganese chemistry, setting the stage for the development of more efficient Mn-based catalysts, aimed at improving processes in both renewable energy and synthetic chemistry. [ABSTRACT FROM AUTHOR]

Biomass provides a promising source of carbon for obtaining environment-friendly carbon materials, but obtaining heteroatom-doped carbon materials (HDCMs) from biomass directly by a green method still remains challenging. This study successfully synthesized nitrogen and phosphorus co-doped porous carbon materials (Y-NPC) by the simple in situ pyrolysis of renewable yeast mixed with water from 800 to 950 °C. Various characterization methods show that nitrogen and phosphorus are doped into the carbon skeleton and mainly exist in the forms of graphite-N, pyridine-N, C–P, P–N, and P–O states. The catalyst Y-NPC-900 °C with a 3D hierarchical porous structure and high P–N content exhibited superior nitro hydrogenation performance and reaction stability using molecular hydrogen and hydrazine hydrate as hydrogen sources under mild conditions. Density functional theory (DFT) calculations and experiments attributed the exceptional catalytic performance to hydrogen activation and the good adsorption ability of substrates over N, P co-doped carbon (NPC). Therefore, this research proposes an eco-friendly and simple synthesis strategy for in situ N, P co-doping metal-free carbon catalysts derived from biomass, showing the significance of N, P co-doping and single N- or P-monodoping in the charge distribution of carbon materials. [ABSTRACT FROM AUTHOR]

This density functional theory (DFT) study explores the efficacy of cooperative catalytic systems in enabling the ionic hydrogenation of N2 with H2, leading to NH3 formation. A set of N-heterocyclic carbene-based pincer tungsten/molybdenum metal complexes of the form [(PCP)M1(H)2] (M1 = W/Mo) were chosen to bind N2 at the respective metal centres. Simultaneously, cationic rhodium/iridium complexes of type [Cp*M2{2-(2-pyridyl)phenyl}(CH3CN)]+ (Cp* = C5(CH3)5 and M2 = Rh/Ir), are employed as cooperative coordination partners for heterolytic H2 splitting. The stepwise transfer of protons and hydrides to the bound N2 and intermediate NxHy units results in the formation of NH3. Interestingly, the calculated results reveal an encouraging low range of energy spans ranging from ∼30 to 42 kcal mol−1 depending on different combinations of ligands and metal complexes. The optimal combination of pincer ligand and metal center allowed for an energy span of unprecedented 29.7 kcal mol−1 demonstrating significant potential for molecular catalysts for the N2/H2 reaction system. While exploring obvious potential off-cycle reactions leading to catalyst deactivation, the computed results indicate that no increase in energy span would need to be expected. [ABSTRACT FROM AUTHOR]

The quantitative structure-property relationship (QSPR) of constrained geometry catalysts (CGCs) has been analyzed by combining density functional theory (DFT) and multivariate linear regression (MLR). QSPR models for determining the reaction energy barriers of ethylene and 1-octene and molecular descriptors were established and validated with a testing set. At the initiation stage, the quaternary QSPR models for ethylene and 1-octene feature R² values of 0.90 and 0.82, respectively, while the corresponding leave-one-out Q² values for ethylene and 1-octene are determined to be 0.82 and 0.69. Using the generated QSPR models, the electronic effect was proven to be more critical for determining the energy barriers of ethylene and 1-octene insertion processes. At the propagation stage, the quaternary QSPR models for ethylene and 1-octene feature R² values of 0.97 and 0.96, respectively, while the corresponding leave-one-out Q² values for ethylene and 1-octene are determined to be 0.93. Particularly, the impact of the steric effect on the energy barriers of ethylene and 1-octene insertion is more pronounced. Furthermore, the correlation between the corresponding energy barriers and experimental activities with three series of CGCs was discussed, which revealed that theoretical calculations are consistent with the experimental results. [ABSTRACT FROM AUTHOR]

The design of low-cost and high-performance bifunctional catalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) is of great significance for overall water splitting. Herein, RuNi single atom alloy (SAA) decorated on reduced graphene oxide (RuNi@rGO) was synthesized by a facile strategy for use as a bifunctional HER/OER catalyst. The as-obtained RuNi@rGO catalyst exhibits outstanding electrocatalytic activities with an ultralow overpotential for the HER (15 mV) and the OER (240 mV) at a current density of 10 mA cm−2. Density functional theory (DFT) calculations demonstrate that the introduction of Ru single atoms can evidently change the electron distribution and coordination environment around Ni, and reduce the intermediate's adsorption free energy of RuNi@rGO, thus facilitating the HER/OER catalytic rate. Moreover, when used as the cathode and anode of a two-electrode system, the RuNi@rGO-based water splitting device exhibits a low potential of 1.52 V at a current density of 10 mA cm−2, as well as a high faradaic efficiency almost up to 100%, making RuNi@rGO bifunctional electrocatalysts attractive for energy storage and conversion. [ABSTRACT FROM AUTHOR]

Hydrogen (H2) is a new type of renewable energy that can meet people's growing energy needs and is environmentally friendly. In order to improve the industrial application prospects and electrochemical performance of hydrogen evolution catalysts, extensive research on transition metal materials has been carried out. Among the many catalytic materials, cobalt is an element with potential for the hydrogen evolution reaction (HER) due to its abundant reserves, low cost, and small energy barrier for H adsorption. This review classifies the latest research on cobalt-based catalysts according to the types of compound, including cobalt-based sulfides, phosphides, carbides, borides, oxides, etc., and summarizes the latest research progress of cobalt-based compound catalysts in acidic and alkaline media. Strategies to tune the properties of cobalt-based compound catalysts for high catalytic activity for HER are focused on, including structural engineering, defect engineering, and doping, etc. The advantages and limitations of each modified approach are reviewed. Not only that, but also the catalytic activity and advantages of the catalyst are evaluated by using density functional theory (DFT) calculation-related descriptors, activity evaluation parameters, etc. Finally, limitations and challenges of cobalt-based materials for HER are presented, as well as prospects for future research. This paper aims to understand the chemical and physical factors that affect cobalt-based catalysts, and to find directions for future research on cobalt-based catalysts. [ABSTRACT FROM AUTHOR]

Investigation of catalytic hydrogenation of CO2 to CO via the reverse water-gas shift (RWGS) was undertaken using Ni/SiO2-based catalysts. Among the array of catalysts tested, the Ni/SiO2 catalyst derived from the reduction of silicalite-1-encapsulated, ligand-protected Ni2+ (Ni0.2@S-1-red) exhibited promising performance. This catalyst demonstrated a CO2 conversion rate approaching the equilibrium conversion of RWGS, a selectivity for CO exceeding 99%, and a high space time yield of CO (9.7 mol gNi -1 h-1). The outcomes observed can be attributed to several factors, such as the highly dispersed Ni0 and Niδ+ species, as well as the presence of bridging oxygen of the Ni-O-Si structure, on which CO2 can be adsorbed moderately. The moderately bonded CO2 on Ni0.2@S-1-red allows for the efficient desorption of its reduced intermediate, i.e. *CO, resulting in the generation of gaseous CO at a rapid rate, consequently preventing its deep hydrogenation to CH4. Complementary Density Functional Theory (DFT) calculations were performed and revealed that CO molecules have poor adsorption and higher adsorption energy on the Ni@S-1 surface compared to the S-1 surface. This supports the rapid desorption of *CO and the observed high selectivity of CO. Moreover, the structure-activity correlation analysis further supports the claim of Ni0.2@S-1-red as a promising RWGS catalyst. [ABSTRACT FROM AUTHOR]

Hydrodeoxygenation (HDO) is an indispensable approach to produce renewable biofuels and value-added chemicals using natural biomass and its derivatives. 2,5-Dimethylfuran (DMF) is considered to be a very promising liquid biofuel, and it can be fabricated by HDO of the biomass derivative 5-hydroxymethylfurfural (HMF). Herein, a highly efficient bifunctional catalyst, Co/HAP(Ce), was fabricated by anchoring highly dispersed Co on Ce-doped hydroxyapatite (HAP(Ce)). Co/HAP(Ce) displayed excellent HDO catalytic activity to convert HMF to DMF, and 99% HMF conversion and 96% DMF selectivity can be obtained under 150 °C, 2 MPa H2 conditions for 5 h. Density functional theory calculations revealed that H2 can be more easily activated by Co/HAP(Ce). Systematic studies confirmed that the high activity of Co/HAP(Ce) can be ascribed to the desired acid–alkali properties, highly dispersed cobalt species and strong metal–support interactions. This research provides a cost effective approach for designing efficient catalysts for HDO of biomass and its derivatives. [ABSTRACT FROM AUTHOR]

Developing highly efficient electrocatalysts is crucially significant for the application of advanced energy conversion. The Fe–N–C single-atom catalyst is promising for CO2 electroreduction reaction (CO2RR) but suffers from insufficient intrinsic activity and inferior conductivity, which could be addressed by redistributing the electron density via heteroatom doping. Herein, we synthesized S-doped Fe–N–C (Fe–SN–C) as an advanced electrocatalyst for CO2RR using a simple trapping–pyrolysis strategy. Density functional theory calculations and experimental results indicate that S doping increases the d-band electrons and conductivity of Fe–SN–C by electron donating, and thus boosts *CO desorption during the CO2RR process and suppresses the competing hydrogen evolution reaction. Consequently, Fe–SN–C exhibits the maximum CO faradaic efficiency of 93% at −0.5 V and the highest partial current density of 10.1 mA cm−2 at −0.8 V for 2e− CO2RR. This finding provides a feasible and controllable method to achieve advanced electrocatalysts for efficient energy conversion. [ABSTRACT FROM AUTHOR]

Direct synthesis of 2,1-benzisoxazole and its related N-heterocyclic compounds via a chemoselective reductive heterocyclization route, which involves hydrogenation and subsequent intramolecular cyclodehydration steps, is a viable and attractive approach. However, the efficient transformation of the feedstocks using hydrogen as a hydrogen source at ambient temperature and atmospheric hydrogen pressure remains a great challenge. Herein, we reported a MgO-incorporated porous carbon composite (MgO@C) stabilized subnanometric Pt cluster (Pt/MgO@C) catalyst prepared by annealing a Mg-containing metal–organic framework, Mg-MOF-74, followed by impregnation of a Pt precursor and further reduction treatment strategy. The as-prepared Pt/MgO@C with ultralow Pt loading (0.078 wt%) exhibited superior catalytic performance for synthesizing 2,1-benzisoxazole derivatives by the reductive heterocyclization methodology. Excellent catalytic activity (conversion ≥ 99%), high chemoselectivity (≥92%), good stability (8 cycles), and broad functional group tolerance (10 substrates) were achieved under very mild conditions (1 bar hydrogen pressure at 303 K) over the developed Pt/MgO@C. Control experiments indicated that a proper amount of basic sites, subnanometric Pt clusters, and a close contact between them synergistically contributed to the extraordinary performance of Pt/MgO@C. Density functional theory calculations showed that the high activity and chemoselectivity of Pt/MgO@C stemmed from the active interfacial sites of Pt/MgO@C simultaneously activating the H2 and substrate, where the formed stable hydroxyl groups contributed to the enhancement of activity. The combined experimental and theoretical approach identified the formation of the –NO and –NHOH groups during the hydrogenation process, and the former corresponds to the rate-determining step. [ABSTRACT FROM AUTHOR]

The oxidation of CO by N2O over M–porphyrin (M = Ti, Fe, Co, Ni, Cu, and Zn) catalysts has been investigated via density functional theory calculations. The whole reaction process is divided into two steps: the catalytic decomposition of N2O that breaks the N–O bond resulting in O–M active species, and the carbon atoms of the CO molecule reaction with O–M to form CO2. For the rate-controlled step of the reaction, the porphyrins of different metal centers appear in different positions. The barrier height of N2O decomposition on Ti–porphyrin is 3.8 kcal mol−1, and the barrier height of CO oxidation is 21.9 kcal mol−1. The rate-controlled step appears in the process of oxidation of CO. However, for Fe–porphyrin, the barrier height of N2O decomposition is 24.2 kcal mol−1, and the barrier height of CO oxidation is 11.4 kcal mol−1. The rate-controlled step appears in the process of N2O decomposition. For the catalytic decomposition of N2O, the Ti–porphyrin has a low activation energy barrier, which may be due to the smaller gap between the highest occupied molecular orbital (HOMO) of the metal porphyrin and the lowest unoccupied molecular orbital (LUMO) of N2O for Ti–porphyrin compared to Fe–porphyrin. [ABSTRACT FROM AUTHOR]

Dimethyldichlorosilane, which is the most important organic silicon monomer, can be prepared using a novel core–shell catalyst. However, the debate continues regarding its redistribution mechanism. In the current study, the redistribution mechanism catalyzed by the ZSM-5(5T)@MIL-53(Al) catalyst was theoretically studied via density functional theory on the level of M06-2X/def2-TZVP. Then, the catalytic performances of different active centers modified with AlCl3 were evaluated. The results showed that the active center of the former was Brønsted acid, while that of the latter modified by AlCl3 was Lewis acid. In addition, Lewis acid increased the catalytic activity in comparison with Brønsted acid. The calculations of activation energy, frequency vibrational analysis, bond order analysis, frontier molecular orbital theory, electronic localization function, and localized orbital locator analyses were in agreement with the said mechanism and results. [ABSTRACT FROM AUTHOR]

Ru(bda)(py)2 (bda = 2,2′-bipyridine-6,6′-dicarboxylate, py = pyridine) has been a significant milestone in the development of water oxidation catalysts. Inspired by Ru(bda)(py)2 and aiming to reduce the use of noble metals, iron (Fe) was introduced to replace the Ru catalytic center in Ru(bda)(py)2. In this study, density functional theory (DFT) calculations were performed on Fe- and Ru(bda)(py)2 catalysts, and a more stable 6-coordinate Fe(bda)(py)2 with one carboxylate group of bda disconnecting with Fe was found. For the first time, theoretical comparisons have been conducted on these three catalysts to compare their catalytic performances, such as reduction potentials and energy profiles of the radical coupling process. Explanations for the high potential of [FeIII(bda)(py)2–H2O]+ and reactivity of [FeV(bda)(py)2–O]+ have been provided. This study can provide insights on Fe(bda)(py)2 from a computational perspective if it is utilized as a water oxidation catalyst. [ABSTRACT FROM AUTHOR]

The effects of Zr single atom modification on the hydrogenation mechanism of CO2 to methanol on the Cu(111) surface were investigated by density functional theory (DFT). In the HCOO pathway, 11 elementary steps were involved, which were analyzed from the aspects of kinetics and thermodynamics of each elementary reaction. bi-HCOO*, HCOOH*, H2COO*, H2COOH*, H2CO* and H3CO* are the key intermediates that are most likely to be generated. The elementary reactions of H2COO*, H2CO* and H3CO* hydrogenation have relatively high activation barriers of about 1 eV, and they are the rate-limiting steps in this pathway. The desorption barriers of HCOOH* and H2CO* are much higher than the energy barriers required for continued hydrogenation; therefore, the formation of by-products is inhibited on the Zr1–Cu single atom catalyst surface. In the COOH pathway, the hydrogenation product trans-COOH* of CO2 can further hydrogenate to t,t-COHOH* through the formation of O-H bonds; then, it facilely dissociates into COH*, and COH* continues to hydrogenate into HCOH*, H2COH* and the final product of CH3OH. The last step is the rate-limiting step, with an activation energy of 1.48 eV. In the RWGS pathway, trans-COOH* transforms to cis-COOH*, and its continued hydrogenation is more favorable than dissociation in terms of kinetics and thermodynamics. The generated HCOOH is incorporated into the HCOO pathway. The results show that the HCOO pathway is more likely to occur and has higher selectivity on Zr-modified Cu-based catalysts. [ABSTRACT FROM AUTHOR]

The removal of sulfur in diesel fuel requires efficient hydrodesulfurization catalysts during the upgrading process. However, although the traditionally prepared CoMoS catalyst is effective for hydrodesulfurization, it often is associated with problems such as a poor activity and deactivation susceptibility at high temperatures. In this work, chemical exfoliation and hydrothermal methods were employed to prepare MoS2 for modification with isolated Co atoms. The results showed that the prepared catalyst had a higher catalytic activity and could be used at lower temperatures. Subsequently, periodic density functional theory (DFT) calculations were used to discuss the effect of isolated Co doping on the catalytic performances of single-layer MoS2. DFT calculations revealed that the electronic structure of the MoS2 basal surface was changed by Co atom doping, making the originally inert basal surface catalytically active. Based on the energetic analysis, the influence of isolated Co atom doping on the adsorption performance, hydrogenolysis activity, and hydrodesulfurization performance of the basal surface is discussed. This work paves a new path for improving HDS catalytic activity via synergistic structure and charge characteristics. [ABSTRACT FROM AUTHOR]

Generation of molecular hydrogen by electrochemical water splitting is a promising approach, and its efficiency strictly depends on the electrocatalyst used. Therefore, it is an ongoing challenge to design materials having improved the electrocatalytic behaviour towards hydrogen evolution reaction. Here, using Co-MOF [Co4(BTC)3(BIm)6] as starting precursor, graphitic carbon encapsulated CoSe2 nanorods have been prepared through a single step selenization method. The carbon network in the CoSe2/C hybrid nanostructure forms channels, facilitating the accessibility of the electrolyte ions and maximizing the utilization of catalytic active centers. This makes the hybrid to show higher electrochemical accessible surface area, lower charge transfer resistance, and improved catalytic durability towards the electrocatalytic hydrogen evolution reaction with respect to the non-noble metal (graphite rod) counter electrode. Specifically, it needs only 253 mV of overpotential to reach the benchmarked current density (10 mA cm−2) with a lower Tafel slope. Further, the experimental findings have been supported by the theoretical analysis of the structure and electronic properties of CoSe2 and CoSe2/C hybrid by density functional theory (DFT) simulations. The interaction between CoSe2 and C is due to charge transfer from Co 3d orbital and Se 4p orbital of CoSe2 to the 2p orbital of carbon. Also, populated electronic states near Fermi level for C doped CoSe2 may infer towards increased conductivity of the material. Computed overpotentials for HER activities show a qualitative order of CoSe2/C < CoSe2, matching nicely with the experimental data. The synergic effect of increased conductivity, improved surface area, and superior electrocatalytic activity due to C doping is responsible for the superior HER catalytic performance. [ABSTRACT FROM AUTHOR]

Excessive CO2 emission has caused severe greenhouse problems. CO2 reduction reaction (CO2RR) is considered to be a promising strategy to effectively reduce CO2 emission, which not only captures CO2 in large quantity, but also produces high value-added chemicals. Herein, CO2RR on the CuPc/graphene single-atomic catalyst has been studied via density functional theory (DFT) calculations. It shows that CO2 is inclined to convert to CH3OH, followed by HCOOH and CH4. The most favored pathway to produce CH3OH is *CO2 → *COOH → *CO → *CHO → *OCH2 → *OCH3 → *OHCH3, for which the potential-limiting step is *CO2 → *COOH (endothermic by 1.41 eV). Both density of states and differential charge further indicate the high reactivity of single atomic Cu, and uncover the effect of electrostatic interaction on the hydrogenation pathway. This study can provide an insight into the structure–reaction relationship for CO2RR on CuPc/graphene, and help guide the design of highly effective catalysts. [ABSTRACT FROM AUTHOR]

5-Hydroxymethylfurfural (HMF) is a versatile furanic compound used for producing various value-added chemicals, including 2,5-dihydromethylfuran (DHMF) and 2,5-dihydromethyltetrahydrofuran (DHMTHF), via selective hydrogenation of HMF. In order to reduce the cost of highly efficient noble metal catalysts, nickel (Ni) and copper (Cu) have been developed as cheaper catalysts for this reaction. These two catalysts show good efficiency but have different selectivity towards HMF hydrogenation products. This work applied plane-wave based density functional theory (DFT) to understand the different activity and selectivity of the Ni and Cu catalysts. The interaction of precursors/products on the Ni(111), Ni(100), Cu(111) and Cu(100) facets was investigated via the adsorption calculation in gas and aqueous phases. The temperature effect was also investigated. Our results revealed that not only the energetic properties but the structural and electronic charge properties are also important for describing the different catalytic behaviors in HMF hydrogenation. [ABSTRACT FROM AUTHOR]

To date, organoseleniums are pre-eminent for peroxide decomposition and radical quenching antioxidant activities. On the contrary, here, a series of Janus-faced aminophenolic diselenides have been prepared from substituted 2-iodoaniline and selenium powder using copper-catalyzed methodology. Subsequently, condensation with substituted salicylaldehyde afforded the Schiff base, which on reduction, yielded the desired substituted aminophenolic diselenides in 72%–88% yields. The generation of reactive oxygen species (ROS) from oxygen gas by the synthesized aminophenolic diselenides was studied by analyzing the oxidation of dichlorofluorescein diacetate (DCFDA) dye and para-nitro-thiophenol by fluorescence and UV-Visible spectroscopic methods. Furthermore, density functional theory calculations and crystal structure analysis revealed the role of functional amine and hydroxyl sites present in the Janus-faced organoselenium catalyst for the activation of molecular oxygen, where NH and phenolic groups bring the oxygen molecule close to the catalyst by N–H⋯O and O–H⋯O intermolecular interactions. Additionally, these functionalities stabilize the selenium-centered radical in the formed transition states. Antioxidant activities of the synthesized diselenides have been explored as the catalyst for the decomposition of hydrogen peroxide using benzenethiol sacrificial co-reductant by a well-established thiol assay. Radical quenching antioxidant activity was studied by the quenching of DPPH radicals at 516 nm by UV-Visible spectroscopy. The structure activity correlation suggests that the electron-rich phenol and electron-rich and sterically hindered selenium center enhance the oxidizing property of the aminophenolic diselenides. Janus-faced diselenides were also evaluated for their cytotoxic effect on HeLa cancer cells via MTT assay, which suggests that the compounds are effective at 15–18 μM concentration against cancer cells. Moreover, the combination with therapeutic anticancer drugs Erlotinib and Doxorubicin showed promising cytotoxicity at the nanomolar concentration (8–28 nM), which is sufficient to suppress the growth of the cancer cells. [ABSTRACT FROM AUTHOR]

The present report focuses on the solvent effect on furfural production from xylose in biphasic systems with methods including combined experiments, molecular dynamics (MD) simulations and density functional theory (DFT) calculations. Six most effective and commonly used biphasic solvents for furfural production were comparatively analyzed and discussed based on the kinetic study, partition coefficient, degradation behavior of furfural in organic solvents, distribution of solvent molecules around xylose/furfural molecules, hydrogen bonding, moving trajectories of xylose/furfural, and the solvation free energy. During the hydrothermal reaction of xylose to furfural in biphasic systems, it was found that the conversion efficiency of biphasic systems can be ordered as DCM/H2O > 2-MTHF/H2O > 2-butanol/H2O ≈ MIBK/H2O > CPME/H2O > toluene/H2O according to the xylose conversion and furfural yield, which are dominated by the solvation free energy (ΔGsol) of furfural in organic solvents, and also be affected by three other factors, namely, the maximum solubility of furfural in organic solvents, the ΔGsol value of organic solvents in water, and the side reaction of furfural in organic solvents. The degradation rate of furfural in 2-butanol was detected to be the fastest, and molecular dynamics simulation data showed that the hydrogen bonding between furfural and 2-butanol may accelerate the degradation of furfural. DCM has excellent extraction ability for furfural, and the maximum furfural yield in the DCM/H2O system (81.64%) is much higher than that in other systems during the hydrothermal reaction without additional catalysts. [ABSTRACT FROM AUTHOR]

The design and synthesis of hybrid core–shell catalysts is of great significance for obtaining an excellent performance of hydrogen evolution reaction (HER). However, it remains a challenge to explore the exact active sites and research the catalytic mechanism for HER. Here, a series of Ni3S2@MOOH/NF (M = Fe, Ni, Cu, Mn and Co) hybrid structures is firstly in-site grown on Ni foam by the typical hydrothermal and electrodeposition methods. The Ni3S2@NiOOH/NF catalyst with a core–shell structure exhibits a relatively low overpotential of 79 mV for HER at a current density of 10 mA cm−2, which is one of the best catalytic activities reported so far. Moreover, it also shows good stability in the long-term durability test. Various spectral analysis and density functional theory calculations demonstrate that NiOOH is favorable for the adsorption of water molecules, and the S atom at the interface between Ni3S2 and NiOOH is favorable for the adsorption of H intermediates, which strongly accelerates the HER process in alkaline solution. This work provides a general strategy for the synthesis of electrocatalytic materials, which can be used for efficient electrocatalytic water splitting reactions. [ABSTRACT FROM AUTHOR]

Density functional theory computations revealed a pivalic acid assisted C–H bond activation mechanism for rhodium catalyzed formation of α-branched amines with C–C and C–N bond couplings. The reaction energies of the [Cp*RhCl2]2 dimer and silver cations indicate that the Cp*RhCl+ cation is the active catalyst. The essential role of pivalic acid is a co-catalyst for the activation of the ortho-C(sp2)–H bond in phenyl(pyrrolidin-1-yl)methanone, while the reaction of NaHCO3 and HCl reduces the overall barrier of the catalytic cycle. In the presence of both pivalic acid and NaHCO3 in the reaction, the C(sp2)–H bond is activated through a concerted metallation deprotonation process, and the C–C bond coupling is the rate-determining step with a total free energy barrier of 23.9 kcal mol−1. Without pivalic acid and NaHCO3, the C(sp2)–H bond can only be activated through a σ-bond metathesis process and the free energy barrier increases to 32.2 kcal mol−1. We also investigated the mechanisms of a side reaction for β-branched amine formation and the reaction without styrene and found that their free energy barriers are 33.4 and 30.5 kcal mol−1, respectively. [ABSTRACT FROM AUTHOR]

Over the past century, the global concentration of environmental nitrate has increased significantly from human activity, which has resulted in the contamination of drinking water and aquatic hypoxia around the world, so the development of effective nitrate-reducing agents is urgent. This work compares three potential macrocycle-based nitrate reduction electrocatalysts: [Co(DIM)]3+, [Co(cyclam)]3+ and [Co(TIM)]3+. Although all three complexes have similar structures, only [Co(DIM)]3+ has been experimentally determined to be an active electrocatalyst for selective nitrate reduction to produce ammonia in water. While [Co(cyclam)]3+ can reduce aqueous nitrate to ammonia and hydroxylamine at heavy metal electrodes, [Co(TIM)]3+ is inactive for the reduction of nitrate. As an initial step to understanding what structural and electronic properties are important for efficient electrocatalysts for nitrate reduction, density functional theory (DFT) was employed to investigate the electronic structure of the three Co complexes, with the reduction potentials calibrated to experimental results. Moreover, DFT was employed to explore four different reaction mechanisms for the first steps of nitrate reduction. The calculated reaction barriers reveal how a combination of electron transfer in a redox non-innocent complex, substrate binding, and intramolecular hydrogen bonding dictates the activity of Co-based catalysts toward nitrate reduction. [ABSTRACT FROM AUTHOR]

Sustainable fuel production from CO2 through electrocatalytic reduction is promising but challenging due to high overpotential and poor product selectivity. Herein, we computed the reaction free energies of electrocatalytic reduction of CO2 to CO and HCOO- using the density functional theory method and screened transition metal(M)--cyclam(L) complexes as molecular catalysts for CO2 reduction. Our results showed that pKa of the proton adduct formed by the protonation of the reduced metal center can be used as a descriptor to select the operating pH of the solution to steer the reaction toward either the CO or hydride cycle. Among the complexes, [LNi]2+ and [LPd]2+ catalyze the reactions by following the CO cycle and are the CO selective catalysts in the pH ranges 1.81-7.31 and 6.10 and higher, respectively. Among the complexes that catalyze the reactions by following the hydride cycle, [LMo]2+ and [LW]3+ are HCOO- selective catalysts and have low limiting potentials of -1.33 V and -1.54 V, respectively. Other complexes, including [LRh]2+, [LIr]2+, [LW]2+, [LCo]2+, and [LTc]2+ catalyze the reactions resulting in either HCOO- from CO2 reduction or H2 from proton reduction; however, HCOO- formation is always thermo-dynamically more favorable. Notably, [LMo]2+, [LW]3+, [LW]2+ and [LCo]2+ have limiting potentials less negative than -1.6 V and are based on Earth-abundant elements, making them attractive for practical application. [ABSTRACT FROM AUTHOR]

In this study, a density functional theory (DFT) method was utilised to predict the reaction mechanism of N-heterocyclic carbene (NHC)-catalysed remote N–H activation in indole aldehydes for the synthesis of enantiomerically enriched oxazinoindole derivatives. Simulation results indicate that the mechanism involves six energetically feasible stages: (a) chemo-selective nucleophilic addition of NHC to indole aldehydes, (b) N,N-diisopropylethylamine (DIEA) and protonated DIEA-assisted simultaneous proton shifts for the generation of Breslow intermediates, (c) oxidation of Breslow intermediates, (d) another DIEA-assisted intermolecular proton shift for the formation of reactive aza-o-quinone methide (aza-o-QM) analogues, (e) stereo-selective [4+2]-cycloaddition of aza-o-QM to a ketonic moiety, and (f) regeneration of NHC with simultaneous formation of the desired product. Chemo- and stereo-selectivity of the titled reaction was analysed by adopting several well-known DFT tools. Conceptual DFT-derived reactivity indices and the frontier molecular orbitals (FMOs) were analysed comprehensively to unravel the real role of NHC in this proposed catalytic cycle. Besides NHC, DIEA and DIEA–H+ were found to play crucial roles in lowering the activation energy barrier of different proton transfer stages. This investigation may help in the rational designing of other NHC-catalysed novel organic transformations. [ABSTRACT FROM AUTHOR]

Electrochemical nitrogen reduction reactions (NRR) under ambient conditions are a promising and attractive way to ammonia (NH3) synthesis. It is significant to develop efficient and low-cost electrocatalysts for nitrogen reduction. Herein, an investigation of single B atom doped C5N2 as a metal-free electrocatalyst for NRR was carried out using density functional theory (DFT) calculations. The results show that the boron atom is preferentially doped into the interstitial site of C5N2. The formed B-interstitial (Bint)-doped C5N2 sufficiently activates the nitrogen (N2) molecule through the "acceptance–donation" process. In particular, N2 can be effectively reduced via an alternating mechanism with a low overpotential (0.38 V). Thus, by carefully controlling the doping sites, the B-doped C5N2 can be an ideal candidate for an efficient NRR, which may provide a new idea in the design of NH3 synthesis catalysts. [ABSTRACT FROM AUTHOR]