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The direct conversion of methane to methanol has attracted increasing interest due to abundant and low-cost natural gas resources. Herein, by anchoring Cr-oxo/-oxyhydroxides on UiO-66 metal–organic frameworks, we demonstrate that reactive anionic oxyl radicals can be formed by controlling the coordination environment based on the results of density functional theory calculations. The anionic oxyl radicals produced at the completely oxidized CrVI site acted as the active species for facile methane activation. The thermodynamically stable CrVI-oxo/-oxyhydroxides with the anionic oxyl radicals catalyze the activation of the methane C–H bond through a homolytic mechanism. An analysis of the results showed that the catalytic performance of the active oxyl species correlates with the reaction energy of methane activation and H adsorption energies. Following methanol formation, N2O can regenerate the active sites on the most stable CrVI oxyhydroxides, i.e., the Cr(O)4Hf species. The present study demonstrated that the anionic oxyl radicals formed on the anchored CrVI oxyhydroxides by tuning the coordination environment enabled facile methane activation and facilitated methanol production. [ABSTRACT FROM AUTHOR]

It is a time-consuming and costly process to develop affordable and high-performance organic photovoltaic materials. Computational methods are essential for accelerating the material discovery process by predicting power conversion efficiencies (PCE). In this study, we propose a deep learning-based framework (DeepAcceptor) to design and discover highly efficient small molecule acceptor materials. Specifically, an experimental dataset is constructed by collecting acceptor data from publications. Then, a deep learning-based model is customized to predict PCEs by applying graph representation learning to Bidirectional Encoder Representations from Transformers (BERT), with the atom, bond, and connection information in acceptor molecular structures as the input (abcBERT). The computational dataset derived from density functional theory (DFT) calculations and the experimental dataset from literature are used to pre-train and fine-tune the model, respectively. The abcBERT model outperforms other state-of-the-art models for the PCE prediction with MAE = 1.78 and R2 = 0.67 on the test set. A molecular generation and screening process is built to find new high-performance acceptors for PM6. Three discovered candidates are further validated by experiment, and the best PCE reaches 14.61%. The released user-friendly interface of DeepAcceptor greatly boosts the accessibility and efficiency of designing and discovering high-performance acceptors. Altogether, the DeepAcceptor framework with abcBERT is promising to predict the PCE and accelerate the discovery of high-performance acceptor materials. [ABSTRACT FROM AUTHOR]

Employing functional building units with microscopic second‐order NLO response has been proposed to explore high performance NLO materials. Herein, structural, electronic and optical properties of non‐centrosymmetric molybdenyl carbonate Cs3MoO4(HCO3) with NLO active functional units have been examined based on density functional theory. Theoretical results are consistent with experimentally mentioned data, confirming the reliable method. Detailed geometric structure, electronic attributes, linear optical properties, and nonlinear optical properties of Cs3MoO4(HCO3) are provided. Analysis of structures, compositions of bands and plots of charge density suggest that asymmetric functional building units [MoO4] and [HCO3] exhibit varying degrees of second‐order Jahn‐Teller distortions, and therefore have a significant impact on the electronic structure and optical properties of Cs3MoO4(HCO3). Maximum absolute value of SHG coefficients at 1064 nm is 0.671 pm/V for d15, which is nearly twice as much as that of KDP. Further researches are needed in future to validate and enhance optical anisotropy characteristic of Cs3MoO4(HCO3) for satisfying the phase matching conditions. Analysis results indicate that microscopic origins of SHG response in Cs3MoO4(HCO3) are complicated, such as geometric environment, induced polar asymmetric functional building units, and electronic properties. Continuous research on structure‐property relationship of NLO materials is needed for exploring more competitive NLO materials. [ABSTRACT FROM AUTHOR]

Materials containing mixed anions, particularly, oxyhalides containing asymmetric functional building units, may lead to the discovery of excellent nonlinear optical (NLO) materials. In the present work, the geometric structure, mechanical properties, electronic structure and optical properties of two d 0– d 10 electron transition-metal oxyhalides Cs2CdV2O6Cl2 and Cs3CdV4O12Br have been systematically determined based on density functional theory. The asymmetric functional building units [V2O7], [V4O13], [CdO2Cl4] and [CdO4Br2] exhibit varying degrees of second-order Jahn−Teller distortions, contributing differently to the macroscopic nonlinearity. Mechanical properties reveal that the two oxyhalides are structurally and mechanically stable. Detailed electronic and optical properties of the two oxyhalides are provided. Optical anisotropy character is exhibited along different polarization vectors, giving a large birefringence for satisfying the phase-matching condition. Maximum absolute values of static second harmonic generation (SHG) coefficients are 4.47 pm V−1 for Cs2CdV2O6Cl2 and 3.72 pm V−1 for Cs3CdV4O12Br, suggesting that Cs2CdV2O6Cl2 and Cs3CdV4O12Br are potential NLO crystals with large SHG coefficients. In particular, unique 3D framework structures give a polar structure superposition of individual moments for asymmetric functional building units. Thus, maximum magnitudes of the total microscopic dipole are achieved, having the largest influence on the SHG response. This study elucidates the relationship between the structure and properties of transition-metal oxyhalides, providing valuable insights for designing NLO materials with excellent performance. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Metalla‐isosilabenzenes and metalla‐isogermabenzenes have been successfully synthesized by the formal [5+1]‐cycloaddition of diethynylsilane or diethynylgermane with simple metal complexes. This is the first example of a heavier Group 14 metalla‐isobenzene isomer bearing a cumulative double bond motif within a metallacycle. These novel complexes were fully characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis. The stabilization of the cyclic metal‐vinylidene complexes has been analyzed using density functional theory (DFT) calculations. When the metalla‐isosilabenzenes bearing Si—H bond were treated with the trityl salt as a hydride scavenger, the formation of silylium cation was observed spectroscopically. Both of metalla‐isosilabenzenes and metalla‐isogermabenzenes can readily undergo migratory insertion reactions to furnish siloles or germoles. [ABSTRACT FROM AUTHOR]

The selective photocatalytic reduction of CO2 to CH4 remains a challenge because there is a need for not only strong adsorption sites for the intermediates, but also optimal proton-feeding sites on the photocatalyst surface. Herein, a synergistic dual-site function between in situ-generated Ni0 and Ni2P on carbon nitride nanosheets (CN) for photocatalytic reduction of CO2 to CH4 is presented. The highest CH4 production rate of 69.03 μmol g−1 h−1 is achieved on Ni2P/CN-0.5 in an aqueous suspension. Detailed analyses show that the promotion of CH4 is closely correlated with the formation of Ni0 sites due to light irradiation, which is confirmed by tracking the compositions of Ni2P/CN-0.5 through XPS and HRTEM characterization. Density functional theory calculations have been combined with CO-TPD and in situ FTIR spectra to reveal the synergy between in situ-generated Ni0 sites and Ni2P. It shows that the Ni0 sites can stabilize the key intermediate *CO, while the Ni0–Ni2P interface can promote *H transfer from Ni2P to Ni0. Therefore, the CO intermediates are rapidly protonated to form CHO* instead of being desorbed from the surface to produce CO, and subsequently CHO* will be converted into CH4. This work demonstrates a new strategy of designing highly efficient photocatalysts with synergistic catalytic sites for CO2 conversion to hydrocarbons. [ABSTRACT FROM AUTHOR]

First‐principles calculations based on density functional theory (DFT) are used to investigate the phase transition characteristics, electronic structures, and optical properties of pure and Co‐doped VO2 (M1 and R phase). Studies show that the metal‐to‐insulator phase transition temperature of VO2 is significantly reduced after Co doping, which is correlated to the decrease of bandgap value. Besides, the decrease of the energy required for electron transition of M1‐phase Co‐doped VO2 corresponds to the imaginary part of the dielectric peak moving to the low‐energy region. For both the M1‐ and R‐phase VO2, the visible light transmissivity of the Co‐doped VO2 is increased than that of pure VO2, which is beneficial to the application of VO2 film as visible windows. In addition, the absorptivity and reflectivity of Co‐doped R‐phase VO2 in the infrared light range are larger than those of M1‐phase VO2, indicating that the Co‐doped VO2 can block more infrared light at higher temperature to fulfill the purpose of lowering temperature. Overall, these results give new insights for the application of Co‐doped VO2 as a photoenergy material to regulate the room temperature. [ABSTRACT FROM AUTHOR]

First‐principles calculations based on density functional theory (DFT) are used to investigate the phase transition characteristics, electronic structures, and optical properties of pure and Co‐doped VO2 (M1 and R phase). Studies show that the metal‐to‐insulator phase transition temperature of VO2 is significantly reduced after Co doping, which is correlated to the decrease of bandgap value. Besides, the decrease of the energy required for electron transition of M1‐phase Co‐doped VO2 corresponds to the imaginary part of the dielectric peak moving to the low‐energy region. For both the M1‐ and R‐phase VO2, the visible light transmissivity of the Co‐doped VO2 is increased than that of pure VO2, which is beneficial to the application of VO2 film as visible windows. In addition, the absorptivity and reflectivity of Co‐doped R‐phase VO2 in the infrared light range are larger than those of M1‐phase VO2, indicating that the Co‐doped VO2 can block more infrared light at higher temperature to fulfill the purpose of lowering temperature. Overall, these results give new insights for the application of Co‐doped VO2 as a photoenergy material to regulate the room temperature. [ABSTRACT FROM AUTHOR]

A clear understanding of the structural transformation of copper-oxide-based oxygen carriers accompanying their reduction by fuels helps to design more efficient oxygen carriers for chemical looping combustion. Herein, density functional theory calculations have been performed on the bulk CuO, CuO(111) surface, and (CuO)32 cluster models with the same number of CuO molecular units to investigate structural transformation accompanying the reduction. The results showed that the averaged reaction energies of desorbing an oxygen molecule from the bulk and surface models are roughly the same [246.2 kJ/(mol O2) and 245.9 kJ/(mol O2), respectively]. The slab model does not significantly lower the overall reaction energy compared to the bulk model. In contrast, the averaged reaction energy using the cluster model is significantly lower [127.5 kJ/(mol O2)] than that of bulk and slab models. The key structural difference is the obvious Cu–Cu bond formation in the cluster model, which would result in nucleation of a metallic Cu phase. The results also showed that different states can be reached by desorbing different number oxygen atoms in a single step, corresponding to different reaction rates, when the system reaches the same level of reduction. These results demonstrate the complexity of reactions involving solid state materials and are consistent with the structural diversity observed experimentally. This study illustrates the importance of particle sizes and reaction conditions in the formation of suboxides during CuO reduction. [ABSTRACT FROM AUTHOR]

Flavins are a class of organic compounds with the basic structure of 7,8-dimethy-10-alkyl isoalloxazine. They are ubiquitous in nature and participate in many biochemical reactions. Due to various existing forms, there is a lack of systematic research on the absorption and fluorescence spectra of flavins. In this study, employing the density functional theory (DFT) and time-dependent (TD) DFT, we calculated the pH-dependent absorption and fluorescence spectra of flavin of three redox states (quinone, semiquinone, and hydroquinone) in solvents. The chemical equilibrium of three redox states of flavins and the pH effect on the absorption spectra and fluorescence spectra of flavins were carefully discussed. The conclusion helps with identifying the existing forms of flavins in solvent with different pH values. [ABSTRACT FROM AUTHOR]

The hydrogen evolution effect of ZrS2 carrier loaded with transition metal single‐atom (SA) was explored by first‐principles method. ZrS2 was constructed with transition metal single‐atom and dual‐atom. The structure–activity relationship of supported single‐atom catalysts was described by electronic properties and hydrogen evolution kinetics. The results show that the ZrS2 carrier‐loaded atomic‐level catalysts are more likely to occur in acidic environments, where the Mo SA load has a higher hydrogen precipitation capacity than the Pt SA. In the case of dual‐atom adsorption, most of the hydrogen reduction processes are higher than that of single atom loading, which indicates that the outer orbital hybridization is more likely to lead to the interfacial charge recombination of the catalyst. Thereinto, Ni/Pt @ZrS2 has the lowest Gibbs free energy (0.08 eV), and the synergistic effect of transition metals induces the deviation of the center of the d‐band from the Fermi level and improves the dissociation ability of H ions. The design provides a new catalytic model for the HER and provides some ideas for understanding the two‐site catalysis. [ABSTRACT FROM AUTHOR]

Defect-riched Co 3 O 4 with tensile strain and metal vacancies has been successfully synthesized. The electronic structure of electrocatalysts has been effectively modulated with the introduction of defects, which leaded to excellent water oxidation ability. [Display omitted] Co 3 O 4 has been widely explored in electrocatalysis but seriously limited by its poor intrinsic ability. Defect engineering is an effective method to improve the electrocatalytic ability of catalysts by regulating electronic structure and optimizing the binding energy with surface adsorbates. Herein, in this work we have successfully integrated metal vacancies and tensile strain into Co 3 O 4. With the formation of metal vacancies, the electronic structure of Co 3 O 4 has been regulated. Moreover, the d-band center of Co 3 O 4 has been modulated with the presence of tensile strain. The electrochemical oxygen evolution reaction (OER) ability of the obtained electrocatalyst was improved dramatically. The overpotential to reach 10 mA cm−2 was only 327 mV. Reaction kinetics was rapidly facilitated as indicated by smaller Tafel slope and charge transfer resistance. Density Functional Theory (DFT) calculations revealed that the relocated atoms induced the formation of tensile strain and made d-band center of electrocatalyst near to Fermi level leading to enhanced the adsorption to reaction intermediates. What's more, the free energy barrier of rate-determining step (RDS) has been decreased with the integration of metal vacancies and tensile strain. This work provides an efficient strategy to develop defective and effective electrocatalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] Photocatalytic CO 2 reduction is a promising method to resolve the energy shortage problem. Developing photocatalysts with strong redox capabilities is urgently needed to achieve high photocatalytic activity. Herein, we synthesized TiO 2 /CsPbBr 3 S-scheme heterojunctions with modulated internal electric field by facet engineering of TiO 2 to control charge transfer for improved photocatalytic activity. Density functional theory (DFT) calculation reveals that there is a wider Fermi level difference between TiO 2 -(1 0 1) and CsPbBr 3 than that between TiO 2 -(0 0 1) and CsPbBr 3 , which will induce more obvious band bending. Subsequently, more efficient spatial separation will occur around the interface. Thus, TiO 2 -(1 0 1)/CsPbBr 3 heterostructures effectively reduce CO 2 into CO with the selectivity of 90.2 % and reduction rate of 12.5 μmol h−1, 15.6 and 5.6 times improvement than that of 101-TiO 2 and TiO 2 -(0 0 1)/CsPbBr 3 , respectively. This report proposes a feasible idea of employing facet engineering to take the advantage of S-scheme heterojunction. [ABSTRACT FROM AUTHOR]

trans-Anethole (trans-AN) is widely applied in food, daily necessities, and pharmaceuticals and is typically available from inefficient natural oil extraction or complex organic transformations over mineral acid or noble metals. Here, a green and sustainable route was developed to stereoselectively produce trans-AN (ca. 90% selectivity) over an organic polymeric phosphonate–hafnium catalyst (PAS–Hf) through the cascade transfer hydrogenation and dehydration of biomass-based 4′-methoxypropiophenone (4-MOPP), with an environmental impact factor (E-factor) of 47.73. The porous structure and the enhanced hydrophobicity of the spherical catalyst PAS–Hf ensured the formation of more accessible and stable Lewis (Hf4+) and Brønsted (SO3H) acid active sites, which could be used for rapid conversion of biomass-based 4-MOPP to AN (100% conversion, 97.2% yield) in 0.5–2 h (TOF: 9.3 h−1). Density functional theory (DFT) calculations elucidated that the addition of PAS–Hf could remarkably facilitate the overall conversion process by decreasing the reaction energy barrier (151.33 to 48.27 kJ mol−1) of the rate-determining step. The good thermal stability and heterogeneity of the bifunctional catalyst were responsible for its constant activity during at least five consecutive cycles. The synergistic/relay catalysis of Lewis acid–base and Brønsted acid species could be extended to more than ten kinds of aldehydes and ketones. This acid–base multi-catalytic protocol has considerable potential in cascade biomass conversion via heterogeneous catalysis without any base additive. [ABSTRACT FROM AUTHOR]

[Display omitted] • Dopants are screened via DFT calculation for γ -Al 2 O 3 catalyst over COS hydrolysis. • Lanthanum has been identified as the most promising dopant in preventing poisoning. • The S resistance of γ -Al 2 O 3 under aerobic conditions has been significantly improved. • La-doped γ -Al 2 O 3 exhibits the highest activity and stability. Catalytic hydrolysis of carbonyl sulfide (COS) is an efficient way of desulfurization for industrial flue gas, while the frequently used Al 2 O 3 -based catalysts always suffer from sulfur poisoning leading to poor stability, especially in the presence of O 2. With this regard, an analysis of the reaction pathway has been conducted, and the tri-coordinated Al in γ -Al 2 O 3 is identified as the responsible site for poisoning, on which produced H 2 S is over-oxidized resulting in active sites covering. Density functional theory (DFT) has been adopted for dopant screening to eliminate tri-coordinated Al on γ -Al 2 O 3 , inhibit H 2 S over-oxidation, and prevent sulfur poisoning. Results show La, Fe, Ni, and Cu all can eliminate tri-coordinated Al, while only La-doped γ -Al 2 O 3 exhibits inhibition to H 2 S oxidation, thus, improving activity and stability for γ -Al 2 O 3. Experiments show COS conversion of 99 % over 30 h can be attained in the presence of O 2 , which agrees well with the DFT calculation. [ABSTRACT FROM AUTHOR]

• Engineering surface structures of metal-oxide catalysts enhance catalytic activity. • The high-index (3 1 0) facets catalysts with oxygen vacancies for VOCs degradation. • The steric effect of the reactants on the (3 1 0) facets promoted catalytic activity. • Toluene and O 2 are simultaneously adsorbed and activated on the two types of sites. Engineering surface structures of metal-oxide catalysts are of utmost significance for boosting their catalytic performances. In this work, we reported the high-index (3 1 0) facets catalysts (MnO x -AA US) with oxygen vacancies for VOCs degradation, which was synthesized via an ultrasonic-assisted redox precipitation process. Interestingly, the excellent catalytic performance of MnO x -AA US catalysts was due to the steric effect between high-index facet with reactants and the simultaneous adsorption-activation of toluene and gaseous oxygen on the high-index (3 1 0) facets with oxygen vacancies. The T 90% value of the (3 1 0) facets catalysts (600 ppm toluene, GHSV = 60,000 mL/g·h, 21 % O 2 /N 2) was significantly lower than that of the previous (0 0 1) facets catalysts. Density functional theory (DFT) calculations, along with in-situ FT-IR spectra, revealed that the tilted adsorption configuration of toluene was conducive to simultaneous reaction with the surrounding activated oxygen species. Such the adsorption configuration of toluene/oxygen contributed to the substantially enhanced catalytic activity of the MnO x -AA US catalyst for VOCs oxidation. This work provides new insights into the roles of high-index facets with oxygen vacancies of MnO x catalysts in the toluene oxidation and paves new avenues for the rational design of highly efficient catalysts for oxidation reactions. [ABSTRACT FROM AUTHOR]

Nowadays, blue fluorescent organic light‐emitting diodes (FOLEDs) have attracted considerable attention from both academia and industry. According to spin statistics, electrical excitation results in the formation of ∼25% singlet excitons and ∼75% triplet excitons (signifying ~75% energy loss), which triggered wide‐ranging efforts to harvest as many triplet excitons as possible. The materials that can convert triplet excitons into singlet excitons from the high‐lying excited triplet states (referred as "hot exciton" channel) to realize high efficiency were reported, which can also efficaciously avoid the accumulation of triplet excitons in T1 state. In this study, by means of density functional theory (DFT) and time‐dependent DFT, we have theoretically investigated the electronic and photophysical properties of 16 newly designed molecules with donor‐bridge‐acceptor framework to search for the blue FOLED materials exploiting the "hot exciton" path. Important properties, such as singlet‐triplet energy gaps, absorption and emission parameters, and reverse intersystem crossing rates (kRISC), of five target molecules were studied. The calculated results demonstrate that thiophene‐diphenylamine (kRISC up to 1.03 × 108 seconds−1) may have promising potential as blue FOLED materials by virtue of the "hot exciton" effect. [ABSTRACT FROM AUTHOR]

The 2D MXenes have attracted great recent attention as the electrocatalytic materials for hydrogen evolution reaction (HER). However, the activity and the modification strategy of the catalytic properties have not been firmly established yet. In this study, we performed density functional theory (DFT) calculations to investigate the stability and HER performance of functionalized Mo2C MXene. The Pourbaix diagram indicates the fully oxidized surface is the most stable state. The oxidized Mo2CO2 is electrically conductive, yet the surface HER activity is unsatisfactory owing to the strong first H adsorption. The doping of transition metals (TM) into the Mo lattice, however, leads to much more enhanced H adsorption and deteriorates the activity. Alternatively, the H binding can be effectively weakened and flexibly tuned by anchoring the TM atoms over the surface with appropriate coverage, and Mn/Fe decoration at 12.5 % ML (monolayer) coverage is identified as the promising candidates with close to zero Gibbs free energy of H adsorption (ΔGH*) for the first H adsorption. The weakening effect arises from charge transfer from TM to surface O, resulting in increased occupancy and weakened O−H bonds. Furthermore, contrary to the weakening effect, the tensile strain leads to enhanced O−H binding by the up‐shifted Op electronic states, which can further modulate the HER performance of TM‐modified Mo2CO2. The synergistic effect between TM modification and strain engineering offers beneficial advantages for the realization of efficient electrochemical HER, which can be applied to other MXenes for electronic and catalytic applications. [ABSTRACT FROM AUTHOR]

A number of compounds including thiobarbituric acid derivative‐based acceptor unit and diverse donor moieties along with two types of π‐conjugated bridges have been constructed to aid in the design of the superior nonlinear optical (NLO) materials. The effect of varying the donor and bridge parts of this donor‐bridge‐acceptor system was analyzed in terms of structural and opto‐electronic parameters such as bond length alternation and ultraviolet‐visible absorption spectra. Various functionals with aug‐cc‐pVDZ basis set including B3LYP, PBE0, PBE38, BMK, CAM‐B3LYP, and ωB97XD were employed to calculate the static and dynamic first‐hyperpolarizabilities, and also the linear polarizabilities. Furthermore, the variation of the static first‐hyperpolarizabilities has been explained satisfactorily in the light of the sum‐over‐states method and two‐level model. The comprehensive study indicates that the coplanar compound D‐5 with the low electronic absorption energy, strongest oscillator strength paired with the largest ground, and excited state dipole moment difference generates a dramatical increase in its static and dynamic first‐hyperpolarizabilities, which would be the most worthwhile target for development as the NLO‐phores. [ABSTRACT FROM AUTHOR]

A mechanistic understanding of catalytic reactions at solid‐liquid interface is limited both experimentally and theoretically but attracts much interest. Using density functional theory calculations (DFT) and ab initio molecular dynamics (AIMD) simulations, we investigated the effect of liquid water on α‐H abstraction, C−C coupling, and dehydration steps of aldol condensation of formaldehyde and acetone on an anatase TiO2(101) surface. The existence of the aqueous phase lowered the Gibbs energy of activation of dehydration step pronouncedly from 187 to 74 kJ/mol through proton transfer mechanism, making the hydrogenation pathway more favorable in the aqueous phase. In contrast, a mixed route prevails in the vapor phase. This work provides insights into the effect of the bulk water through a proton transfer mechanism on the dehydrogenation, C−C coupling, and dehydration steps. [ABSTRACT FROM AUTHOR]

Re-doped Ni(111) (Re@Ni(111)) surface was used as a model to investigate the effect of Re on the C O bond scission and on the selectivity of CO 2 methanation on a Ni-based catalyst. Three pathways, including CO 2 dissociation into CO* followed by CO* hydrogenation, CO 2 reduction through the HCOO* and COOH* intermediates, were analyzed based on the results from the density functional theory calculations. The results indicate that the presence of Re significantly lowers the activation barrier of C O bond cleavage due to the strong affinity of Re to O but has no significant effect on the hydrogenation steps. Microkinetic analysis showed that the presence of Re greatly increases the selectivity toward CH 4 . Analysis of surface coverage of the adsorbed species showed that CO* and H* were the most abundant species on the Ni(111) surface whereas appreciable amount of O adatoms were present on Re@Ni(111) in addition to CO* and H*, with the O adatoms on the Re sites. On both surfaces, increasing H 2 partial pressure resulted in an increase in H* coverage but decreased CO* coverage. The strong affinity of Re toward O makes Re@Ni(111) more effective for C O bond scission and thereby enhances methane selectivity. [ABSTRACT FROM AUTHOR]

[Display omitted] • DFT calculation and TC results show that CuO5-Zn1 is formed on SnO2(1 1 0) surface. • CuO5-Zn1 sites on SnO2(1 1 0) surface has a high OEP of 2.80 V. • Ultra-high OEP is caused by the enhanced covalency of Cu-O-Zn. • Explored the law of covalent change caused by Zn. • The enhanced covalency of Cu-O-Zn has been found at the first time SnO2 on surface. SnO 2 is an anode material with the potential to form a high oxygen evolution potential for organic wastewater treatment. Previous experiments found that CuZn, co-doped with SnO 2 surfaces were suspected to form Cu-O-Zn sites with high catalytic activity. By utilising DFT calculations combined with previous experimental results, it was found that CuO 5 -Zn 1 active sites were formed on the (1 1 0) surface of CuZn co-doped SnO 2 with an oxygen evolution potential of 2.80 V (vs CHE). The electronic density of states, charge density distribution, Bader charge and charge density difference analysis indicated that the formation of ultra-high oxygen evolution potential was caused by the enhanced covalency of Cu-O-Zn. The indirect covalent enhancement between transition metal atoms found on the SnO 2 surface means that atomically regulated and controlled catalytic activity can be achieved on the SnO 2 surface. [ABSTRACT FROM AUTHOR]