Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental...Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental protection. However, the existing “acceptance-donation” mechanism is only applicable to bimetallic catalysts and nonmetallic double-atom catalysts containing boron atoms. Herein, a novel “capture-activation-recapture” mechanism for metal-nonmetal double-atom catalyst is proposed to solve the problem by adjusting the coordination environments of nonmetallic atoms and utilizing the activation effect of metal atoms on nitrogen. Based on this mechanism, the nitrogen reduction reaction (NRR) activity of 48 structures is calculated by density functional theory calculation, and four candidates are selected as outstanding electrocatalytic nitrogen reduction catalysts: Si-Fe@NG (U_(L) = –0.14 V), Si-Co@NG (U_(L)= –0.15 V), Si-Mo@BP1 (U_(L) = 0 V), and Si-Re@BP1 (U_(L) = –0.02 V). The analyses of electronic properties further confirm “capture-activation-recapture” mechanism and suggest that the difference in valence electron distribution between metal and Si atoms triggers the activation of N≡N bonds. In addition, a machine learning approach is utilized to generate an expression and an intrinsic descriptor that considers the coordination environment to predict the limiting potential. This study offers profound insight into the synergistic mechanism of TM and Si for NRR and guidance in the design of novel double-atom nitrogen fixation catalysts.展开更多
Two-electron(2 e^(-))oxygen reduction reaction(ORR)shows great promise for on-site electrochemical synthesis of hydrogen peroxide(H_(2)O_(2)).However,it is still a great challenge to design efficient electrocatalysts ...Two-electron(2 e^(-))oxygen reduction reaction(ORR)shows great promise for on-site electrochemical synthesis of hydrogen peroxide(H_(2)O_(2)).However,it is still a great challenge to design efficient electrocatalysts for H_(2)O_(2)synthesis.To address this issue,the logical design of the active site by controlling the geometric and electronic structures is urgently desired.Therefore,using density functional theory(DFT)computations,two kinds of hybrid double-atom supported on C_(2)N nanosheet(RuCu@C_(2)N and PdCu@C_(2)N)are screened out and their H_(2)O_(2)performances are predicted.PdCu@C_(2)N exhibits higher activity for H_(2)O_(2)synthesis with a lower overpotential of 0.12 V than RuCu@C_(2)N(0.59 V),Ru_(3)Cu(110)facet(0.60 V),and PdCu(110)facet(0.54 V).In aqueous phase,the adsorbed O_(2)is further stabilized with bulk H_(2)0 and the thermodynamic rate-determining step of 2 e^(-) ORR change.The activation barrier on PdCu@C_(2)N is 0.43 eV lower than the one on RuCu@C_(2)N with 0.68 eV.PdCu@C_(2)N is near the top of 2 e^(-) ORR volcano plot,and exhibits high selectivity of H_(2)O_(2.)This work provides guidelines for designing highly effective hybrid double-atom electrocatalysts(HDACs)for H_(2)O_(2)synthesis.展开更多
The rational design of a novel catalytic center with a sound basis remains both challenging and rewarding for the electrochemical reduction of N2(e NRR),which has provided a feasible route for achieving clean and sust...The rational design of a novel catalytic center with a sound basis remains both challenging and rewarding for the electrochemical reduction of N2(e NRR),which has provided a feasible route for achieving clean and sustainable NH3production under ambient conditions.Herein,using density functional theory calculations,we demonstrate that hybrid metal(M)-boron(B)double-atom catalysts(DACs)embedded in gC_(2)N substrate(M-B@C_(2)N,M=3d,4d and 5d transition metals)can achieve both high catalytic activity and high selectivity in e NRR.The proposed M-B@C_(2)N DACs have exhibited impressive feasibility and stability thanks to the resilient and robust C_(2)N substrate with abundant pyridinic N atoms distributed among right-sized pore structures.Our results reveal that like the metal center,the embedded B atom can actively involve in N≡N bond activation viaπ*-backdonation mechanism concomitant with the substantial charge transfer to adsorbed*N2,leading to sizable NAN bond elongation.Accordingly,both adsorption energy and NAN bond length of*N2can be employed as catalytic descriptors for predicting e NRR activity in terms of the limiting potentials(UL).Using high-throughput screening method,we found that six M-B@C_(2)N candidates have stood out as the outstanding electrocatalysts for driving e NRR,namely,M=Ti(UL=0 V),Mo(UL=0 V),Nb(UL=-0.04 V),W(UL=-0.23 V),Zr(UL=-0.26 V),V(UL=-0.28 V).The underlying origin is attributed to the balanced and constrained N-affinity of M-B dual site working in synergy,which can thus be used as one important guide of catalyst design.展开更多
The severe environmental problems and the demand for energy urgently require electrocatalysis to replace Haber-Bosch for the nitrogen reduction reaction(NRR).The descriptors and important properties of single-atom and...The severe environmental problems and the demand for energy urgently require electrocatalysis to replace Haber-Bosch for the nitrogen reduction reaction(NRR).The descriptors and important properties of single-atom and homonuclear double-atom catalysts have been preliminarily explored,but the relationship between the inherent properties and catalytic activity of heteronuclear double-atom catalysts with better performance remains unclear.Therefore,it is very significant to explore the prediction expressions of catalytic activity of heteronuclear double-atom catalysts based on their inherent properties and find the rule for selecting catalytic centers.Herein,by summarizing the free energy for the key steps of NRR on 55 catalysts calculated through the first-principle,the expressions of predicting the free energy and the corresponding descriptors are deduced by the machine learning,and the strategy for selecting the appropriate catalytic center is proposed.The selection strategy for the central atom of heteronuclear double-atom catalysts is that the atomic number of central B atom should be between group VB and VIIIB,and the electron difference between central A atom and B atom should be large enough,and the selectivity of NRR or hydrogen evolution reaction(HER)could be calculated through the prediction formula.Moreover,five catalysts are screened to have low limiting potential and excellent selectivity,and are further analyzed by electron transfer.This work explores the relationship between the inherent properties of heteronuclear double-atom catalysts and the catalytic activity,and puts forward the rules for selecting the heteronuclear double-atom catalytic center,which has guiding significance for the experiment.展开更多
Electrochemical CO reduction(ECOR)as a potential strategy for producing valuable chemicals and fuels has captured substantial attention.However,the currently available electrocatalysts suffer from poor selectivity and...Electrochemical CO reduction(ECOR)as a potential strategy for producing valuable chemicals and fuels has captured substantial attention.However,the currently available electrocatalysts suffer from poor selectivity and low Faradaic efficiency,limiting their industrial application.Herein,we systematically investigate the potential of homonuclear bimetallic electrocatalysts,Tm_(2)@C_(9)N_(4)(TM=Fe,Co,Ni,and Cu),for the ECOR through extensive density functional theory calculations.Our findings suggest that all four proposed monolayers exhibit exceptional stability,making them highly suitable for experimental synthesis and practical applications.Interestingly,these transition-metal dual atoms anchored on C_(9)N_(4)monolayers show great potential in facilitating the production of high-value C_(2)products,such as C_(2)H_(5)OH and C_(2)H_(4),due to the significantly low limiting potentials(-0.06~-0.46 V)and small kinetic energy barriers(0.54–1.08 eV)for the CO coupling process.Moreover,with the exception of Ni_(2)@C_(9)N_(4),these bimetallic catalysts demonstrate the impressive suppression of the competitive hydrogen evolution reaction(HER),leading to a high selectivity for C_(2)products in ECOR.Our predictions would accelerate the development of high-performance C_(9)N_(4)-based dual-atom catalysts for the ECOR.展开更多
Developing efficient electrocatalysts for nitrogen reduction reaction(NRR)is crucial to replace the both energy-intensive and environment-malignant Haber-Bosch process.Here using density functional theory calculations...Developing efficient electrocatalysts for nitrogen reduction reaction(NRR)is crucial to replace the both energy-intensive and environment-malignant Haber-Bosch process.Here using density functional theory calculations,we systematically studied the potential of the heteronuclear 3 d transition metal dimers anchored graphdiyne monolayers(FeM@and NiM@GDY,M=Ti,V,Cr,Mn,Fe,Co,Ni,and Cu)as efficient NRR catalysts.Among all the studied double-atom catalysts(DACs),FeCo@and NiCo@GDY are the most promising with excellent NRR catalytic activity,high ability to suppress the competing hydrogen evolution reaction(HER),and good stability.For both FeCo@and NiCo@GDY,NRR prefers to the distal pathway with the calculated onset potentials of -0.44 and -0.36 V,respectively,which are comparable and even better than their homonuclear counterparts.Moreover,FeCo@and NiCo@GDY have higher ability to suppress HER than Fe_(2)@ and Co_(2)@GDY,which may result from the modulated d state electronic structure due to the synergy effect of the heteronuclear atoms in the DACs.Our work not only suggests that FeCo@and NiCo@GDY hold great promises as efficient,low-cost,and stable DACs for NRR,but also further provides a strategy,i.e.alloying the atomic metal catalysts,to improve the NRR catalytic activity and/or selectivity.展开更多
Double-atom catalysts(DACs)have emerged as an enhanced platform of single-atom catalyst for promoting electrocatalytic CO_(2) reduction reaction(CO_(2) RR).Herein,we present a density-functional theory study on CO_(2)...Double-atom catalysts(DACs)have emerged as an enhanced platform of single-atom catalyst for promoting electrocatalytic CO_(2) reduction reaction(CO_(2) RR).Herein,we present a density-functional theory study on CO_(2) RR performance of seven C_(2) N-supported homo-and heteronuclear DACs,denoted as M_(2)@C_(2) N.Our results demonstrate that there exists substantial synergistic effect of dual-metal-atom N_(2) M_(2) N_(2) active site and C_(2) N matrix on O=C=O bond activation.The dual-atom M_(2) sites are able to drive CO_(2) RR beyond C1 products with low limiting potential(UL).Specifically,C_(2) H4 formation is preferred on FeM@C_(2) N(M=Fe,Co,Ni,Cu)versus CH4 formation on CuM@C_(2) N(M=Co,Ni,Cu).Furthermore,^(*)CO+^(*)CO cobinding strength can serve as a descriptor for CO_(2) RR activity for making C_(2) products such that the moderate binding results in the lowest UL.Remarkably,C-affinity matters most to C-C bond coupling and C_(2) H4 formation while both C-and O-affinity control CH4 formation.Our results provide theoretical insight into rational design of DACs for efficient CO_(2) RR.展开更多
Being progressively applied in the design of highly active catalysts for energy devices,machine learning(ML)technology has shown attractive ability of dramatically reducing the computational cost of the traditional de...Being progressively applied in the design of highly active catalysts for energy devices,machine learning(ML)technology has shown attractive ability of dramatically reducing the computational cost of the traditional density functional theory(DFT)method,showing a particular advantage for the simulation of intricate system catalysis.Starting with a basic description of the whole workflow of the novel DFT-based and ML-accelerated(DFT-ML)scheme,and the common algorithms useable for machine learning,we presented in this paper our work on the development and performance test of a DFT-based ML method for catalysis program(DMCP)to implement the DFT-ML scheme.DMCP is an efficient and user-friendly program with the flexibility to accommodate the needs of performing ML calculations based on the data generated by DFT calculations or from materials database.We also employed an example of transition metal phthalocyanine double-atom catalysts as electrocatalysts for carbon reduction reaction to exhibit the general workflow of the DFT-ML hybrid scheme and our DMCP program.展开更多
Electrocatalytic nitrogen reduction reaction(NRR)is an environmentally friendly method for sustainable ammonia synthesis under ambient conditions.Searching for efficient NRR electrocatalysts with high activity and sel...Electrocatalytic nitrogen reduction reaction(NRR)is an environmentally friendly method for sustainable ammonia synthesis under ambient conditions.Searching for efficient NRR electrocatalysts with high activity and selectivity is currently urgent but remains great challenge.Herein,we systematically investigate the NRR catalytic activities of single and double transition metal atoms(TM=Fe,Co,Ni and Mo)anchored on g-C_(6)N_(6) monolayers by performing first-principles calculation.Based on the stability,activity,and selectivity analysis,Mo_(2)@g-C_(6)N_(6) monolayer is screened out as the most promising candidate for NRR.Further exploration of the reaction mechanism demonstrates that the Mo dimer anchored on g-C_(6)N_(6) can sufficiently activate and efficiently reduce the inert nitrogen molecule to ammonia through a preferred distal pathway with a particularly low limiting potential of -0.06 V.In addition,we find that Mo_(2)@g-C_(6)N_(6) has excellent NRR selectivity over the competing hydrogen evolution reaction,with the Faradaic efficiency being 100%.Our work not only predicts a kind of ideal NRR electrocatalyst but also encouraging more experimental and theoretical efforts to develop novel double-atom catalysts(DACs)for NRR.展开更多
In this study,we selected 10 Co-based double-atom catalysts(DACs)catalysts,namely CoMN_(6)-gra(OH)(M?Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn),and investigated their oxygen reduction reactions(ORR)catalytic performances with/with...In this study,we selected 10 Co-based double-atom catalysts(DACs)catalysts,namely CoMN_(6)-gra(OH)(M?Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn),and investigated their oxygen reduction reactions(ORR)catalytic performances with/without considering the magnetic coupling by means of density functional theory(DFT)calculations.It was found that CoNiN_(6)-gra(OH),CoCuN_(6)-gra(OH),and CoZnN_(6)-gra(OH)exhibit good catalytic activity of ORR(with low overpotentials of 0.33,0.34 and 0.23 V,respectively)when the magnetic coupling is considered.In particular,magnetic changes in CoMN_(6)-gra(OH)candidates play a vital role in their ORR catalytic activity.Interestingly,the d-band center can be utilized to well rationalize the ORR catalytic activity.This work highlights the importance of considering the magnetic coupling to well predict the activity of ORR catalysts,and discloses that the manipulation of the magnetic coupling between transition metal atoms is an emerging and powerful approach for the development of high-performance electrocatalysts for ORR and other related reactions.展开更多
The reliance on fossil fuels intensifies CO_(2) emissions,worsening political and environmental challenges.CO_(2) capture and conversion present a promising solution,influenced by industrialization and urbanization.In...The reliance on fossil fuels intensifies CO_(2) emissions,worsening political and environmental challenges.CO_(2) capture and conversion present a promising solution,influenced by industrialization and urbanization.In recent times,catalytic conversion of CO_(2) into fuels and chemical precursors,particularly methane,are gaining traction for establishing a sustainable,carbon-neutral economy due to methane’s advantages in renewable energy applications.Though homogeneous and heterogeneous catalysts are available for the conversion of CO_(2) to methane,the efficiency is found to be higher in heterogeneous catalysts.Therefore,this review focuses only on the heterogeneous catalysts.In this context,the efficient heterogeneous catalysts with optimum utility are yet to be obtained.Therefore,the quest for suitable catalyst for the catalytic conversion of CO_(2) to CH4 is still continuing and designing efficient catalysts requires assessing their synthetic feasibility,often achieved through computational methods like density functional theory simulations,providing insights into reaction mechanisms,rate-limiting steps,catalytic cycle,activation of C=O bonds and enhancing understanding while lowering costs.In this context,this review examines the conversion of CO_(2) to CH4 using seven distinct types of catalysts,including single and double atom catalysts,metal organic frameworks,metalloporphyrins,graphdiyne and graphitic carbon nitrite and alloys with some case studies.The main focus of this review is to offer a detailed and extensive examination of diverse catalyst design approaches and their utilization in CH4 production,with a specific emphasis on computational aspects.It explores the array of design methodologies used to identify reaction pathways and investigates the critical role of computational tools in their refinement and enhancement.We believe this review will help budding researchers to explore the possibilities of designing catalysts for the CO_(2) to CH4 conversion from computational framework.展开更多
基金supports by the National Natural Science Foundation of China(52271113)the Natural Science Foundation of Shaanxi Province,China(2020JM 218)+1 种基金the Fundamental Research Funds for the Central Universities(CHD300102311405)HPC platform,Xi’an Jiaotong University.
文摘Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental protection. However, the existing “acceptance-donation” mechanism is only applicable to bimetallic catalysts and nonmetallic double-atom catalysts containing boron atoms. Herein, a novel “capture-activation-recapture” mechanism for metal-nonmetal double-atom catalyst is proposed to solve the problem by adjusting the coordination environments of nonmetallic atoms and utilizing the activation effect of metal atoms on nitrogen. Based on this mechanism, the nitrogen reduction reaction (NRR) activity of 48 structures is calculated by density functional theory calculation, and four candidates are selected as outstanding electrocatalytic nitrogen reduction catalysts: Si-Fe@NG (U_(L) = –0.14 V), Si-Co@NG (U_(L)= –0.15 V), Si-Mo@BP1 (U_(L) = 0 V), and Si-Re@BP1 (U_(L) = –0.02 V). The analyses of electronic properties further confirm “capture-activation-recapture” mechanism and suggest that the difference in valence electron distribution between metal and Si atoms triggers the activation of N≡N bonds. In addition, a machine learning approach is utilized to generate an expression and an intrinsic descriptor that considers the coordination environment to predict the limiting potential. This study offers profound insight into the synergistic mechanism of TM and Si for NRR and guidance in the design of novel double-atom nitrogen fixation catalysts.
基金supported by the National Natural Science Foundation of China(Grant No 21625604,21671172,21776251,21706229 and 91934302)。
文摘Two-electron(2 e^(-))oxygen reduction reaction(ORR)shows great promise for on-site electrochemical synthesis of hydrogen peroxide(H_(2)O_(2)).However,it is still a great challenge to design efficient electrocatalysts for H_(2)O_(2)synthesis.To address this issue,the logical design of the active site by controlling the geometric and electronic structures is urgently desired.Therefore,using density functional theory(DFT)computations,two kinds of hybrid double-atom supported on C_(2)N nanosheet(RuCu@C_(2)N and PdCu@C_(2)N)are screened out and their H_(2)O_(2)performances are predicted.PdCu@C_(2)N exhibits higher activity for H_(2)O_(2)synthesis with a lower overpotential of 0.12 V than RuCu@C_(2)N(0.59 V),Ru_(3)Cu(110)facet(0.60 V),and PdCu(110)facet(0.54 V).In aqueous phase,the adsorbed O_(2)is further stabilized with bulk H_(2)0 and the thermodynamic rate-determining step of 2 e^(-) ORR change.The activation barrier on PdCu@C_(2)N is 0.43 eV lower than the one on RuCu@C_(2)N with 0.68 eV.PdCu@C_(2)N is near the top of 2 e^(-) ORR volcano plot,and exhibits high selectivity of H_(2)O_(2.)This work provides guidelines for designing highly effective hybrid double-atom electrocatalysts(HDACs)for H_(2)O_(2)synthesis.
基金supported by the National Natural Science Foundation of China(21673137)the support from the Program for Top Talents in Songjiang District of Shanghai。
文摘The rational design of a novel catalytic center with a sound basis remains both challenging and rewarding for the electrochemical reduction of N2(e NRR),which has provided a feasible route for achieving clean and sustainable NH3production under ambient conditions.Herein,using density functional theory calculations,we demonstrate that hybrid metal(M)-boron(B)double-atom catalysts(DACs)embedded in gC_(2)N substrate(M-B@C_(2)N,M=3d,4d and 5d transition metals)can achieve both high catalytic activity and high selectivity in e NRR.The proposed M-B@C_(2)N DACs have exhibited impressive feasibility and stability thanks to the resilient and robust C_(2)N substrate with abundant pyridinic N atoms distributed among right-sized pore structures.Our results reveal that like the metal center,the embedded B atom can actively involve in N≡N bond activation viaπ*-backdonation mechanism concomitant with the substantial charge transfer to adsorbed*N2,leading to sizable NAN bond elongation.Accordingly,both adsorption energy and NAN bond length of*N2can be employed as catalytic descriptors for predicting e NRR activity in terms of the limiting potentials(UL).Using high-throughput screening method,we found that six M-B@C_(2)N candidates have stood out as the outstanding electrocatalysts for driving e NRR,namely,M=Ti(UL=0 V),Mo(UL=0 V),Nb(UL=-0.04 V),W(UL=-0.23 V),Zr(UL=-0.26 V),V(UL=-0.28 V).The underlying origin is attributed to the balanced and constrained N-affinity of M-B dual site working in synergy,which can thus be used as one important guide of catalyst design.
基金supports by the National Natural Science Foundation of China(NSFC,52271113)the Natural Science Foundation of Shaanxi Province,China(2020JM 218)+1 种基金the Fundamental Research Funds for the Central Universities(CHD300102311405)HPC platform,Xi’an Jiaotong University。
文摘The severe environmental problems and the demand for energy urgently require electrocatalysis to replace Haber-Bosch for the nitrogen reduction reaction(NRR).The descriptors and important properties of single-atom and homonuclear double-atom catalysts have been preliminarily explored,but the relationship between the inherent properties and catalytic activity of heteronuclear double-atom catalysts with better performance remains unclear.Therefore,it is very significant to explore the prediction expressions of catalytic activity of heteronuclear double-atom catalysts based on their inherent properties and find the rule for selecting catalytic centers.Herein,by summarizing the free energy for the key steps of NRR on 55 catalysts calculated through the first-principle,the expressions of predicting the free energy and the corresponding descriptors are deduced by the machine learning,and the strategy for selecting the appropriate catalytic center is proposed.The selection strategy for the central atom of heteronuclear double-atom catalysts is that the atomic number of central B atom should be between group VB and VIIIB,and the electron difference between central A atom and B atom should be large enough,and the selectivity of NRR or hydrogen evolution reaction(HER)could be calculated through the prediction formula.Moreover,five catalysts are screened to have low limiting potential and excellent selectivity,and are further analyzed by electron transfer.This work explores the relationship between the inherent properties of heteronuclear double-atom catalysts and the catalytic activity,and puts forward the rules for selecting the heteronuclear double-atom catalytic center,which has guiding significance for the experiment.
基金supported by the Science and Technology Research Project of Hubei Provincial Department of Education(No.D20212603)Hubei University of Arts and Science(No.2020kypytd002)+1 种基金National Natural Science Foundation of China(No.22303098)Natural Science Foundation of Hubei Province(No.2022CFC030)。
文摘Electrochemical CO reduction(ECOR)as a potential strategy for producing valuable chemicals and fuels has captured substantial attention.However,the currently available electrocatalysts suffer from poor selectivity and low Faradaic efficiency,limiting their industrial application.Herein,we systematically investigate the potential of homonuclear bimetallic electrocatalysts,Tm_(2)@C_(9)N_(4)(TM=Fe,Co,Ni,and Cu),for the ECOR through extensive density functional theory calculations.Our findings suggest that all four proposed monolayers exhibit exceptional stability,making them highly suitable for experimental synthesis and practical applications.Interestingly,these transition-metal dual atoms anchored on C_(9)N_(4)monolayers show great potential in facilitating the production of high-value C_(2)products,such as C_(2)H_(5)OH and C_(2)H_(4),due to the significantly low limiting potentials(-0.06~-0.46 V)and small kinetic energy barriers(0.54–1.08 eV)for the CO coupling process.Moreover,with the exception of Ni_(2)@C_(9)N_(4),these bimetallic catalysts demonstrate the impressive suppression of the competitive hydrogen evolution reaction(HER),leading to a high selectivity for C_(2)products in ECOR.Our predictions would accelerate the development of high-performance C_(9)N_(4)-based dual-atom catalysts for the ECOR.
基金supported by the National Natural Science Foundation of China(Grant Nos.11704005 and 11774078)the Program for Science&Technology Innovation Talents in Universities of Henan Province(Grant No.20HASTIT028)。
文摘Developing efficient electrocatalysts for nitrogen reduction reaction(NRR)is crucial to replace the both energy-intensive and environment-malignant Haber-Bosch process.Here using density functional theory calculations,we systematically studied the potential of the heteronuclear 3 d transition metal dimers anchored graphdiyne monolayers(FeM@and NiM@GDY,M=Ti,V,Cr,Mn,Fe,Co,Ni,and Cu)as efficient NRR catalysts.Among all the studied double-atom catalysts(DACs),FeCo@and NiCo@GDY are the most promising with excellent NRR catalytic activity,high ability to suppress the competing hydrogen evolution reaction(HER),and good stability.For both FeCo@and NiCo@GDY,NRR prefers to the distal pathway with the calculated onset potentials of -0.44 and -0.36 V,respectively,which are comparable and even better than their homonuclear counterparts.Moreover,FeCo@and NiCo@GDY have higher ability to suppress HER than Fe_(2)@ and Co_(2)@GDY,which may result from the modulated d state electronic structure due to the synergy effect of the heteronuclear atoms in the DACs.Our work not only suggests that FeCo@and NiCo@GDY hold great promises as efficient,low-cost,and stable DACs for NRR,but also further provides a strategy,i.e.alloying the atomic metal catalysts,to improve the NRR catalytic activity and/or selectivity.
基金supported by the National Natural Science Foundation of China(21673137)the Science and Technology Commission of Shanghai Municipality(16ZR1413900,18030501100)+1 种基金the support from the Program for Top Talents in Songjiang District of Shanghaithe support from the Talent Program of Shanghai University of Engineering Science。
文摘Double-atom catalysts(DACs)have emerged as an enhanced platform of single-atom catalyst for promoting electrocatalytic CO_(2) reduction reaction(CO_(2) RR).Herein,we present a density-functional theory study on CO_(2) RR performance of seven C_(2) N-supported homo-and heteronuclear DACs,denoted as M_(2)@C_(2) N.Our results demonstrate that there exists substantial synergistic effect of dual-metal-atom N_(2) M_(2) N_(2) active site and C_(2) N matrix on O=C=O bond activation.The dual-atom M_(2) sites are able to drive CO_(2) RR beyond C1 products with low limiting potential(UL).Specifically,C_(2) H4 formation is preferred on FeM@C_(2) N(M=Fe,Co,Ni,Cu)versus CH4 formation on CuM@C_(2) N(M=Co,Ni,Cu).Furthermore,^(*)CO+^(*)CO cobinding strength can serve as a descriptor for CO_(2) RR activity for making C_(2) products such that the moderate binding results in the lowest UL.Remarkably,C-affinity matters most to C-C bond coupling and C_(2) H4 formation while both C-and O-affinity control CH4 formation.Our results provide theoretical insight into rational design of DACs for efficient CO_(2) RR.
文摘Being progressively applied in the design of highly active catalysts for energy devices,machine learning(ML)technology has shown attractive ability of dramatically reducing the computational cost of the traditional density functional theory(DFT)method,showing a particular advantage for the simulation of intricate system catalysis.Starting with a basic description of the whole workflow of the novel DFT-based and ML-accelerated(DFT-ML)scheme,and the common algorithms useable for machine learning,we presented in this paper our work on the development and performance test of a DFT-based ML method for catalysis program(DMCP)to implement the DFT-ML scheme.DMCP is an efficient and user-friendly program with the flexibility to accommodate the needs of performing ML calculations based on the data generated by DFT calculations or from materials database.We also employed an example of transition metal phthalocyanine double-atom catalysts as electrocatalysts for carbon reduction reaction to exhibit the general workflow of the DFT-ML hybrid scheme and our DMCP program.
基金supported by the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(No.2020KJ008)the Natural Science Foundation of Tianjin(No.18JCQNJC76000)+3 种基金the College Students'Innovation and Entrepreneurship Training Program of Tianjin(No.202110065112)Science and Technology Research Project of Hubei Provincial De-partment of Education(No.D20212603)Hubei University of Arts and Science(Nos.2020kypytd002,XK2021024)China Scholarship Council.
文摘Electrocatalytic nitrogen reduction reaction(NRR)is an environmentally friendly method for sustainable ammonia synthesis under ambient conditions.Searching for efficient NRR electrocatalysts with high activity and selectivity is currently urgent but remains great challenge.Herein,we systematically investigate the NRR catalytic activities of single and double transition metal atoms(TM=Fe,Co,Ni and Mo)anchored on g-C_(6)N_(6) monolayers by performing first-principles calculation.Based on the stability,activity,and selectivity analysis,Mo_(2)@g-C_(6)N_(6) monolayer is screened out as the most promising candidate for NRR.Further exploration of the reaction mechanism demonstrates that the Mo dimer anchored on g-C_(6)N_(6) can sufficiently activate and efficiently reduce the inert nitrogen molecule to ammonia through a preferred distal pathway with a particularly low limiting potential of -0.06 V.In addition,we find that Mo_(2)@g-C_(6)N_(6) has excellent NRR selectivity over the competing hydrogen evolution reaction,with the Faradaic efficiency being 100%.Our work not only predicts a kind of ideal NRR electrocatalyst but also encouraging more experimental and theoretical efforts to develop novel double-atom catalysts(DACs)for NRR.
基金financially supported in China by the National Natural Science Foundation of China(Grant Nos.11704203,11964024)the“Grassland Talents”project of Inner Mongolia Autonomous Region,China(Grant No.12000–12102613)+1 种基金the Young Science and Technology Talents Cultivation Project of Inner Mongolia University,China(21221505)the computational support from PARATEAR,and in USA by the National Science Foundation-Centers of Research Excellence in Science and Technology(NSF-CREST Center)for Innovation,Research and Education in Environmental Nanotechnology(CIRE2N)(Grant No.HRD-1736093).
文摘In this study,we selected 10 Co-based double-atom catalysts(DACs)catalysts,namely CoMN_(6)-gra(OH)(M?Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn),and investigated their oxygen reduction reactions(ORR)catalytic performances with/without considering the magnetic coupling by means of density functional theory(DFT)calculations.It was found that CoNiN_(6)-gra(OH),CoCuN_(6)-gra(OH),and CoZnN_(6)-gra(OH)exhibit good catalytic activity of ORR(with low overpotentials of 0.33,0.34 and 0.23 V,respectively)when the magnetic coupling is considered.In particular,magnetic changes in CoMN_(6)-gra(OH)candidates play a vital role in their ORR catalytic activity.Interestingly,the d-band center can be utilized to well rationalize the ORR catalytic activity.This work highlights the importance of considering the magnetic coupling to well predict the activity of ORR catalysts,and discloses that the manipulation of the magnetic coupling between transition metal atoms is an emerging and powerful approach for the development of high-performance electrocatalysts for ORR and other related reactions.
基金National Key Research and Development Program of China(Grant No.2022YFE0208400).
文摘The reliance on fossil fuels intensifies CO_(2) emissions,worsening political and environmental challenges.CO_(2) capture and conversion present a promising solution,influenced by industrialization and urbanization.In recent times,catalytic conversion of CO_(2) into fuels and chemical precursors,particularly methane,are gaining traction for establishing a sustainable,carbon-neutral economy due to methane’s advantages in renewable energy applications.Though homogeneous and heterogeneous catalysts are available for the conversion of CO_(2) to methane,the efficiency is found to be higher in heterogeneous catalysts.Therefore,this review focuses only on the heterogeneous catalysts.In this context,the efficient heterogeneous catalysts with optimum utility are yet to be obtained.Therefore,the quest for suitable catalyst for the catalytic conversion of CO_(2) to CH4 is still continuing and designing efficient catalysts requires assessing their synthetic feasibility,often achieved through computational methods like density functional theory simulations,providing insights into reaction mechanisms,rate-limiting steps,catalytic cycle,activation of C=O bonds and enhancing understanding while lowering costs.In this context,this review examines the conversion of CO_(2) to CH4 using seven distinct types of catalysts,including single and double atom catalysts,metal organic frameworks,metalloporphyrins,graphdiyne and graphitic carbon nitrite and alloys with some case studies.The main focus of this review is to offer a detailed and extensive examination of diverse catalyst design approaches and their utilization in CH4 production,with a specific emphasis on computational aspects.It explores the array of design methodologies used to identify reaction pathways and investigates the critical role of computational tools in their refinement and enhancement.We believe this review will help budding researchers to explore the possibilities of designing catalysts for the CO_(2) to CH4 conversion from computational framework.
