Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,su...Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,sulfide oxidation reactions in the sulfur cathode,and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances.Thanks to the“adsorption-catalysis”synergetic effects,the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li_(2)S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers,inhibiting polysulfide shuttling.Meanwhile,the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth.In this review,the various active catalysts in modulating lithium behaviors are summarized,especially for the defect-rich catalysts and single atomic catalysts.The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted.Furthermore,the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected,shedding light on the future practical development.展开更多
Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utiliza...Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.展开更多
The oxygen reduction reaction(ORR)could be effectively regulated by adjusting electron configurations and optimizing chemical bonds.Herein,we have achieved the modulation of electron distribution in Fe single atomic(F...The oxygen reduction reaction(ORR)could be effectively regulated by adjusting electron configurations and optimizing chemical bonds.Herein,we have achieved the modulation of electron distribution in Fe single atomic(Fe_(SA))sites through Fe atomic clusters(Fe_(AC))via a confined pyrolysis approach,thereby enhancing their intrinsic ORR activity.X-ray absorption spectroscopy has confirmed that the presence of iron atomic dusters could influence the electron distribution at Fe-N_(4)sites.The Fe_(SA)/Fe_(AC)-NC catalyst exhibits a half-wave potential of 0.88 V,surpassing the individual Fe_(SA)-NC structure.Through electronic structure analysis,it could be seen that iron atom clusters can affect Fe-N_(4)sites through long-range effects,and then effectively lower reaction barriers and enhance the reaction kinetics at Fe-N_(4)sites.The synthetic approach might pave the way for constructing highly active catalysts with tunable atomic structures,representing an effective and universal technique for electron modulation in M-N-C systems.This work provides enlightenment for the exploration of more efficient single-atom electrocatalysts and the optimization of the performance of atomic electrocatalysts.Furthermore,a zinc-air battery assembled using it on their cathode deliver a high peak power density(205.7 mW cm^(-2))and a high-specific capacity of 807.5 mA h g^(-1).This study offers a fresh approach to effectively enhance the synergistic interaction of between Fe single atom and Fe atomic clusters for improving ORR activity and energy storage.展开更多
Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-perform...Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
Single-atom catalysts(SACs),in which isolated metal atoms such as palladium(Pd)are anchored on solid supports,promise breakthroughs in energy conversion and catalysis.However,balancing their activity(reaction speed)an...Single-atom catalysts(SACs),in which isolated metal atoms such as palladium(Pd)are anchored on solid supports,promise breakthroughs in energy conversion and catalysis.However,balancing their activity(reaction speed)and stability(longevity)remains challenging,as the interplay between metal atoms,supports,and reactants is poorly understood.展开更多
The electrochemical nitrogen reduction reaction(eNRR)presents a sustainable alternative to the energy-intensive Haber-Bosch process for ammonia(NH_(3))production.This review examines the fundamental principles of eNRR...The electrochemical nitrogen reduction reaction(eNRR)presents a sustainable alternative to the energy-intensive Haber-Bosch process for ammonia(NH_(3))production.This review examines the fundamental principles of eNRR,emphasizing the critical roles of proton-exchange membranes and electrolytes in facilitating efficient nitrogen(N_(2))reduction.Special attention is given to single-atom catalysts(SACs),highlighting their unique structural and electronic properties that contribute to enhanced catalytic performance.The discussions encompass SACs based on precious metals,non-precious metals,and non-metallic materials,delving into their synthesis methods,coordination environments,and activity in the eNRR.This review also elucidates current challenges in the field and proposes future research directions aimed at optimizing SACs design to enhance eNRR efficiency.展开更多
Photocatalysis is widely regarded as a highly promising sustainable technique for addressing the challenges posed by environmental pollution and energy provision.In recent years,metal-loaded MOFs has become a rising s...Photocatalysis is widely regarded as a highly promising sustainable technique for addressing the challenges posed by environmental pollution and energy provision.In recent years,metal-loaded MOFs has become a rising star within the domain of photocatalysis due to its high specific surface area and porosity,adjustable structure,diverse and abundant catalytic components,which has exhibited excellent photocatalytic activity and exhibit great potential in a range of disciplines.In this paper,the principles for evaluating the photocatalytic performance of MOFs-based materials were firstly introduced,and some typical examples were also listed accordingly.Along with this,particular emphasis is paid to the main factors affecting the photocatalytic performance of metal-loaded MOFs.Then the synthesis and design strategies of MOFs loaded metal entities of varying sizes(single atoms,nanoclusters,and nanoparticles),and their applications in photocatalytic CO_(2)reduction,hydrogen production,photooxidation and photocatalytic hydrogenation were summarized and discussed.Finally,the opportunities and challenges faced in this kind of MOFs-based composites were analyzed from different perspectives.This report is expected to help researchers design and develop high-performance MOFs-based photocatalytic materials.展开更多
Electrochemical nitrogen reduction reaction(ENRR)is emerging as a favorable option to the power-intensive Haber-Bosch process for ammonia synthesis.However,obstacles such as poor selectivity,low production rates,and c...Electrochemical nitrogen reduction reaction(ENRR)is emerging as a favorable option to the power-intensive Haber-Bosch process for ammonia synthesis.However,obstacles such as poor selectivity,low production rates,and competition against the hydrogen evolution reaction hinder its practical implementation.To address these,the design of highly active catalysts is critical.Single-atom catalysts(SACs)have shown great potential because of their maximized atom utilization,but their limited stability and low metal loading restrict their performances.On the other hand,dual-atom catalysts(DACs)are atomic catalysts with two metal atoms nearby and offer enhanced electrocatalytic performances by aligning with the N≡N bond to enhance N2 reduction efficiency,potentially overcoming the limitations of SAC.This review discusses recent advances in SACs and more importantly DACs for ENRR,highlighting their advantages,limitations,and the need for advanced characterization techniques to better understand catalyst behavior.The review concludes by underscoring the importance of research to optimize these catalysts for efficient and sustainable nitrogen fixation.展开更多
The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylatio...The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylation reaction remains challenging which hasn't been much reported.Herein,we developed a new metal-porous ligand polymers Pd1@POL-PPh_(n)Cy_(m)(n+m=3)with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C-C bonds,including alkynes,alkenes,and allenes.X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates.With the electrically fine-tuned single atom palladium catalysts,we realized theα-germanium addition for the first time,obtaining corresponding allyl germanium and alkyl germanium compounds.展开更多
In this work,atomic Co catalysts are anchored on a three-dimensional(3D)interconnected g-C_(3)N_(4)(SACo-CN)through Co-N coordination,which exhibit efficient charge carrier transition and low activation energy barrier...In this work,atomic Co catalysts are anchored on a three-dimensional(3D)interconnected g-C_(3)N_(4)(SACo-CN)through Co-N coordination,which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate(PMS).The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples.The 3D interconnected structure,combined with the synergistic interplay between Co-N coordination and visible light irradiation,results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation.This leads to a degradation rate of 98.8%for oxytetracycline(OTC)within 30 min under visible light.The research proposes three potential mineralization pathways with eight intermediates,leading to a significant decrease in the toxicity of the intermediates.This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.展开更多
To solve the problem of slow kinetics in oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)and promote the development of bifunctional electrocatalysts,several two-dimensional CrSe_(2)-based single-atom ...To solve the problem of slow kinetics in oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)and promote the development of bifunctional electrocatalysts,several two-dimensional CrSe_(2)-based single-atom catalysts(SACs)were constructed using 3d transition metal(TM)atoms.Density functional theory(DFT)was employed to explore the electrocatalytic mechanisms of ORR/OER.The results showed that most of the TM atoms prefer to be anchored at site H,and the negative binding energy proved the excellent structural stability of these SACs.The hybridization between the orbitals of O 2p and TM 3d contributes to the charge transfer.Furthermore,the 3d TM atoms can act as active sites to activate the adsorbates,thereby improving the catalytic efficiency of the substrate.Significantly,Ni/CrSe_(2)exhibits the most outstanding ORR/OER catalytic performance,indicating its potential as a bifunctional electrocatalyst for ORR/OER.展开更多
Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is...Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.展开更多
Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The...Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The active sites are traditionally believed to be Au nanoclusters or nanoparticles in the size range of 0.5–5 nm. Only in the last few years have single‐atom Au catalysts been proved to be active for CO oxidation. Recent advances in both experimental and theoretical studies on single‐atom Au catalysts unambiguously demonstrated that when dispersed on suitable oxide supports the Au single atoms can be extremely active for CO oxidation. In this mini‐review, recent advances in the development of Au single‐atom catalysts are discussed, with the aim of illus‐trating their unique catalytic features during CO oxidation.展开更多
Formaldehyde(HCHO) is a common indoor pollutant, long-term exposure to HCHO may harm human health. Its efficient removal at mild conditions is still challenging. The catalytic oxidation of HCHO molecules on a single a...Formaldehyde(HCHO) is a common indoor pollutant, long-term exposure to HCHO may harm human health. Its efficient removal at mild conditions is still challenging. The catalytic oxidation of HCHO molecules on a single atomic catalyst, Ti-decorated Ti3C2O2(Ti/Ti3C2O2) monolayer, is investigated by performing the first principles calculations in this work. It demonstrates that Ti atoms can be easily well dispersed at the form of single atom on Ti3C2O2 monolayer without aggregation. For HCHO catalytic oxidation, both Langmuir-Hinshelwood(LH) and Eley-Rideal(ER) mechanisms are considered. The results show that the step of HCHO dissociative adsorption on Ti/Ti3C2O2 with activated O2 can release high energy of 4.05 e V based on the ER mechanism, which can help to overcome the energy barrier(1.04 e V) of the subsequent reaction steps. The charge transfer from *OH group to CO molecule(dissociated from HCHO) not only promotes *OH group activation but also plays an important role in the H2 O generation along the ER mechanism. Therefore, HCHO can be oxidized easily on Ti/Ti3C2O2 monolayer, this work could provide significant guidance to develop effective non-noble metal catalysts for HCHO oxidation and broaden the applications of MXene-based materials.展开更多
The increasing demand for clean energy and growing concerns regarding environmental sustainability have led to greater attention devoted toward the production of clean fuels via green chemistry.In this respect,ammonia...The increasing demand for clean energy and growing concerns regarding environmental sustainability have led to greater attention devoted toward the production of clean fuels via green chemistry.In this respect,ammonia is a green alternative to fossil fuels and can serve as a clean energy source.There is now great interest in realizing the electrochemical reduction in atmospheric nitrogen(N_(2))for cheap,environmentally friendly and reliable ammonia(NH_(3))production worldwide.However,the robustness of the triple bond in N2 and the low efficiency of candidate catalysts limit the utility of this conversion.Single atom catalysts have been found to be more effective than nanoparticles due to their unique properties,and thus have been studied extensively for the nitrogen reduction reaction.In this review,we have covered the recent advances in design and synthesis of noble metal and non-noble metal single atom catalysts for the electrochemical reduction in nitrogen during the years 2018-2022.The catalyst efficiencies,with reference to coordination preferences and theoretical studies have been discussed.Moreover,we also provide insights into the current challenges and some considerations for further future studies.展开更多
Supported and colloidal single‐atom catalysts(SACs),which possess excellent catalytic properties,are particularly important in both fundamental studies and practical applications.The progress made in the preparation ...Supported and colloidal single‐atom catalysts(SACs),which possess excellent catalytic properties,are particularly important in both fundamental studies and practical applications.The progress made in the preparation methods,characterization,catalytic performances and mechanisms of SACs anchored to metal oxides,two‐dimensional materials and the surface of metal nanoclusters(NCs)are reviewed.The different techniques for SAC fabrication,including conventional solution methods based on co‐precipitation,incipient wetness co‐impregnation,and the chemical vapor deposition method,as well as the newer atom layer deposition(ALD)and galvanic replacement methods,are summarized.The main results from experimental and theoretical studies of various catalytic reactions over SACs,including oxidation reactions,hydrogenation,water gas shift,photocatalytic H2evolution and electrochemical reactions,are also discussed.Moreover,the electronic properties of the single atoms and their interactions with the supports are described to assist in understanding the origin of the high catalytic activity and selectivity of SACs.Finally,possible future research directions of SACs and their applications are proposed.展开更多
Metal atoms atomically dispersed on an inorganic metal‐based support compose a unique category of single atom catalysts(SACs)and have important applications in catalytic photoreduction reactions,including H_(2) evolu...Metal atoms atomically dispersed on an inorganic metal‐based support compose a unique category of single atom catalysts(SACs)and have important applications in catalytic photoreduction reactions,including H_(2) evolution reaction,CO_(2) reduction reaction,and N_(2) reduction reaction.In this minreview,we summarized the typical metal‐support interaction(M‐SI)patterns for successful anchoring of single‐atom metals on metallic compound supports.Subsequently,the contribution of the dispersed single metal atoms and M‐SI to photocatalytic reactions with improved activity,selectivity,and stability are highlighted,such as by accelerating charge transfer,regulating band structure of the support,acting as the reductive sites,and/or increasing catalytic selectivity.Finally,some challenges and perspectives of future development are proposed.We anticipate that this minireview will be a beneficial supplement for a comprehensive perception of metal‐based material supported SACs and their application in heterogeneous photo‐reductive catalysis.展开更多
Single atom catalyst(SAC)refers to a novel catalyst with the active metal atoms individually anchored on the support.Single atom catalysts present the unique appeal due to the high atomic availability and specific act...Single atom catalyst(SAC)refers to a novel catalyst with the active metal atoms individually anchored on the support.Single atom catalysts present the unique appeal due to the high atomic availability and specific activity,as well as the high pathway selectivity.Herein,we summarized the classification,preparation,characterization,and application of single atom catalysts.Finally,the current bottlenecks and the outlooks of the SAC research are discussed.展开更多
Metal single atom catalysts(SACs)have been attracting increasing attention in recent years owing to their incredibleperformance in several key catalytic reactions such as the oxygen reduction reaction and CO oxidation...Metal single atom catalysts(SACs)have been attracting increasing attention in recent years owing to their incredibleperformance in several key catalytic reactions such as the oxygen reduction reaction and CO oxidation.The construction of well dis-persed stable SACs can not only make it possible to understand the catalytic reactions on the atomic scale,but is also important for developing novel industrial catalysts.Recent efforts have been focused on dispersing metal SACs on carbon substrates rather than on metals or metal oxides for improved catalytic behavior.Especially,graphene-based materials have proven to be excellent candidates for supporting SACs due to their unique structural and electronic properties.Nevertheless,the anchoring mechanism between metal SACs and carbon substrates is not well understood.Here we review the many roles of carbon materials as the support of SACs and highlight the anchoring mechanism.We also propose some suggestions to improve the experimental and theoretical research methods to expand the number of applications and realize industrial applications.展开更多
基金fellowship funding supported by the Alexander von Humboldt Foundationfinancial funding support from the Natural Science Foundation of Jiangsu Province(BK.20210636)Natural Science Foundation of China(21773294 and 21972164)。
文摘Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,sulfide oxidation reactions in the sulfur cathode,and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances.Thanks to the“adsorption-catalysis”synergetic effects,the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li_(2)S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers,inhibiting polysulfide shuttling.Meanwhile,the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth.In this review,the various active catalysts in modulating lithium behaviors are summarized,especially for the defect-rich catalysts and single atomic catalysts.The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted.Furthermore,the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected,shedding light on the future practical development.
基金financially supported by the National Key Research and Development Program of China (2018YFA0702002)the Beijing Natural Science Foundation (Z210016)the National Natural Science Foundation of China (21935001)。
文摘Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.
基金supported by the National Natural Science Foundations of China(Nos:22271018,22309012 and 22302013)the NSF of Guangdong Province(Nos:2023A1515010554 and 2024A1515010307)。
文摘The oxygen reduction reaction(ORR)could be effectively regulated by adjusting electron configurations and optimizing chemical bonds.Herein,we have achieved the modulation of electron distribution in Fe single atomic(Fe_(SA))sites through Fe atomic clusters(Fe_(AC))via a confined pyrolysis approach,thereby enhancing their intrinsic ORR activity.X-ray absorption spectroscopy has confirmed that the presence of iron atomic dusters could influence the electron distribution at Fe-N_(4)sites.The Fe_(SA)/Fe_(AC)-NC catalyst exhibits a half-wave potential of 0.88 V,surpassing the individual Fe_(SA)-NC structure.Through electronic structure analysis,it could be seen that iron atom clusters can affect Fe-N_(4)sites through long-range effects,and then effectively lower reaction barriers and enhance the reaction kinetics at Fe-N_(4)sites.The synthetic approach might pave the way for constructing highly active catalysts with tunable atomic structures,representing an effective and universal technique for electron modulation in M-N-C systems.This work provides enlightenment for the exploration of more efficient single-atom electrocatalysts and the optimization of the performance of atomic electrocatalysts.Furthermore,a zinc-air battery assembled using it on their cathode deliver a high peak power density(205.7 mW cm^(-2))and a high-specific capacity of 807.5 mA h g^(-1).This study offers a fresh approach to effectively enhance the synergistic interaction of between Fe single atom and Fe atomic clusters for improving ORR activity and energy storage.
基金supported by the National Natural Science Foundation of China(No.21571062)the Program for Professor of Special Appointment(Eastern Scholar)at the Shanghai Institutions of Higher Learning to JGL,and the Fundamental Research Funds for the Central Universities(No.222201717003)。
文摘Exploiting non-precious metal catalysts with excellent oxygen reduction reaction(ORR)performance for energy devices is paramount essential for the green and sustainable society development.Herein,low-cost,high-performance biomass-derived ORR catalysts with an asymmetric Fe-N_(3)P configuration was prepared by a simple pyrolysis-etching technique,where carboxymethyl cellulose(CMC)was used as the carbon source,urea and 1,10-phenanthroline iron complex(FePhen)as additives,and Na_(3)PO_(4)as the phosphorus dopant and a pore-forming agent.The CMC-derived FeNPC catalyst displayed a large specific area(BET:1235 m^(2)g^(-1))with atomically dispersed Fe-N_(3)P active sites,which exhibited superior ORR activity and stability in alkaline solution(E_(1/2)=0.90 V vs.RHE)and Zn-air batteries(P_(max)=149 mW cm^(-2))to commercial Pt/C catalyst(E_(1/2)=0.87 V,P_(max)=118 mW cm^(-2))under similar experimental conditions.This work provides a feasible and costeffective route toward highly efficient ORR catalysts and their application to Zn-air batteries for energy conversion.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
文摘Single-atom catalysts(SACs),in which isolated metal atoms such as palladium(Pd)are anchored on solid supports,promise breakthroughs in energy conversion and catalysis.However,balancing their activity(reaction speed)and stability(longevity)remains challenging,as the interplay between metal atoms,supports,and reactants is poorly understood.
基金supported by the PhD Research Project of Yan'an University(No.YAU202411439)Shaanxi Province College Students Innovation and Entrepreneurship Training Program(No.S202410719170)Princess Nourah bint Abdulrahman University Researchers Supporting Project(No.PNURSP2025R398)。
文摘The electrochemical nitrogen reduction reaction(eNRR)presents a sustainable alternative to the energy-intensive Haber-Bosch process for ammonia(NH_(3))production.This review examines the fundamental principles of eNRR,emphasizing the critical roles of proton-exchange membranes and electrolytes in facilitating efficient nitrogen(N_(2))reduction.Special attention is given to single-atom catalysts(SACs),highlighting their unique structural and electronic properties that contribute to enhanced catalytic performance.The discussions encompass SACs based on precious metals,non-precious metals,and non-metallic materials,delving into their synthesis methods,coordination environments,and activity in the eNRR.This review also elucidates current challenges in the field and proposes future research directions aimed at optimizing SACs design to enhance eNRR efficiency.
基金supported by the Beijing Natural Science Foundation(No.L233011)Guangdong Province Natural Science Foundation(No.2022A1515011918)USTB Research Center for International People-to-People Exchange in Science.Technology and Civilization(No.2023KFYB003)。
文摘Photocatalysis is widely regarded as a highly promising sustainable technique for addressing the challenges posed by environmental pollution and energy provision.In recent years,metal-loaded MOFs has become a rising star within the domain of photocatalysis due to its high specific surface area and porosity,adjustable structure,diverse and abundant catalytic components,which has exhibited excellent photocatalytic activity and exhibit great potential in a range of disciplines.In this paper,the principles for evaluating the photocatalytic performance of MOFs-based materials were firstly introduced,and some typical examples were also listed accordingly.Along with this,particular emphasis is paid to the main factors affecting the photocatalytic performance of metal-loaded MOFs.Then the synthesis and design strategies of MOFs loaded metal entities of varying sizes(single atoms,nanoclusters,and nanoparticles),and their applications in photocatalytic CO_(2)reduction,hydrogen production,photooxidation and photocatalytic hydrogenation were summarized and discussed.Finally,the opportunities and challenges faced in this kind of MOFs-based composites were analyzed from different perspectives.This report is expected to help researchers design and develop high-performance MOFs-based photocatalytic materials.
基金supported by the National Research Foundation of Korea(2022R1C1C2005786,RS-2023-00256106,RS-2023-00207831,RS-2024-00346153).
文摘Electrochemical nitrogen reduction reaction(ENRR)is emerging as a favorable option to the power-intensive Haber-Bosch process for ammonia synthesis.However,obstacles such as poor selectivity,low production rates,and competition against the hydrogen evolution reaction hinder its practical implementation.To address these,the design of highly active catalysts is critical.Single-atom catalysts(SACs)have shown great potential because of their maximized atom utilization,but their limited stability and low metal loading restrict their performances.On the other hand,dual-atom catalysts(DACs)are atomic catalysts with two metal atoms nearby and offer enhanced electrocatalytic performances by aligning with the N≡N bond to enhance N2 reduction efficiency,potentially overcoming the limitations of SAC.This review discusses recent advances in SACs and more importantly DACs for ENRR,highlighting their advantages,limitations,and the need for advanced characterization techniques to better understand catalyst behavior.The review concludes by underscoring the importance of research to optimize these catalysts for efficient and sustainable nitrogen fixation.
基金supported by the National Natural Science Foundation of China(Nos.22201049,22471046)the Ba-Gui Youth Top-notch Talents Project of Guangxithe National HighLevel Personnel of Special Support Program for Young Top-notch Talents(9th batch)。
文摘The selective addition reaction of unsaturated C-C bonds has always been a classic and constant research topic.Different from well-developed hydroboration,hydrosilylation,and hydrostannylation reaction,hydrogermylation reaction remains challenging which hasn't been much reported.Herein,we developed a new metal-porous ligand polymers Pd1@POL-PPh_(n)Cy_(m)(n+m=3)with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C-C bonds,including alkynes,alkenes,and allenes.X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates.With the electrically fine-tuned single atom palladium catalysts,we realized theα-germanium addition for the first time,obtaining corresponding allyl germanium and alkyl germanium compounds.
基金financial support from the National Natural Science Foundation of China(Nos.22276159,J2224005)the Key research project plan for higher education institutions of Henan province(No.24ZX009)+1 种基金the Development Program for Key Young Teachers in Colleges and Universities of Henan Province(No.2020GGJS146)the Starting Research Fund of Xinxiang Medical University(No.XYBSKYZZ201911)。
文摘In this work,atomic Co catalysts are anchored on a three-dimensional(3D)interconnected g-C_(3)N_(4)(SACo-CN)through Co-N coordination,which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate(PMS).The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples.The 3D interconnected structure,combined with the synergistic interplay between Co-N coordination and visible light irradiation,results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation.This leads to a degradation rate of 98.8%for oxytetracycline(OTC)within 30 min under visible light.The research proposes three potential mineralization pathways with eight intermediates,leading to a significant decrease in the toxicity of the intermediates.This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.
基金supported by the Key Project of NSFC-Henan Joint Fund(No.U2004209)the National Natural Science Foundation of China(No.21603109)。
文摘To solve the problem of slow kinetics in oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)and promote the development of bifunctional electrocatalysts,several two-dimensional CrSe_(2)-based single-atom catalysts(SACs)were constructed using 3d transition metal(TM)atoms.Density functional theory(DFT)was employed to explore the electrocatalytic mechanisms of ORR/OER.The results showed that most of the TM atoms prefer to be anchored at site H,and the negative binding energy proved the excellent structural stability of these SACs.The hybridization between the orbitals of O 2p and TM 3d contributes to the charge transfer.Furthermore,the 3d TM atoms can act as active sites to activate the adsorbates,thereby improving the catalytic efficiency of the substrate.Significantly,Ni/CrSe_(2)exhibits the most outstanding ORR/OER catalytic performance,indicating its potential as a bifunctional electrocatalyst for ORR/OER.
基金supported by Beijing Natural Science Foundation(No.8244060)China Postdoctoral Science Foundation(No.2023M730143)+3 种基金the National Natural Science Foundation of China(No.22425601)the National Key R&D Program of China(No.2023YFB3810801)Beijing Nova Program(No.20240484659)the R&D Program of Beijing Municipal Education Commission(No.KZ202210005011).
文摘Volatile organic compounds(VOCs)exhausted from industrial processes are the major atmospheric pollutants,which could destroy the ecological environment and make hazards to human health seriously.Catalytic oxidation is regarded as the most competitive strategy for the efficient elimination of low-concentration VOCs.Supported noble metal catalysts are preferred catalysts due to their excellent low-temperature catalytic activity.To further lower the cost of catalysts,single atom catalysts(SAC)have been fabricated and extensively studied for application in VOCs oxidation due to their 100%atom-utilization efficiency and unique catalytic performance.In this review,we comprehensively summarize the recent advances in supported noble metal(e.g.,Pt,Pd,Au,and Ag)catalysts and SAC for VOCs oxidation since 2015.Firstly,this paper focuses on some important influencing factors that affect the activity of supported noble metal catalysts,including particle size,valence state and dispersion of noble metals,properties of the support,metal oxide/ion modification,preparation method,and pretreatment conditions of catalysts.Secondly,we briefly summarize the catalytic performance of SAC for typical VOCs.Finally,we conclude the key influencing factors and provide the prospects and challenges of VOCs oxidation.
文摘Low‐temperature CO oxidation is important for both fundamental studies and practical applica‐tions. Supported gold catalysts are generally regarded as the most active catalysts for low‐temperature CO oxidation. The active sites are traditionally believed to be Au nanoclusters or nanoparticles in the size range of 0.5–5 nm. Only in the last few years have single‐atom Au catalysts been proved to be active for CO oxidation. Recent advances in both experimental and theoretical studies on single‐atom Au catalysts unambiguously demonstrated that when dispersed on suitable oxide supports the Au single atoms can be extremely active for CO oxidation. In this mini‐review, recent advances in the development of Au single‐atom catalysts are discussed, with the aim of illus‐trating their unique catalytic features during CO oxidation.
文摘Formaldehyde(HCHO) is a common indoor pollutant, long-term exposure to HCHO may harm human health. Its efficient removal at mild conditions is still challenging. The catalytic oxidation of HCHO molecules on a single atomic catalyst, Ti-decorated Ti3C2O2(Ti/Ti3C2O2) monolayer, is investigated by performing the first principles calculations in this work. It demonstrates that Ti atoms can be easily well dispersed at the form of single atom on Ti3C2O2 monolayer without aggregation. For HCHO catalytic oxidation, both Langmuir-Hinshelwood(LH) and Eley-Rideal(ER) mechanisms are considered. The results show that the step of HCHO dissociative adsorption on Ti/Ti3C2O2 with activated O2 can release high energy of 4.05 e V based on the ER mechanism, which can help to overcome the energy barrier(1.04 e V) of the subsequent reaction steps. The charge transfer from *OH group to CO molecule(dissociated from HCHO) not only promotes *OH group activation but also plays an important role in the H2 O generation along the ER mechanism. Therefore, HCHO can be oxidized easily on Ti/Ti3C2O2 monolayer, this work could provide significant guidance to develop effective non-noble metal catalysts for HCHO oxidation and broaden the applications of MXene-based materials.
基金financially supported by the National Natural Science Foundation of China(No.21972010)Beijing Natural Science Foundation(No.2192039)。
文摘The increasing demand for clean energy and growing concerns regarding environmental sustainability have led to greater attention devoted toward the production of clean fuels via green chemistry.In this respect,ammonia is a green alternative to fossil fuels and can serve as a clean energy source.There is now great interest in realizing the electrochemical reduction in atmospheric nitrogen(N_(2))for cheap,environmentally friendly and reliable ammonia(NH_(3))production worldwide.However,the robustness of the triple bond in N2 and the low efficiency of candidate catalysts limit the utility of this conversion.Single atom catalysts have been found to be more effective than nanoparticles due to their unique properties,and thus have been studied extensively for the nitrogen reduction reaction.In this review,we have covered the recent advances in design and synthesis of noble metal and non-noble metal single atom catalysts for the electrochemical reduction in nitrogen during the years 2018-2022.The catalyst efficiencies,with reference to coordination preferences and theoretical studies have been discussed.Moreover,we also provide insights into the current challenges and some considerations for further future studies.
基金supported by the National Natural Science Foundation of China(51472184 and 51472185)the Science and Technology Support Program of Hubei Province(2013BHE003)the Program for Innovative Teams of Outstanding Young and Middle-Aged Researchers in the Higher Education Institutions of Hubei Province(T201602)~~
文摘Supported and colloidal single‐atom catalysts(SACs),which possess excellent catalytic properties,are particularly important in both fundamental studies and practical applications.The progress made in the preparation methods,characterization,catalytic performances and mechanisms of SACs anchored to metal oxides,two‐dimensional materials and the surface of metal nanoclusters(NCs)are reviewed.The different techniques for SAC fabrication,including conventional solution methods based on co‐precipitation,incipient wetness co‐impregnation,and the chemical vapor deposition method,as well as the newer atom layer deposition(ALD)and galvanic replacement methods,are summarized.The main results from experimental and theoretical studies of various catalytic reactions over SACs,including oxidation reactions,hydrogenation,water gas shift,photocatalytic H2evolution and electrochemical reactions,are also discussed.Moreover,the electronic properties of the single atoms and their interactions with the supports are described to assist in understanding the origin of the high catalytic activity and selectivity of SACs.Finally,possible future research directions of SACs and their applications are proposed.
文摘Metal atoms atomically dispersed on an inorganic metal‐based support compose a unique category of single atom catalysts(SACs)and have important applications in catalytic photoreduction reactions,including H_(2) evolution reaction,CO_(2) reduction reaction,and N_(2) reduction reaction.In this minreview,we summarized the typical metal‐support interaction(M‐SI)patterns for successful anchoring of single‐atom metals on metallic compound supports.Subsequently,the contribution of the dispersed single metal atoms and M‐SI to photocatalytic reactions with improved activity,selectivity,and stability are highlighted,such as by accelerating charge transfer,regulating band structure of the support,acting as the reductive sites,and/or increasing catalytic selectivity.Finally,some challenges and perspectives of future development are proposed.We anticipate that this minireview will be a beneficial supplement for a comprehensive perception of metal‐based material supported SACs and their application in heterogeneous photo‐reductive catalysis.
基金the financial support from the National Natural Science Foundation of China(No.22001228)“Double-First Class”University Construction Project(Nos.C176220100022 and C176220100042)+1 种基金Major Science and Technology Project of Precious Metal Materials Genetic Engineering in Yunnan Province(Nos.2019ZE001-1,202002AB080001-6)the Yunnan Science and Technology Bureau and Yunnan University(No.2019FY003025)。
文摘Single atom catalyst(SAC)refers to a novel catalyst with the active metal atoms individually anchored on the support.Single atom catalysts present the unique appeal due to the high atomic availability and specific activity,as well as the high pathway selectivity.Herein,we summarized the classification,preparation,characterization,and application of single atom catalysts.Finally,the current bottlenecks and the outlooks of the SAC research are discussed.
文摘Metal single atom catalysts(SACs)have been attracting increasing attention in recent years owing to their incredibleperformance in several key catalytic reactions such as the oxygen reduction reaction and CO oxidation.The construction of well dis-persed stable SACs can not only make it possible to understand the catalytic reactions on the atomic scale,but is also important for developing novel industrial catalysts.Recent efforts have been focused on dispersing metal SACs on carbon substrates rather than on metals or metal oxides for improved catalytic behavior.Especially,graphene-based materials have proven to be excellent candidates for supporting SACs due to their unique structural and electronic properties.Nevertheless,the anchoring mechanism between metal SACs and carbon substrates is not well understood.Here we review the many roles of carbon materials as the support of SACs and highlight the anchoring mechanism.We also propose some suggestions to improve the experimental and theoretical research methods to expand the number of applications and realize industrial applications.
