Recently, the electrochemical N2 reduction reaction （NRR） in aqueous electrolytes at ambient temperature and pressure has demonstrated its unique advantages and potentials. The reactants are directly derived from ga...Recently, the electrochemical N2 reduction reaction （NRR） in aqueous electrolytes at ambient temperature and pressure has demonstrated its unique advantages and potentials. The reactants are directly derived from gaseous N2 and water, which are naturally abundant, and NH3 production is important for fertilizers and other industrial applications. To improve the conversion yield and selectivity （mainly competing with water reduction）, electrocatalysts must be rationally designed to optimize the mass transport, chemisorption, and transduction pathways of protons and electrons. In this review, we summarize recent progress in the electrochemical NRR. Studies of electrocatalyst designs are summarized for different categories, including metal-based catalysts, metal oxide-derived catalysts, and hybrid catalysts. Strategies for enhancing the NRR performance based on the facet orientation, metal oxide interface, crystallinity, and nitrogen vacancies are presented. Additional system designs, such as lithium-nitrogen batteries, and the solvent effect are introduced. Finally, existing challenges and prospects are discussed.展开更多
The capability of electrocatalytic reducti on of carbon dioxide(CO2)using nitrogen(N)-doped carb on strongly depe nds on the N-dopi ng level and their types.In this work,we developed a strategy to generate mesoporous ...The capability of electrocatalytic reducti on of carbon dioxide(CO2)using nitrogen(N)-doped carb on strongly depe nds on the N-dopi ng level and their types.In this work,we developed a strategy to generate mesoporous N-doped carb on frameworks with tun able configurati ons and contents of N dopants,by using a secondary doping process via the treatment of N,N-dimethylformamide(DMF)solvent.The obtained mesoporous N-doped carbon(denoted as MNC-D)served as an efficient electrocatalyst for electroreduction of CO2 to CO.A high Faradaic efficiency of^92%and a partial current density for CO of-6.8 mA·cm^-2 were achieved at a potential of-0.58 V vs.RHE.Electrochemical analyses further revealed that the active sites within the N-doped carb on catalysts were the pyridinic N and defects gen erated by the DMF treatme nt,which enhan ced the activati on and adsorpti on CO2 molecules.Our study suggests a new approach to develop efficie nt carb on-based catalysts for potential scalable CO2 reduction reaction(CO2RR)to fuels and chemicals.展开更多
Preciously tuning the surface composition of noble metal nanoparticles with the particle size of only 2 nm or less by alloying with other metals represents a powerful strategy to boost their electrocatalytic selectivi...Preciously tuning the surface composition of noble metal nanoparticles with the particle size of only 2 nm or less by alloying with other metals represents a powerful strategy to boost their electrocatalytic selectivity.However,the synthesis of ultrafine nanoalloys and tuning their surface composition remain challenging.In this report,ultrafine CuPd nanoalloys with the particle size of ca.2 nm are synthesized based on the galvanic replacement reaction between presynthesized Cu nanoparticles and Pd2+precursors,and the tuning of their surface compositions is also achieved by changing the atom ratios of Cu/Pd.For the electrocatalytic reduction of CO2,Cu5Pd5 nanoalloys show the CO Faradaic efficiency(FE)of 88%at−0.87 V,and the corresponding mass activity reaches 56 A/g that is much higher than those of Cu8Pd2 nanoalloys,Cu3Pd7 nanoalloys and most of previously reported catalysts.Density functional theory uncovers that with the increase of Pd on the surface of the ultrafine CuPd nanoalloys,the adsorbed energy of both of intermediate COOH*and CO*to the Pd sites is strengthened.The Cu5Pd5 nanoalloys with the optimal surface composition better balance the adsorption of COOH*and desorption of CO*,achieving the highest selectivity and activity.The difficult liberation of absorbed CO*on the surface of Cu3Pd7 nanoalloys provides carbon source to favor the production of ethylene,endowing the Cu3Pd7 nanoalloys with the highest selectivity for ethylene among these ultrafine CuPd nanoalloys.展开更多
Developing electrocatalysts that exhibit both high activity and ammonia selectivity for nitrate reduction is a significant and demanding challenge,primarily due to the complex nature of the multiple-electron reduction...Developing electrocatalysts that exhibit both high activity and ammonia selectivity for nitrate reduction is a significant and demanding challenge,primarily due to the complex nature of the multiple-electron reduction process involved.An encouraging approach involves coupling highly active precious metals with transition metals to enhance catalytic performance through synergy.Here,we report a ruthenium-nickel alloy catalyst with nanosheets(Ru-Ni NSs)structure that achieves a remarkable ammonia Faradaic efficiency of approximately 95.93%,alongside a yield rate of up to 6.11 g·h^(−1)·cm^(−2).Moreover,the prepared Ru-Ni NSs exhibit exceptional stability during continuous nitrate reduction in a flow reactor for 100 h,maintaining a Faradaic efficiency of approximately 90%and an ammonia yield of 37.4 mg·L^(−1)·h^(−1)using 0.05 M nitrate alkaline electrolyte.Mechanistic studies reveal that the catalytic process follows a two-step pathway,in which HONO serves as a migration intermediate.The presence of a partially oxidized Ru(002)surface enhances the adsorption of nitrate and facilitates the release of the migration intermediate by adjusting the strength of the electrostatic and covalent interactions between the adsorbate and the surface,respectively.On the other hand,the Ni(111)surface promotes the utilization of the migration intermediate and requires less energy for NH_(3)desorption.This tandem process contributes to a high catalytic activity of Ru-Ni NSs towards nitrate reduction.展开更多
Electrochemical nitrogen reduction reaction(ENRR) provides a promising strategy to achieve sustainable synthesis of ammonia. However, despite great efforts devoted to this research field, the problems such as low ener...Electrochemical nitrogen reduction reaction(ENRR) provides a promising strategy to achieve sustainable synthesis of ammonia. However, despite great efforts devoted to this research field, the problems such as low energy efficiency and weak selectivity still impede its practical implementation. Most of the research to date has been concentrated on creating sophisticated electrocatalysts, and adequate knowledge of electrolytes is still lacking. Herein, the recent progress in electrolytes for ENRR, including alkaline, neutral,acidic, water-in-salt, organic, ionic liquid, and mixed water-organic electrolytes, is thoroughly reviewed to obtain an in-depth understanding of their effects on electrocatalytic performance. Recently developed representative electrocatalysts in various types of electrolytes are also introduced, and future research priorities of different electrolytes are proposed to develop new and efficient ENRR systems.展开更多
The recent development of Cu-based electrocatalysts for electrochemical reduction of carbon dioxide（CO） has attracted much attention due to their unique activity and selectivity compared to other metal catalysts. Pa...The recent development of Cu-based electrocatalysts for electrochemical reduction of carbon dioxide（CO） has attracted much attention due to their unique activity and selectivity compared to other metal catalysts. Particularly, Cu is the unique electrocatalyst for COelectrochemical reduction with high selectivity to generate a variety of hydrocarbons. In this review, we mainly summarize the recent advances on the rational design of Cu nanostructures, the composition regulation of Cu-based alloys, and the exploitation of advanced supports for improving the catalytic activity and selectivity toward electrochemical reduction of CO. The special focus is to demonstrate how to enhance the activity and selectivity of Cubased electrocatalyst for COreduction. The perspectives and challenges for the development of Cu-based electrocatalysts are also addressed. We hope this review can provide timely and valuable insights into the design of advanced electrocatalytic materials for COelectrochemical reduction.展开更多
Electrochemical reduction of CO2 to produce value-added feedstock chemicals using high-performance electrocatalysts is a promising protocol to address the excessive CO2 in the atmosphere and the energy crisis. However...Electrochemical reduction of CO2 to produce value-added feedstock chemicals using high-performance electrocatalysts is a promising protocol to address the excessive CO2 in the atmosphere and the energy crisis. However, the high overpotential, low current density, and poor product selectivity for CO2 electroreduction greatly impede their practical applications. In this work, we develop an efficient catalyst for CO2 reduction to CO consisting of well-dispersed ZrO2 nanoparticles tightly anchored on nitrogendoped carbon nanosheets(ZrO2/N-C) for the first time. Importantly, the ZrO2 nanoparticles possess oxygen vacancies and defects, which regulate the electronic structure of catalyst and thus greatly enhance the electrocatalytic activity. Specifically, ZrO2/N-C demonstrates a high CO Faradaic efficiency(FE) of 64% at-0.4 V vs. the reversible hydrogen electrode(RHE) and a respectable current density of ~2.6 m A cm-2 in CO2-saturated 0.5 M KHCO 3 solution. This work opens a new avenue for developing excellent catalysts for CO2 electroreduction with metal oxide/heteroatom-doped carbon composite structure.展开更多
Carbon dioxide transformation to fuels or chemicals provides an attractive approach for its utilization as feedstock and its emission reduction. Herein, we report a gas-phase electrocatalytic reduction of CO2 in an el...Carbon dioxide transformation to fuels or chemicals provides an attractive approach for its utilization as feedstock and its emission reduction. Herein, we report a gas-phase electrocatalytic reduction of CO2 in an electrolytic cell, constructed using phosphoric acid-doped polybenz- imidazole （PBI） membrane, which allowed operation at 170 ℃ Pt/C and PtMo/C with variable ratio of Pt/Mo were studied as the cathode catalysts. The results showed that PtMo/C catalysts significantly enhanced CO formation and inhibited CH4 formation compared with Pt/C catalyst. Characterization by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy revealed that most Mo species existed as MoO3 in PtMo/C catalysts and the interaction between Pt and MoOx was likely responsible for the enhanced CO formation rate although these bicomponent catalysts in general had a larger particle size than Pt/C catalyst.展开更多
Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides...Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides have attracted attention as promising nature-inspired materials due to multiple adsorption sites which are enhanced by the covalent character of sulfur.This article summarizes the current status regarding the utilization and development of metal sulfide materials as CO_(2)RR electrocatalysts.First,the research background and basic principles of electrochemical CO_(2)RR are introduced.Next,an overview of the main obstacles to developing efficient CO_(2)RR electrocatalysts is presented.The section is followed by a summary of the empirical evidence supporting the application of metal sulfides as CO_(2)RR electrocatalysts beside nature-inspired motivation.The summary of synthesis methods of various metal sulfides is also presented.Furthermore,the paper also highlights the recent works on metal sulfide as efficient CO_(2)RR including the undertaking strategy on the activity enhancement,and finally,discusses the challenges and prospect of metal sulfides-based CO_(2)RR electrocatalysts.Despite recent efforts,metal sulfides remain relatively unexplored as materials for CO_(2)RR electrocatalytic applications.Therefore,this review aims to stimulate novel ideas and research for improved catalyst designs and functionality.展开更多
Ammonia is not only an important platform chemical for industrial and agri-cultural use but is also a novel energy-carrying molecule.The electrochemical reduction method for ambient ammonia synthesis is emerging as a ...Ammonia is not only an important platform chemical for industrial and agri-cultural use but is also a novel energy-carrying molecule.The electrochemical reduction method for ambient ammonia synthesis is emerging as a promising strategy for the replacement of the current Haber–Bosch ammonia synthesis method,which consumes a large amount of energy and natural gas(hydrogen resource)while releasing substantial greenhouse gases(eg,carbon dioxide).The challenges in electrochemical ammonia synthesis,also known as nitrogen reduc-tion reaction,primarily include the cleavage of extremely stable N≡N bonds and the competitive hydrogen evolution reaction in routine aqueous media,which significantly leads to a low production rate and Faradaic efficiency.The ratio-nal design and engineering of the electrocatalyst/electrolyte interface are crucial to address these challenges.Herein,recent achievements for catalyst/electrolyte interface engineering are reviewed to provide insights into enhancing the pro-duction rate and Faradaic efficiency.Perspectives on future research and devel-opment of the electrochemical ammonia synthesis from theory to practice will be provided.展开更多
The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce C...The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce CO_(2) emissions is a global priority. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is strongly believed to be a promising alternative to fossil fuel-based technologies for the production of value-added chemicals. So far, the implementation of CO_(2)RR is hindered by associated electrochemical reactions, such as low selectivity, hydrogen evolution reaction(HER), and additional overpotential induced in some cases. As a result, it is necessary to conduct a timely evaluation of the state-of-the-art strategies in CO_(2)RR, with a focus on the engineering of the electrocatalytic systems. Catalyst morphology is one factor that plays a critical role in overcoming these drawbacks and significantly contributes to enhancing product selectivity and Faradaic efficiency(FE). This review article summarizes the recent advances in the rational design of electrocatalysts with various morphologies and the influence of these morphologies on CO_(2)RR. To compare literature findings in a meaningful way, the article focuses on results reported under a well-defined period and considers the first three rows of the d-block metal catalysts. The discussion typically covers the design of nanostructured catalysts and the molecular-level understanding of morphology-performance relationship in terms of activity, selectivity, and stability during CO_(2) electrolysis. Among others, it would be convenient to recommend a comprehensive discussion on the morphologies of single metals and heterostructures, with a detailed emphasis on their impact on CO_(2) conversion.展开更多
文摘Recently, the electrochemical N2 reduction reaction （NRR） in aqueous electrolytes at ambient temperature and pressure has demonstrated its unique advantages and potentials. The reactants are directly derived from gaseous N2 and water, which are naturally abundant, and NH3 production is important for fertilizers and other industrial applications. To improve the conversion yield and selectivity （mainly competing with water reduction）, electrocatalysts must be rationally designed to optimize the mass transport, chemisorption, and transduction pathways of protons and electrons. In this review, we summarize recent progress in the electrochemical NRR. Studies of electrocatalyst designs are summarized for different categories, including metal-based catalysts, metal oxide-derived catalysts, and hybrid catalysts. Strategies for enhancing the NRR performance based on the facet orientation, metal oxide interface, crystallinity, and nitrogen vacancies are presented. Additional system designs, such as lithium-nitrogen batteries, and the solvent effect are introduced. Finally, existing challenges and prospects are discussed.
基金We thank the following funding agencies for supporting this work:the National Key Research and Development Program of China(Nos.2017YFA0206901 and 2018YFA0209401)the National Natural Science Foundation of China(No.21773036)+1 种基金the Science and Technology Commission of Shanghai Municipality(Nos.17JC1402000 and 19XD1420400)the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-07-E00045).
文摘The capability of electrocatalytic reducti on of carbon dioxide(CO2)using nitrogen(N)-doped carb on strongly depe nds on the N-dopi ng level and their types.In this work,we developed a strategy to generate mesoporous N-doped carb on frameworks with tun able configurati ons and contents of N dopants,by using a secondary doping process via the treatment of N,N-dimethylformamide(DMF)solvent.The obtained mesoporous N-doped carbon(denoted as MNC-D)served as an efficient electrocatalyst for electroreduction of CO2 to CO.A high Faradaic efficiency of^92%and a partial current density for CO of-6.8 mA·cm^-2 were achieved at a potential of-0.58 V vs.RHE.Electrochemical analyses further revealed that the active sites within the N-doped carb on catalysts were the pyridinic N and defects gen erated by the DMF treatme nt,which enhan ced the activati on and adsorpti on CO2 molecules.Our study suggests a new approach to develop efficie nt carb on-based catalysts for potential scalable CO2 reduction reaction(CO2RR)to fuels and chemicals.
基金National Natural Science Foundation of China,Grant/Award Numbers:21573240,21706265,21922813The would like to acknowledge the support provided by the National Natural Science Foundation of China(Grant no.:21573240 and 21706265)+2 种基金the Center for Mesoscience,Institute of Process Engineering,Chinese Academy of Sciences(MPCS-2017-A-02)State Key Laboratory of Multiphase Complex Systems(MPCS-2019-A-09)National Science Fund for Excellent Young Scholars(21922813).
文摘Preciously tuning the surface composition of noble metal nanoparticles with the particle size of only 2 nm or less by alloying with other metals represents a powerful strategy to boost their electrocatalytic selectivity.However,the synthesis of ultrafine nanoalloys and tuning their surface composition remain challenging.In this report,ultrafine CuPd nanoalloys with the particle size of ca.2 nm are synthesized based on the galvanic replacement reaction between presynthesized Cu nanoparticles and Pd2+precursors,and the tuning of their surface compositions is also achieved by changing the atom ratios of Cu/Pd.For the electrocatalytic reduction of CO2,Cu5Pd5 nanoalloys show the CO Faradaic efficiency(FE)of 88%at−0.87 V,and the corresponding mass activity reaches 56 A/g that is much higher than those of Cu8Pd2 nanoalloys,Cu3Pd7 nanoalloys and most of previously reported catalysts.Density functional theory uncovers that with the increase of Pd on the surface of the ultrafine CuPd nanoalloys,the adsorbed energy of both of intermediate COOH*and CO*to the Pd sites is strengthened.The Cu5Pd5 nanoalloys with the optimal surface composition better balance the adsorption of COOH*and desorption of CO*,achieving the highest selectivity and activity.The difficult liberation of absorbed CO*on the surface of Cu3Pd7 nanoalloys provides carbon source to favor the production of ethylene,endowing the Cu3Pd7 nanoalloys with the highest selectivity for ethylene among these ultrafine CuPd nanoalloys.
基金the National Natural Science Foundation of China(No.22006018)the General Project of Zhejiang Provincial Department of Education(No.Y202250180)+2 种基金the key Research and Development Project of Science and Technology Department of Zhejiang Province(No.2023C02019)the National Key Research and Development Program of China(No.2022YFE0127800)the Talent Startingup Project of Research Development Fund of Zhejiang A&F University(No.2034020103).
文摘Developing electrocatalysts that exhibit both high activity and ammonia selectivity for nitrate reduction is a significant and demanding challenge,primarily due to the complex nature of the multiple-electron reduction process involved.An encouraging approach involves coupling highly active precious metals with transition metals to enhance catalytic performance through synergy.Here,we report a ruthenium-nickel alloy catalyst with nanosheets(Ru-Ni NSs)structure that achieves a remarkable ammonia Faradaic efficiency of approximately 95.93%,alongside a yield rate of up to 6.11 g·h^(−1)·cm^(−2).Moreover,the prepared Ru-Ni NSs exhibit exceptional stability during continuous nitrate reduction in a flow reactor for 100 h,maintaining a Faradaic efficiency of approximately 90%and an ammonia yield of 37.4 mg·L^(−1)·h^(−1)using 0.05 M nitrate alkaline electrolyte.Mechanistic studies reveal that the catalytic process follows a two-step pathway,in which HONO serves as a migration intermediate.The presence of a partially oxidized Ru(002)surface enhances the adsorption of nitrate and facilitates the release of the migration intermediate by adjusting the strength of the electrostatic and covalent interactions between the adsorbate and the surface,respectively.On the other hand,the Ni(111)surface promotes the utilization of the migration intermediate and requires less energy for NH_(3)desorption.This tandem process contributes to a high catalytic activity of Ru-Ni NSs towards nitrate reduction.
基金financially supported by the National Natural Science Foundation of China (No.22272150)the Major Program of Zhejiang Provincial Natural Science Foundation of China(Nos.LD22B030002 and LZ23B030002)+1 种基金the Zhejiang Provincial Ten Thousand Talent Program (No.2021R51009)the Key Science and Technology Project of Jinhua City (No.2020-1-044)。
文摘Electrochemical nitrogen reduction reaction(ENRR) provides a promising strategy to achieve sustainable synthesis of ammonia. However, despite great efforts devoted to this research field, the problems such as low energy efficiency and weak selectivity still impede its practical implementation. Most of the research to date has been concentrated on creating sophisticated electrocatalysts, and adequate knowledge of electrolytes is still lacking. Herein, the recent progress in electrolytes for ENRR, including alkaline, neutral,acidic, water-in-salt, organic, ionic liquid, and mixed water-organic electrolytes, is thoroughly reviewed to obtain an in-depth understanding of their effects on electrocatalytic performance. Recently developed representative electrocatalysts in various types of electrolytes are also introduced, and future research priorities of different electrolytes are proposed to develop new and efficient ENRR systems.
基金financially supported by the Natural Scientific Foundation of China(no.21503116)the Open Funds of the State Key Laboratory of Organic-Inorganic Composites,Beijing University of Chemical Technology(oic-201601008)+2 种基金the Qingdao Basic&Applied Research Project(15-9-1-100-jch)Taishan Scholars Program of Shandong Province(no.tsqn20161004)the Youth 1000 Talent Program of China
文摘The recent development of Cu-based electrocatalysts for electrochemical reduction of carbon dioxide（CO） has attracted much attention due to their unique activity and selectivity compared to other metal catalysts. Particularly, Cu is the unique electrocatalyst for COelectrochemical reduction with high selectivity to generate a variety of hydrocarbons. In this review, we mainly summarize the recent advances on the rational design of Cu nanostructures, the composition regulation of Cu-based alloys, and the exploitation of advanced supports for improving the catalytic activity and selectivity toward electrochemical reduction of CO. The special focus is to demonstrate how to enhance the activity and selectivity of Cubased electrocatalyst for COreduction. The perspectives and challenges for the development of Cu-based electrocatalysts are also addressed. We hope this review can provide timely and valuable insights into the design of advanced electrocatalytic materials for COelectrochemical reduction.
基金The financial supports from the National 1000 Young Talents Program of Chinathe National Natural Science Foundation of China (Grant no. 21603078)
文摘Electrochemical reduction of CO2 to produce value-added feedstock chemicals using high-performance electrocatalysts is a promising protocol to address the excessive CO2 in the atmosphere and the energy crisis. However, the high overpotential, low current density, and poor product selectivity for CO2 electroreduction greatly impede their practical applications. In this work, we develop an efficient catalyst for CO2 reduction to CO consisting of well-dispersed ZrO2 nanoparticles tightly anchored on nitrogendoped carbon nanosheets(ZrO2/N-C) for the first time. Importantly, the ZrO2 nanoparticles possess oxygen vacancies and defects, which regulate the electronic structure of catalyst and thus greatly enhance the electrocatalytic activity. Specifically, ZrO2/N-C demonstrates a high CO Faradaic efficiency(FE) of 64% at-0.4 V vs. the reversible hydrogen electrode(RHE) and a respectable current density of ~2.6 m A cm-2 in CO2-saturated 0.5 M KHCO 3 solution. This work opens a new avenue for developing excellent catalysts for CO2 electroreduction with metal oxide/heteroatom-doped carbon composite structure.
基金supported by the Ministry of Science and Technology of China(Grant No:2012CB215500 and 2013CB933100)the National Natural Science Foundation of China(Grant No:21103178 and 21033009)
文摘Carbon dioxide transformation to fuels or chemicals provides an attractive approach for its utilization as feedstock and its emission reduction. Herein, we report a gas-phase electrocatalytic reduction of CO2 in an electrolytic cell, constructed using phosphoric acid-doped polybenz- imidazole （PBI） membrane, which allowed operation at 170 ℃ Pt/C and PtMo/C with variable ratio of Pt/Mo were studied as the cathode catalysts. The results showed that PtMo/C catalysts significantly enhanced CO formation and inhibited CH4 formation compared with Pt/C catalyst. Characterization by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy revealed that most Mo species existed as MoO3 in PtMo/C catalysts and the interaction between Pt and MoOx was likely responsible for the enhanced CO formation rate although these bicomponent catalysts in general had a larger particle size than Pt/C catalyst.
基金The present work was supported by JSPS KAKENHI(Grant number 18H05159)in Scientific Research on Innovative Areas“Innovations for Light Energy Conversion(I4 LEC)”from MEXT,Japan,and was also supported by the JST Strategic International Collaborative Research Program(SICORP),Japan(Grant number JPMJSC18H7)International Science and Technology Cooperation Program(Grant No.2017YFE0127800),China.
文摘Seeking and developing efficient CO_(2)reduction reaction(CO_(2)RR)electrocatalysts is a hot topic in this era of global warming.Among material candidates for sustainable and cost-effective applications,metal sulfides have attracted attention as promising nature-inspired materials due to multiple adsorption sites which are enhanced by the covalent character of sulfur.This article summarizes the current status regarding the utilization and development of metal sulfide materials as CO_(2)RR electrocatalysts.First,the research background and basic principles of electrochemical CO_(2)RR are introduced.Next,an overview of the main obstacles to developing efficient CO_(2)RR electrocatalysts is presented.The section is followed by a summary of the empirical evidence supporting the application of metal sulfides as CO_(2)RR electrocatalysts beside nature-inspired motivation.The summary of synthesis methods of various metal sulfides is also presented.Furthermore,the paper also highlights the recent works on metal sulfide as efficient CO_(2)RR including the undertaking strategy on the activity enhancement,and finally,discusses the challenges and prospect of metal sulfides-based CO_(2)RR electrocatalysts.Despite recent efforts,metal sulfides remain relatively unexplored as materials for CO_(2)RR electrocatalytic applications.Therefore,this review aims to stimulate novel ideas and research for improved catalyst designs and functionality.
基金Natural Sciences and Engineering Research Council of Canada(NSERC)Fonds de Recherche du Québec-Nature et Technologies(FRQNT)+4 种基金Centre Québécois sur les Materiaux Fonctionnels(CQMF)Institut National de la Recherche Scien-tifique(INRS)National Natural Science Foundation of China,Grant/Award Num-bers:21805064,51803042International Postdoctoral Exchange Fellowship Pro-gram by the Office of China Postdoctoral Council,Grant/Award Number:20180072FRQNT for the Postdoctoral scholarship,Grant/Award Number:274384。
文摘Ammonia is not only an important platform chemical for industrial and agri-cultural use but is also a novel energy-carrying molecule.The electrochemical reduction method for ambient ammonia synthesis is emerging as a promising strategy for the replacement of the current Haber–Bosch ammonia synthesis method,which consumes a large amount of energy and natural gas(hydrogen resource)while releasing substantial greenhouse gases(eg,carbon dioxide).The challenges in electrochemical ammonia synthesis,also known as nitrogen reduc-tion reaction,primarily include the cleavage of extremely stable N≡N bonds and the competitive hydrogen evolution reaction in routine aqueous media,which significantly leads to a low production rate and Faradaic efficiency.The ratio-nal design and engineering of the electrocatalyst/electrolyte interface are crucial to address these challenges.Herein,recent achievements for catalyst/electrolyte interface engineering are reviewed to provide insights into enhancing the pro-duction rate and Faradaic efficiency.Perspectives on future research and devel-opment of the electrochemical ammonia synthesis from theory to practice will be provided.
文摘The continued increase in population and the industrial revolution have led to an increase in atmospheric carbon dioxide(CO_(2)) concentration. Consequently, developing and implementing effective solutions to reduce CO_(2) emissions is a global priority. The electrochemical CO_(2) reduction reaction(CO_(2)RR) is strongly believed to be a promising alternative to fossil fuel-based technologies for the production of value-added chemicals. So far, the implementation of CO_(2)RR is hindered by associated electrochemical reactions, such as low selectivity, hydrogen evolution reaction(HER), and additional overpotential induced in some cases. As a result, it is necessary to conduct a timely evaluation of the state-of-the-art strategies in CO_(2)RR, with a focus on the engineering of the electrocatalytic systems. Catalyst morphology is one factor that plays a critical role in overcoming these drawbacks and significantly contributes to enhancing product selectivity and Faradaic efficiency(FE). This review article summarizes the recent advances in the rational design of electrocatalysts with various morphologies and the influence of these morphologies on CO_(2)RR. To compare literature findings in a meaningful way, the article focuses on results reported under a well-defined period and considers the first three rows of the d-block metal catalysts. The discussion typically covers the design of nanostructured catalysts and the molecular-level understanding of morphology-performance relationship in terms of activity, selectivity, and stability during CO_(2) electrolysis. Among others, it would be convenient to recommend a comprehensive discussion on the morphologies of single metals and heterostructures, with a detailed emphasis on their impact on CO_(2) conversion.
