Protonic solid oxide electrolysis cells(P-SOECs)are a promising technology for water electrolysis to produce green hydrogen.However,there are still challenges related key materials and anode/electrolyte interface.P-SO...Protonic solid oxide electrolysis cells(P-SOECs)are a promising technology for water electrolysis to produce green hydrogen.However,there are still challenges related key materials and anode/electrolyte interface.P-SOECs with Zr-rich electrolyte,called Zr-rich side P-SOECs,possess high thermodynamically stability under high steam concentrations but the large reaction resistances and the current leakage,thus the inferior performances.In this study,an efficient functional interlayer Ba_(0.95)La_(0.05)Fe_(0.8)Zn_(0.2)O_(3-δ)(BLFZ)in-between the anode and the electrolyte is developed.The electrochemical performances of P-SOECs are greatly enhanced because the BLFZ can greatly increase the interface contact,boost anode reaction kinetics,and increase proton injection into electrolyte.As a result,the P-SOEC yields high current density of 0.83 A cm^(-2) at 600℃ in 1.3 Vamong all the reported Zr-rich side cells.This work not only offers an efficient functional interlayer for P-SOECs but also holds the potential to achieve P-SOECs with high performances and long-term stability.展开更多
The electrochemical reduction of carbon dioxide(CO_(2))into value-added chemicals and fuels has been extensively studied as a promising strategy for mitigating environmental issues and achieving sustainable energy con...The electrochemical reduction of carbon dioxide(CO_(2))into value-added chemicals and fuels has been extensively studied as a promising strategy for mitigating environmental issues and achieving sustainable energy conversion.Substantial efforts have been made to improve the understanding of CO_(2)reduction reaction(CO_(2)RR)mechanisms by computational and spectroscopic studies.An in-depth understanding of CO_(2)RR mechanism can provide the guidance and criteria for designing high-efficiency catalysts,and hence,steering CO_(2)RR to desired products.This review systematically discusses the formation mechanisms and reaction pathways of various CO_(2)RR products,including C_(1)products(CO,HCOOH,and CH_(4)),C_(2)products(C_(2)H_(4),C_(2)H_(5)OH,and CH_(3)COOH),and C_(3+)products(C_(3)H_(6),C_(3)H_(7)OH,and others).The reaction pathways are elucidated by analyzing the adsorption behavior,energy barriers,and intermediate coupling steps involved in the generation of each product.Particular emphasis is placed on the key intermediates,such as^(*)OCHO,^(*)COOH,^(*)CO,^(*)OCCOH,and^(*)CCO,which play crucial roles in determining the product selectivity.The effects of catalyst composition,morphology,and electronic structure on the adsorption and activation of these intermediates are also discussed.Moreover,advanced characterization techniques,including in-situ spectroscopy and isotopic labeling experiments,are highlighted for their contributions to unraveling the reaction mechanisms.The review aims to provide critical insights to reveal the activity-determining para meters and underlying CO_(2)RR mechanisms,which will guide the rational design of next-generation electrocatalysts for selective CO^(2)RR towards high-value products.展开更多
CO_(2)-to-CO electrolyzer technology converts carbon dioxide into carbon monoxide using electrochemical methods,offering significant environmental and energy benefits by aiding in greenhouse gas mitigation and promoti...CO_(2)-to-CO electrolyzer technology converts carbon dioxide into carbon monoxide using electrochemical methods,offering significant environmental and energy benefits by aiding in greenhouse gas mitigation and promoting a carbon circular economy.Recent study by Strasser et al.in Nature Chemical Engineering presents a high-performance CO_(2)-to-CO electrolyzer utilizing a NiNC catalyst with nearly 100%faradaic efficiency,employing innovative diagnostic tools like the carbon crossover coefficient(CCC)to address transport-related failures and optimize overall efficiency.Strasser’s research demonstrates the potential of NiNC catalysts,particularly NiNC-IMI,for efficient CO production in CO_(2)-to-CO electrolyzers,highlighting their high selectivity and performance.However,challenges such as localized CO_(2)depletion and mass transport limitations underscore the need for further optimization and development of diagnostic tools like CCC.Strategies for optimizing catalyst structure and operational parameters offer avenues for enhancing the performance and reliability of electrochemical CO_(2)reduction catalysts.展开更多
Molecular catalysts can effectively steer the electrocatalytic acetylene semihydrogenation into ethylene,but realizing high Faradaic efficiency(FE)at industrial current densities remains a challenge.Herein,we report a...Molecular catalysts can effectively steer the electrocatalytic acetylene semihydrogenation into ethylene,but realizing high Faradaic efficiency(FE)at industrial current densities remains a challenge.Herein,we report a ligand engineering strategy that utilizes polymeric N–heterocyclic carbene(NHC)as a hydrophobic ligand to modulate the microenvironment of Cu sites.This polymeric NHC imparts appropriate hydrophobic properties for the chelated Cu sites,thereby moderating the H_(2)O transport and enabling easy access of acetylene.Consequently,the polymeric NHC chelated Cu exhibits an FE_(ethylene)of~97%at a current density of 500 m A/cm^(2)in a flow cell.Particularly in a zero-gap reactor,the FE_(ethylene)consistently exceeds 86%across current densities from 100 m A/cm^(2)to 400 m A/cm^(2),reaching an optimal FEethyleneof 98%at 200 m A/cm^(2)and achieving durable operation for 155 h at 100 m A/cm^(2).This work provides a promising paradigm to regulate the microenvironment of molecular catalysts for improving electrocatalytic performances under industrial current densities.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
To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange me...To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange membrane system for reducing CO_(2) to formic acid with a Pb±Pb SO_(4) composite catalyst derived from waste lead-acid batteries based on the lattice carbon activation mechanism.Up to 93%Faradaic efficiency was realized when formic acid was produced by this technology.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
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
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
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
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
Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic perf...Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic performance and electrochemical behavior of complex metal oxides,especially perovskite oxides,is rarely reported.Here,the inorganic perovskite oxide Ag-doped(La_(0.8)Sr_(0.2))_(0.95)Ag_(0.05)MnO_(3-δ)(LSA0.05M)is reported as an efficient electrocatalyst for ECR to CO for the first time,which exhibits a Faradaic efficiency(FE)of 84.3%,a remarkable mass activity of 75Ag^(-1)(normalized to the mass of Ag),and stability of 130 h at a moderate overpotential of 0.79 V.The LSA0.05M catalyst experiences structure reconstruction during ECR,creating the in operando-formed interface between the perovskite and the evolved Ag phase.The evolved Ag is uniformly distributed with a small particle size on the perovskite surface.Theoretical calculations indicate the reconstruction of LSA0.05M during ECR and reveal that the perovskite-Ag interface provides adsorption sites for CO_(2) and accelerates the desorption of the*CO intermediate to enhance ECR.This study presents a novel high-performance perovskite catalyst for ECR andmay inspire the future design of electrocatalysts via the in operando formation of metal-metal oxide interfaces.展开更多
Ionomers play a vital role in the preparation of electrodes for CO_(2) electroreduction,and controlling the ionomer configuration on the catalyst surface offers an effective strategy for adjusting the surface microenv...Ionomers play a vital role in the preparation of electrodes for CO_(2) electroreduction,and controlling the ionomer configuration on the catalyst surface offers an effective strategy for adjusting the surface microenvironment of the electrode,thereby influencing the distribution of CO_(2) electroreduction products.In this study,we demonstrate that Nafion,a commonly used ionomer,exhibits distinct aggregation behaviors in solvents with different dielectric constant(ε)values.These differences in aggregation result in varied Nafion arrangements on the catalyst surface,which in turn affect the binding of*CO and*H intermediates,enabling control over product distribution.For example,over a Cu nanosheet catalyst at 800 mA cm2,the Faradaic efficiency for multicarbon products increases from 67.5%to 90.5%simply by changing the dispersion solvent from low-εdimethyl sulfoxide to moderate-εisopropanol.This work introduces a novel approach for finetuning CO_(2) electroreduction product distribution through manipulation of the dispersion solvent without requiring modifications to the catalyst or ionomer.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
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
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
基金financial support from the JSPS KAKENHI Grant-in-Aid for Scientific Research(B),No.21H02035KAKENHI Grant-in-Aid for Challenging Research(Exploratory),No.21K19017+2 种基金KAKENHI Grant-in-Aid for Transformative Research Areas(B),No.21H05100National Natural Science Foundation of China,No.22409033 and No.22409035Basic and Applied Basic Research Foundation of Guangdong Province,No.2022A1515110470.
文摘Protonic solid oxide electrolysis cells(P-SOECs)are a promising technology for water electrolysis to produce green hydrogen.However,there are still challenges related key materials and anode/electrolyte interface.P-SOECs with Zr-rich electrolyte,called Zr-rich side P-SOECs,possess high thermodynamically stability under high steam concentrations but the large reaction resistances and the current leakage,thus the inferior performances.In this study,an efficient functional interlayer Ba_(0.95)La_(0.05)Fe_(0.8)Zn_(0.2)O_(3-δ)(BLFZ)in-between the anode and the electrolyte is developed.The electrochemical performances of P-SOECs are greatly enhanced because the BLFZ can greatly increase the interface contact,boost anode reaction kinetics,and increase proton injection into electrolyte.As a result,the P-SOEC yields high current density of 0.83 A cm^(-2) at 600℃ in 1.3 Vamong all the reported Zr-rich side cells.This work not only offers an efficient functional interlayer for P-SOECs but also holds the potential to achieve P-SOECs with high performances and long-term stability.
基金financially supported by the National Natural Science Foundation of China(Grants 22225901,21975237 and 51702312)the Fundamental Research Funds for the Central Universities(Grant WK2340000101)+5 种基金the USTC Research Funds of the Double First-Class Initiative(Grant YD2340002007 and YD9990002017)the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(Grant RERU2022007)the China Postdoctoral Science Foundation(Grants 2023M733371,2024M750006 and 2023T160617)Postdoctoral Fellowship Program(Grade C)of China Postdoctoral Science Foundation(GZC20230008)the Natural Science Foundation Youth Project of Anhui Province(2408085QB065)the Postdoctoral Research Funding Project of Anhui Province(2023B727)。
文摘The electrochemical reduction of carbon dioxide(CO_(2))into value-added chemicals and fuels has been extensively studied as a promising strategy for mitigating environmental issues and achieving sustainable energy conversion.Substantial efforts have been made to improve the understanding of CO_(2)reduction reaction(CO_(2)RR)mechanisms by computational and spectroscopic studies.An in-depth understanding of CO_(2)RR mechanism can provide the guidance and criteria for designing high-efficiency catalysts,and hence,steering CO_(2)RR to desired products.This review systematically discusses the formation mechanisms and reaction pathways of various CO_(2)RR products,including C_(1)products(CO,HCOOH,and CH_(4)),C_(2)products(C_(2)H_(4),C_(2)H_(5)OH,and CH_(3)COOH),and C_(3+)products(C_(3)H_(6),C_(3)H_(7)OH,and others).The reaction pathways are elucidated by analyzing the adsorption behavior,energy barriers,and intermediate coupling steps involved in the generation of each product.Particular emphasis is placed on the key intermediates,such as^(*)OCHO,^(*)COOH,^(*)CO,^(*)OCCOH,and^(*)CCO,which play crucial roles in determining the product selectivity.The effects of catalyst composition,morphology,and electronic structure on the adsorption and activation of these intermediates are also discussed.Moreover,advanced characterization techniques,including in-situ spectroscopy and isotopic labeling experiments,are highlighted for their contributions to unraveling the reaction mechanisms.The review aims to provide critical insights to reveal the activity-determining para meters and underlying CO_(2)RR mechanisms,which will guide the rational design of next-generation electrocatalysts for selective CO^(2)RR towards high-value products.
基金the University of Oxford for the Mathematical, Physical and Life Sciences Division (MPLS) Enterprise and Innovation Fellowshipthe support of Massachusetts Institute of Technology+1 种基金the support of the National Key R&D Program of China (2021YFB3801600)the National Natural Science Foundation of China (22325204)。
文摘CO_(2)-to-CO electrolyzer technology converts carbon dioxide into carbon monoxide using electrochemical methods,offering significant environmental and energy benefits by aiding in greenhouse gas mitigation and promoting a carbon circular economy.Recent study by Strasser et al.in Nature Chemical Engineering presents a high-performance CO_(2)-to-CO electrolyzer utilizing a NiNC catalyst with nearly 100%faradaic efficiency,employing innovative diagnostic tools like the carbon crossover coefficient(CCC)to address transport-related failures and optimize overall efficiency.Strasser’s research demonstrates the potential of NiNC catalysts,particularly NiNC-IMI,for efficient CO production in CO_(2)-to-CO electrolyzers,highlighting their high selectivity and performance.However,challenges such as localized CO_(2)depletion and mass transport limitations underscore the need for further optimization and development of diagnostic tools like CCC.Strategies for optimizing catalyst structure and operational parameters offer avenues for enhancing the performance and reliability of electrochemical CO_(2)reduction catalysts.
基金supported by the National Natural Science Foundation of China(Nos.22475170,52101271,22375166)the Guangdong Basic and Applied Basic Research Foundation(Nos.2020A1515111017,2024A1515011977)the Key Research and Development Program of Shaanxi Province(No.2024GX-YBXM379)。
文摘Molecular catalysts can effectively steer the electrocatalytic acetylene semihydrogenation into ethylene,but realizing high Faradaic efficiency(FE)at industrial current densities remains a challenge.Herein,we report a ligand engineering strategy that utilizes polymeric N–heterocyclic carbene(NHC)as a hydrophobic ligand to modulate the microenvironment of Cu sites.This polymeric NHC imparts appropriate hydrophobic properties for the chelated Cu sites,thereby moderating the H_(2)O transport and enabling easy access of acetylene.Consequently,the polymeric NHC chelated Cu exhibits an FE_(ethylene)of~97%at a current density of 500 m A/cm^(2)in a flow cell.Particularly in a zero-gap reactor,the FE_(ethylene)consistently exceeds 86%across current densities from 100 m A/cm^(2)to 400 m A/cm^(2),reaching an optimal FEethyleneof 98%at 200 m A/cm^(2)and achieving durable operation for 155 h at 100 m A/cm^(2).This work provides a promising paradigm to regulate the microenvironment of molecular catalysts for improving electrocatalytic performances under industrial current densities.
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supported by the Natural Science Foundation of China (No. 22268003)。
文摘To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange membrane system for reducing CO_(2) to formic acid with a Pb±Pb SO_(4) composite catalyst derived from waste lead-acid batteries based on the lattice carbon activation mechanism.Up to 93%Faradaic efficiency was realized when formic acid was produced by this technology.
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 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.
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.
基金Australian Centre for Neutron ScatteringAustralian Nuclear Science and Technology Organisation,Grant/Award Number:MI8046+1 种基金Max Planck-POSTECH-Hsinchu Center for Complex Phase MaterialsHigh-Performance Computing Center of Nanjing Tech University。
文摘Electrochemical carbon dioxide(CO_(2))reduction(ECR)is a promising technology to produce valuable fuels and feedstocks from CO_(2).Despite large efforts to develop ECR catalysts,the investigation of the catalytic performance and electrochemical behavior of complex metal oxides,especially perovskite oxides,is rarely reported.Here,the inorganic perovskite oxide Ag-doped(La_(0.8)Sr_(0.2))_(0.95)Ag_(0.05)MnO_(3-δ)(LSA0.05M)is reported as an efficient electrocatalyst for ECR to CO for the first time,which exhibits a Faradaic efficiency(FE)of 84.3%,a remarkable mass activity of 75Ag^(-1)(normalized to the mass of Ag),and stability of 130 h at a moderate overpotential of 0.79 V.The LSA0.05M catalyst experiences structure reconstruction during ECR,creating the in operando-formed interface between the perovskite and the evolved Ag phase.The evolved Ag is uniformly distributed with a small particle size on the perovskite surface.Theoretical calculations indicate the reconstruction of LSA0.05M during ECR and reveal that the perovskite-Ag interface provides adsorption sites for CO_(2) and accelerates the desorption of the*CO intermediate to enhance ECR.This study presents a novel high-performance perovskite catalyst for ECR andmay inspire the future design of electrocatalysts via the in operando formation of metal-metal oxide interfaces.
基金supported by the National Natural Science Foundation of China(22273108,22293015,and 22121002)the Beijing Natural Science Foundation(2222043)+2 种基金the CAS Project for Young Scientists in Basic Research(YSBR-050)the ICCAS Carbon Neutral Chemistry program(CCNC-202403)National Key Research and Development Program of China(2023YFA1507400)。
文摘Ionomers play a vital role in the preparation of electrodes for CO_(2) electroreduction,and controlling the ionomer configuration on the catalyst surface offers an effective strategy for adjusting the surface microenvironment of the electrode,thereby influencing the distribution of CO_(2) electroreduction products.In this study,we demonstrate that Nafion,a commonly used ionomer,exhibits distinct aggregation behaviors in solvents with different dielectric constant(ε)values.These differences in aggregation result in varied Nafion arrangements on the catalyst surface,which in turn affect the binding of*CO and*H intermediates,enabling control over product distribution.For example,over a Cu nanosheet catalyst at 800 mA cm2,the Faradaic efficiency for multicarbon products increases from 67.5%to 90.5%simply by changing the dispersion solvent from low-εdimethyl sulfoxide to moderate-εisopropanol.This work introduces a novel approach for finetuning CO_(2) electroreduction product distribution through manipulation of the dispersion solvent without requiring modifications to the catalyst or ionomer.
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.
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.
