Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has been developed as a promising and attractive strategy to close the anthropogenic carbon cycle.Among various reduction products,multi-carbon(C_(2+))oxygenate and h...Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has been developed as a promising and attractive strategy to close the anthropogenic carbon cycle.Among various reduction products,multi-carbon(C_(2+))oxygenate and hydrocarbon compounds are desirable value-added fuels or chemicals.Extensive researches have revealed the crucial role of local CO_(2)and H_(2)O concentrations(or the adsorption of ^(*)CO and ^(*)H)close to the electrode/catalyst surface in manipulating multi-carbon generation pathways.In this mini reviews,we mainly summarized the recent progress of this field over the past five years.The modulating strategies for the hydrogen and carbon species ratio can be divided into three categories,i.e.,catalyst morphology,electrolyte composition and mass transfer.The effectiveness of the aforementioned strategies in promoting multi-carbon product selectivity was discussed in detail from the perspectives of tuning the local CO_(2)and H_(2)O concentrations and the subsequent thermodynamic-and kinetic-controlled ^(*)CO and ^(*)H ratios.Finally,the critical challenges remaining in balancing the ratio of CO_(2)and H_(2)O as well as potential upgrading directions for future research are addressed.展开更多
Compared to single-atom catalysts,supported metal clusters can exhibit enhanced activity and designated selectivity in heterogeneous catalysis due to their unique geometric and electronic features.Herein,by means of c...Compared to single-atom catalysts,supported metal clusters can exhibit enhanced activity and designated selectivity in heterogeneous catalysis due to their unique geometric and electronic features.Herein,by means of comprehensive density functional theory (DFT) computations,we systematically investigated the potential of several Ni clusters supported on graphdiyne (Ni_(x)/GDY,x=1–6) for CO_(2) reduction reaction (CO_(2)RR).Our results revealed that,due to the strong interaction between Ni atoms and sp-hybridized C atoms,these supported Ni clusters on GDY exhibit high stabilities and excellent electronic properties.In particular,according to the computed free energy profiles for CO_(2)RR on these Ni_(x)/GDY systems,the anchored Ni_(4) cluster was revealed to exhibit high CO_(2)RR catalytic activity with a small limiting potential and moderate kinetic barrier for C–C coupling,and CH_(4),C_(2)H_(5)OH,and C_(3)H_(7)OH were identified as the main products,which can be attributed to its strong capacity for CO_(2) activation due to its unique configuration and excellent electronic properties.Thus,by carefully controlling the precise numbers of atoms in sub-nano clusters,the spatially confined Ni clusters can perform as promising CO_(2)RR catalysts with high-efficiency and high-selectivity,which may provide a useful guidance to further develop novel and low-cost metal clusters-based catalysts for sustain CO_(2)conversion to valuable chemicals and fuels.展开更多
Strain engineering on metal-based catalysts has been utilized as an efficacious strategy to regulate the mechanism and pathways in various electrocatalytic reactions.However,controlling strain and establishing the str...Strain engineering on metal-based catalysts has been utilized as an efficacious strategy to regulate the mechanism and pathways in various electrocatalytic reactions.However,controlling strain and establishing the strain-activity relationship still remain significant challenges.Herein,three different and continuous tensile strains(CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%)are successfully induced by introducing heteroatoms with different atomic radius.The catalytic performances of CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%display a positive correlation against tensile strains in electrochemical CO_(2) reduction reaction(CO_(2)RR).Specifically,CuAg-4.33%exhibits superior catalytic performance with a 77.9%Faradaic efficiency of multi-carbon products at−300mA cm^(-2) current density,significantly higher than those of pristine Cu(Cu-0%).Theoretical calculations and in situ spectroscopies verify that tensile strain can affect the d-band center of Cu,thereby altering the binding energy of*CO intermediates and Gibbs free energies of the C-C coupling procedure.This work might highlight a new method for precisely regulating the lattice strain of metallic catalysts in different electrocatalytic reactions.展开更多
For CO_(2) electroreduction;efficient catalysts with superior selectivity toward multi-carbon(C_(2+))products(such as C_(2)H_(4);C_(2)H_(5)OH;etc.)are intensely desired.Amorphous Cu-based catalysts show appealing perf...For CO_(2) electroreduction;efficient catalysts with superior selectivity toward multi-carbon(C_(2+))products(such as C_(2)H_(4);C_(2)H_(5)OH;etc.)are intensely desired.Amorphous Cu-based catalysts show appealing performance on the crucial C–C coupling;but their synthesis procedures are complicated and their actual mechanisms are still unclear.In this work;surface amorphization has been implemented on Cu_(2)(OH)_(2)CO_(3) catalysts by a very simple microwave-induction method;improving the Faradaic efficiency for C_(2+)products(FE_(C_(2+)))up to 86%(increased by~26%than that on Cu_(2)(OH)_(2)CO_(3))at a partial current density of 258 mA cm^(-2);and a high FEC_(2+)of 75%at 500 m A cm^(-2)in a flow cell.Moreover;the catalyst exhibits good stability.In situ investigations disclose that the amorphous surface optimizes the adsorption state(binding mode and coverage)of key intermediate*CO and stabilizes Cu^(+)pieces;facilitating the dimerization of*CO into*OCCO and hydrogenation to*OC_(2)H_(5);ultimately achieving high yields of C_(2+)products.This work highlights a simple microwave approach for surface amorphization and the roles of amorphous features in CO_(2) reduction to C_(2+)products;which could be valuable references for designing highperformance catalysts for CO_(2) electroreduction.展开更多
Electrocatalytic CO_(2) reduction reaction(CRR)is considered as a sustainable approach to converting CO_(2) into high value-added chemicals,assisting the goal of carbon peaking and carbon neutrality.Electrochemical CR...Electrocatalytic CO_(2) reduction reaction(CRR)is considered as a sustainable approach to converting CO_(2) into high value-added chemicals,assisting the goal of carbon peaking and carbon neutrality.Electrochemical CRR can be easily regulated by controlling the electrocatalyst,electrolyte,and reactor to produce various chemicals.Among different products,multi-carbon(C_(2+))products draw widespread attention for their high energy density and value along with complex reaction mechanisms.It is well recognized that*CO intermediate plays vital role in forming C_(2+)products and Cu is the only metal catalyst which can efficiently electro-reduce CO_(2) to C_(2+)products.Therefore,researchers developed many strategies to increase the amount of*CO intermediate and further enhance the performance of C_(2+)products.Recently,designing tandem electrocatalysts consisted of Cu and the materials which can convert CO_(2) to*CO intermediate has become a hotspot and achieved great achievements.In this review,we will summary the recent progress in tandem electrocatalysts for CO_(2) reduction to prepare C_(2+)products,including the origin and fundamental mechanism of tandem electrocatalysis,the strategies of catalyst design,and regulation principles.In addition,some newest findings,like Cu tandem catalysts can achieve to produce C_(2+)products,are well introduced.Finally,the remaining challenges and prospects for future development are also proposed.展开更多
【目的】为保护并优化高度城镇化地区的碳汇空间,有必要系统研究其时空演变特征及规律。【方法】本研究聚焦苏南地区“城镇尺度”的碳汇空间,在研究其时空演变特征的基础上,结合斑块生成土地利用变化模拟(patch-generating land use sim...【目的】为保护并优化高度城镇化地区的碳汇空间,有必要系统研究其时空演变特征及规律。【方法】本研究聚焦苏南地区“城镇尺度”的碳汇空间,在研究其时空演变特征的基础上,结合斑块生成土地利用变化模拟(patch-generating land use simulation,PLUS)模型和聚类分析法研判不同城镇综合响应状态,并提出差异化的碳汇空间管控策略。【结果】1)2000—2020年苏南地区碳汇空间面积大幅减少,减少区域高度集中于高价值碳汇空间。碳汇空间格局在城镇尺度上未因城镇化而全面瓦解,表现出较强的稳定性。2)通过对自然增长情景、碳汇保护情景、碳汇强化情景3种情景的模拟,发现加大碳汇空间保护力度能够实现高质量碳汇空间扩张,但需要警惕生态功能单一化风险,避免盲目追求“高碳汇系数”。3)在3种模拟情景下,大部分城镇碳汇空间结构较稳定,建议通过存量挖潜与功能置换等方式优化碳汇空间;而部分敏感型城镇则呈现差异化演变路径,需根据其具体风险类型,实施更具针对性的管控策略。【结论】快速城镇化地区碳汇空间面积虽然呈现缩减趋势,但在城镇尺度表现出稳定性与敏感性共存的特征。这一特性可通过多情景模拟研判,从而为制定差异化的城镇碳汇空间管控策略提供科学依据。展开更多
Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing ...Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing products,including C1 products(carbon monoxide,formic acid,etc),C2 products(ethylene,ethanol,etc.)and multi-carbon products(e.g.,n-propanol),provides beneficial fuel and chemicals for industrial production.The complexity of the multi-proton transfer processes and difficulties of C-C coupling in electrochemical CO_(2) reduction toward multi-carbon(C2+)products have attracted increasing concerns on the design of catalysts in comparison with those of C1 products.In this paper,we review the main advances in the syntheses of multi-carbon products through electrocatalytic carbon dioxide reduction in recent years,introduce the basic principles of electrocatalytic CO_(2)RR,and detailly elucidate two widely accepted mechanisms of C-C coupling reactions.Among abundant nanomaterials,copper-based catalysts are outstanding catalysts for the preparation of multi-carbon chemicals in electrochemical CO_(2)RR attributing to effective C-C coupling reactions.Regarding the different selectivity of multi-carbon chemicals but extensively applied copper-based catalysts,we classify and summarize various Cu-based catalysts through separating diverse multi-carbon products,where the modification of spatial and electronic structures is beneficial to increase the coverage of CO or lower the activation energy barrier for forming C-C bond to form the key intermediates and increase the production of multi-carbon products.Challenges and prospects involving the fundamental and development of copper-based catalysts in electrochemical CO_(2) reduction reaction are also proposed.展开更多
基金supported by the National Natural Science Foundation of China(No.52309132)Shandong Provincial Natural Science Foundation(No.ZR2023ME014).
文摘Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)has been developed as a promising and attractive strategy to close the anthropogenic carbon cycle.Among various reduction products,multi-carbon(C_(2+))oxygenate and hydrocarbon compounds are desirable value-added fuels or chemicals.Extensive researches have revealed the crucial role of local CO_(2)and H_(2)O concentrations(or the adsorption of ^(*)CO and ^(*)H)close to the electrode/catalyst surface in manipulating multi-carbon generation pathways.In this mini reviews,we mainly summarized the recent progress of this field over the past five years.The modulating strategies for the hydrogen and carbon species ratio can be divided into three categories,i.e.,catalyst morphology,electrolyte composition and mass transfer.The effectiveness of the aforementioned strategies in promoting multi-carbon product selectivity was discussed in detail from the perspectives of tuning the local CO_(2)and H_(2)O concentrations and the subsequent thermodynamic-and kinetic-controlled ^(*)CO and ^(*)H ratios.Finally,the critical challenges remaining in balancing the ratio of CO_(2)and H_(2)O as well as potential upgrading directions for future research are addressed.
基金financially supported by the Natural Science Funds (NSF) for Distinguished Young Scholar of Heilongjiang Province (JC2018004)the Specialized Fund for the Doctoral Research of Jilin Engineering Normal University (BSKJ201916)。
文摘Compared to single-atom catalysts,supported metal clusters can exhibit enhanced activity and designated selectivity in heterogeneous catalysis due to their unique geometric and electronic features.Herein,by means of comprehensive density functional theory (DFT) computations,we systematically investigated the potential of several Ni clusters supported on graphdiyne (Ni_(x)/GDY,x=1–6) for CO_(2) reduction reaction (CO_(2)RR).Our results revealed that,due to the strong interaction between Ni atoms and sp-hybridized C atoms,these supported Ni clusters on GDY exhibit high stabilities and excellent electronic properties.In particular,according to the computed free energy profiles for CO_(2)RR on these Ni_(x)/GDY systems,the anchored Ni_(4) cluster was revealed to exhibit high CO_(2)RR catalytic activity with a small limiting potential and moderate kinetic barrier for C–C coupling,and CH_(4),C_(2)H_(5)OH,and C_(3)H_(7)OH were identified as the main products,which can be attributed to its strong capacity for CO_(2) activation due to its unique configuration and excellent electronic properties.Thus,by carefully controlling the precise numbers of atoms in sub-nano clusters,the spatially confined Ni clusters can perform as promising CO_(2)RR catalysts with high-efficiency and high-selectivity,which may provide a useful guidance to further develop novel and low-cost metal clusters-based catalysts for sustain CO_(2)conversion to valuable chemicals and fuels.
基金Basic and Applied Basic Research Foundation of Guangdong Province,Grant/Award Numbers:2022B1515120084,2023A1515012776National Natural Science Foundation of China,Grant/Award Numbers:22172099,U21A20312Shenzhen Science and Technology Program,Grant/Award Number:RCYX20200714114535052。
文摘Strain engineering on metal-based catalysts has been utilized as an efficacious strategy to regulate the mechanism and pathways in various electrocatalytic reactions.However,controlling strain and establishing the strain-activity relationship still remain significant challenges.Herein,three different and continuous tensile strains(CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%)are successfully induced by introducing heteroatoms with different atomic radius.The catalytic performances of CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%display a positive correlation against tensile strains in electrochemical CO_(2) reduction reaction(CO_(2)RR).Specifically,CuAg-4.33%exhibits superior catalytic performance with a 77.9%Faradaic efficiency of multi-carbon products at−300mA cm^(-2) current density,significantly higher than those of pristine Cu(Cu-0%).Theoretical calculations and in situ spectroscopies verify that tensile strain can affect the d-band center of Cu,thereby altering the binding energy of*CO intermediates and Gibbs free energies of the C-C coupling procedure.This work might highlight a new method for precisely regulating the lattice strain of metallic catalysts in different electrocatalytic reactions.
基金supported by the National Natural Science Foundation of China(22208363,52204323)the Science and Technology Commission of Shanghai(20520711900,21YF1416300).
文摘For CO_(2) electroreduction;efficient catalysts with superior selectivity toward multi-carbon(C_(2+))products(such as C_(2)H_(4);C_(2)H_(5)OH;etc.)are intensely desired.Amorphous Cu-based catalysts show appealing performance on the crucial C–C coupling;but their synthesis procedures are complicated and their actual mechanisms are still unclear.In this work;surface amorphization has been implemented on Cu_(2)(OH)_(2)CO_(3) catalysts by a very simple microwave-induction method;improving the Faradaic efficiency for C_(2+)products(FE_(C_(2+)))up to 86%(increased by~26%than that on Cu_(2)(OH)_(2)CO_(3))at a partial current density of 258 mA cm^(-2);and a high FEC_(2+)of 75%at 500 m A cm^(-2)in a flow cell.Moreover;the catalyst exhibits good stability.In situ investigations disclose that the amorphous surface optimizes the adsorption state(binding mode and coverage)of key intermediate*CO and stabilizes Cu^(+)pieces;facilitating the dimerization of*CO into*OCCO and hydrogenation to*OC_(2)H_(5);ultimately achieving high yields of C_(2+)products.This work highlights a simple microwave approach for surface amorphization and the roles of amorphous features in CO_(2) reduction to C_(2+)products;which could be valuable references for designing highperformance catalysts for CO_(2) electroreduction.
基金supported by National Natural Science Foundation of China(Nos.22202065 and 22409159)Natural Science Foundation of Hubei Province of China(No.2024AFB1004)+1 种基金Natural Science Basic Research Program of Shaanxi(Nos.2024JC-YBQN-0119 and 2023SYJ04)the financial support from CHN Energy Zhejiang Ninghai Power Generation CO.Ltd.(No.GJNY-23-122).
文摘Electrocatalytic CO_(2) reduction reaction(CRR)is considered as a sustainable approach to converting CO_(2) into high value-added chemicals,assisting the goal of carbon peaking and carbon neutrality.Electrochemical CRR can be easily regulated by controlling the electrocatalyst,electrolyte,and reactor to produce various chemicals.Among different products,multi-carbon(C_(2+))products draw widespread attention for their high energy density and value along with complex reaction mechanisms.It is well recognized that*CO intermediate plays vital role in forming C_(2+)products and Cu is the only metal catalyst which can efficiently electro-reduce CO_(2) to C_(2+)products.Therefore,researchers developed many strategies to increase the amount of*CO intermediate and further enhance the performance of C_(2+)products.Recently,designing tandem electrocatalysts consisted of Cu and the materials which can convert CO_(2) to*CO intermediate has become a hotspot and achieved great achievements.In this review,we will summary the recent progress in tandem electrocatalysts for CO_(2) reduction to prepare C_(2+)products,including the origin and fundamental mechanism of tandem electrocatalysis,the strategies of catalyst design,and regulation principles.In addition,some newest findings,like Cu tandem catalysts can achieve to produce C_(2+)products,are well introduced.Finally,the remaining challenges and prospects for future development are also proposed.
文摘【目的】为保护并优化高度城镇化地区的碳汇空间,有必要系统研究其时空演变特征及规律。【方法】本研究聚焦苏南地区“城镇尺度”的碳汇空间,在研究其时空演变特征的基础上,结合斑块生成土地利用变化模拟(patch-generating land use simulation,PLUS)模型和聚类分析法研判不同城镇综合响应状态,并提出差异化的碳汇空间管控策略。【结果】1)2000—2020年苏南地区碳汇空间面积大幅减少,减少区域高度集中于高价值碳汇空间。碳汇空间格局在城镇尺度上未因城镇化而全面瓦解,表现出较强的稳定性。2)通过对自然增长情景、碳汇保护情景、碳汇强化情景3种情景的模拟,发现加大碳汇空间保护力度能够实现高质量碳汇空间扩张,但需要警惕生态功能单一化风险,避免盲目追求“高碳汇系数”。3)在3种模拟情景下,大部分城镇碳汇空间结构较稳定,建议通过存量挖潜与功能置换等方式优化碳汇空间;而部分敏感型城镇则呈现差异化演变路径,需根据其具体风险类型,实施更具针对性的管控策略。【结论】快速城镇化地区碳汇空间面积虽然呈现缩减趋势,但在城镇尺度表现出稳定性与敏感性共存的特征。这一特性可通过多情景模拟研判,从而为制定差异化的城镇碳汇空间管控策略提供科学依据。
基金supported by the National Key R&D Program of China(2021YFA1500700)the National Nature Science Foundation of China(22102057)Shanghai Sailing Program(21YF1409400).
文摘Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing products,including C1 products(carbon monoxide,formic acid,etc),C2 products(ethylene,ethanol,etc.)and multi-carbon products(e.g.,n-propanol),provides beneficial fuel and chemicals for industrial production.The complexity of the multi-proton transfer processes and difficulties of C-C coupling in electrochemical CO_(2) reduction toward multi-carbon(C2+)products have attracted increasing concerns on the design of catalysts in comparison with those of C1 products.In this paper,we review the main advances in the syntheses of multi-carbon products through electrocatalytic carbon dioxide reduction in recent years,introduce the basic principles of electrocatalytic CO_(2)RR,and detailly elucidate two widely accepted mechanisms of C-C coupling reactions.Among abundant nanomaterials,copper-based catalysts are outstanding catalysts for the preparation of multi-carbon chemicals in electrochemical CO_(2)RR attributing to effective C-C coupling reactions.Regarding the different selectivity of multi-carbon chemicals but extensively applied copper-based catalysts,we classify and summarize various Cu-based catalysts through separating diverse multi-carbon products,where the modification of spatial and electronic structures is beneficial to increase the coverage of CO or lower the activation energy barrier for forming C-C bond to form the key intermediates and increase the production of multi-carbon products.Challenges and prospects involving the fundamental and development of copper-based catalysts in electrochemical CO_(2) reduction reaction are also proposed.
