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
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
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
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
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
The photocatalytic CO_(2)reduction reaction(CO_(2)RR)represents a promising solution to alleviate environmental and energy issues stemming from CO_(2)emissions while simultaneously enabling the production of high-valu...The photocatalytic CO_(2)reduction reaction(CO_(2)RR)represents a promising solution to alleviate environmental and energy issues stemming from CO_(2)emissions while simultaneously enabling the production of high-value multi-carbon fuels.However,the efficient generation of multi-carbon products remains challenging due to high kinetic barriers,sluggish C–C coupling processes,and intricate reaction pathways.This review provides a comprehensive overview of the latest advancements in synthesizing C_(2+)products through CO_(2)photoreduction,highlighting the crucial role of active site design and the C–C coupling mechanism.Specifically,we emphasize the correlation between the structure of active sites and the key intermediates of C–C coupling,which is fundamental for achieving deep photoconversion of CO_(2).Finally,we offer a glimpse into future challenges and prospects,outlining potential directions for the development of CO_(2)-to-multicarbon photoconversion,aiming to contribute novel insights to this exciting field.展开更多
柔性负荷参与新型电力系统的优化调度对于提高新能源的消纳能力具有显著作用,但目前柔性负荷潜力尚未充分挖掘。针对这一问题,提出一种基于源荷预测的日前-日内优化调度方法。首先,采用麻雀搜索算法优化卷积长短时记忆神经网络(sparrow ...柔性负荷参与新型电力系统的优化调度对于提高新能源的消纳能力具有显著作用,但目前柔性负荷潜力尚未充分挖掘。针对这一问题,提出一种基于源荷预测的日前-日内优化调度方法。首先,采用麻雀搜索算法优化卷积长短时记忆神经网络(sparrow search algorithm is used to optimize the convolutional long-term and short-term memory neural network,SSA-CNN-LSTM)对新能源和负荷进行日前和日内功率预测;其次,根据柔性负荷的特性和需求响应灵活性,将负荷分为可平移、可转移和可削减负荷等不同类型,以考虑阶梯式碳交易成本的系统运行成本和污染气体排放最优为目标构建源荷互动的日前-日内两阶段低碳环境经济调度模型;最后,利用改进多目标灰狼算法(multi-objective grey wolf algorithm,MOGWO)对模型进行求解。算例分析表明,通过对柔性负荷分类参与调度较传统方式总成本降低8.6%、污染物排放减少4.1%、新能源消纳能力提高4.2%,在多时间尺度内显著降低新能源和负荷响应的不确定性并提高新型电力系统的低碳环境经济综合效益。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.
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.
基金supported by the National Natural Science Foundation of China(22302002,22375006)the University Science Research Project of Anhui Province(2022AH050182,2022AH020020)。
文摘The photocatalytic CO_(2)reduction reaction(CO_(2)RR)represents a promising solution to alleviate environmental and energy issues stemming from CO_(2)emissions while simultaneously enabling the production of high-value multi-carbon fuels.However,the efficient generation of multi-carbon products remains challenging due to high kinetic barriers,sluggish C–C coupling processes,and intricate reaction pathways.This review provides a comprehensive overview of the latest advancements in synthesizing C_(2+)products through CO_(2)photoreduction,highlighting the crucial role of active site design and the C–C coupling mechanism.Specifically,we emphasize the correlation between the structure of active sites and the key intermediates of C–C coupling,which is fundamental for achieving deep photoconversion of CO_(2).Finally,we offer a glimpse into future challenges and prospects,outlining potential directions for the development of CO_(2)-to-multicarbon photoconversion,aiming to contribute novel insights to this exciting field.
文摘柔性负荷参与新型电力系统的优化调度对于提高新能源的消纳能力具有显著作用,但目前柔性负荷潜力尚未充分挖掘。针对这一问题,提出一种基于源荷预测的日前-日内优化调度方法。首先,采用麻雀搜索算法优化卷积长短时记忆神经网络(sparrow search algorithm is used to optimize the convolutional long-term and short-term memory neural network,SSA-CNN-LSTM)对新能源和负荷进行日前和日内功率预测;其次,根据柔性负荷的特性和需求响应灵活性,将负荷分为可平移、可转移和可削减负荷等不同类型,以考虑阶梯式碳交易成本的系统运行成本和污染气体排放最优为目标构建源荷互动的日前-日内两阶段低碳环境经济调度模型;最后,利用改进多目标灰狼算法(multi-objective grey wolf algorithm,MOGWO)对模型进行求解。算例分析表明,通过对柔性负荷分类参与调度较传统方式总成本降低8.6%、污染物排放减少4.1%、新能源消纳能力提高4.2%,在多时间尺度内显著降低新能源和负荷响应的不确定性并提高新型电力系统的低碳环境经济综合效益。
