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
为兼顾“双碳”目标与能源保供底线,提升能源系统源荷侧降碳能力,在有效挖掘系统降碳潜能的同时,缓解火电装机总量增长与风电消纳之间的矛盾,文章将绿氨生产、氨煤混燃以及多种灵活性资源结合构成绿氨耦合发电单元,同时考虑碳捕集等低...为兼顾“双碳”目标与能源保供底线,提升能源系统源荷侧降碳能力,在有效挖掘系统降碳潜能的同时,缓解火电装机总量增长与风电消纳之间的矛盾,文章将绿氨生产、氨煤混燃以及多种灵活性资源结合构成绿氨耦合发电单元,同时考虑碳捕集等低碳技术,并应用碳排放流理论,提出了考虑绿氨替代与多元阶梯碳势需求响应的综合能源虚拟电厂(integrated energy virtual power plant,IEVPP)低碳经济调度模型,以降低系统碳排放并提升系统经济性。首先,将绿氨替代作为解决风电供用能不匹配问题的手段,并将其与燃煤机组掺氨技术结合,分析其能量流动与低碳特性;其次,将电-碳-氢-氨多元耦合过程引入IEVPP,从而促进了风电消纳,提升了系统调节能力;最后,依托碳排放流理论,通过动态碳排放因子提出了多元阶梯碳势需求响应模型,从源荷两侧充分挖掘系统降碳潜能。算例仿真分析结果表明,所构建的考虑绿氨替代IEVPP联合多元阶梯碳势需求响应可有效降低系统碳排放量,提升系统经济性。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.
文摘为兼顾“双碳”目标与能源保供底线,提升能源系统源荷侧降碳能力,在有效挖掘系统降碳潜能的同时,缓解火电装机总量增长与风电消纳之间的矛盾,文章将绿氨生产、氨煤混燃以及多种灵活性资源结合构成绿氨耦合发电单元,同时考虑碳捕集等低碳技术,并应用碳排放流理论,提出了考虑绿氨替代与多元阶梯碳势需求响应的综合能源虚拟电厂(integrated energy virtual power plant,IEVPP)低碳经济调度模型,以降低系统碳排放并提升系统经济性。首先,将绿氨替代作为解决风电供用能不匹配问题的手段,并将其与燃煤机组掺氨技术结合,分析其能量流动与低碳特性;其次,将电-碳-氢-氨多元耦合过程引入IEVPP,从而促进了风电消纳,提升了系统调节能力;最后,依托碳排放流理论,通过动态碳排放因子提出了多元阶梯碳势需求响应模型,从源荷两侧充分挖掘系统降碳潜能。算例仿真分析结果表明,所构建的考虑绿氨替代IEVPP联合多元阶梯碳势需求响应可有效降低系统碳排放量,提升系统经济性。
