利用可再生的电能将CO_(2)还原为高附加值的化学品和燃料,对于缓解温室效应并实现碳中和具有重要的意义。开发了一种简单有效的方法制备非金属P元素掺杂的In_(2)O_(3)纳米颗粒,并将其用于电催化CO_(2)还原制甲酸盐。在H型电解池中,在-1....利用可再生的电能将CO_(2)还原为高附加值的化学品和燃料,对于缓解温室效应并实现碳中和具有重要的意义。开发了一种简单有效的方法制备非金属P元素掺杂的In_(2)O_(3)纳米颗粒,并将其用于电催化CO_(2)还原制甲酸盐。在H型电解池中,在-1.45 V vs.RHE电位下,P掺杂的In_(2)O_(3)纳米催化剂的产甲酸法拉第效率达到88.2%,同时具有优异的稳定性。进一步的实验分析和理论研究表明,掺杂在In_(2)O_(3)晶格中的P元素显著促进了CO_(2)分子的吸附和活化,降低了形成*HCOO中间体的吉布斯自由能,同时加强了对*HCOO的吸附作用,最终促进了甲酸盐的合成。阐明了非金属元素P掺杂对提升CO_(2)还原反应性能的分子机制,同时也为其他金属氧化物基的高性能电催化剂的设计提供了一种可行的策略。展开更多
Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is chall...Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction(HER).In this study,dendritic Cu/Cu_(2)O with abundant Cu^(0)/Cu^(+)interfaces and numerous dendritic curves was synthesized in a CO_(2)atmosphere,resulting in the high selectivity and current density of the C_(2)products.Dendritic Cu/Cu_(2)O achieved a C_(2)Faradaic efficiency of 69.8%and a C_(2)partial current density of 129.5 mA cm^(-2)in an H-cell.Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field,leading to a localized CO_(2)concentration.Additionally,DRT analysis showed that a dendritic struc-ture with a high curvature actively adsorbed the surrounding high concentration of CO_(2),enhancing the mass transfer rate and achieving a high current density.During the experiment,the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu^(0)/Cu^(+)on the catalyst surface,which resulted in improved ethylene selectivity.Under the optimal atomic ratio of Cu^(0)/Cu^(+),the charge transfer resistance was minimized,and the desorption rate of the intermediates was low,favoring C_(2)generation.Density functional theory calculations indicated that the Cu^(0)/Cu^(+)interfaces exhibited a lower Gibbs free energy for the rate-determining step,enhancing C_(2)H4 formation.The Cu/Cu_(2)O catalyst also exhibited a low Cu d-band center,which enhanced the adsorption stability of*CO on the surface and facilitated C_(2)formation.This observa-tion explained the higher yield of C_(2)products at the Cu^(0)/Cu^(+)interface than that of H_(2)under rapid mass transfer.The results of the net present value model showed that the H-cell holds promising industrial prospects,contingent upon i展开更多
Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activit...Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activity.However,the effect of the local coordination environment of Co sites on CO_(2) reduction reaction pathways is still unclear.In this study,we investigated the CO_(2) reduction reaction pathways on Co‐N_(4) sites supported on conjugated N_(4)‐macrocyclic ligands with 1,10‐phenanthroline subunits(Co‐N_(4)‐CPY)by density functional theory calculations.The local coordination environment of single‐atom Co sites with N substituted by O(Co‐N_(3)O‐CPY)and C(Co‐N_(3)C‐CPY)was studied for comparison.The calculation results revealed that both C and O coordination break the symmetry of the primary CoN_(4) ligand field and induce charge redistribution of the Co atom.For Co‐N_(4)‐CPY,CO was confirmed to be the main product of CO_(2)RR.HCOOH is the primary product of Co‐N_(3)O‐CPY because of the greatly increased energy barrier of CO_(2) to*COOH.Although the energy barrier of CO_(2) to*COOH is reduced on Co‐N_(3)C‐CPY,the desorption process of*CO becomes more difficult.CH3OH(or CH_(4))are obtained by further*CO hydrogenation reduction when using Co‐N_(3)C‐CPY.This work provides new insight into the effect of the local coordination environment of single‐atom sites on CO_(2) reduction reaction pathways.展开更多
Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental ...Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse fields.In order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate interactions.Subsequently,the nano‐catalyst design with precise manipulation at the atomic level can be attained.In this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and thermocatalysis.Finally,a brief conclusion and future research directions on nano‐catalysis have also been presented.展开更多
Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural phot...Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.展开更多
The electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)producing HCOOH and CO is one of the most promising approaches for storing renewable electricity as chemical energy in fuels.SnO_(2) is a good catalyst ...The electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)producing HCOOH and CO is one of the most promising approaches for storing renewable electricity as chemical energy in fuels.SnO_(2) is a good catalyst for CO_(2)-to-HCOOH or CO_(2)-to-CO conversion,with different crystal planes participating the catalytic process.Among them,(110)surface SnO_(2) is very stable and easy to synthesisze.By changing the ratio of Sn:O for SnO_(2)(110),we have two typical SnO_(2) thin films:fully oxidized(stoichiometric)and partially reduced.In this work,we are concerned with different metals(Fe,Co,Ni,Cu,Ru,Rh,Pd,Ag,Os,Ir,Pt,and Au)-doped SnO_(2)(110)with different activity and selectivity for CO_(2) RR.All these changes are manipulated by adjusting the ratio of Sn:O in(110)surface.The results show that stochiometric and reduced Cu/Ag doped SnO_(2)(110)have different selectivity for CO_(2) RR.More specifically,stochiometric Cu/Ag-doped SnO_(2)(110)tends to generate CO(g).Meanwhile,the reduced surface tends to generate HCOOH(g).Moreover,we also considered the competitive hydrogen evolution reaction(HER).The catalysts SnO_(2)(110)doped by Ru,Rh,Pd,Os,Ir,and Pt have high activity for HER,and others are good catalysts for CO_(2) RR.展开更多
Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selectiv...Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.展开更多
文摘利用可再生的电能将CO_(2)还原为高附加值的化学品和燃料,对于缓解温室效应并实现碳中和具有重要的意义。开发了一种简单有效的方法制备非金属P元素掺杂的In_(2)O_(3)纳米颗粒,并将其用于电催化CO_(2)还原制甲酸盐。在H型电解池中,在-1.45 V vs.RHE电位下,P掺杂的In_(2)O_(3)纳米催化剂的产甲酸法拉第效率达到88.2%,同时具有优异的稳定性。进一步的实验分析和理论研究表明,掺杂在In_(2)O_(3)晶格中的P元素显著促进了CO_(2)分子的吸附和活化,降低了形成*HCOO中间体的吉布斯自由能,同时加强了对*HCOO的吸附作用,最终促进了甲酸盐的合成。阐明了非金属元素P掺杂对提升CO_(2)还原反应性能的分子机制,同时也为其他金属氧化物基的高性能电催化剂的设计提供了一种可行的策略。
文摘Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multicarbon products is an efficient approach for ad-dressing the energy crisis and achieving carbon neutrality.In H-cells,achieving high-current C_(2)products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction(HER).In this study,dendritic Cu/Cu_(2)O with abundant Cu^(0)/Cu^(+)interfaces and numerous dendritic curves was synthesized in a CO_(2)atmosphere,resulting in the high selectivity and current density of the C_(2)products.Dendritic Cu/Cu_(2)O achieved a C_(2)Faradaic efficiency of 69.8%and a C_(2)partial current density of 129.5 mA cm^(-2)in an H-cell.Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field,leading to a localized CO_(2)concentration.Additionally,DRT analysis showed that a dendritic struc-ture with a high curvature actively adsorbed the surrounding high concentration of CO_(2),enhancing the mass transfer rate and achieving a high current density.During the experiment,the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu^(0)/Cu^(+)on the catalyst surface,which resulted in improved ethylene selectivity.Under the optimal atomic ratio of Cu^(0)/Cu^(+),the charge transfer resistance was minimized,and the desorption rate of the intermediates was low,favoring C_(2)generation.Density functional theory calculations indicated that the Cu^(0)/Cu^(+)interfaces exhibited a lower Gibbs free energy for the rate-determining step,enhancing C_(2)H4 formation.The Cu/Cu_(2)O catalyst also exhibited a low Cu d-band center,which enhanced the adsorption stability of*CO on the surface and facilitated C_(2)formation.This observa-tion explained the higher yield of C_(2)products at the Cu^(0)/Cu^(+)interface than that of H_(2)under rapid mass transfer.The results of the net present value model showed that the H-cell holds promising industrial prospects,contingent upon i
文摘Single‐atom catalysts have been proposed as promising electrocatalysts for CO_(2) reduction reactions(CO_(2)RR).Co‐N_(4) active sites have attracted wide attention owing to their excellent CO selectivity and activity.However,the effect of the local coordination environment of Co sites on CO_(2) reduction reaction pathways is still unclear.In this study,we investigated the CO_(2) reduction reaction pathways on Co‐N_(4) sites supported on conjugated N_(4)‐macrocyclic ligands with 1,10‐phenanthroline subunits(Co‐N_(4)‐CPY)by density functional theory calculations.The local coordination environment of single‐atom Co sites with N substituted by O(Co‐N_(3)O‐CPY)and C(Co‐N_(3)C‐CPY)was studied for comparison.The calculation results revealed that both C and O coordination break the symmetry of the primary CoN_(4) ligand field and induce charge redistribution of the Co atom.For Co‐N_(4)‐CPY,CO was confirmed to be the main product of CO_(2)RR.HCOOH is the primary product of Co‐N_(3)O‐CPY because of the greatly increased energy barrier of CO_(2) to*COOH.Although the energy barrier of CO_(2) to*COOH is reduced on Co‐N_(3)C‐CPY,the desorption process of*CO becomes more difficult.CH3OH(or CH_(4))are obtained by further*CO hydrogenation reduction when using Co‐N_(3)C‐CPY.This work provides new insight into the effect of the local coordination environment of single‐atom sites on CO_(2) reduction reaction pathways.
文摘Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse fields.In order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate interactions.Subsequently,the nano‐catalyst design with precise manipulation at the atomic level can be attained.In this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and thermocatalysis.Finally,a brief conclusion and future research directions on nano‐catalysis have also been presented.
文摘Photosynthesis in nature has been deemed as the most significant biochemical reaction,which maintains a relatively stable content of O_(2) and CO_(2) in the atmosphere.Herein,for a deeper comprehension of natural photosynthesis,an artificial photosynthesis model reaction of photochemical CO_(2) to CO conversion(CO_(2)+2 H^(+)+2e^(-)→CO+H_(2)O)catalyzed by a homogeneous hexanuclear ring cobalt complex{K_(2)[CoO_(3)PCH_(2)N(CH_(2)CO_(2))_(2)]}_(6)(Co6 complex)is developed.Using the[Ru(bpy)_(3)]^(2+)as a photosensitizer and TEOA as a sacrificial electron donor,an optimal turnover frequency of 503.3 h^(‒1) and an apparent quantum efficiency of 0.81%are obtained.The good photocatalytic CO_(2) reduction performance is attributed to the efficient electron transfer between Co6 complex and[Ru(bpy)_(3)]^(2+),which boosts the photogenerated carriers separation of the photosensitizer.It is confirmed by the j‐V curves,light‐assisted UV‐vis curves,steady‐state photoluminescence spectra and real‐time laser flash photolysis experiments.In addition,the proposed catalytic mechanism for CO_(2) reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment,Pourbaix diagram and density functional theory calculations.
基金supported by the Ministry of Science and Technology(No.2017YFA0204904,No.2016YFA0400900,and No.2016YFA0200600)the National Natural Science Foundation of China(No.21973086 and No.21633006)。
文摘The electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)producing HCOOH and CO is one of the most promising approaches for storing renewable electricity as chemical energy in fuels.SnO_(2) is a good catalyst for CO_(2)-to-HCOOH or CO_(2)-to-CO conversion,with different crystal planes participating the catalytic process.Among them,(110)surface SnO_(2) is very stable and easy to synthesisze.By changing the ratio of Sn:O for SnO_(2)(110),we have two typical SnO_(2) thin films:fully oxidized(stoichiometric)and partially reduced.In this work,we are concerned with different metals(Fe,Co,Ni,Cu,Ru,Rh,Pd,Ag,Os,Ir,Pt,and Au)-doped SnO_(2)(110)with different activity and selectivity for CO_(2) RR.All these changes are manipulated by adjusting the ratio of Sn:O in(110)surface.The results show that stochiometric and reduced Cu/Ag doped SnO_(2)(110)have different selectivity for CO_(2) RR.More specifically,stochiometric Cu/Ag-doped SnO_(2)(110)tends to generate CO(g).Meanwhile,the reduced surface tends to generate HCOOH(g).Moreover,we also considered the competitive hydrogen evolution reaction(HER).The catalysts SnO_(2)(110)doped by Ru,Rh,Pd,Os,Ir,and Pt have high activity for HER,and others are good catalysts for CO_(2) RR.
文摘Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.
