The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for t...The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for this reaction,they typically suffer from disadvantages such as the need for severe reaction conditions,catalyst loss,and large amounts of soluble co-catalysts.On the other hand,the development of heterogeneous catalysts featuring multiple and cooperative active sites,remains challenging and desirable.In this study,we prepared a series of porous organic catalysts(POP-PBnCl-TPPMg-x)via the copolymerization metal-porphyrin compounds and phosphonium salt monomers in various ratios.The resulting materials contain both Lewis-acidic and Lewis-basic active sites.The molecular-level combination of these sites in the same polymer allows these active sites to work synergistically,giving rise to excellent performance in the cycloaddition reaction of CO_(2)with epoxides,under mild conditions(40℃ and 1 atm CO_(2))in the absence of soluble co-catalysts.POP-PBnCl-TPPMg-12 can also efficiently fixate CO_(2)under low-CO_(2)-concentration(15%v/v N2)conditions representative of typical CO_(2)compositions in industrial exhaust gases.More importantly,this catalyst shows excellent recyclability and can easily be separated and reused at least five times while maintaining its activity.In view of their heterogeneous nature and excellent catalytic performance,the obtained catalysts are promising candidates for the transformation of industrially generated CO_(2)into high value-added chemicals.展开更多
Feasible construction of cathode materials with highly dispersed active sites can extend the tri‐ple‐phase boundaries,and therefore leading to enhanced electrode kinetics for CO_(2) electrolysis in solid oxide elect...Feasible construction of cathode materials with highly dispersed active sites can extend the tri‐ple‐phase boundaries,and therefore leading to enhanced electrode kinetics for CO_(2) electrolysis in solid oxide electrolysis cell(SOEC).Herein,highly dispersed nickel species with low loading(1.0 wt%)were trapped within the La_(0.8)Sr_(0.2)FeO_(3)–δ‐Ce_(0.8)Sm_(0.2)O_(2)–δvia a facial mechanical milling ap‐proach,which demonstrated excellent CO_(2) electrolysis performance.The highly dispersed nickel species can significantly alter the electronic structures of the LSF‐SDC without affecting its porous network and facilitate oxygen vacancy formation,thus greatly promote the CO_(2) electrolysis perfor‐mance.The highest current density of 1.53 A·cm^(-2) could be achieved when operated under 800℃ at 1.6 V,which is about 91%higher than the LSF‐SDC counterpart.展开更多
High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,...High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,a widely-utilized“building block”in today’s chemical industry.Thus,it offers an intriguing and promising means to radically change the way of chemical manufacturing and achieve carbon neutrality using renewable energy sources,CO_(2),and water.Albeit with the great potential of HT-CO_(2)RR,this carbon utilization approach,unfortunately,has been suffering coke formation that is seriously detrimental to its energy efficiency and operating lifetime.In recent years,much effort has been added to understanding the mechanism of coke formation,managing reaction conditions to mitigate coke formation,and devising coke-formation-free electrode materials.These investigations have substantially advanced the HT-CO_(2)RR toward a practical industrial technology,but the resulting coke formation prevention strategies compromise activity and energy efficiency.Future research may target exploiting the control over both catalyst design and system design to gain selectivity,energy efficiency,and stability synchronously.Therefore,this perspective overviews the progress of research on coke formation in HT-CO_(2)RR,and elaborates on possible future directions that may accelerate its practical implementation at a large scale.展开更多
Over the past three decades,the drawdown of atmospheric CO_(2) in vegetation and soil has fueled net ecosystem production(NEP).Here,a global land-surface model(CABLE)is used to estimate the trend in NEP and its respon...Over the past three decades,the drawdown of atmospheric CO_(2) in vegetation and soil has fueled net ecosystem production(NEP).Here,a global land-surface model(CABLE)is used to estimate the trend in NEP and its response to atmospheric CO_(2),climate change,biological nitrogen(N)fixation,and N deposition under future conditions from 2031 to 2100 in the Belt and Road region.The trend of NEP simulated by CABLE decreases from 0.015 Pg carbon(C)yr^(-2) under present conditions(1936–2005)to−0.023 Pg C yr^(-2) under future conditions.In contrast,the trend in NEP of the CMIP6 ensemble changes from 0.014 Pg C yr^(-2) under present conditions to−0.009 Pg C yr^(-2) under future conditions.This suggests that the trend in the C sink for the Belt and Road region will likely decline in the future.The significant difference in the NEP trend between present and future conditions is mainly caused by the difference in the impact of climate change on NEP.Considering the responses of soil respiration(RH)or net primary production(NPP)to surface air temperature,the trend in surface air temperature changes from 0.01℃ yr^(-1) under present conditions to 0.05℃ yr^(-1) under future conditions.CABLE simulates a greater response of RH to surface temperature than that of NPP under future conditions,which causes a decreasing trend in NEP.In addition,the greater decreasing trend in NEP under future conditions indicates that the C-climate-N interaction at the regional scale should be considered.It is important to estimate the direction and magnitude of C sinks under the C neutrality target.展开更多
文摘The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for this reaction,they typically suffer from disadvantages such as the need for severe reaction conditions,catalyst loss,and large amounts of soluble co-catalysts.On the other hand,the development of heterogeneous catalysts featuring multiple and cooperative active sites,remains challenging and desirable.In this study,we prepared a series of porous organic catalysts(POP-PBnCl-TPPMg-x)via the copolymerization metal-porphyrin compounds and phosphonium salt monomers in various ratios.The resulting materials contain both Lewis-acidic and Lewis-basic active sites.The molecular-level combination of these sites in the same polymer allows these active sites to work synergistically,giving rise to excellent performance in the cycloaddition reaction of CO_(2)with epoxides,under mild conditions(40℃ and 1 atm CO_(2))in the absence of soluble co-catalysts.POP-PBnCl-TPPMg-12 can also efficiently fixate CO_(2)under low-CO_(2)-concentration(15%v/v N2)conditions representative of typical CO_(2)compositions in industrial exhaust gases.More importantly,this catalyst shows excellent recyclability and can easily be separated and reused at least five times while maintaining its activity.In view of their heterogeneous nature and excellent catalytic performance,the obtained catalysts are promising candidates for the transformation of industrially generated CO_(2)into high value-added chemicals.
文摘Feasible construction of cathode materials with highly dispersed active sites can extend the tri‐ple‐phase boundaries,and therefore leading to enhanced electrode kinetics for CO_(2) electrolysis in solid oxide electrolysis cell(SOEC).Herein,highly dispersed nickel species with low loading(1.0 wt%)were trapped within the La_(0.8)Sr_(0.2)FeO_(3)–δ‐Ce_(0.8)Sm_(0.2)O_(2)–δvia a facial mechanical milling ap‐proach,which demonstrated excellent CO_(2) electrolysis performance.The highly dispersed nickel species can significantly alter the electronic structures of the LSF‐SDC without affecting its porous network and facilitate oxygen vacancy formation,thus greatly promote the CO_(2) electrolysis perfor‐mance.The highest current density of 1.53 A·cm^(-2) could be achieved when operated under 800℃ at 1.6 V,which is about 91%higher than the LSF‐SDC counterpart.
文摘High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,a widely-utilized“building block”in today’s chemical industry.Thus,it offers an intriguing and promising means to radically change the way of chemical manufacturing and achieve carbon neutrality using renewable energy sources,CO_(2),and water.Albeit with the great potential of HT-CO_(2)RR,this carbon utilization approach,unfortunately,has been suffering coke formation that is seriously detrimental to its energy efficiency and operating lifetime.In recent years,much effort has been added to understanding the mechanism of coke formation,managing reaction conditions to mitigate coke formation,and devising coke-formation-free electrode materials.These investigations have substantially advanced the HT-CO_(2)RR toward a practical industrial technology,but the resulting coke formation prevention strategies compromise activity and energy efficiency.Future research may target exploiting the control over both catalyst design and system design to gain selectivity,energy efficiency,and stability synchronously.Therefore,this perspective overviews the progress of research on coke formation in HT-CO_(2)RR,and elaborates on possible future directions that may accelerate its practical implementation at a large scale.
基金funded by the National Natural Science Foundation of China[grant numbers 41630532,41975112,42175142,and 42175013].
文摘Over the past three decades,the drawdown of atmospheric CO_(2) in vegetation and soil has fueled net ecosystem production(NEP).Here,a global land-surface model(CABLE)is used to estimate the trend in NEP and its response to atmospheric CO_(2),climate change,biological nitrogen(N)fixation,and N deposition under future conditions from 2031 to 2100 in the Belt and Road region.The trend of NEP simulated by CABLE decreases from 0.015 Pg carbon(C)yr^(-2) under present conditions(1936–2005)to−0.023 Pg C yr^(-2) under future conditions.In contrast,the trend in NEP of the CMIP6 ensemble changes from 0.014 Pg C yr^(-2) under present conditions to−0.009 Pg C yr^(-2) under future conditions.This suggests that the trend in the C sink for the Belt and Road region will likely decline in the future.The significant difference in the NEP trend between present and future conditions is mainly caused by the difference in the impact of climate change on NEP.Considering the responses of soil respiration(RH)or net primary production(NPP)to surface air temperature,the trend in surface air temperature changes from 0.01℃ yr^(-1) under present conditions to 0.05℃ yr^(-1) under future conditions.CABLE simulates a greater response of RH to surface temperature than that of NPP under future conditions,which causes a decreasing trend in NEP.In addition,the greater decreasing trend in NEP under future conditions indicates that the C-climate-N interaction at the regional scale should be considered.It is important to estimate the direction and magnitude of C sinks under the C neutrality target.
