Lewis acid(LA)and Lewis base(LB)sites on catalyst surfaces play a pivotal role in catalytic reactions.By precisely modulating the type,density,and spatial distribution of these Lewis acid/base sites,catalytic performa...Lewis acid(LA)and Lewis base(LB)sites on catalyst surfaces play a pivotal role in catalytic reactions.By precisely modulating the type,density,and spatial distribution of these Lewis acid/base sites,catalytic performance indicators such as catalytic activity,selectivity,and stability can be effectively optimized.As a result,they become essential parameters that must be considered in the design and development of high-efficiency catalysts.This study proposes a surface engineering method to accurately control the concentration of surface LA and LB sites in defect-laden In_(2)O_(3-x)(OH)_(y)(denoted as N-n%-IO),establishing three types of LB/LA stoichiometric ratios with different photocatalytic CO_(2)hydrogenation performances.It is demonstrated that the LB-rich system(LB/LA>1)shows suppressed activity.In contrast,the balanced stoichiometric ratio system(LB/LA=1)attains an optimal methanol yield(179.79μmol g^(-1)h^(-1))and selectivity(43.67%),while the LA-rich system(LB/LA<1)exhibits the best CO production rate(1913.76μmol g^(-1)h^(-1))and selectivity(94.96%).Systematic experiments disclose that the balanced LB/LA system with adjacent surface frustrated Lewis pairs(SFLPs)can effectively facilitate the adsorption/activation of reactants,stabilize intermediates,and regulate the dynamic behavior of photo-generated carriers.However,the imbalanced LB/LA systems either lack necessary active sites or can only follow an oxygen vacancy-mediated pathway during photocatalytic CO_(2)hydrogenation.This work offers a comprehensive understanding of the crucial functions of surface Lewis acid/base sites in the product distribution of solar-driven CO_(2)reduction.展开更多
Ecological experiments were conducted to examine the effects of seawater containing elevated par- tial pressure of carbon dioxide （p CO2 800 × 10 -6 , 2 000 × 10 -6 , 5 000 × 10 -6 and 10 000 × 10...Ecological experiments were conducted to examine the effects of seawater containing elevated par- tial pressure of carbon dioxide （p CO2 800 × 10 -6 , 2 000 × 10 -6 , 5 000 × 10 -6 and 10 000 × 10 -6 ） on the survival and reproduction of female Acartia pacifica, Acartia spinicauda, Calanus sinicus and Centropages tenuiremis, which are the dominant copepods in the southern coastal waters of China. The results show that the effects of elevated p CO2 on the survival rates of copepods were species-specific. C. sinicus, which was a macro-copepod, had a higher survival rate （62.01%–71.96%） than the other three species （5.00%–26.67%） during the eight day exposure. The egg production rates of C. sinicus, A. spinicauda and C. tenuiremis were significantly inhibited by the increased p CO2 and the exposure time duration. There were significantly negative impacts on the egg hatching success of A. spinicauda and C. tenuiremis in the p CO2 2 000 × 10 -6 and 10 000 × 10 -6 groups, and, in addition, the exposure time had noticeably impacts on these rates too. This study indicates that the reproductive performances of copepods were sensitive to elevated p CO2 , and that the response of different copepod species to acidified seawater was different. Furthermore, the synergistic effects of seawater acidification and climate change or other pollutant stresses on organisms should be given more attention.展开更多
基金supported by the National Natural Science Foundation of China(22172086,22105117)the Taishan Scholars Program of Shandong Province(202103064)the Major Basic Research Project of Shandong Province(ZR2021ZD06)。
文摘Lewis acid(LA)and Lewis base(LB)sites on catalyst surfaces play a pivotal role in catalytic reactions.By precisely modulating the type,density,and spatial distribution of these Lewis acid/base sites,catalytic performance indicators such as catalytic activity,selectivity,and stability can be effectively optimized.As a result,they become essential parameters that must be considered in the design and development of high-efficiency catalysts.This study proposes a surface engineering method to accurately control the concentration of surface LA and LB sites in defect-laden In_(2)O_(3-x)(OH)_(y)(denoted as N-n%-IO),establishing three types of LB/LA stoichiometric ratios with different photocatalytic CO_(2)hydrogenation performances.It is demonstrated that the LB-rich system(LB/LA>1)shows suppressed activity.In contrast,the balanced stoichiometric ratio system(LB/LA=1)attains an optimal methanol yield(179.79μmol g^(-1)h^(-1))and selectivity(43.67%),while the LA-rich system(LB/LA<1)exhibits the best CO production rate(1913.76μmol g^(-1)h^(-1))and selectivity(94.96%).Systematic experiments disclose that the balanced LB/LA system with adjacent surface frustrated Lewis pairs(SFLPs)can effectively facilitate the adsorption/activation of reactants,stabilize intermediates,and regulate the dynamic behavior of photo-generated carriers.However,the imbalanced LB/LA systems either lack necessary active sites or can only follow an oxygen vacancy-mediated pathway during photocatalytic CO_(2)hydrogenation.This work offers a comprehensive understanding of the crucial functions of surface Lewis acid/base sites in the product distribution of solar-driven CO_(2)reduction.
基金The State Oceanic Administration Foundation of China under contract No.200805029
文摘Ecological experiments were conducted to examine the effects of seawater containing elevated par- tial pressure of carbon dioxide （p CO2 800 × 10 -6 , 2 000 × 10 -6 , 5 000 × 10 -6 and 10 000 × 10 -6 ） on the survival and reproduction of female Acartia pacifica, Acartia spinicauda, Calanus sinicus and Centropages tenuiremis, which are the dominant copepods in the southern coastal waters of China. The results show that the effects of elevated p CO2 on the survival rates of copepods were species-specific. C. sinicus, which was a macro-copepod, had a higher survival rate （62.01%–71.96%） than the other three species （5.00%–26.67%） during the eight day exposure. The egg production rates of C. sinicus, A. spinicauda and C. tenuiremis were significantly inhibited by the increased p CO2 and the exposure time duration. There were significantly negative impacts on the egg hatching success of A. spinicauda and C. tenuiremis in the p CO2 2 000 × 10 -6 and 10 000 × 10 -6 groups, and, in addition, the exposure time had noticeably impacts on these rates too. This study indicates that the reproductive performances of copepods were sensitive to elevated p CO2 , and that the response of different copepod species to acidified seawater was different. Furthermore, the synergistic effects of seawater acidification and climate change or other pollutant stresses on organisms should be given more attention.
