利用太阳辐射驱动光电催化还原CO_(2)制备碳基化学品可减少碳排放,同时将不稳定的太阳能转化为可长期存储的化学能,极具吸引力.但半导体光电极的太阳光谱吸收范围窄且载流子复合严重制约了效率的提升,并且将CO_(2)还原为具有高附加值的C...利用太阳辐射驱动光电催化还原CO_(2)制备碳基化学品可减少碳排放,同时将不稳定的太阳能转化为可长期存储的化学能,极具吸引力.但半导体光电极的太阳光谱吸收范围窄且载流子复合严重制约了效率的提升,并且将CO_(2)还原为具有高附加值的C_(2)及以上碳基化学品需要多电子转移,十分具有挑战性.本工作构建了Ag纳米颗粒(AgNPs)与Cu_(2)O的复合光电阴极,通过负载AgNPs形成局域表面等离激元共振效应将太阳光谱吸收范围拓宽至近红外区,光电流提升至2.02 mA·cm^(-2),并通过热电子注入与能带弯曲共同抑制析氢、促进C—C偶联,在0 V vs. RHE下将CO_(2)还原为乙醇,法拉第效率可达81.3%.证实了等离激元效应促进光电催化还原CO_(2)制备C_(2)以上碳基化学品的可行性,并为高效光电极设计提供了新思路.展开更多
The preparation and application of supported gold and copper catalysts are fundamentally and practically very important.Herein,we confirm that the Au-Cu promoted In_(2)O_(3) catalyst demonstrates a significant electro...The preparation and application of supported gold and copper catalysts are fundamentally and practically very important.Herein,we confirm that the Au-Cu promoted In_(2)O_(3) catalyst demonstrates a significant electronic metal-support interaction(EMSI),which plays a critical role in CO_(2) hydrogenation to methanol and leads to significantly improved activity,compared to the mono-metallic Au and Cu promoted In_(2)O_(3)catalysts.This interaction arises from electron transfer between the oxygen deficient In_(2)O_(3) support and the bimetallic clusters,rendering both Au and Cu clusters positively charged.The presence of Cu^(3+)stabilizes and optimizes the content of oxygen vacancies,leading to a more pronounced positive charge on Au clusters(Au^(3+)).The ability to activate H_(2) is thus enhanced.CO adsorption on Au-Cu/In_(2)O_(3) is also stronger than Au/In_(2)O_(3).This results in higher methanol selectivity of Au-Cu/In_(2)O_(3),with which CO hydrogenation pathway is taken for CO_(2) hydrogenation to methanol.The enhanced H_(2) activation and stronger CO adsorption over Au-Cu/In_(2)O_(3) are key factors in boosting the activity for methanol formation from CO_(2)hvdrogenation.展开更多
文摘利用太阳辐射驱动光电催化还原CO_(2)制备碳基化学品可减少碳排放,同时将不稳定的太阳能转化为可长期存储的化学能,极具吸引力.但半导体光电极的太阳光谱吸收范围窄且载流子复合严重制约了效率的提升,并且将CO_(2)还原为具有高附加值的C_(2)及以上碳基化学品需要多电子转移,十分具有挑战性.本工作构建了Ag纳米颗粒(AgNPs)与Cu_(2)O的复合光电阴极,通过负载AgNPs形成局域表面等离激元共振效应将太阳光谱吸收范围拓宽至近红外区,光电流提升至2.02 mA·cm^(-2),并通过热电子注入与能带弯曲共同抑制析氢、促进C—C偶联,在0 V vs. RHE下将CO_(2)还原为乙醇,法拉第效率可达81.3%.证实了等离激元效应促进光电催化还原CO_(2)制备C_(2)以上碳基化学品的可行性,并为高效光电极设计提供了新思路.
基金supported by the National Natural Science Foundation of China(22138009)the Fundamental Research Funds for the Central Universities of China。
文摘The preparation and application of supported gold and copper catalysts are fundamentally and practically very important.Herein,we confirm that the Au-Cu promoted In_(2)O_(3) catalyst demonstrates a significant electronic metal-support interaction(EMSI),which plays a critical role in CO_(2) hydrogenation to methanol and leads to significantly improved activity,compared to the mono-metallic Au and Cu promoted In_(2)O_(3)catalysts.This interaction arises from electron transfer between the oxygen deficient In_(2)O_(3) support and the bimetallic clusters,rendering both Au and Cu clusters positively charged.The presence of Cu^(3+)stabilizes and optimizes the content of oxygen vacancies,leading to a more pronounced positive charge on Au clusters(Au^(3+)).The ability to activate H_(2) is thus enhanced.CO adsorption on Au-Cu/In_(2)O_(3) is also stronger than Au/In_(2)O_(3).This results in higher methanol selectivity of Au-Cu/In_(2)O_(3),with which CO hydrogenation pathway is taken for CO_(2) hydrogenation to methanol.The enhanced H_(2) activation and stronger CO adsorption over Au-Cu/In_(2)O_(3) are key factors in boosting the activity for methanol formation from CO_(2)hvdrogenation.
