Reconcile the contradictory wettability requirements for the reduction and oxidation half-reactions in overall CO_(2) photoreduction via alternately hydrophobic surfaces  

作　　者：Hailing Huo Ting Hu Chengxi Huang Fang Wu Tongyu Wang Xuan Liu Liang Zhang Qiang Ju Zhiqing Zhong Hongbin Xing Erjun Kan Ang Li 

机构地区：[1]MIIT Key Laboratory of Semiconductor Microstructure and Quantum Sensing,Nanjing University of Science and Technology,Nanjing 210094,Jiangsu,China [2]College of Information Science and Technology,Nanjing Forestry University,Nanjing 210037,Jiangsu,China

出　　处：《Journal of Energy Chemistry》2024年第6期202-212,I0006,共12页能源化学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(22378204,22008121,51790492);the National Outstanding Youth Science Fund Project of National Natural Science Foundation of China(T2125004);the Funding of NJUST(No.TSXK2022D002);the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_0454)。

摘　　要：The overall photocatalytic CO_(2) reduction reaction(OPCRR)that can directly convert CO_(2) and H_(2)O into fuels represents a promising renewable energy conversion technology.As a typical redox reaction,the OPCRR involves two half-reactions:the CO_(2) reduction half-reaction(CRHR)and the water oxidation half-reaction(WOHR).Generally,both half-reactions can be promoted by adjusting the wettability of catalysts.However,there is a contradiction in wettability requirements for the two half-reactions.Specifically,CRHR prefers a hydrophobic surface that can accumulate more CO_(2) molecules on the active sites,ensuring the appropriate ratio of gas-phase(CO_(2))to liquid-phase(H_(2)O)reactants.Conversely,the WOHR prefers a hydrophilic surface that can promote the departure of the gaseous product(O_(2))from the catalyst surface,preventing isolation between active sites and the reactant(H_(2)O).Here,we successfully reconciled the contradictory wettability requirements for the CRHR and WOHR by creating an alternately hydrophobic catalyst.This was achieved through a selectively hydrophobic modification method and a charge-transfer-control strategy.Consequently,the collaboratively promoted CRHR and WOHR led to a significantly enhanced OPCRR with a solar-to-fuel conversion efficiency of 0.186%.Notably,in ethanol production,the catalyst exhibited a 10.64-fold increase in generation rate(271.44μmol g^(-1)h~(-1))and a 4-fold increase in selectivity(55.77%)compared to the benchmark catalyst.This innovative approach holds great potential for application in universal overall reactions involving gas participation.

关 键 词：HYDROPHOBIC HYDROPHILIC Gas transport Overall CO_(2)photoreduction Z-scheme 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学] X701[环境科学与工程—环境工程]