物理化学学报2025，Vol.41Issue(9)：83-96,14.DOI:10.1016/j.actphy.2025.100099
通过边缘活性位点调控解析光热催化中析氢与二氧化碳还原的界面竞争
Decoding the interfacial competition between hydrogen evolution and CO2 reduction via edge-active-site modulation in photothermal catalysis
摘要
Abstract
Solar-driven photothermal catalytic CO2 conversion with H2O is a promising approach to produce sustainable fuels and chemicals.However,the competition between hydrogen evolution reaction(HER)and CO2 reduction reaction(CO2RR)results in unsatisfactory product selectivity.Noble metal nanoparticles(NMNPs)are widely used cocatalysts to introduce active sites on semiconductors,with unique active sites at the metal-semiconductor interfacial edges playing a critical role in the competitive mechanisms.Herein,we prepared a series of NMNPs loaded on Al-doped SrTiO3 with abundant interfacial edge sites for continuous photothermal catalytic CO2 and H2O conversion.Different NMNPs demonstrated distinct CO2-induced effects on hydrogen evolution.The key intermediate interactions were investigated by in situ diffuse reflectance infrared Fourier-transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations.The results revealed that bidentate carbonate(b-CO32-)tended to occupy the edge sites at the metal-semiconductor interfaces,competitively consuming the active sites for *H adsorption and altering the energy barrier of hydrogen evolution.The predominant site-blocking effect of b-CO32-on Rh-loaded catalysts was verified through establishing a simplified geometric model to quantify the correlation of particle sizes,active site proportions and CO2-induced hydrogen production variations.Controlling Rh nanoparticle size can tune the proportion of edge sites,which involves a trade-off between *H coverage and CO2 activation and promotes the CO2RR process toward methane production.This work initially unravels the interfacial competitive mechanism between HER and CO2RR via edge-active-site modulation,hoping to provide valuable insights for the rational catalyst design and offer potential strategies to enhance CO2 conversion efficiency.关键词
光热催化/析氢/二氧化碳还原/活性位点/界面竞争Key words
Photothermal catalysis/Hydrogen evolution/CO2 reduction/Active site/Interfacial competition分类
化学化工引用本文复制引用
洪佳楠,许辰宇,刘烟,黎昌棋,王梦琳,张彦威..通过边缘活性位点调控解析光热催化中析氢与二氧化碳还原的界面竞争[J].物理化学学报,2025,41(9):83-96,14.基金项目
This work was financially supported by the Zhejiang Provincial Natural Science Foundation of China(LDT23E06014E06),the National Natural Science Foundation of China(52341602),the Zhejiang Provincial Natural Science Foundation of China(LQ24E060001),the National Key Research and Development Project(2023YFC3710800),and the Fundamental Research Funds for the Central Universities(2022ZFJH04). 浙江省自然科学基金(LDT23E06014E06),国家自然科学基金(52341602),浙江省自然科学基金(LQ24E060001),国家重点研发计划(2023YFC3710800)及中央高校基本科研业务费专项资金(2022ZFJH04)资助 （LDT23E06014E06）
