基于配体效应协同调控异质结氧化还原位点的d带中心用于光解水制氢  

Synergistically regulating d-band centers of heterojunction redox sites by ligand effect for photocatalytic H_(2)evolution

作　　者：吴园霄 曲梦茹 姜淑娟 张建军 宋少青 Yuanxiao Wu;Mengru Qu;Shujuan Jiang;Jianjun Zhang;Shaoqing Song(School of Materials Science&Chemical Engineering,Ningbo University,Ningbo 330013,China;School of New Energy,Ningbo University of Technology,Ningbo 315336,China;Laboratory of Solar Fuel,Faculty of Materials Science and Chemistry,China University of Geosciences,Wuhan 430078,China)

机构地区：[1]School of Materials Science&Chemical Engineering,Ningbo University,Ningbo 330013,China [2]School of New Energy,Ningbo University of Technology,Ningbo 315336,China [3]Laboratory of Solar Fuel,Faculty of Materials Science and Chemistry,China University of Geosciences,Wuhan 430078,China

出　　处：《Science China Materials》2024年第2期524-531,共8页中国科学（材料科学）（英文版）

基　　金：supported by the National Natural Science Foundation of China(51972177,22372084);the Key Project of Zhejiang Province(2023C3016);the Natural Science Foundation of Ningbo City(2021J067)。

摘　　要：光催化水解离制氢过程中,光生载流子由生成位点向氧化还原位点艰难的动力学迁移及随后与中间产物反应大的过电位问题还没有被解决,严重阻碍了太阳光子转化为氢能的效率(STH).本文基于配体效应协同调控材料d带中心构建了CeO_(2)纳米线负载Ni_(2)P异质结光催化剂,继而解决上述动力学瓶颈.原位漫反射傅里叶变换红外光谱、霍尔效应等表征揭示光生电子和空穴在自发局域电场推动下,分别迁移至Ni_(2)P还原位点和CeO_(2)氧化位点,接着促使吸附在此的活性中间产物发生脱氢和氧耦合反应.性能测试显示,在AM 1.5G模拟太阳光辐照下,室温下的STH值达到了1.13%.本研究为通过协同调节d带中心提高异质结光催化剂的STH提供了独特的策略.Stiff transportation behaviors in kinetics for photo-excited charges from their generation sites to corresponding redox sites as well as subsequent large reaction overpotential of these charges with intermediates during splitting H_(2)O have not been solved yet,which extremely hinders solar photon energy conversion into H_(2)(STH).Herein,CeO_(2)nanowires-anchored Ni_(2)P nanoparticles were built to solve the above dynamical issues by synchronously modifying d-band centers(εd)with ligand effect.Photon-excited electrons and holes were separately propelled to Ni_(2)P as the reductive site and CeO_(2)as the oxidative site within the spontaneously formed localized electric field for the dehydrogenation and coupling of active oxyhydrogen intermediates,respectively,characterized by in situ diffuse reflectance infrared Fourier transform spectroscopy and Hall effect tests.Consequently,a STH of 1.13%was achieved at room temperature under AM 1.5G irradiation.The study supplies a unique insight to enhance STH over heterojunction photocatalysts by synchronously tunningεd.

关 键 词：HETEROJUNCTION d-band center H_(2)O splitting H_(2)energy PHOTOCATALYSIS 

分 类 号：O643.36[理学—物理化学] TQ116.2[理学—化学]