摘要
Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO_(2),and it's especially challenging to develop a facile method to modify the dispersion of atomical photocatalytic sites.We herein report an ion-loading pyrolysis route to in-situ anchor Pd single atoms as well as twinned Pd nanoparticles on ultra-thin graphitic carbon nitride nanosheets(PdTP/Pd_(SA)-CN)for high-efficiency photoreduction of CO_(2).The anchored Pd twinned nanoparticles donate electrons to adjacent single Pd–N_(4) sites through the carbon nitride networks,and the optimized PdTP/Pd_(SA)-CN photocatalyst exhibits a CO evolution rate up to 46.5μmol g^(-1) h^(-1) with nearly 100%selectivity.As revealed by spectroscopic and theoretical analyses,the superior photocatalytic activity is attributed to the lowered desorption barrier of carbonyl species at electron-enriched Pd single atoms,together with the improved efficiencies of light-harvesting and charge separation/transport.This work has demonstrated the engineering of the electron density of single active sites with twinned metal nanoparticles assisted by strong electronic interaction with the support of the atomic metal,and unveiled the underlying mechanism for expedited photocatalytic efficiency.
基金
We appreciate the financial support from the National Natural Science Foundation of China(22272150,22102145)
the Major Program of Zhejiang Provincial Natural Science Foundation(LD22B030002)
Zhejiang Provincial Ten Thousand Talent Program(2021R51009)
Zhejiang Provincial Natural Science Foundation of China(LQ23B030006,LY22B030012)
Shandong Provincial Natural Science Foundation of China(2020MB053)
the Fundamental Research Funds for the Central Universities(DUT22RC(3)084).
