Electron-enriched single-Pd-sites on g-C3N4 nanosheets achieved by in-situ anchoring twinned Pd nanoparticles for efficient CO2 photoreduction

Abstract

Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO₂, 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 (Pd_TP/Pd_SA-CN) for high-efficiency photoreduction of CO₂. The anchored Pd twinned nanoparticles donate electrons to adjacent single Pd–N₄ sites through the carbon nitride networks, and the optimized Pd_TP/Pd_SA-CN photocatalyst exhibits a CO evolution rate up to 46.5 ​μmol ​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.