In Situ Loading of Cu Nanocrystals on CsCuCl3 for Selective Photoreduction of CO2 to CH4.

Abstract

Rational design and facile synthesis of efficient environmentally friendly all-inorganic lead-free halide perovskite catalysts are of great significance in photocatalytic CO2 reduction. Aiming at photogenerated charge carrier separation and CO2 reaction dynamics, in this paper, a CsCuCl3 /Cu nanocrystals (NCs) heterojunction catalyst is designed and synthesized via a simple acid-etching solution process by using Cu2 O as the sacrificed template. Due to the disproportionation reaction of Cu2 O induced by concentrated hydrochloric acid, Cu NCs can be deposited onto the surface of CsCuCl3 microcrystals directly and tightly. As revealed by photoelectrochemical analysis, in situ Fourier transform infrared spectra, etc., the Cu NCs contribute a lot to extracting photoelectrons of CsCuCl3 to improve the charge separation efficiency, regulating the CO2 adsorption and activation, and also stabilizing the reaction intermediates. Therefore, CsCuCl3 /Cu heterojunction exhibits a total electron consumption rate of 58.77µmol g-1 h-1 , which is 2.9-fold of that of single CsCuCl3 . Moreover, high CH4 selectivity of up to 92.7% is achieved, which is much higher than that of CsCuCl3 (50.4%) and most lead-free halide perovskite-based catalysts. This work provides an ingenious but simple strategy to rationally design cocatalysts in situ decorated perovskite catalysts for manipulating both the catalytic activity and the product selectivity.