Hydrogen production from coal gasification provides a cleaning approach to convert coal resource into chemical energy, but the key procedures of coal gasification and thermal catalytic water–gas shift (WGS) reaction in this energy technology still suffer from high energy cost. We herein propose adopting a solar–driven WGS process instead of traditional thermal catalysis, with the aim of greatly decreasing the energy consumption. Under light irradiation, the CuOx/Al2O3 delivers excellent catalytic activity (122 μmol gcat−1 s−1 of H2 evolution and >95 % of CO conversion) which is even more efficient than noble‐metal‐based catalysts (Au/Al2O3 and Pt/Al2O3). Importantly, this solar‐driven WGS process costs no electric/thermal power but attains 1.1 % of light‐to‐energy storage. The attractive performance of the solar‐driven WGS reaction over CuOx/Al2O3 can be attributed to the combined photothermocatalysis and photocatalysis.

Hydrogen production from coal gasification provides a cleaning approach to convert coal resource into chemical energy, but the key procedures of coal gasification and thermal catalytic water–gas shift (WGS) reaction in this energy technology still suffer from high energy cost. We herein propose adopting a solar–driven WGS process instead of traditional thermal catalysis, with the aim of greatly decreasing the energy consumption. Under light irradiation, the CuOx/Al2O3 delivers excellent catalytic activity (122 μmol gcat−1 s−1 of H2 evolution and >95 % of CO conversion) which is even more efficient than noble‐metal‐based catalysts (Au/Al2O3 and Pt/Al2O3). Importantly, this solar‐driven WGS process costs no electric/thermal power but attains 1.1 % of light‐to‐energy storage. The attractive performance of the solar‐driven WGS reaction over CuOx/Al2O3 can be attributed to the combined photothermocatalysis and photocatalysis.