Synergistic metal halide perovskite@metal-organic framework hybrids for photocatalytic CO2 reduction
Saandra Sharma, Noah Jacob, G. Krishnamurthy Grandhi, Mahendra B. Choudhary, Swathi Ippili, Venkatesha R. Hathwar, Paola Vivo, Rabindranath Lo, M. Motapothula, Kolleboyina Jayaramulu
Abstract
The photocatalytic reduction of carbon dioxide (CO 2 ) into multi-electron carbon products remains challenging due to the inherent stability of CO 2 and slow multi-electron transfer kinetics. Here in, we synthesized a hybrid material, cesium copper halide (Cs 3 Cu 2 I 5 ) intercalated onto two-dimensional (2D) cobalt-based zeolite framework (ZIF-9-III) nanosheets (denoted as Cs 3 Cu 2 I 5 @ZIF-1) through a simple mechanochemical grinding. The synergy in the hybrid effectively reduces CO 2 to carbon monoxide (CO) at 110 μmol/g/h and methane at 5 μmol/g/h with high selectivity, suppressing hydrogen evolution. Further, we have investigated additional Cs 3 Cu 2 I 5 @ZIF hybrids with varying ZIF-9-III amounts, confirming their selective CO 2 reduction to methane over hydrogen. Density functional theory (DFT) calculations reveal a non-covalent interaction between Cs 3 Cu 2 I 5 and ZIF-9-III, with electron transfer suggesting potential for improved photocatalysis.