The photocatalytic reduction of carbon dioxide (CO2) into multi-electron carbon products remains challenging due to the inherent stability of CO2 and slow multi-electron transfer kinetics. Here in, we synthesized a hybrid material, cesium copper halide (Cs3Cu2I5) intercalated onto two-dimensional (2D) cobalt-based zeolite framework (ZIF-9-III) nanosheets (denoted as Cs3Cu2I5@ZIF-1) through a simple mechanochemical grinding. The synergy in the hybrid effectively reduces CO2 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 Cs3Cu2I5@ZIF hybrids with varying ZIF-9-III amounts, confirming their selective CO2 reduction to methane over hydrogen. Density functional theory (DFT) calculations reveal a non-covalent interaction between Cs3Cu2I5 and ZIF-9-III, with electron transfer suggesting potential for improved photocatalysis.

Department of Materials Science and Engineering Chungnam National University Daejeon 34134 Republic of Korea

Department of Physics SRM University AP Andhra Pradesh Amaravati Andhra Pradesh 522502 India

Hybrid Porous Materials Laboratory Department of Chemistry Indian Institute of Technology Jammu Jammu and Kashmir 181221 India

Hybrid Solar Cells Faculty of Engineering and Natural Sciences Tampere University P O Box 541 33014 Tampere Finland

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences v v i Flemingovo nám 2 160 00 Prague Czech Republic

School of Physical and Applied Sciences Goa University Taleigao Plateau Goa 403206 India

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