Switching the product selectivity from methane to methanol in CO2 hydrogenation via Cu-modified vacancy engineering at MoS2 edge sites

The catalytic hydrogenation of carbon dioxide (CO 2 ) to methanol (CH 3 OH) represents a promising strategy for mitigating carbon emissions and closing the carbon cycle. This study demonstrates that the incorporation of Cu into MoS 2 catalysts significantly enhances methanol selectivity and productivity. Through a combination of transmission electron microscope, X-ray diffraction, Raman, electron paramagnetic resonance, X-ray photoelectron spectroscopy, diffuse reflectance Infrared Fourier transform spectroscopy, X-ray absorption spectroscopy, temperature-programmed desorption, and kinetic analysis, we reveal that Cu modifies edge sulfur vacancies, thereby suppressing methane formation and promoting methanol synthesis. At 220 °C and 5 MPa, the 2%Cu/MoS 2 catalyst achieves 85.5% selectivity toward CH 3 OH, and the methanol formation rate reaches 7.88 mmol g -1 cat h -1 (0.256 mmol m - 2 MoS 2 h -1 ), representing the highest performance among MoS 2 -based catalysts under comparable conditions. This work provides an efficient and potentially scalable approach for designing advanced MoS 2 -based catalysts for CO 2 hydrogenation.