Wettability Engineering of Solar Methanol Synthesis

Engineering the wettability of surfaces with hydrophobic organics has myriad applications in heterogeneous catalysis and the large-scale chemical industry; however, the mechanisms behind may surpass the proverbial hydrophobic kinetic benefits. Herein, the well-studied In₂O₃ methanol synthesis photocatalyst has been used as an archetype platform for a hydrophobic treatment to enhance its performance. With this strategy, the modified samples facilitated the tuning of a wide range of methanol production rates and selectivity, which were optimized at 1436 μmol g_cat^-1 h^-1 and 61%, respectively. Based on in situ DRIFTS and temperature-programmed desorption-mass spectrometry, the surface-decorated alkylsilane coating on In₂O₃ not only kinetically enhanced the methanol synthesis by repelling the produced polar molecules but also donated surface active H to facilitate the subsequent hydrogenation reaction. Such a wettability design strategy seems to have universal applicability, judged by its success with other CO₂ hydrogenation catalysts, including Fe₂O₃, CeO₂, ZrO₂, and Co₃O₄. Based on the discovered kinetic and mechanistic benefits, the enhanced hydrogenation ability enabled by hydrophobic alkyl groups unleashes the potential of the surface organic chemistry modification strategy for other important catalytic hydrogenation reactions.