Metal-support interactions in heterogeneous catalytic hydrogen production of formic acid

Hydrogen (H2) is regarded as a novel energy carrier with huge development potential, and it will be essential in future clean energy systems. Given the existing challenges in direct H2 storage and delivery, effective H2 storage carriers, such as formic acid, for on-site H2 production have received widespread attention. Recently, supported heterogeneous catalysts have made significant progress in formic acid decomposition (FAD) toward H2, to overcome the shortcomings of homogeneous catalysts' poor stability, separation difficulty, and serious pollution. Herein, we summarize the catalytic mechanism of H2 production from FAD catalyzed by heterogeneous catalysts, thoroughly discuss the optimization of FAD performance based on MSI regulation according to metal (size, composition, and atomic arrangement), support (composition, surface modification, heteroatom doping, and confinement), and treatment (heat and plasma), as well as propose a rational design and precise construction approach for efficient FAD catalytic structures according to MSI. This review improves the development of the ideal heterogeneous FAD catalysts, to meet the demand for on-site H2 production in the future green energy system.