Green synthesis of hydrogen and formaldehyde from methanol with enhanced quantum efficiency

Abstract

Catalytic hydrogen production from methanol offers a promising green route for safe and convenient hydrogen storage and transport and on-demand generation but remains challenging. Here we report a modulated single-atom-based catalytic cluster, assisted by a photon–phonon co-driven strategy, capable of achieving efficient hydrogen production from methanol solution with co-generation of green formaldehyde. By stabilizing Pt single atoms on TiO 2 surface through Li-modulated microenvironments, the PtLi 2 cluster-immobilized TiO 2 catalyst achieves an exceptional hydrogen production rate of 4.36 mol g −1 h −1 at 150 °C, corresponding to an overall quantum yield as high as 184%. Furthermore, a 21.2 wt% concentrated formaldehyde solution is synthesized, offering a potential commercial product for medical use. Here Li serves five distinct functions: retarding charge recombination, facilitating electron transfer, weakening H adsorption, particularly maximizing the Pt 2+ dispersion rather than Pt 0 and stabilizing single-atom Pt species on the catalyst surface. The resulting system enables stable operation for at least 19 days with a high apparent turnover frequency, bringing this sustainable synthetic pathway closer to practical implementation.