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Cooperative Shunt Photocatalysis of Pt Single Atoms and Nanoparticles for Efficient Methanol Conversion to Hydrogen
Youyu Pang1, Linjia Li2, Qijing Bu3
1College of Chemistry, Jilin University, Changchun, P.R. China.
Abstract:
Photocatalytic methanol dehydrogenation requires not only charge separation but, more critically, synchronized and rapid consumption of photogenerated electrons and holes-an unmet challenge in conventional Pt-based photocatalysts. Here we report a photocatalytic platform in which Pt single atoms (Pt SA) and Pt nanoparticles (Pt NP) are uniformly integrated on crystalline carbon nitride (CCN), denoted CCN-Pt SA+NP, via photoinduced reduction of chloroplatinic acid. In situ spectroscopic analyses reveal that spatially separated Pt SA/Pt NP redox pairs enable balanced and rapid photocarrier utilization, yielding closely matched TA-derived decay time constants of photogenerated holes and electrons of 405.1 and 386.7 ps, respectively. This synchronized charge consumption effectively suppresses recombination. Meanwhile, Pt single-atom sites enhance methanol adsorption and lower the energy barrier for the initial O─H bond cleavage, favoring the generation of alkoxy intermediates. The accelerated hole consumption and proton supply at the oxidation site further facilitate proton-electron coupling reactions on Pt nanoparticles. Consequently, the optimized CCN-Pt SA+NP catalyst delivers exceptional photocatalytic performance, achieving H2 and HCHO evolution rates of 24.5 and 22.6 mmol g-1 h-1, respectively, with an H2-to-HCHO ratio approaching unity. This work establishes a general strategy for engineering single-atom/nanoparticle redox pairs to realize matched electron-hole consumption and selective, low-carbon methanol-to-hydrogen conversion.
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