Reductive Supramolecular In Situ Construction of Nano-Platinum Effectively Couples Cathodic Hydrogen Evolution and Anodic Alcohol Oxidation.

The deployment of high-performance catalysts and the acceleration of anodic reaction kinetics are key measures to achieve maximum energy efficiency in overall water electrolysis hydrogen production systems. Here, an innovative strategy is developed by directly constructing a supramolecular framework embedded with boron clusters and cucurbituril as reducing agent. This approach enabled the in situ conversion of Pt⁴⁺ into highly dispersed, small-sized nano-platinum, which are subsequently distributed on a boron-carbon-nitrogen (BCN) matrix. The resulting Pt/BNHCSs catalyst demonstrates the ability to facilitate electrocatalytic water splitting for hydrogen production across multiple scenarios while simultaneously accelerating the anodic methanol oxidation kinetics, significantly outperforming commercial Pt/C catalyst in various aspects. The cathodic hydrogen evolution-anodic methanol oxidation coupling system constructed using the Pt/BNHCSs greatly reduces the overall energy consumption of the electrolysis system. In situ attenuated total reflection Fourier transform infrared and online differential electrochemical mass spectrometry reveals that the catalyst interface enhances H₂O adsorption and promotes the CH₃OH→CO conversion process, and density functional theory calculations indicated that the BCN support facilitated the evolution of H₂O to H₂ and CH₃OH to CO, elucidating the mechanism by which Pt/BNHCSs simultaneously promoted hydrogen production and methanol oxidation.