PtRu Intra‐Cluster Electron Modulation Accelerates Multi‐Scenario Hydrogen Evolution Reaction

In situ reduction of Pt⁴⁺ and Ru³⁺ into highly dispersed small-sized heterojunction clusters in hollow carbon materials by using the strategy of reducing agent preset into supramolecular framework. The Ru→Pt electron transfer in the PtRu clusters modulates the electronic structure, promotes the adsorption and activation of H₂O in both directions, and realizes the electrolysis of H₂O-to-H₂ in various scenarios.

Abstract

The development of advanced nanomaterial manufacturing technology and the in-depth analysis of the structure-activity relationship are conducive to the sustainable development of platinum-based catalysts in terms of low cost and high performance. The in situ conversion of Pt⁴⁺ and Ru³⁺ is creatively achieved into highly dispersed, small-sized heterojunction clusters in the confined space by reductant preset framework materials, and these clusters benefited from the hollow carbon spheres gap supramolecular self-assembly strategy to achieve high exposure. The intra-cluster Ru→Pt electron transfer and induced electronic structure modulation enhance the adsorption and activation of H₂O molecules at the interface, accelerating the desorption coupling of [H] at the Pt or Ru site. As a catalyst, PtRu/BNHCSs have achieved significant hydrogen production from electrolyzed water in multiple scenarios, exceeding the performance of the commercial Pt/C catalyst. These scenarios include high-current water splitting to hydrogen in both pH-neutral and simulated seawater, direct seawater hydrogen production, and anion-exchange membrane integrated continuous and efficient electrolytic hydrogen production. In situ Fourier transform infrared and in situ Raman interface monitoring techniques reveal the interfacial adsorption behavior of H₂O, providing important experimental and theoretical insights for understanding and revealing the synergistic effect and the interfacial reaction behavior of intra-cluster atoms of PtRu heterojunction.