Conventional strategies for enhancing platinum’s hydrogen evolution reaction (HER) activity, like alloying or heteroatom-doping, usually suffer from component leaching. We presented a paradigm shift from modifying Pt to remotely engineering its electronic environment. By co-anchoring isolated Ce single atoms, Pt single atoms, and Pt nanoclusters on an N-doped reduced graphene oxide (Ce₁-Pt₁Pt_n/N-rGO) matrix, we constructed an atomic-scale “electron pump”. The architecture enables the unidirectional and spontaneous flow of electrons from the Ce sites, through the N-rGO conduit, into Pt active centers as validated experimentally and theoretically. This remote charge donation optimally tailors the Pt electronic structure, down-shifting its d-band center and optimizing the hydrogen adsorption. The resulting catalyst achieves an ultralow overpotential of 20 mV at 10 mA·cm⁻² and a superior Pt mass activity of 7.0 A·mg_Pt⁻¹ at −200 mV, outperforming commercial Pt/C and the Pt₁Pt_n/N-rGO benchmark. Furthermore, it exhibits exceptional stability, retaining an activity of more than 92% after 200 h. This work establishes a novel “remote electron modulator” catalysts, providing a generic pathway for optimizing the performance of noble metals beyond traditional alloy or strain effects.

Ultrafine and highly dispersed Pd nanoparticles have drawn considerable attention with high activity, selectivity and atomic efficiency. In this paper, amorphous Pd(Ⅱ)-complex solid spheres with ~ 5 nm Pd nanoparticles loaded on were successfully achieved through a simple and gentle one-pot solution method with vitamin B1 simultaneously as complexing agent and reducing agent. An ultrathin mesoporous SiO₂ shell was then coated at the surface of Pd(Ⅱ-0) spheres as the armor which could prevent the dissolution of Pd(Ⅱ) during the catalytic process. The combination of Pd(Ⅱ) and Pd(0) endowed Pd(Ⅱ-0)@m-SiO₂ catalyst an excellent performance in eco-friendly aqueous media Suzuki reactions. The high activity, productivity and recyclability were all comparable with the best Pd catalysts ever reported. The ingenious formation of amorphous Pd(Ⅱ)/crystal Pd(0) with enhanced catalytic performances provides a new, scalable strategy to practical promotion of Suzuki cross-coupling reactions.