Tuning the Spin State of Co Accelerates Hydrogen Evolution Reaction of Pt Nanoparticles

Abstract

The quest for dynamic and cost-effective electrocatalysts to substitute carbon-supported platinum (Pt) in alkaline hydrogen evolution reaction (HER) remains a pressing challenge. The incorporation of transition metal atoms through electron donation and spin regulation dominates the HER performance of Pt nanoparticles. Herein, we demonstrate that Co-N coordination was utilized to regulate and stabilize the chemical microenvironment of Pt nanoparticles to fabricate hybrid electrocatalysts (Pt/CoNC). The resultant Pt/CoNC delivers ultralow overpotentials of 15.2 and 171.2 mV at current densities of 10 and 100 mA cm⁻², surpassing commercial Pt/C. The poisoning tests, where η₁₀ values of Pt/CoNC depict negative shifts of 161 and 13 mV by potassium thiocyanide (KSCN) and ethylenediaminetetraacetic acid disodium (EDTA), suggest the combined impact of Pt nanoparticles and Co-N coordination on HER, with Pt nanoparticles playing a decisive role. The magnetic characterization and spin density diagrams reveal that Pt induces a higher spin state of Co²⁺, creating a wider spin-related channel for electron donation to Pt. Moreover, Co-N effectively modifies the electronic structure of Pt, thereby reducing the energy barriers for H₂O dissociation (from 0.41 to −0.22 eV) and H₂ generation (from −0.35 to 0.03 eV). This finding provides insights to fabricate advanced electrocatalysts through regulating spin state and modulating interfacial electron transfer.

Keywords

density functional theory / electron transfer / hydrogen evolution reaction / Pt nanoparticles / spin-state regulation

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