Ultrasmall and Highly Dispersed Pt Entities Deposited on Mesoporous N‐doped Carbon Nanospheres by Pulsed CVD for Improved HER

Vapor-based deposition techniques are emerging approaches for the design of carbon-supported metal powder electrocatalysts with tailored catalyst entities, sizes, and dispersions. Herein, a pulsed CVD (Pt-pCVD) approach is employed to deposit different Pt entities on mesoporous N-doped carbon (MPNC) nanospheres to design high-performance hydrogen evolution reaction (HER) electrocatalysts. The influence of consecutive precursor pulse number (50-250) and deposition temperature (225-300 °C) are investigated. The Pt-pCVD process results in highly dispersed ultrasmall Pt clusters (≈1 nm in size) and Pt single atoms, while under certain conditions few larger Pt nanoparticles are formed. The best MPNC-Pt-pCVD electrocatalyst prepared in this work (250 pulses, 250 °C) reveals a Pt HER mass activity of 22.2 ± 1.2 A mg-1Pt at -50 mV versus the reversible hydrogen electrode (RHE), thereby outperforming a commercially available Pt/C electrocatalyst by 40% as a result of the increased Pt utilization. Remarkably, after optimization of the Pt electrode loading, an ultrahigh Pt mass activity of 56 ± 2 A mg-1Pt at -50 mV versus RHE is found, which is among the highest Pt mass activities of Pt single atom and cluster-based electrocatalysts reported so far.