Synergistic Cascade Hydrogen Evolution Boosting via Integrating Surface Oxophilicity Modification with Carbon Layer Confinement

Abstract

The lack of highly efficient catalysts severely hinders large‐scale application of electrochemical hydrogen evolution reaction (HER) for hydrogen production from water. Herein, synergistic cascade hydrogen evolution boosting by combining the strategies of carbon layer confinement and surface oxophilicity modification is realized. The carbon layers confined ultrafine RuCr nanoparticles (RuCr@C) exhibit outstanding HER activity (j10 = 19 mV, turnover frequency = 4.25 H2 s‐1), surpassing the benchmark Pt/C and most of the reported HER catalysts. Combined experimental verifications and theoretical simulations reveal that surface adsorption modification and electronic structure regulation synergistically boosts the HER kinetics over the RuCr@C catalyst. The Volmer step is accelerated by stabilizing the final state of water dissociation (*H and *OH) through Cr doping, and the Heyrovsky step is promoted via carbon layers confinement. As such, this work highlights a synergistic cascade strategy to boost HER kinetics which is of fundamental importance to accelerate future advances in electrocatalysis.

Constructing stable charge redistribution through strong metal–support interaction for overall water splitting in acidic solution

“…The DOS near the Fermi level is also crucial for the interaction between adsorbates (such as H* for the HER) and the catalytic site, and the higher electron density near the Fermi level means higher H* adsorption. 54,55 As shown in Fig. 4f, the d-band center of Pt–RuO 2 @KB is calculated to be −1.43 eV, which is higher than the −2.17 eV of Pt@KB and −2.52 eV of RuO 2 @KB, suggesting that the Pt–RuO 2 @KB heterostructure composed of Pt and RuO 2 has better HER activity, which better verifies the above experimental results.…”

Theoretical Screening of Transition Metal-Embedded Ti2N for High-Efficiency Hydrogen Evolution Reaction

“…1−4 As an uphill hydrogen evolution reaction (HER) requires high voltage (1.8−2.0 V), the sluggish kinetics makes practical application difficult. 5,6 In this regard, Pt/Pd-based metal catalysts are regarded as unrivaled catalysts in minimizing overpotential and increasing reaction rates. However, Pt and Pd are of low natural abundance and are expensive.…”

“…Hydrogen is the most potential renewable source to alternative fossil fuels and is viably produced in an environmentally friendly manner by electroreduction of H 2 O to high purity H 2 . − As an uphill hydrogen evolution reaction (HER) requires high voltage (1.8–2.0 V), the sluggish kinetics makes practical application difficult. , In this regard, Pt/Pd-based metal catalysts are regarded as unrivaled catalysts in minimizing overpotential and increasing reaction rates. However, Pt and Pd are of low natural abundance and are expensive. , Therefore, a great deal of experimental and theoretical work has been carried out to search for Pt/Pd alternative catalysts. − Recently, single-atom catalysts (SACs), which provide excellent catalytic activity, are considered to be effective to reduce the cost of traditional pure Pt/Pd catalysts .…”

Recent progress on the long‐term stability of hydrogen evolution reaction electrocatalysts

“…67 Moreover, due to the scarcity of precious metal resources and high preparation technology costs, the long-term development goal is to effectively improve the utilization efficiency of precious metal atoms, reduce metal load and stabilize metal sites to ensure high activity and stability. Investigations with the target toward improvements on the catalytic stability of those precious metals for hydrogen evolution have been reported through the alloying with other metals, 68 spacing confinements, 69 metal-support interaction through anchoring, fixing precious metals on functional supports, 70 and the local regulations of coordination environment. 71…”