Atomic‐Scale Configuration Enables Fast Hydrogen Migration for Electrocatalysis of Acidic Hydrogen Evolution

Abstract

The efficiency of hydrogen evolution reaction (HER) electrocatalysts under acidic conditions is largely determined by the equilibrium of hydrogen adsorption/desorption on the catalyst surface. A promising strategy for enhancing the performance of multimetal‐supported HER electrocatalysts is the utilization of hydrogen spillover. However, current heterostructured catalysts often present challenges such as high interfacial transport barriers, extended reaction paths, and intricate synthesis processes. Addressing these limitations, a novel orthorhombic SrHf1−xRuxO3−δ perovskite oxide is proposed as an exemplary model for an atomic‐level configuration design strategy. This material exhibits a unique synergistic effect of multiple atomic‐level catalytic sites between Hf/Ru pairs, overcoming the aforementioned challenges. This study presents a new cooperative mechanism for HER, consisting of three steps: proton adsorption on the Hf site, hydrogen migration via a strong O‐bridge site, and H2 detachment from the Ru active site. The high conductivity and unusual charge redistribution within the Hf‐O‐Ru structure further enhance the specific acidic HER activity of SrHf1−xRuxO3−δ. This research paves the way for designing high‐performance HER catalysts for acidic media, leveraging hydrogen spillover and atomic‐scale configurations. The findings have significant implications for the development of efficient, cost‐effective, and environmentally friendly hydrogen production technologies.

Chlorine-Induced Surface Reconstruction of Perovskite Oxide Boosts Oxygen Evolution Reaction Activity

“…Notably, the PBSCFCl0.3 catalyst exhibits a notably higher concentration of highly oxidized oxygen species in comparison to the original PBSCF. It is widely recognized that O 2 2– /O – species are intimately associated with oxygen vacancies, which are regarded as the intrinsic active sites for oxygen electrocatalysis. , This observation underscores the enhanced electrocatalytic potential of the PBSCFCl0.3 catalyst. The increase in the O 2 2– /O – concentration caused by Cl doping contributes to enhance the bifunctionality of PBSCFCl0.3.…”

Cu intercalation and defect engineering realize an atomic-scale hydrogen spillover effect in NbS2 to boost acidic hydrogen evolution

“…25 To further shorten the reaction pathway and reduce the energy barrier, a hydrogen spillover-based single-component catalyst (HSSCC) system was also designed with atomic-level multiple catalytic sites. 26,27 Previous works reported that the hydrogen spillover can be utilized to obtain excellent HER performance in HSBCC systems such as Pt/CoP, 28 Pt/WO 3− x , 29 Pt/RuCeO x -PA, 30 and V o -Pt/TiO 2 , 31 and two HSSCC materials, namely La 2 Sr 2 PtO 7+ δ 26 and SrHf 1− x Ru x O 3− δ , were also reported. 27 For TMD-based systems, binary-component systems with a hydrogen spillover effect have been reported in MoS 2 /NiPS 3 32 and CQDs@MoS 2 , 33 but an HSSCC based on TMDs is still lacking.…”

“…26,27 Previous works reported that the hydrogen spillover can be utilized to obtain excellent HER performance in HSBCC systems such as Pt/CoP, 28 Pt/WO 3− x , 29 Pt/RuCeO x -PA, 30 and V o -Pt/TiO 2 , 31 and two HSSCC materials, namely La 2 Sr 2 PtO 7+ δ 26 and SrHf 1− x Ru x O 3− δ , were also reported. 27 For TMD-based systems, binary-component systems with a hydrogen spillover effect have been reported in MoS 2 /NiPS 3 32 and CQDs@MoS 2 , 33 but an HSSCC based on TMDs is still lacking. Based on the van der Waals gap in their structure, chemical intercalation can be performed as a route to induce multiple catalytic sites in TMDs to realize the HSSCC.…”

Hydrogen Spillover Phenomenon at the Interface of Metal-Supported Electrocatalysts for Hydrogen Evolution

“…Hydrogen spillover from Pt to WO 3 was proposed to explain such high HER activity, which promoted hydrogen desorption, re-exposure of the Pt surface, and subsequent proton adsorption for the next cycle. Later, several hydrogen-spillover-based electrocatalysts have been reported and experimentally and theoretically demonstrated, including Ir/SiNWs, Ir/Rh metallene, PtCu/WO 3 , Ru/WO 3– x , Ru/W 18 O 49 , Pt/RuCeO x , Pt/La 2 Sr 2 O 7+δ , Pt/MoO 3 , OH – modified NiO loaded on Cu, ethylene glycol (EG)-modified Pt loaded CoP, PtIr alloys loaded CoP, RuFe alloys loaded CoP, MoS 2 /NiPS 3 , Ni 3 S 2 /Cr 2 S 3 , PtIr/MoS 2 , Cu nanodots-decorated Ni 3 S 2 , and SrHf 1– x Ru x O 3−δ . − ,− In these cases, the hydrogen spillover phenomenon significantly enhances the HER electrocatalytic activity accompanied by reduced metal usage. Therefore, understanding how to enable this hydrogen spillover phenomenon at the electrocatalytic interface and its nature has been quintessential for creating a new paradigm for designing high-performance electrocatalysts.…”