Electronic metal–support interaction modulates single-atom platinum catalysis for hydrogen evolution reaction

Abstract

Tuning metal–support interaction has been considered as an effective approach to modulate the electronic structure and catalytic activity of supported metal catalysts. At the atomic level, the understanding of the structure–activity relationship still remains obscure in heterogeneous catalysis, such as the conversion of water (alkaline) or hydronium ions (acid) to hydrogen (hydrogen evolution reaction, HER). Here, we reveal that the fine control over the oxidation states of single-atom Pt catalysts through electronic metal–support interaction significantly modulates the catalytic activities in either acidic or alkaline HER. Combined with detailed spectroscopic and electrochemical characterizations, the structure–activity relationship is established by correlating the acidic/alkaline HER activity with the average oxidation state of single-atom Pt and the Pt–H/Pt–OH interaction. This study sheds light on the atomic-level mechanistic understanding of acidic and alkaline HER, and further provides guidelines for the rational design of high-performance single-atom catalysts.

Strategies for Electrochemically Sustainable H2 Production in Acid

“…One of the simplest approaches to access low‐cost noble metals with reservation of acidic HER activity is preparation of single atom Pt, of which the average oxidation state has strong correlation with the Pt–H interaction, thus tuning the HER activity. [ 44 ] The optimal oxidation state of Pt was evaluated to be ≈+2. By a self‐reduction method to approach this oxidation state, we can obtain a high HER activity of the single atom Pt catalyst with overpotential of only 25 mV at 10 mA cm –2 .…”

“…[ 45 ] The preparation of stable single atom Pt requires strong metal‐support interaction, by which the high‐energy barrier would limit Pt diffusion on the surface to form clusters/nanoparticles, thus demonstrating the structural stability. [ 44 ] Among the other noble metals reported thus far, metallic Ru loaded on triazine‐ring‐doped carbon, multi‐walled carbon nanotubes, or edge‐carboxylic‐acid‐functionalized graphene nanoplatelets have shown great potential for HER in acidic media. [ 46 , 47 , 48 ] However, the supported Ru‐based catalysts suffer from particle aggregations arising from the migration and deposition of Ru‐based particles partly because of insufficient interactions with the support.…”

Realistic Modelling of Dynamics at Nanostructured Interfaces Relevant to Heterogeneous Catalysis

“…By the same token, support-catalyst interaction can dramati-cally affect the stability of the latter with respect to the gas phase. Conversely, the effects of electronic [61], reactive [62], and strong metal-support interactions [63,64] have been strong drivers in the study and analysis of the dynamics of supported nanostructured metal catalysts.…”

Recent advances in MoS2-based materials for electrocatalysis

“…10 The electrochemical hydrogen evolution reaction, which converts water into high-purity H 2 , is a viable, efficient, and environmentally-friendly way to mitigate severe energy shortages and greenhouse gas emissions. 11–14 Similar to H 2 , ammonia (NH 3 ), with a high energy density, is a potential carbon-free transportation fuel. 15 It is also a crucial feedstock for fertilizers and has become the second highest produced chemical in the world.…”