Manipulating the Coordination Chemistry of RuN(O)C Moieties for Fast Alkaline Hydrogen Evolution Kinetics

Abstract

The coordination chemistry of the metal‐support interface largely determines the electrocatalytic performance of heterostructured electrocatalysts. However, it remains a great challenge to effectively manipulate the interface chemistry of heterostructures at the atomic level. Herein, functionalized carbon‐supported Ru heterostructured electrocatalysts are designed that contain abundant RuN(O)C moieties with a view towards fast hydrogen evolution reaction (HER). The coordination chemistry of the RuN(O)C moieties, and hence, the geometric and electronic structures of the Ru species can be precisely modulated via an appropriate annealing treatment. Specifically, the optimal heterostructured electrocatalyst delivers the highest specific activity by far among reported Ru‐based electrocatalysts, and the turnover frequency value reaches 32 s−1 at the overpotential (η) of 100 mV, which also surpasses the state‐of‐the‐art Pt/C catalyst in alkaline media. The interface engineering of the heterostructured electrocatalyst not only facilitates H2O adsorption and dissociation with help from the RuN(O)C moieties, but also further optimizes the adsorption behavior of H on the metallic Ru species, thereby inducing accelerated hydrogen evolution kinetics in both alkaline and acidic media. The present results demonstrate the successful atomic‐level interface engineering of carbon‐supported Ru‐based heterostructures and shed new light on the development of advanced electrocatalysts for fast hydrogen evolution, and beyond.

Supported Sub‐Nanometer Clusters for Electrocatalysis Applications

“…[1,2] The reaction kinetics of alkaline hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR) is much slower than those in acidic environment. [3,4] CO 2 RR and NRR face the problems of poor selectivity and low current density. [5,6] The key role to solve these problems is to design advanced electrocatalyst as it largely determdavines the selectivity, activity, and durability of the electrocatalytic system.…”

Rational Design of Better Hydrogen Evolution Electrocatalysts for Water Splitting: A Review

“…Interface effect refers to the interface between two types of active materials due to strong bonding, electronic interaction or synergistic effect, which can form more active centers than individual components. [ 250 , 251 , 252 , 253 , 254 , 255 , 256 , 257 , 258 , 259 , 260 , 261 , 262 , 263 , 264 , 265 , 266 , 267 , 268 , 269 ] The complex electronic structures of interfacial electrocatalysts make the fundamental investigations of structure‐activity relationships still remain as a great challenge. Nevertheless, this complexity also introduces various structural features that can be adjusted advantageously.…”

Several Key Factors for Efficient Electrocatalytic Water Splitting: Active Site Coordination Environment, Morphology Changes and Intermediates Identification

“…[26] SAC has received much attention due to its highly homogeneous active site and geometric configuration, which lead to a significant enhancement in catalytic activity and is considered as the best model for studying interfacial reactions because of its simple coordination structure and more exposed active sites. [27] For example, Yu et al designed a Pt single-atom loaded hollow carbon sphere called Pt 1 /NMHCS for efficient HER. [28] The dispersion state and coordination environment of Pt atoms were confirmed by HAADF-STEM (Figure 3a), X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) investigations (Figure 3b, c).…”

“…A typical achievement in interfacial chemistry field is single‐atom site heterogeneous catalysts and subsequently single‐atom catalysis (SAC) [26] . SAC has received much attention due to its highly homogeneous active site and geometric configuration, which lead to a significant enhancement in catalytic activity and is considered as the best model for studying interfacial reactions because of its simple coordination structure and more exposed active sites [27] . For example, Yu et al.…”