Electrochemical Oxidation Encapsulated Ru Clusters Enable Robust Durability for Efficient Oxygen Evolution

Abstract

Electrochemical oxidization and thermodynamic instability agglomeration are a primary challenge in triggering metal‐support interactions (MSIs) by immobilizing metal atoms on a carrier to achieve efficient oxygen evolution reactions (OER). Herein, Ru clusters anchored to the VS2 surface and the VS2 nanosheets embedded vertically in carbon cloth (Ru‐VS2@CC) are deliberately designed to realize high reactivity and exceptional durability. In situ Raman spectroscopy reveals that the Ru clusters are preferentially electro‐oxidized to form RuO2 chainmail, both affording sufficient catalytic sites and protecting the internal Ru core with VS2 substrates for consistent MSIs. Theoretical calculations elucidate that electrons across the Ru/VS2 interface aggregate toward the electro‐oxidized Ru clusters, while the electronic coupling of Ru 3p and O 2p orbitals boosts a positive shift in the Fermi energy level of Ru, optimizing the adsorption capacity of the intermediates and diminishing the migration barriers of the rate‐determining steps. Therefore, the Ru‐VS2@CC catalyst demonstrated ultra‐low overpotentials of 245 mV at 50 mA cm−2, while the zinc–air battery maintained a narrow gap (0.62 V) after 470 h of reversible operation. This work has transformed the corrupt into the miraculous and paved a new way for the development of efficient electrocatalysts.

Robust Ru‐VO2 Bifunctional Catalysts for All‐pH Overall Water Splitting

“…As shown in Figure a, the relatively weak Raman peaks located at 429 and 523 cm −1 are ascribed to the Ru─O bond and did not change significantly with the voltage gradually increased (OCP‐1.5 V vs RHE), indicating that Ru NPs were not oxidized to Ru δ + ( δ > 0) in the OER process, which may be due to the synergistic effect between Ru NPs and VO 2 . [ 31 ] The peaks at 977 and 1054 cm −1 are assigned to the symmetric stretching vibration mode of SO 4 2− . [ 15b ] Meanwhile, when the voltage is greater than 1.3 V (vs RHE), the peak around 1028 cm −1 is caused by the vibration of superoxide (*O 2 − ) adsorbed on the catalyst surface.…”

A self-phosphorized carbon-based monolithic chainmail electrode for high-current-density and durable alkaline water splitting

“…The observed strong Co–P bonding and the absence of Co–N x further suggest that N atoms are mainly doped in the carbon skeleton in addition to the P doping. The N and P doping on the carbon membrane matrix is conducive to enable a high electron transfer efficiency via charge transfer interactions between the N and P lone pairs and the π-system of the carbon lattice, 32,46 while those on the graphitic carbon shell are believed to modify the chemical and electronic microenvironment of active sites on the Co 2 P core, 26–31,39 thus optimizing the adsorption energy of the reactant and intermediates to facilitate electrocatalytic reactions.…”

“…Recently, carbon-based chainmail electrocatalysts prepared by embedding metal active components within a porous carbon matrix have been established as a new class of advanced carbon-based electrocatalysts for water splitting with superior performance. 26–31 The strong coupling of encapsulated metal particles and the carbon shell enables a favorable “inside-to-out” electron penetration effect to enhance the electrocatalytic activity. Meanwhile, the carbon shell effectively prevents core metal particles from aggregation and structural deterioration at high current density.…”

RuIn Solid-Solution Alloy Nanoparticles with Enhanced Hydrogen Evolution Reaction Activity

“…Platinum group metal (PGM) nanoparticles (NPs) have been widely studied due to their excellent catalytic properties. − In particular, as a less expensive PGM, ruthenium (Ru) has attracted interest as a catalyst for various reactions, such as the nitrate reduction reaction, , ammonia borane dehydrogenation reaction, , CO oxidation reaction, , oxygen evolution reaction, , and hydrogen evolution reaction (HER) . To improve the catalytic performance, various strategies have been adopted, such as morphology modification, , phase regulation, , surface modification, and components adjustment. − Among them, alloying, the mixing of constituents at the atomic scale, is an important technique for controlling the properties of NPs. − By adjustment of the constituents and/or the composition, alloying enables the electronic structure to be tuned so as to improve the catalytic activity.…”

“…P latinum group metal (PGM) nanoparticles (NPs) have been widely studied due to their excellent catalytic properties. 1−5 In particular, as a less expensive PGM, ruthenium (Ru) has attracted interest as a catalyst for various reactions, such as the nitrate reduction reaction, 6,7 ammonia borane dehydrogenation reaction, 8,9 CO oxidation reaction, 10,11 oxygen evolution reaction, 12,13 and hydrogen evolution reaction (HER). 14 To improve the catalytic performance, various strategies have been adopted, such as morphology modification, 15,16 phase regulation, 17,18 surface modification, 19 and components adjustment.…”