Mechanochemically Assisted Synthesis of Ruthenium Clusters Embedded in Mesoporous Carbon for an Efficient Hydrogen Evolution Reaction

Abstract

Ruthenium (Ru) clusters are reported as efficient electrocatalysts for the hydrogen evolution reaction (HER). However, a precise and facile synthetic protocol for preparing Ru clusters is still a challenge. Herein, a facile mechanochemically assisted strategy was proposed to synthesize ruthenium clusters embedded in mesoporous carbon (Ru‐CN/MC). Importantly, for the synthesis of Ru‐CN/MC, melamine was utilized not only as a capping agent to stabilize Ru clusters, but also to provide N sites for the carbon support. The well‐designed Ru‐CN/MC exhibits impressive HER performance in 1 M KOH, which shows an extremely low overpotential of 17 mV at a current density of 10 mA cm−2. More importantly, excellent long‐term electrochemical stability in both alkaline and acid electrolyte was achieved for Ru‐CN/MC. Therefore, the developed synthesis method for Ru clusters and the subsequent insightful investigations on the HER performance shed light on new opportunities for exploring highly efficient and renewable HER electrocatalysts.

Bimetallic ZIF-Derived Co/N-Codoped Porous Carbon Supported Ruthenium Catalysts for Highly Efficient Hydrogen Evolution Reaction

“…As can been seen in the high-resolution XPS spectrum of Zn 2p in Ru-pCo@NC ( Figure S3b ), the Zn signal is hardly detected, and the Zn content is measured to be only 0.12%, confirming the almost evaporation of Zn species during the high-temperature calcination process. In Figure 3 a, the high-resolution spectrum of Ru 3d in Ru-pCo@NC, which partially overlaps with C 1s, can be deconvoluted into Ru 3d 5/2 (281.8 eV) and Ru 3d 3/2 (286.4 eV) of zero-valence Ru (Ru 0 ) [ 29 ], along with C–C/C=C (284.6 eV), C–O/C–N (285.5 eV), and C=O (288.4 eV) [ 30 ]. It is known that the Ru 3p 3/2 and Ru 3p 1/2 peaks of Ru 0 generally appear at 462.5 and 484.9 eV [ 31 ].…”

Advances in the Electrocatalytic Hydrogen Evolution Reaction by Metal Nanoclusters‐based Materials

“…Besides the carbon‐based supports discussed above, other carbon materials with different morphology and structures have also been used for anchoring MNCs, such as the 3D hollow carbon nanospheres, [ 179 ] carbon nanofiber, [ 180 ] 2D graphdiyne, [ 181 ] carbon black, [ 182 ] phenolic resin derived mesoporous carbon, [ 183 ] and tannic acid derived thermostable carbon. [ 184 ] For example, using the mesoporous carbon spheres with a hollow interior as support, Wan et al synthesized Pt cluster electrocatalysts (Pt 5 /HMCS) for hydrogen evolution (Figure 18m,n).…”

“…The relationship between the d-band center values and ΔG H* is shown in Figure 18l, it shows that the electronic coupling with Pt and Co components causes the charge redistribution and lowers the d-band center of Pt far from its Fermi level, which not only leads to a decrease of the ΔG H* (approaching zero), but also improves kinetics and activity of the HER. [176,178] Besides the carbon-based supports discussed above, other carbon materials with different morphology and structures have also been used for anchoring MNCs, such as the 3D hollow carbon nanospheres, [179] carbon nanofiber, [180] 2D graphdiyne, [181] carbon black, [182] phenolic resin derived mesoporous carbon, [183] and tannic acid derived thermostable carbon. [184] For example, using the mesoporous carbon spheres with a hollow interior as support, Wan et al synthesized Pt cluster electrocatalysts (Pt 5 /HMCS) for hydrogen evolution (Figure 18m,n).…”

Solid-State Reaction Synthesis of Nanoscale Materials: Strategies and Applications

“…For example, following the impregnation SSR technique (Figure A), SBA-15 was used by Prieto et al for the synthesis of CuZn NCs and by Fan et al for the synthesis of transition metal oxide–cerium oxide hybrid NCs. Instead of wet impregnation, metal precursors can also be directly included in mesoporous supports via solid-state grinding to induce the confined solid-state growth of metal NCs. − Peng et al used dendritic mesoporous silica to confine the synthesis of Ni NCs, resulting in a “catalyst-in-corona” system. Furthermore, Liu et al reported a sintering-resistant nanocatalyst system of Pt NCs in wide-mouthed compartments and investigated the possibility of NC sintering (Figure B).…”