Highly active ruthenium sites stabilized by modulating electron-feeding for sustainable acidic oxygen-evolution electrocatalysis

作者：Wang, Kexin; Wang, Yali; Yang, Bin; Li, Zhongjian; Qin, Xuetao; Zhang, Qinghua; Lei, Lecheng; Qiu, Ming^*; Wu, Gang^*; Hou, Yang^*

来源：Energy & Environmental Science, 2022, 15(6): 2356-2365.

DOI：10.1039/d1ee03610f

• WATER OXIDATION
• REDUCTION
• CATALYST
• OXIDES
• RUO2
• NI

Designing acid-stable oxygen evolution reaction (OER) electrocatalysts with low noble-metal content to facilitate the sluggish kinetics is crucial for sustaining green hydrogen generation. Herein, we developed a rutile-structured ruthenium-manganese solid solution oxide with oxygen vacancies (Mn0.73Ru0.27O2-delta) by using an electron-feeding modulation strategy to stabilize the catalyst structure and accelerate the OER kinetics. Due to the optimal electronic structure and enhanced electrical conductivity, the Mn0.73Ru0.27O2-delta catalyst displayed a low overpotential of 208 mV to reach 10 mA cm(-2) current density in 0.5 M H2SO4 electrolyte, outperforming the benchmark RuO2 and most previously reported noble-metal based OER catalysts. Experimental characterization verified that the electron transfer occurred from Ru to Mn atoms with the bridging O atom, which was further enhanced with the existence of oxygen vacancies. Therefore, the center Ru active sites in an electron-deficient state is favorable for bonding with active oxygen intermediates. Meanwhile, theoretical calculations revealed that the simultaneous incorporation of Mn components and O vacancies significantly decreased the anti-bonding spin states of Ru's d-orbitals, which modulated the adsorption and desorption energy barriers of elementary reactions on the active Ru sites, thus boosting the overall OER kinetics.

• 单位
  浙江大学; y