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用于高性能酸性析氧反应的稳健界面Ru中心

Robust Interface Ru Centers for High-Performance Acidic Oxygen Evolution.

作者信息

Cui Xiaoju, Ren Pengju, Ma Chao, Zhao Jia, Chen Ruixue, Chen Shiming, Rajan N Pethan, Li Haobo, Yu Liang, Tian Zhongqun, Deng Dehui

机构信息

Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.

State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.

出版信息

Adv Mater. 2020 Jun;32(25):e1908126. doi: 10.1002/adma.201908126. Epub 2020 May 17.

Abstract

RuO is considered as the state-of-the-art electrocatalyst for the oxygen evolution reaction (OER) in acidic media. However, its practical application is largely hindered by both the high reaction overpotential and severe electrochemical corrosion of the active centers. To overcome these limitations, innovative design strategies are necessary, which remains a great challenge. Herein, robust interface Ru centers between RuO and graphene, via a controllable oxidation of graphene encapsulating Ru nanoparticles, are presented to efficiently enhance both the activity and stability of the acidic OER. Through precisely controlling the reaction interface, a much lower OER overpotential of only 227 mV at 10 mA cm in acidic electrolyte, compared with that of 290 mV for commercial RuO , but a significantly higher durability than the commercial RuO , are achieved. Density functional theory (DFT) calculations reveal that the interface Ru centers between the RuO and the graphene can break the classic scaling relationships between the free energies of HOO* and HO* to reduce the limiting potential, rendering an enhancement in the intrinsic OER activity and the resistance to over-oxidation and corrosion for RuO .

摘要

RuO被认为是酸性介质中析氧反应(OER)的最先进电催化剂。然而,其实际应用在很大程度上受到高反应过电位和活性中心严重电化学腐蚀的阻碍。为了克服这些限制,创新的设计策略是必要的,而这仍然是一个巨大的挑战。在此,通过对包裹Ru纳米颗粒的石墨烯进行可控氧化,在RuO和石墨烯之间构建了坚固的界面Ru中心,以有效提高酸性OER的活性和稳定性。通过精确控制反应界面,在酸性电解质中,在10 mA cm时的OER过电位仅为227 mV,相比商业RuO的290 mV要低得多,同时耐久性比商业RuO显著更高。密度泛函理论(DFT)计算表明,RuO和石墨烯之间的界面Ru中心可以打破HOO和HO自由能之间的经典比例关系,从而降低极限电位,提高RuO的本征OER活性以及抗过氧化和抗腐蚀能力。

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