Ru/Rh Cation Doping and Oxygen-Vacancy Engineering of FeOOH Nanoarrays@Ti3 C2 Tx MXene Heterojunction for Highly Efficient and Stable Electrocatalytic Oxygen Evolution.
Ru/Rh Cation Doping and Oxygen-Vacancy Engineering of FeOOH Nanoarrays@Ti3 C2 Tx MXene Heterojunction for Highly Efficient and Stable Electrocatalytic Oxygen Evolution.
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DOI：
10.1002/smll.202200173
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发表时间：
2022-05
期刊：
影响因子：
13.3
通讯作者：
Bing Zhang;Jiongwei Shan;Xinying Wang;Yanjie Hu;Yunyong Li
中科院分区：
文献类型：
--
作者：
Bing Zhang;Jiongwei Shan;Xinying Wang;Yanjie Hu;Yunyong Li
氢氧化物有望作为高效的非贵金属析氧反应电催化剂，但其导电性差和结构不稳定性极大地阻碍了其发展。在此，作者开发了一种阳离子掺杂和氧空位工程策略，以制备具有丰富氧空位的Ru/Rh掺杂的FeOOH纳米阵列，其原位生长在Ti 3 C2 Tx MXene（Ru/Rh-FeOOH@ Ti 3 C2 Tx）上，作为高效的OER电催化剂。优化后的Rh/Ru-FeOOH@ Ti 3 C2 Tx电催化剂在Ru/Rh阳离子调控、氧空位工程以及MXene与FeOOH之间的异质结协同作用下，表现出优异的OER活性和100 h的稳定性。特别地，3% Rh-FeOOH@ Ti 3 C2 Tx电催化剂在10 mA cm-2和306 mV下仅需要223 mV的过电位以达到100 mA cm-2，这上级商业IrO 2催化剂和大多数报道的基于羟基氧化物的电催化剂。此外，通过系统的理论计算、动力学、热力学和微观结构分析，证实Ru/Rh阳离子掺杂和氧空位的综合作用明显提高了FeOOH的本征电导率和晶格缺陷，暴露出更多的活性中心，从而降低了吸附/脱附能垒和活化能，提高了电催化剂的比活性和催化动力学。而与MXene的原位杂交增强了结构稳定性。这项工作清楚地证实，阳离子掺杂和氧空位工程提供了一个联合战略的电子结构调制和设计的高效廉价的OER电催化剂。
Oxyhydroxides hold promise as highly-efficient non-noble electrocatalysts for the oxygen evolution reaction (OER), but their poor conductivity and structural instability greatly impede their progress. Herein, the authors develop a cation-doping and oxygenvacancy engineering strategy to fabricate Ru/Rh-doped FeOOH nanoarrays with abundant oxygen-vacancies in situ grown on Ti3 C2 Tx MXene (Ru/Rh-FeOOH@Ti3 C2 Tx ) as highly-efficient OER electrocatalysts. Benefiting from Ru/Rh-cation regulation, oxygenvacancy engineering, and heterojunction synergy between MXene and modulated FeOOH, the optimized Rh/Ru-FeOOH@Ti3 C2 Tx electrocatalysts exhibit excellent OER activities and remarkable stabilities with 100 h. Particularly, 3%Rh-FeOOH@Ti3 C2 Tx electrocatalyst only needs a 223 mV overpotential at 10 mA cm-2 and 306 mV to reach 100 mA cm-2 , which is superior to commercial IrO2 catalyst and most reported oxyhydroxide-based electrocatalysts. Further, systematically theoretical caculation, kinetics, thermodynamics, and microstructural analysis verify that the integration of Ru/Rh-cation doping and oxygen vacancy obviously enhances the intrinsic conductivity and lattice defects of FeOOH and expose more active sites, thereby decreasing the adsorption/desorption energy barrier and activation energy, and improving the specific activity and catalytic kinetics of electrocatalysts, whereas in situ hybridization with MXene strengthens the structural stability. This work clearly confirms that cationdoping and oxygen-vacancy engineering offers a joint strategy for the electronic structure modulation and design of highly-efficient inexpensive OER electrocatalysts.