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调节铑与二氧化铈之间的电荷转移以促进碱性电解质中的氢氧化反应。

Modifying charge transfer between rhodium and ceria for boosted hydrogen oxidation reaction in alkaline electrolyte.

作者信息

Ke Xiaofeng, Zhou Feng, Chen Yihuang, Zhao Mei, Yang Yun, Jin Huile, Dong Youqing, Zou Chao, Chen Xi'an, Zhang Lijie, Wang Shun

机构信息

Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325000, PR China.

Institute of New Materials & Industry Technology, College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325000, PR China.

出版信息

J Colloid Interface Sci. 2023 Nov 15;650(Pt B):1842-1850. doi: 10.1016/j.jcis.2023.07.060. Epub 2023 Jul 11.

Abstract

Sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline solution has restricted the rapid development of hydrogen economy. Constructing catalyst with metal-oxide heterostructures can enhance HOR performance; however, little studies concentrate on charge transfer between them, and the corresponding effects on reactions remain unclear. Herein, we report charge-transfer-adjustable CeO/Rh interfaces uniformly dispersed on multiwalled carbon nanotube (CNT), which exhibit excellent alkaline HOR performance. Results confirm that the charge transfer from Rh to CeO could be conveniently tuned via thermal treatment. Consequently, the adsorption free energies of H* in Rh sites and OH* adsorption strength in CeO could be adjusted, as corroborated by density functional theory study. The optimized CeO/Rh interfaces exhibit an exchange current density and a mass-specific kinetic current of 0.53 mA cm and 830 A g at an overpotential of 50 mV, respectively, which surpasses most of the advanced noble-metal-based electrocatalysts. This work provides a new insight of harnessing charge transfer of heterostructure to enhance catalytic activities.

摘要

碱性溶液中氢氧化反应(HOR)的缓慢动力学限制了氢能经济的快速发展。构建具有金属氧化物异质结构的催化剂可以提高HOR性能;然而,很少有研究关注它们之间的电荷转移,以及对反应的相应影响仍不清楚。在此,我们报道了均匀分散在多壁碳纳米管(CNT)上的电荷转移可调的CeO/Rh界面,其表现出优异的碱性HOR性能。结果证实,通过热处理可以方便地调节从Rh到CeO的电荷转移。因此,Rh位点上H的吸附自由能和CeO中OH的吸附强度可以得到调节,密度泛函理论研究证实了这一点。优化后的CeO/Rh界面在50 mV过电位下的交换电流密度和质量比动力学电流分别为0.53 mA cm和830 A g,超过了大多数先进的贵金属基电催化剂。这项工作为利用异质结构的电荷转移来增强催化活性提供了新的见解。

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