尖晶石钴氧化物的晶面调控与析氧活性研究

doi:10.13208/j.electrochem.210848

摘要/Abstract

摘要：

由可再生能源驱动的水分解是一种有前途的生产清洁能源的技术,而发生在阳极的析氧反应是水分解反应的速率决定步骤。本文通过调整催化剂的晶面,暴露更多的有效活性位点调控尖晶石钴氧化物析氧反应活性。在三个合成晶面(100)、(111)和(110)中,(100)晶面本征活性最高。结合原位红外和DFT计算分析可知,OER反应在氧化钴晶体的(100)平面上反应能垒最低。XPS分析进一步表明,纳米立方体表面具有最高的Co³⁺/Co²⁺比值,该结果表明Co³⁺是更活跃的析氧反应活性位点。

关键词: 电解水, 析氧反应, 尖晶石钴氧化物, 晶面依赖性, 纳米立方体

Abstract:

Water splitting is a promising technology to produce clean hydrogen if powered by renewable energies, where oxygen evolution is the rate determining step at an anode. Here we adjust the different crystal planes of the cobalt oxides catalyst to expose more effective active sites through a hydrothermal process, so as to improve the reaction activity for oxygen evolution. The samples were well characterized by TEM, SEM and XRD. Among the three synthetic crystal planes (100), (111) and (110) of spinel cobalt oxides, the (100) crystal plane has the highest intrinsic activity. Combining in-situ infrared and DFT calculations, we observed that the oxygen evolution reaction reached the lowest energy barrier on the (100) plane of the cobalt oxide crystal. Further XPS analysis showed that the highest Co³⁺/Co²⁺ ratio was observed on the surface of the nanocube samples, indicating that Co³⁺ is a more active site for oxygen evolution catalytic activity.

Key words: water splitting, oxygen evolution, spinel cobalt oxide, facet dependent, nanocubes

张丽桦, 揣宏媛, 刘海, 范群, 况思宇, 张生, 马新宾. 尖晶石钴氧化物的晶面调控与析氧活性研究[J]. 电化学（中英文）, 2022, 28(2): 2108481.

Li-Hua Zhang, Hong-Yuan Chuai, Hai Liu, Qun Fan, Si-Yu Kuang, Sheng Zhang, Xin-Bin Ma. Facet Dependent Oxygen Evolution Activity of Spinel Cobalt Oxides[J]. Journal of Electrochemistry, 2022, 28(2): 2108481.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.210848

https://electrochem.xmu.edu.cn/CN/Y2022/V28/I2/2108481

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Sample	Co³⁺ 779.8 eV	Co²⁺ 781.7 eV	Area ratio of Co³⁺/Co²⁺
Nanoparticles	472324	261451	1.81
Nanocubes	202091	88356	2.29
Plate-like sheets	464940	224563	2.07

Sample	Nanoparticles	Nanocubes	Plate-like sheets
Electrode potential	1.80 V	1.75 V	1.69 V
Overpotential	570 mV	520 mV	460 mV

Sample	C_dl(mF·cm^-2)	ECSA (cm²)	R_f
Nanoparticles	1.21	2.42	20.17
Nanocubes	0.52	1.04	8.67
Plate-like sheets	2.51	5.02	41.83