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 Co ³⁺/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.

导出引用管理器 EndNote|Ris|BibTeX

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

图/表 9

Figure 1.

Figure 2.

Figure 3.

Table 1

Figure 4.

Table 2

Table 3

Figure 5.

Figure 6.

参考文献 30

[1]	Jamesh M I, Sun X M. Recent progress on earth abundant electrocatalysts for oxygen evolution reaction (OER) in alkaline medium to achieve efficient water splitting - A review[J]. J. Power Sources, 2018, 400:31-68. doi: 10.1016/j.jpowsour.2018.07.125 URL
[2]	Jiang H, Gu J X, Zheng X S, Liu M, Qiu X Q, Wang L B, Li W Z, Chen Z F, Ji X B, Li J. Defect-rich and ultrathin N doped carbon nanosheets as advanced trifunctional metal-free electrocatalysts for the ORR, OER and HER[J]. Energy Environ. Sci., 2019, 12(1):322-333. doi: 10.1039/C8EE03276A URL
[3]	Jahan M, Liu Z L, Loh K P. A Graphene oxide and coppercentered metal organic framework composite as a tri-functional catalyst for HER, OER, and ORR[J]. Adv. Funct. Mater., 2013, 23(43):5363-5372. doi: 10.1002/adfm.v23.43 URL
[4]	Zhang L H, Fan Q, Li K, Zhang S, Ma X B. First-row transition metal oxide oxygen evolution electrocatalysts: regulation strategies and mechanistic understandings[J]. Sustain. Energy Fuels, 2020, 4(11):5417-5432. doi: 10.1039/D0SE01087A URL
[5]	Jamesh M I, Harb M. Tuning the electronic structure of the earth-abundant electrocatalysts for oxygen evolution reaction (OER) to achieve efficient alkaline water splitting - A review[J]. J. Energy Chem., 2021, 56:299-342. doi: 10.1016/j.jechem.2020.08.001 URL
[6]	Zhang S, Fan Q, Xia R, Meyer T J. CO₂ reduction: from homogeneous to heterogeneous electrocatalysis[J]. Accounts Chem. Res., 2020, 53(1):255-264. doi: 10.1021/acs.accounts.9b00496 URL
[7]	Liu H, Su Y Q, Kuang S Y, Hensen E J M, Zhang S, Ma X B. Highly efficient CO₂ electrolysis within a wide operation window using octahedral tin oxide single crystals[J]. J. Mater. Chem. A, 2021, 9(12):7848-7856. doi: 10.1039/D1TA00285F URL
[8]	Karmakar A, Karthick K, Sankar S S, Kumaravel S, Madhu R, Kundu S. A vast exploration of improvising synthetic strategies for enhancing the OER kinetics of LDH structures: a review[J]. J. Mater. Chem. A, 2021, 9(3):1314-1352. doi: 10.1039/D0TA09788H URL
[9]	Duan Y, Sun S N, Sun Y M, Xi S B, Chi X, Zhang Q H, Ren X, Wang J X, Ong S J H, Du Y H, Gu L, Grimaud A, Xu Z C J. Mastering surface reconstruction of metastable spinel oxides for better water oxidation[J]. Adv. Mater., 2019, 31(12):1807898. doi: 10.1002/adma.v31.12 URL
[10]	Sun Y M, Liao H B, Wang J R, Chen B, Sun S N, Ong S J H, Xi S B, Diao C Z, Du Y H, Wang J O, Breese M B H, Li S Z, Zhang H, Xu Z C J. Author Correction: Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides[J]. Nat. Catal., 2020, 3(11):959. doi: 10.1038/s41929-020-00548-z URL
[11]	Reier T, Oezaslan M, Strasser P. Electrocatalytic oxygen evolution reaction (OER) on Ru, Ir, and Pt Catalysts: A comparative study of nanoparticles and bulk materials[J]. ACS Catal., 2012, 2(8):1765-1772. doi: 10.1021/cs3003098 URL
[12]	Acedera R A E, Gupta G, Mamlouk M, Balela M D L. Solution combustion synjournal of porous Co₃O₄ nanoparticles as oxygen evolution reaction (OER) electrocatalysts in alkaline medium[J]. J. Alloy. Compd., 2020, 836:154919. doi: 10.1016/j.jallcom.2020.154919 URL
[13]	Wang C X, Shi P H, Cai X D, Xu Q J, Zhou X J, Zhou X L, Yang D, Fan J C, Min Y L, Ge H H, Yao W F. Synergistic effect of Co₃O₄ nanoparticles and graphene as catalysts for peroxymonosulfate-based orange II degradation with high oxidant utilization efficiency[J]. J. Phys. Chem. C, 2016, 120(1):336-344. doi: 10.1021/acs.jpcc.5b10032 URL
[14]	Xiao Z, Huang Y C, Dong C L, Xie C, Liu Z J, Du S Q, Chen W, Yan D F, Tao L, Shu Z W, Zhang G H, Duan H G, Wang Y Y, Zou Y Q, Chen R, Wang S Y. Operando identification of the dynamic behavior of oxygen vacancyrich Co₃O₄ for oxygen evolution reaction[J]. J. Am. Chem. Soc., 2020, 142(28):12087-12095. doi: 10.1021/jacs.0c00257 URL
[15]	Peng Y, Hajiyani H, Pentcheva R. Influence of Fe and Ni Doping on the OER Performance at the Co₃O₄ (001) Surface: Insights from DFT+ U Calculations[J]. ACS Catal., 2021, 11(9):5601-5613. doi: 10.1021/acscatal.1c00214 URL
[16]	Xu L, Jiang Q Q, Xiao Z H, Li X Y, Huo J, Wang S Y, Dai L M. Plasma-engraved Co₃O₄ nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction[J]. Angew. Chem. Int. Ed., 2016, 128(17):5363-5367. doi: 10.1002/ange.201600687 URL
[17]	Zhang Y X, Ding F, Deng C, Zhen S Y, Li X Y, Xue Y F, Yan Y M, Sun K N. Crystal plane-dependent electrocatalytic activity of Co₃O₄ toward oxygen evolution reaction[J]. Catal. Commun., 2015, 67:78-82. doi: 10.1016/j.catcom.2015.04.012 URL
[18]	Liu L, Jiang Z Q, Fang L, Xu H T, Zhang H J, Gu X, Wang Y. Probing the crystal plane effect of Co₃O₄ for enhanced electrocatalytic performance toward efficient overall water splitting[J]. ACS Appl. Mater. Inter., 2017, 9(33):27736-27744. doi: 10.1021/acsami.7b07793 URL
[19]	Liu Q F, Chen Z P, Yan Z, Wang Y, Wang E D, Wang S, Wang S D, Sun G Q. Crystal-plane-dependent activity of spinel Co₃O₄ towards water splitting and the oxygen reduction reaction[J]. ChemElectroChem, 2018, 5(7):1080-1086. doi: 10.1002/celc.201701302 URL
[20]	Zhu K Y, Zhu X F, Yang W S. Application of in situ techniques for the characterization of NiFe-based oxygen evolution reaction (OER) electrocatalysts[J]. Angew. Chem. Int. Ed., 2019, 58(5):1252-1265. doi: 10.1002/anie.201802923 URL
[21]	Xiao X L, Liu X F, Zhao H, Chen D F, Liu F Z, Xiang J H, Hu Z B, Li Y D. Facile shape control of Co₃O₄ and the effect of the crystal plane on electrochemical performance[J]. Adv. Mater., 2012, 24(42):5762-5766. doi: 10.1002/adma.v24.42 URL
[22]	Zhang J J, Wang H H, Zhao T J, Zhang K X, Wei X, Li X H, Hirano S I, Chen J S. Oxygen vacancy engineering of Co₃O₄ nanocrystals through coupling with metal support for water oxidation[J]. ChemSusChem, 2017, 10(14):2875-2879. doi: 10.1002/cssc.v10.14 URL
[23]	He D, Song X Y, Li W Q, Tang C Y, Liu J C, Ke Z J, Jiang C Z, Xiao X H. Active electron density modulation of Co₃O₄-based catalysts enhances their oxygen evolution performance[J]. Angew. Chem. In.t Ed., 2020, 132(17):6996-7002. doi: 10.1002/ange.v132.17 URL
[24]	Kumar K, Canaff C, Rousseau J, Arrii-Clacens S, Napporn T W, Habrioux A, Kokoh K B. Effect of the oxide-carbon heterointerface on the activity of Co₃O₄/NRGO nano-composites toward ORR and OER[J]. J. Phys. Chem. C, 2016, 120(15):7949-7958. doi: 10.1021/acs.jpcc.6b00313 URL
[25]	Tang D, Ma Y, Liu Y, Wang K K, Liu Z, Li W Z, Li J. Amorphous three-dimensional porous Co₃O₄ nanowire network toward superior OER catalysis by lithium-induced[J]. J. Alloy Compd., 2021, 893:162287. doi: 10.1016/j.jallcom.2021.162287 URL
[26]	Zhou X M, Xia Z M, Tian Z M, Ma Y Y, Qu Y Q. Ultrathin porous Co₃O₄ nanoplates as highly efficient oxygen evolution catalysts[J]. J. Mater. Chem. A, 2015, 3(15):8107-8114. doi: 10.1039/C4TA07214F URL
[27]	McCrory C C L, Jung S, Peters J C, Jaramillo T F. Bench-marking heterogeneous electrocatalysts for the oxygen evolution reaction[J]. J. Am. Chem. Soc., 2013, 135(45):16977-16987. doi: 10.1021/ja407115p URL
[28]	Ma T Y, Dai S, Jaroniec M, Qiao S Z. Metal-organic framework derived hybrid Co₃O₄-carbon porous nanowire arrays as reversible oxygen evolution electrodes[J]. J. Am. Chem. Soc., 2014, 136(39):13925-13931. doi: 10.1021/ja5082553 URL
[29]	Song K, Cho E, Kang Y M. Morphology and active-site engineering for stable round-trip efficiency Li-O₂ batteries: A search for the most active catalytic site in Co₃O₄[J]. ACS Catal., 2015, 5(9):5116-5122. doi: 10.1021/acscatal.5b01196 URL
[30]	Yao Y C, Hu S L, Chen W X, Huang Z Q, Wei W C, Yao T, Liu R R, Zang K T, Wang X Q, Wu G, Yuan W J, Yuan T W, Zhu B Q, Liu W, Li Z J, He D S, Xue Z G, Wang Y, Zheng X S, Dong J C, Chang C R, Chen Y X, Hong X, Luo J, Wei S Q, Li W X, Strasser P, Wu Y E, Li Y D. Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis[J]. Nat. Catal., 2019, 2(4):304-313. doi: 10.1038/s41929-019-0246-2 URL

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