构建氧空位调控的钼酸钴纳米片用于高效催化析氧反应

doi:10.1016/S1872-2067(22)64137-8

催化学报 ›› 2022, Vol. 43 ›› Issue (9): 2434-2442.DOI: 10.1016/S1872-2067(22)64137-8

构建氧空位调控的钼酸钴纳米片用于高效催化析氧反应

蒋婷婷^a, 谢伟伟^a, 耿仕鹏^b, 李如春^b, 宋树芹^b^,^*(), 王毅^a^,^#()

^a中山大学化学工程与技术学院, 广东省低碳化学与过程节能重点实验室, 聚合物复合材料及功能材料教育部重点实验室, 广东广州510275
^b中山大学材料科学与工程学院, 广东广州510275

收稿日期:2022-05-17 接受日期:2022-05-30 出版日期:2022-09-18 发布日期:2022-07-20
通讯作者: 宋树芹,王毅
基金资助:
国家自然科学基金(21975292);国家自然科学基金(21978331);国家自然科学基金(21905311);国家自然科学基金(92061124);广州科技项目(201707010079);广东省基础与应用基础研究基金(2020A1515010343);广东省基础与应用基础研究基金(2021A1515010167)

Constructing oxygen vacancy-regulated cobalt molybdate nanoflakes for efficient oxygen evolution reaction catalysis

Tingting Jiang^a, Weiwei Xie^a, Shipeng Geng^b, Ruchun Li^b, Shuqin Song^b^,^*(), Yi Wang^a^,^#()

^aThe Key Lab of Low-Carbon Chemistry & Energy Conservation of Guangdong Province, PCFM Lab, School of Chemical Engineering and Technology, Sun Yat-sen University, Guangzhou 510275, Guangdong, China
^bSchool of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, China

Received:2022-05-17 Accepted:2022-05-30 Online:2022-09-18 Published:2022-07-20
Contact: Shuqin Song, Yi Wang
Supported by:
National Natural Science Foundation of China(21975292);National Natural Science Foundation of China(21978331);National Natural Science Foundation of China(21905311);National Natural Science Foundation of China(92061124);Guangzhou Science and Technology Project(201707010079);Guangdong Basic and Applied Basic Research Foundation(2020A1515010343);Guangdong Basic and Applied Basic Research Foundation(2021A1515010167)

摘要/Abstract

摘要：

析氧反应(OER)是金属-空气电池、电解水等绿色可再生能源转换与储存系统的核心反应, 其复杂的4电子-质子耦合反应导致其动力学过程缓慢从而使得系统过电位较高, 目前主要依赖于RuO₂或IrO₂贵金属催化剂提升其反应速率, 但贵金属高成本和低稳定性严重限制其大规模应用. 因此, 开发高活性、高稳定性的廉价非贵金属催化剂具有重要的实际意义, 已成为现阶段的研究热点. 钼酸钴(CoMoO₄)作为典型的ABO₄型催化材料, 不仅价格低廉、储量丰富, 而且其双金属特性可构筑有效的活性位点提升OER反应动力学. 前期研究发现, 通过阴离子掺杂、氧空位工程、电子结构调控、表面修饰等策略可增强ABO₄型催化剂的OER催化活性. 特别是氧空位工程可调节过渡金属氧化物的电子结构, 提高其导电性能, 增加催化位点活性, 从而提高过渡金属氧化物的催化性能.

本文在石墨毡(GF)上原位生长CoMoO₄纳米片, 并提出一种简单的H₂/Ar还原策略精确调控CoMoO₄的氧化状态, 制备一系列不同氧空位含量的CoMoO₄电催化剂(CoMoO₄-O_v-n@GF), 并采用X射线光电子能谱(XPS)、电子自旋共振(EPR)、电化学测试等表征手段及密度泛函理论计算(DFT)研究了氧空位含量对CoMoO₄电催化OER性能的影响. 扫描电镜结果表明, 花瓣状CoMoO₄纳米薄片整齐地生长在GF上, 经还原热处理后纳米薄片结构未被破坏. 透射电镜结果表明, 经还原后CoMoO₄出现了大量缺陷, 且显示出多晶的特性. XPS及EPR测试结果表明, 通过改变热处理时间(0.5‒3 h)可以实现氧空位含量的精准调控, 热处理时间越长, CoMoO₄氧空位含量越多. 电化学测试结果表明, 氧空位含量对CoMoO₄电催化OER性能起到了重要的调节作用, 其中具有最优氧空位含量的CoMoO₄-O_v-2@GF表现出最佳的OER活性, 在10 mA cm^‒2下的过电位仅为296 mV, Tafel斜率为62.4 mV dec^-1, 其性能接近贵金属催化剂RuO₂@GF. DFT理论计算结果表明, 加入氧空位可以将CoMoO₄的能隙从1.98 eV缩小至1.14 eV, 从而提升CoMoO₄纳米片的电子传导性能; 同时氧空位的增加进一步降低了OER决速步的反应中间体的自由能, 这也加速了OER动力学过程. 实验及理论计算结果都表明构建氧空位可以有效地调节CoMoO₄纳米片的催化性能. 综上, 本工作不仅开发了一种高效的氧空位构筑方法, 而且深入研究了氧空位对双金属氧化物电催化OER的影响,对通过构筑氧空位提升OER电催化剂活性相关工作有借鉴意义.

关键词: 析氧反应, 氧空位, 钼酸钴, 纳米片, 密度泛函理论

Abstract:

Oxygen evolution reaction (OER) is the dominant step for plenty of energy conversion and storage technologies. However, the OER suffers from sluggish kinetics and high overpotential due to its complex 4-electron/proton transfer mechanism. Thus, developing efficient electrocatalysts is particularly urgent to accelerate OER catalysis but still remains a great challenge. Herein, we have synthesized the novel cobalt molybdate nanoflakes (CoMoO₄-O_v-n@GF) with adjustable oxygen vacancies contents by in situ constructing CoMoO₄ nanoflakes on graphite felt (GF) and annealing treatment under the reduction atmosphere. The best-performing CoMoO₄-O_v-2@GF with optimal oxygen vacancies content shows splendid electrocatalytic performance with the low overpotential (296 mV at 10 mA cm^‒2) and also small Tafel slope (62.4 mV dec^‒1) in alkaline solution, which are comparable to those of the RuO₂@GF. The experimental and the density functional theory calculations results reveal that the construction of optimal oxygen vacancies in CoMoO₄ can expose more active sites, narrow the band-gap to increase the electrical conductivity, and modulate the free energy of the OER-related intermediates to accelerate OER kinetics, thus improving its intrinsic activity.

Key words: Oxygen evolution reaction, Oxygen vacancy, Cobalt molybdate, Nanoflake, Density functional theory

蒋婷婷, 谢伟伟, 耿仕鹏, 李如春, 宋树芹, 王毅. 构建氧空位调控的钼酸钴纳米片用于高效催化析氧反应[J]. 催化学报, 2022, 43(9): 2434-2442.

Tingting Jiang, Weiwei Xie, Shipeng Geng, Ruchun Li, Shuqin Song, Yi Wang. Constructing oxygen vacancy-regulated cobalt molybdate nanoflakes for efficient oxygen evolution reaction catalysis[J]. Chinese Journal of Catalysis, 2022, 43(9): 2434-2442.

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https://www.cjcatal.com/CN/Y2022/V43/I9/2434

图/表 9

Fig. 1. Preparation process schematic of CoMoO4-Ov-n@GF.

Fig. 2. XRD patterns of the as-prepared samples.

Fig. 3. SEM images (a-c) and EDS element mappings (d-g) of CoMoO4-Ov-2@GF.

Fig. 4. (a-c) TEM images of CoMoO4-Ov-2@GF. (d) High-resolution TEM images derived from the locally enlarged region of (c). (e) SAED patterns of CoMoO4-Ov-2@GF.

Fig. 5. Co 2p (a), Mo 3d (b) and O 1s (c) XPS spectra of CoMoO4-related materials. (d) Oxygen vacancies content (denoted as circle) and Mo5+ content (denoted as square) as functions of annealing treatment time.

Fig. 6. EPR spectra of CoMoO4-related materials.

Fig. 7. LSV curves (a), overpotential (b) at 10 and 100 mA cm-2 and Tafel plots (c) of GF, RuO2@GF, CoMoO4-Ov-2@GF and CoMoO4@GF. (d) The overpotential at 10 mA cm-2 (denoted as square) and Tafel slope (denoted as circle) as functions of oxygen vacancies content.

Fig. 8. Nyquist plots (a) and Cdl values (b) of GF, CoMoO4-Ov-2@GF and CoMoO4@GF. (c) Comparison of specific current density of CoMoO4-Ov-2@GF and CoMoO4@GF at 1.58 V. (d) LSV curves before and after i-t measurement at 1.53 V and i-t curves at 1.53, 15.8 and 1.61 V for CoMoO4-Ov-2@GF.

Fig. 9. (a) Co 3d, Mo 4d, and total PDOS of CoMoO4 and CoMoO4-Ov. (b) Free-energy diagrams and the intermediates models for CoMoO4 and CoMoO4-Ov.

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构建氧空位调控的钼酸钴纳米片用于高效催化析氧反应

Constructing oxygen vacancy-regulated cobalt molybdate nanoflakes for efficient oxygen evolution reaction catalysis

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