活化高熵氧化物中部分金属位点显著增强热催化和电催化

doi:10.1016/S1872-2067(23)64409-2

催化学报 ›› 2023, Vol. 48: 235-246.DOI: 10.1016/S1872-2067(23)64409-2

活化高熵氧化物中部分金属位点显著增强热催化和电催化

米金星^a^,¹, 陈孝平^b^,¹, 丁亚军^a, 张良柱^a, 马军^c, 康辉^c, 吴籼虹^a, 刘岳峰^c, 陈建军^b^,^*(), 吴忠帅^a^,^*()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023
^b清华大学环境学院, 环境模拟与污染控制国家重点联合实验室, 北京100084
^c中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 辽宁大连116023

收稿日期:2022-01-03 接受日期:2022-02-08 出版日期:2023-05-18 发布日期:2023-04-20
通讯作者: * 电子信箱: wuzs@dicp.ac.cn (吴忠帅),chenjianjun@tsinghua.edu.cn (陈建军).
作者简介:第一联系人：
¹共同第一作者
基金资助:
中国博士后科学基金(2021M693125);大连市高层次人才创新支持计划(2019RT09);中国科学院洁净能源创新研究院合作基金(DNL202016);中国科学院洁净能源创新研究院合作基金(DNL202019);中国科学院洁净能源创新研究院-榆林学院联合基金(YLU-DNL Fund 2021002);中国科学院洁净能源创新研究院-榆林学院联合基金(YLU-DNL Fund 2021009)

Activation of partial metal sites in high-entropy oxides for enhancing thermal and electrochemical catalysis

Jinxing Mi^a^,¹, Xiaoping Chen^b^,¹, Yajun Ding^a, Liangzhu Zhang^a, Jun Ma^c, Hui Kang^c, Xianhong Wu^a, Yuefeng Liu^c, Jianjun Chen^b^,^*(), Zhong-Shuai Wu^a^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bState Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China
^cDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2022-01-03 Accepted:2022-02-08 Online:2023-05-18 Published:2023-04-20
Contact: * E-mail: chenjianjun@tsinghua.edu.cn (J. Chen),wuzs@dicp.ac.cn (Z.-S. Wu).
About author:First author contact:
¹Contributed equally to this work.
Supported by:
China Postdoctoral Science Foundation(2021M693125);Dalian Innovation Support Plan for High Level Talents(2019RT09);Dalian National Laboratory for Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS(DNL202016);Dalian National Laboratory for Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS(DNL202019);Joint Fund of the Yulin University, and the Dalian National Laboratory for Clean Energy(YLU-DNL Fund 2021002);Joint Fund of the Yulin University, and the Dalian National Laboratory for Clean Energy(YLU-DNL Fund 2021009)

摘要/Abstract

摘要：

高熵氧化物(HEOs)作为一种新兴材料受到科研工作者的广泛关注, 并推动了高熵陶瓷材料(碳化物、硫化物、氟化物等)的发展及其在介电、磁学、储氢以及能源转化等领域中的应用. 其中, HEOs由于丰富的活性位点、可调节的比表面积、稳定的晶体结构、独特的几何相容性和电子结构等特性在催化化学领域展示出广阔的应用前景. 然而, 受制于HEOs的结构特点和难以精确调控的物化性质, 当前的研究主要围绕HEOs制备方法的探索及其在不同催化反应中的尝试. 在以HEOs为基体进行的催化反应中, 也有将贵金属与HEOs复合进行催化剂制备和催化应用的研究报道, 但效果并不理想. 因此, 如何直接对HEOs进行改性并提升其催化性能是低成本高效促进HEOs在催化领域发展的重要途径.
本文首先采用固相燃烧法制备CuCoNiZnAl HEOs, 同时在制备过程中加入硫脲后通过焙烧处理来进行物化性质的原位调节(记为CuCoNiZnAl-T), 随后采用碱液对CuCoNiZnAl-T处理来实现形貌的改变和物化性质的进一步优化(记为CuCoNiZnAl-T-NaOH). X射线粉末衍射结果表明, 硫脲添加和碱处理未改变CuCoNiZnAl-T-NaOH的晶型结构. 电镜结果表明, CuCoNiZnAl和CuCoNiZnAl-T均呈现出较大的颗粒状, 而CuCoNiZnAl-T-NaOH具有大片层形貌结构和明显的晶格扭曲. 此外, H₂程序升温还原、X射线光电子能谱和He程序升温脱附结果表明, CuCoNiZnAl-T-NaOH不仅具有容易还原的铜、镍、钴的氧化物物种, 而且具有高含量和更活泼的晶格氧物种. 因此, CuCoNiZnAl-T-NaOH在活性测试中展示出较好的CO₂加氢和CO氧化催化性能. 其中CuCoNiZnAl-T-NaOH在催化CO氧化反应中, 当转化率达到50%时所需转化温度为176 °C, 比相同条件下CuCoNiZnAl和CuCoNiZnAl-T作为催化剂达到同样催化效果时所需转化温度分别低36和21 °C. 此外, 当CuCoNiZnAl-T-NaOH用作锂氧电池电极材料时也展示出较好的电催化活性(放电/充电容量为12049/9901 mAh/g)和循环稳定性(2500 h). 随后, 以CO₂加氢反应为研究对象, 进一步采用近常压X射线光电子能谱进行反应机理分析, 结果表明, 相对于CuCoNiZnAl而言, CuCoNiZnAl-T在CO₂加氢反应过程中表面镍和钴的氧化物物种与活化的晶格氧之间更容易进行电子转移, 这种增强的电子传输能力和更强的CO₂吸附能力有利于CO₂加氢反应的进行. 推断这种电子传输能力的提升同样有利于CO氧化和锂氧电池性能的提升. 综上, 本文为HEOs催化剂的简洁制备和物化性质改善提供了技术借鉴, 有望进一步推进HEOs的改性制备和在其他领域的功能化应用发展.

关键词: 高熵氧化物, 固相燃烧法, 金属位点活化, 催化氧化还原, 锂氧电池

Abstract:

High-entropy oxides (HEOs) have been tentatively and prospectively applied for chemical catalysis and energy storage. However, further enhancing their performance is difficult owing to the difficulty in precisely regulating the physical-chemical properties. In this work, a general in-situ modulation strategy of solid-phase combustion involving thiourea addition and alkali liquor treatment is developed to activate metal sites and lattice oxygen species of CuCoNiZnAl HEOs. Consequently, compared with pristine HEOs, the activated HEOs not only display higher CO₂ hydrogenation and CO oxidation activities but also significantly enhanced electrocatalytic performance (discharge/charge capacities of 12049/9901 mAh/g) with excellent cycle stability (2500 h) for Li-O₂ batteries. The superior performance of the activated HEOs is attributed to its facile electron transferability. This simple and effective strategy could be easily applied on a large scale, guiding the development of highly active heterogeneous HEO catalysts for various functional applications.

Key words: High entropy oxides, Solid phase combustion, Metal sites activation, Catalytic redox, Li-O₂ battery

米金星, 陈孝平, 丁亚军, 张良柱, 马军, 康辉, 吴籼虹, 刘岳峰, 陈建军, 吴忠帅. 活化高熵氧化物中部分金属位点显著增强热催化和电催化[J]. 催化学报, 2023, 48: 235-246.

Jinxing Mi, Xiaoping Chen, Yajun Ding, Liangzhu Zhang, Jun Ma, Hui Kang, Xianhong Wu, Yuefeng Liu, Jianjun Chen, Zhong-Shuai Wu. Activation of partial metal sites in high-entropy oxides for enhancing thermal and electrochemical catalysis[J]. Chinese Journal of Catalysis, 2023, 48: 235-246.

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图/表 6

Fig. 1. XRD patterns (a), N2 adsorption-desorption isotherms (inset: pore size distribution profiles) (b), H2-TPR profiles (c), and Raman spectra (d) of CuCoNiZnAl, CuCoNiZnAl-T, and CuCoNiZnAl-T-NaOH.

Fig. 2. SEM images of CuCoNiZnAl (a), CuCoNiZnAl-T (b), and CuCoNiZnAl-T-NaOH (c). HRTEM images of CuCoNiZnAl (d), CuCoNiZnAl-T (e), and CuCoNiZnAl-T-NaOH (f). STEM image (g) and Cu (h), Co (i), Ni (j), Zn (k), and Al (l) elemental distributions in CuCoNiZnAl-T-NaOH examined at nanometer scale using STEM-EDS.

Fig. 3. O 1s XPS spectra (a) and He-TPD profiles (b) of CuCoNiZnAl, CuCoNiZnAl-T, and CuCoNiZnAl-T-NaOH. (c) Schematic diagram illustrating the physical-chemical property evolution from CuCoNiZnAl to CuCoNiZnAl-T and then to CuCoNiZnAl-T-NaOH.

Fig. 4. (a) Rates for CO2 hydrogenation. (b) CO conversion for CO oxidation. (c) Initial discharge-charge profiles at a current density of 200 mA/g for an Li-O2 battery using CuCoNiZnAl, CuCoNiZnAl-T, and CuCoNiZnAl-T-NaOH as cathodes. (d) Typical discharge-charge profiles of the CuCoNiZnAl-T-NaOH cathode under a voltage range of 2.0-4.5 V at 200 mA/g. (e) Cycling performance of CuCoNiZnAl-T-NaOH cathode under a capacity limit of 500 mA h/g at 200 mA/g.

Fig. 5. In-situ Co 2p (a), Ni 2p (b), and O 1s (c) XPS spectra of CuCoNiZnAl, and Co 2p (d), Ni 2p (e), and O 1s (f) XPS spectra of CuCoNiZnAl-T in contact with 0.1 mbar H2 at 400 °C, 0.1 mbar CO2 at 350 °C, and 0.4 mbar of CO2 (0.1 mbar) + H2 (0.3 mbar) at 350 °C.

Fig. 6. Mechanism of CO2 hydrogenation over CuCoNiZnAl-T catalyst.

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活化高熵氧化物中部分金属位点显著增强热催化和电催化

Activation of partial metal sites in high-entropy oxides for enhancing thermal and electrochemical catalysis

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