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

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

Chinese Journal of Catalysis ›› 2023, Vol. 48: 235-246.DOI: 10.1016/S1872-2067(23)64409-2

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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)

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64409-2

https://www.cjcatal.com/EN/Y2023/V48/I5/235

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

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