氧空位介导的不对称Ni-Ov-Co位点构建用于低温高效N2O分解

doi:10.1016/S1872-2067(26)65119-4

催化学报 ›› 2026, Vol. 90: 276-286.DOI: 10.1016/S1872-2067(26)65119-4

氧空位介导的不对称Ni-Ov-Co位点构建用于低温高效N₂O分解

李冰芷, 黎刚刚^*(), 赵泽宇, 张凤莲, 张中申, 程杰, 郝郑平^*()

中国科学院大学环境材料与污染控制技术研究中心, 挥发性有机物污染控制材料与技术国家工程实验室, 北京 101408

收稿日期:2026-02-23 接受日期:2026-04-17 出版日期:2026-11-18 发布日期:2026-09-09
通讯作者: *电子信箱: zphao@ucas.ac.cn (郝郑平),
liganggang@ucas.ac.cn (黎刚刚).
基金资助:
国家自然科学基金(22206185);国家重点研发计划(2023YFC3707500);国家重点研发计划(2022YFB3504200);中国博士后科学基金(2022M723109);中央高校基本科研业务费

Oxygen vacancy-mediated asymmetric Ni-Ov-Co sites for efficient low-temperature N₂O decomposition

Bingzhi Li, Ganggang Li^*(), Zeyu Zhao, Fenglian Zhang, Zhongshen Zhang, Jie Cheng, Zhengping Hao^*()

National Engineering Laboratory for VOCs Pollution Control Material & Technology, Research Center for Environmental Material and Pollution Control Technology, University of Chinese Academy of Sciences, Beijing 101408, China

Received:2026-02-23 Accepted:2026-04-17 Online:2026-11-18 Published:2026-09-09
Contact: *E-mail:zphao@ucas.ac.cn(Z. Hao),liganggang@ucas.ac.cn(G. Li).
Supported by:
National Natural Science Foundation of China(22206185);National Key Research and Development Program of China(2023YFC3707500);National Key Research and Development Program of China(2022YFB3504200);China Postdoctoral Science Foundation(2022M723109);Fundamental Research Funds for the Central Universities

摘要/Abstract

摘要：

一氧化二氮(N₂O)是一种具有强温室效应且大气停留寿命较长的气体, 同时也是当前主要的臭氧消耗物质之一, 其高效去除对大气环境保护与缓解温室效应具有重要意义. 直接催化分解法因无需还原剂、无二次污染, 被认为是最具应用价值的N₂O消除技术. 然而, 由于N₂O分子中N-O键能较高, 实现低温条件下的高效活化仍面临巨大挑战, 其核心在于构建具有独特电子结构与优异反应活性的催化位点. 尖晶石型Co基氧化物因其灵活的阳离子占位及多价态特性, 在N₂O分解反应中表现出良好潜力, 尤其是氧空位在N₂O活化过程中起关键作用. 然而, 如何通过结构调控实现氧空位电子结构的优化, 特别是构建高效的不对称活性位点用于N₂O分解反应, 仍缺乏系统研究.

本文通过溶剂热法合成了一系列具有不同几何构型的尖晶石钴基氧化物催化剂, 并通过引入不同电负性的元素(Ni > Co > Al)实现对八面体位点的定向调控. 其中, Ni取代八面体位点的Co后, 由于Ni与Co之间的电子相互作用及电负性差异, 诱导了显著的晶格畸变, 从而促进了催化剂表面氧空位的生成, 并构建不对称Ni-Ov-Co活性位点. 催化性能测试表明, 富含不对称位点的NiCo₂O₄在N₂O分解反应中表现出优异活性, 其90%转化温度(T₉₀)仅为340 °C, 分别较Co₃O₄和CoAl₂O₄降低约50和140 °C. 材料结构表征与结合密度泛函理论计算的结果表明, 不对称Ni-Ov-Co活性位点的构建提高了Co的平均价态, 并增强了Co-O键的共价性, 从而显著调控了氧空位附近的电子分布. 相比于对比催化剂中的对称Co-Ov-Co和Al-Ov-Al位点, 不对称Ni-Ov-Co位点不仅具有更高的氧空位浓度, 还表现出更强的N₂O吸附能力和电子传递能力. 进一步反应机理的研究揭示, N₂O分解遵循Langmuir-Hinshelwood机理, 其中N-O键断裂和O-O偶联为关键步骤. NiCo₂O₄中的不对称Ni-Ov-Co位点可同时降低上述两个步骤的反应能垒, 从而显著加速反应动力学过程.

综上, 本文通过几何构型调控构建了不对称Ni-Ov-Co活性位点, 并揭示了不对称氧空位在调控电子结构及提升N₂O分解性能中的关键作用, 为通过几何工程构建高效活性位点提供了新思路.

关键词: 尖晶石氧化物, 非对称氧空位, N₂O分解, 反应机理, 几何工程

Abstract:

The environmental persistence and potent greenhouse effect of N₂O call for efficient catalytic decomposition to address its environmental impact. However, achieving low-temperature N-O bond activation remains challenging due to the difficulty of constructing highly active sites. Herein, spinel cobalt oxides with controlled geometric configurations are successfully fabricated via the incorporation of heteroatoms. The Ni-substituted octahedral Co promotes the formation of oxygen vacancy, generating an asymmetric Ni-Ov-Co structure. Notably, NiCo₂O₄ catalyst with abundant asymmetric Ni-Ov-Co structure displays remarkable catalytic performance with a T₉₀ of 340 °C, which is 50 and 140 °C lower than that of comparative Co₃O₄ and CoAl₂O₄ catalysts, respectively. Structural characterizations and density functional theory calculation reveal that asymmetric Ni-Ov-Co sites possess high Co-O covalency and strong N₂O adsorption capacity, thus reducing the energy barriers in the key steps of N-O bond cleavage and O-O bond formation and boosting the catalytic activity. Moreover, the results of the mechanism research demonstrate that N₂O decomposition on asymmetric Ni-Ov-Co sites follows the Langmuir-Hinshelwood mechanism. This work underpins the design of asymmetric active sites in spinel oxides as efficient catalysts for greenhouse gas removal.

Key words: Spinel oxide, Asymmetric oxygen vacancy, N₂O decomposition, Reaction mechanism, Geometric engineering

李冰芷, 黎刚刚, 赵泽宇, 张凤莲, 张中申, 程杰, 郝郑平. 氧空位介导的不对称Ni-Ov-Co位点构建用于低温高效N₂O分解[J]. 催化学报, 2026, 90: 276-286.

Bingzhi Li, Ganggang Li, Zeyu Zhao, Fenglian Zhang, Zhongshen Zhang, Jie Cheng, Zhengping Hao. Oxygen vacancy-mediated asymmetric Ni-Ov-Co sites for efficient low-temperature N₂O decomposition[J]. Chinese Journal of Catalysis, 2026, 90: 276-286.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65119-4

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图/表 6

Fig. 1. Structural and morphological characterization of spinel oxide catalysts. (a-c) Crystal structure models of NiCo2O4, Co3O4, and CoAl2O4. (d-f) Rietveld-refined XRD patterns of NiCo2O4, Co3O4, and CoAl2O4. (g-i) HAADF-STEM images of NiCo2O4, Co3O4, and CoAl2O4.

Fig. 2. Electronic structure and defect characterization of spinel oxide catalysts. Co K-edge XANES (a) and Fourier-transformed EXAFS spectra (b) of NiCo2O4, Co3O4, and CoAl2O4. (c) UV-vis spectra. (d) Raman spectra. (e) EPR spectra. O 1s (f) and Co 2p (g) XPS spectra.

Fig. 3. Catalytic performance and stability of spinel oxide catalysts toward N2O decomposition. (a) N2O decomposition profiles over NiCo2O4, Co3O4, and CoAl2O4. (b) Reaction rates of the catalysts at different temperatures. (c) Arrhenius plots used to calculate apparent activation energies. (d) Stability tests conducted at 340 °C. (e) Tolerance evaluation of NiCo2O4 in the presence of potential impurities (O2, NO, and H2O). (f) The comparison of T90 for different reported catalysts (the X-axis has no physical significance).

Fig. 4. Redox properties and electronic structure analysis of spinel oxide catalysts. H2-TPR profiles (a), O2-TPD profiles (b), PDOS (c) of Ni, Co, Al, and O orbitals, the blue dashed line implies the Fermi level energy (Ef). (d) Computed charge distributions of metal and oxygen atoms. (e) Calculated N2O adsorption energies on different surface sites of perfect surfaces of NiCo2O4, Co3O4, and CoAl2O4 spinel oxides.

Fig. 5. Model structures of N2O adsorbed on CoTh sites (a,b), CoOh sites (c,d), NiOh sites (e,f) in NiCo2O4 without and with an oxygen vacancy, respectively. The blue balls represent Co, red balls represent O, green balls represent Ni, and purple balls represent N.

Fig. 6. Mechanistic investigation of N2O decomposition over spinel oxide catalysts. (a,b) TPSR profiles of isotopically labeled Co318O4 and NiCo218O4. (c) Calculated free energy diagrams for N2O decomposition on Co3O4 (311) and NiCo2O4 (311) surfaces with oxygen vacancy.

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氧空位介导的不对称Ni-Ov-Co位点构建用于低温高效N₂O分解

Oxygen vacancy-mediated asymmetric Ni-Ov-Co sites for efficient low-temperature N₂O decomposition

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