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无机材料学报

• 研究论文 •    

CuCoNiCeMn高熵氧化物的制备及烧结烟气CO催化氧化性能

刘健1, 安伟佳1, 高勤2, 李建华3, 杨宗翔4, 王骁1, 梁英华1, 葛佳琪1, 崔文权1   

  1. 1.华北理工大学 化学工程学院, 河北省环境光电催化材料重点实验室, 唐山 063210;
    2.河北省生态环境科学研究院, 石家庄 050000;
    3.开滦新材料有限公司, 唐山 063018;
    4.天津大学 环境科学与工程学院, 天津 300354
  • 收稿日期:2026-02-06 修回日期:2026-05-27
  • 作者简介:刘健(2000-), 男, 硕士研究生. E-mail: liujian0731@yeah.net
  • 基金资助:
    京津冀环境综合治理国家科技重大专项(2024ZD1200402)

Preparation of CuCoNiCeMn High-entropy Oxide and Its Catalytic Oxidation Performance for CO in Sintering Flue Gas

LIU Jian1, AN Weijia1, GAO Qin2, LI Jianhua3, YANG Zongxiang4, WANG Xiao1, LIANG Yinghua1, GE Jiaqi1, CUI Wenquan1   

  1. 1. Hebei Provincial Key Laboratory of Environmental Photoelectrocatalytic Materials, College of Chemical Engineering, North China University of Science and Technology, Tangshan 063210, China;
    2. Hebei Provincial Academy of Ecological and Environmental Sciences, Shijiazhuang 050000, China;
    3. Kailuan New Materials Co., Ltd., Tangshan 063018, China;
    4. School of Environmental Science and Engineering, Tianjin University, Tianjin 300354
  • Received:2026-02-06 Revised:2026-05-27
  • About author:LIU Jian (2000-), male, Master candidate. E-mail: liujian0731@yeah.net
  • Supported by:
    Beijing-Tianjin-Hebei Comprehensive Environmental Management National Science and Technology Major Project (2024ZD1200402)

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摘要： 钢铁烧结工序是工业CO排放的主要来源, 具有风量大、组分复杂、波动范围广等特点, 治理难度较高。针对上述问题, 利用高熵氧化物(HEO)中多组分的协同效应, 围绕制备工艺优化开展系统研究, 探讨了高熵合金氧化物对CO催化氧化性能的影响规律, 考察了其抗水、抗硫性能, 并提出了其在CO催化氧化过程中的作用机制。结果表明, 采用溶胶-凝胶法制备的催化剂具有丰富的多价态金属离子及氧空位, 在160 ℃、空速48000 mL·g-1·h-1条件下CO转化率达到95%以上, 低温活性(CO转化率达到50%时的温度T50为101 ℃)显著优于共沉淀法和水热法, 并详细讨论了制备参数(柠檬酸比例、溶液pH、煅烧温度)等对CO催化氧化性能的影响规律。表征结果证实, 多价态金属离子之间的电子转移与氧空位的协同作用是提升催化活性的关键。该催化剂在10%(体积分数)H2O环境中仍保持98%的CO转化率, 并在280 ℃、72000 mL·g-1·h-1空速下稳定运行24 h, 展现出优异的抗水性与热稳定性, 推测其催化氧化CO遵循Mars-van Krevelen (MvK)机制。本研究揭示了HEO中多金属价态协同、晶格氧与吸附氧共存及氧空位主导的反应机理, 为设计低成本、高性能的非贵金属CO催化氧化催化剂提供了新的理论与实验依据。

关键词: 高熵氧化物, CO催化氧化, 溶胶-凝胶法, 低温催化

Abstract: The iron ore sintering process is a major source of industrial CO emissions, characterized by large gas volumes, complex compositions, and wide fluctuations, making abatement challenging. To address this, the synergistic effects of multi-components in high-entropy oxides (HEOs) were exploited. A systematic study on preparation process optimization was conducted to explore the influence of high-entropy alloy oxides on CO catalytic oxidation, along with their water and sulfur resistance, and the underlying mechanism. Results show that catalysts prepared by the Sol-Gel method possess abundant multivalent metal ions and oxygen vacancies, achieving >95% CO conversion at 160 ℃ and a gas hourly space velocity (GHSV) of 48000 mL·g-1·h-1, with low-temperature activity (temperature corresponding to a CO conversion rate of 50% (T50)=101 ℃) significantly better than co-precipitation and hydrothermal methods. The effects of preparation parameters (citric acid ratio, solution pH, and calcination temperature) on catalytic performance were detailed. Characterization results confirm that electron transfer among multivalent metal ions and the synergy with oxygen vacancies are key to enhanced activity. The catalyst retains 98% CO conversion under 10% (in volume) H2O and operates stably for 24 h at 280 ℃ and 72000 mL·g-1·h-1, demonstrating excellent water resistance and thermal stability. It is speculated that its catalytic oxidation follows the Mars-van Krevelen (MvK) mechanism. This study reveals the reaction mechanism governed by multi-metal valence synergy, coexistence of lattice and adsorbed oxygen, and oxygen vacancies in HEOs, providing new theoretical and experimental foundations for designing low-cost, high-performance non-noble metal CO oxidation catalysts.

Key words: high-entropy oxide, CO catalytic oxidation, Sol-Gel method, low-temperature catalysis

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