铁基催化剂热催化CO2加氢制乙醇: 水管理和铁基碳化物/氧化物比例的关键作用

doi:10.1016/S1872-2067(26)65065-6

催化学报 ›› 2026, Vol. 86: 112-124.DOI: 10.1016/S1872-2067(26)65065-6

铁基催化剂热催化CO₂加氢制乙醇: 水管理和铁基碳化物/氧化物比例的关键作用

刘晓洁^a, 余治甫^a, 李奇^a, 王阳^a^,^*(), 毕鑫泽^a, 霍凯旋^a, 李丁尧^a, 苑志昂^a, 闫怡帆^a, 李士斌^a, 鲁宜武^d, 刘强^d, 王文行^a^,^c, 吴明铂^a^,^b^,^*()

^a 中国石油大学(华东)新能源学院, 山东青岛 266580
^b 青岛科技大学化工学院, 山东青岛 266042
^c 聊城大学化学化工学院, 山东省化学储能与新型电池技术重点实验室, 山东聊城 252059
^d 山东能源集团有限公司, 煤气化及煤基先进材料国家工程研究中心, 山东济南 250014

收稿日期:2025-10-16 接受日期:2025-12-16 出版日期:2026-07-05 发布日期:2026-06-12
通讯作者: ^*电子信箱: wangyang@upc.edu.cn (王阳),
wumb@upc.edu.cn/wumb@qust.edu.cn (吴明铂).
基金资助:
山东省重点研发计划(2024ZLGX08);国家重点研发计划(2023YFB4104500);国家重点研发计划(2023YFB4104502);国家自然科学基金(22478436);山东能源集团有限公司科技创新项目(SNKJ2023A03)

Fe-based catalyst for thermo-catalytic CO₂ hydrogenation into ethanol: The essential role of water management and Fe-based carbide/oxide ratio

Xiaojie Liu^a, Zhifu Yu^a, Qi Li^a, Yang Wang^a^,^*(), Xinze Bi^a, Kaixuan Huo^a, Dingyao Li^a, Zhiang Yuan^a, Yifan Yan^a, Shibin Li^a, Yiwu Lu^d, Qiang Liu^d, Wenhang Wang^a^,^c, Mingbo Wu^a^,^b^,^*()

^a College of New Energy, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^b College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao 266042, Shandong, China
^c Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong, China
^d National Engineering Research Center of Coal Gasification and Coal-Based Advanced Materials, Shandong Energy Group Co., Ltd., Jinan 250014, Shandong, China

Received:2025-10-16 Accepted:2025-12-16 Online:2026-07-05 Published:2026-06-12
Supported by:
Key Research and Development Program of Shandong Province(2024ZLGX08);National Key Research and Development Program of China(2023YFB4104500);National Key Research and Development Program of China(2023YFB4104502);National Natural Science Foundation of China(22478436);Science and Technology Innovation Project of the Shandong Energy Group Co., Ltd.(SNKJ2023A03)

摘要/Abstract

摘要：

随着全球工业化进程加剧, 二氧化碳(CO₂)过量排放引发了严峻的环境与能源挑战. 将CO₂热催化转化为高附加值的乙醇, 不仅能实现碳资源的有效循环利用, 还能提供重要的基础化学品. 铁基催化剂因其独特的C-O键活化和C-C偶联能力, 在CO₂加氢制乙醇反应中极具潜力. 然而, 该反应伴随逆水煤气变换(RWGS)过程会产生大量副产物水(H₂O), 极易诱导铁基活性相(如χ-Fe₅C₂)发生过度氧化而失活, 导致乙醇选择性低且副产物难以控制. 因此, 如何通过催化剂结构设计精准调控反应微环境中的水浓度, 维持铁基活性相中碳化物与氧化物的动态平衡, 是突破CO₂加氢制乙醇性能瓶颈的科学难题.

针对上述挑战, 本文提出了一种基于疏水碳限域与双组分串联协同的创新策略, 旨在通过精准调控反应微环境中的水浓度来实现活性相的动态平衡. 为此, 设计并构建了一种由疏水碳层包裹的铁基催化剂(NaFe@C)与K修饰的CuZnAl催化剂(KCZA)组成的双组分串联催化体系(NaFe@C&KCZA). 微观结构表征显示, NaFe@C表面形成了约2-3 nm厚的碳层, 其水接触角达141.6°, 表现出优异的疏水性能. 在该体系中, KCZA组分主要负责通过RWGS反应活化CO₂并提供CO及含氧中间体(CH_xO, x = 0, 1或2); 而NaFe@C组分则利用其外部碳层的疏水特性, 构建了独特的“水管理”机制, 有效阻隔了由KCZA产生的过量H₂O向内部铁活性位点的扩散. ⁵⁷Fe穆斯堡尔谱分析证实, 这种疏水限域效应有效避免了χ-Fe₅C₂活性相的过度氧化, 从而实现了优化的Fe₃O₄/χ-Fe₅C₂相比例. 性能测试表明, 在320 ºC和5 MPa的优化条件下, 该催化体系实现了35.0%的乙醇选择性. 结合红外光谱及密度泛函理论计算深入解析了反应机理, CO-DRIFTS结果表明, 适量的Fe₃O₄相通过界面电子相互作用调节了χ-Fe₅C₂表面的电子密度, 使关键中间体CO在表面的桥式与线式吸附构型达到最佳平衡; 同时, 优化的Fe₃O₄/χ-Fe₅C₂比例显著降低了决速步—即亚甲基(CH₂*)与CO进行C-C偶联生成乙醇前驱体(CH₂CO*)的反应能垒(从单纯碳化物的1.49 eV降低至1.31 eV), 从而在分子层面阐明了乙醇合成性能提升的根本原因.

综上, 本工作通过构筑疏水碳限域的铁基双组分催化体系, 创新性地实现了对反应水微环境的精准管理及活性相动态演变的有效调控, 揭示了“水微环境-活性相动态平衡-产物选择性”之间的构效关系. 该策略不仅解决了铁基催化剂易被水过度氧化失活的问题, 也为理性设计CO₂或合成气定向转化为高值化学品的高效催化剂提供了重要的理论指导.

关键词: CO₂加氢, 双组分催化, 乙醇合成, 水管理, 活性相动态调控

Abstract:

CO₂ hydrogenation to ethanol represents a pivotal pathway for valuable utilization of greenhouse gas CO₂, yet conventional catalysts are still limited by active-phase instability and undesirable byproduct selectivity. Herein, we propose a dual-components catalyst system synergized by hydrophobic carbon-encapsulated Fe-based catalyst (NaFe@C) and K modified CuZnAl component (KCZA), which achieves ultra-high ethanol selectivity of 35% under optimized conditions (5 MPa and 320 °C). KCZA initiates the CO₂ activation via reverse water-gas shift reaction and supplies oxygen-containing intermediates (mainly CH_xO*, x = 0, 1, or 2). NaFe@C component is mainly responsible for the C-O activation for CH_x* formation and C-C coupling between CH_x* and CH_xO*, as well as the following hydrogenation step for ethanol synthesis. Notably, the hydrophobic carbon shell in NaFe@C plays a critical role in tailoring the oxidation behaviors of Fe-based active sites and optimizing the phase ratio of Fe₃O₄/χ-Fe₅C₂ via water management. Multiple characterization and theoretical simulation results clarify that the unique electronic property of Fe-based active sites endowed by the optimized phase ratio is beneficial to boost the ethanol synthesis performance by balancing the coverage of key intermediates and lowering the energy barrier of essential steps. This work is promising to provide guidance for the rational design of advanced catalysts for targeted transformation of CO₂ or syngas into ethanol and beyond.

Key words: CO₂ hydrogenation, Dual-components catalysis, Ethanol synthesis, Water management, Active phase dynamic regulation

刘晓洁, 余治甫, 李奇, 王阳, 毕鑫泽, 霍凯旋, 李丁尧, 苑志昂, 闫怡帆, 李士斌, 鲁宜武, 刘强, 王文行, 吴明铂. 铁基催化剂热催化CO₂加氢制乙醇: 水管理和铁基碳化物/氧化物比例的关键作用[J]. 催化学报, 2026, 86: 112-124.

Xiaojie Liu, Zhifu Yu, Qi Li, Yang Wang, Xinze Bi, Kaixuan Huo, Dingyao Li, Zhiang Yuan, Yifan Yan, Shibin Li, Yiwu Lu, Qiang Liu, Wenhang Wang, Mingbo Wu. Fe-based catalyst for thermo-catalytic CO₂ hydrogenation into ethanol: The essential role of water management and Fe-based carbide/oxide ratio[J]. Chinese Journal of Catalysis, 2026, 86: 112-124.

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Fig. 1. Structural characterization and surface properties. TEM (a,b) and HRTEM (c) images of the NaFe@C catalyst. (d) HAADF-STEM image of the spent NaFe@C catalyst and the corresponding elemental mapping images of Fe, C, and Na elements. (e) H2O droplet contact angle tests.

Fig. 2. Catalytic performance of CO2 hydrogenation to ethanol. (a) CO2 conversion and product selectivity of four catalysts. (b) Comparison of CO2 conversion and ethanol selectivity from NaFe@C&KCZA with the results reported in other literature. Reaction conditions: 320 °C, 5 MPa (31.7% CO2, 63.3% H2, and 5.0% Ar), 15 mL min-1, and time on stream (TOS) = 8 h. Catalyst weight: 0.3 g of NaFe catalyst, 0.36 g of NaFe@C catalyst, NaFe&KCZA (total weight: 0.6 g), or NaFe@C&KCZA (total weight: 0.66 g). The two catalyst powders were mixed and granulated (20-40 mesh) and mixed with an equal volume of quartz sand in the reactor.

Fig. 3. Catalyst characterization. (a) XRD patterns of post-reaction catalysts. 57Fe Mössbauer spectra of NaFe (b), NaFe@C (c), NaFe&KCZA (d), and NaFe@C&KCZA (e) catalysts after catalytic testing.

Fig. 4. Schematic diagrams of H2O microenvironment regulation by NaFe (a), NaFe@C (b), NaFe&KCZA (c), and NaFe@C&KCZA (d) catalysts. The phase compositions of Fe-based active sites tailored by H2O management are also given.

Fig. 5. In-situ XRD patterns of NaFe@C&KCZA catalyst under H2 reduction (a) and carburizing (b) atmospheres.

Fig. 6. CO-DRIFTS of the reference sample dominated by χ-Fe5C2 phase (a), spent NaFe@C&KCZA catalyst (b), and spent NaFe@C catalyst (c).

Fig. 7. (a) In-situ DRIFT spectra of high-pressure (3 MPa) CO2 hydrogenation reaction on NaFe@C&KCZA catalyst. (b) Reaction pathway for ethanol synthesis from CO2 hydrogenation.

Fig. 8. Theoretical simulations and mechanistic analysis of ethanol synthesis via Fe-based catalysts. (a) Differential charge density plots of χ-Fe5C2, Fe3O4/χ-Fe5C2 (M), and Fe3O4/χ-Fe5C2 (H) models. The yellow and cyan electron clouds represent electron accumulation and depletion, respectively. (b) Valence electron counts for Fe-based species in the three models. Species evolution from CO to CH2* (c) and the energy profiles (d) for C-C coupling between CH2* and CO*, and the subsequent hydrogenation steps via the three models. Key: transition state (TS), Fe (purple), C (dark gray), O (red), and H (white).

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铁基催化剂热催化CO₂加氢制乙醇: 水管理和铁基碳化物/氧化物比例的关键作用

Fe-based catalyst for thermo-catalytic CO₂ hydrogenation into ethanol: The essential role of water management and Fe-based carbide/oxide ratio

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