FeTi强相互作用促进CO2高效加氢制低碳烯烃

doi:10.1016/S1872-2067(24)60268-8

催化学报 ›› 2025, Vol. 71: 146-157.DOI: 10.1016/S1872-2067(24)60268-8

FeTi强相互作用促进CO₂高效加氢制低碳烯烃

梁昊^a, 张书南^a^,^*(), 张若楠^a, 周浩志^a, 夏林^b, 孙予罕^a^,^b, 王慧^a^,^b^,^*()

^a上海科技大学2060研究院, 低碳复合能源工程科学实验室, 上海 201203
^b中国科学院上海高等研究院, 中科院低碳转化科学与工程重点实验室, 上海 201210

收稿日期:2024-12-26 接受日期:2025-02-09 出版日期:2025-04-18 发布日期:2025-04-13
通讯作者: * 电子信箱: zhangshn2@shanghaitech.edu.cn (张书南), wanghh@sari.ac.cn (王慧).
基金资助:
国家重点研发项目(2022YFA1504800);国家自然科学基金(22308215);国家自然科学基金(22478409);国家自然科学基金(22108289);国家自然科学基金(22279158);中海油化工与新材料研究院研究经费(YJSCZX07956YJ)

Strong interaction between Fe and Ti compositions for effective CO₂ hydrogenation to light olefins

Hao Liang^a, Shunan Zhang^a^,^*(), Ruonan Zhang^a, Haozhi Zhou^a, Lin Xia^b, Yuhan Sun^a^,^b, Hui Wang^a^,^b^,^*()

^aInstitute of Carbon Neutrality, ShanghaiTech University, Shanghai 201203, China
^bCAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China

Received:2024-12-26 Accepted:2025-02-09 Online:2025-04-18 Published:2025-04-13
Contact: * E-mail: zhangshn2@shanghaitech.edu.cn (S. Zhang), wanghh@sari.ac.cn (H. Wang).
Supported by:
National Key R&D Program of China(2022YFA1504800);National Natural Science Foundation of China(22308215);National Natural Science Foundation of China(22478409);National Natural Science Foundation of China(22108289);National Natural Science Foundation of China(22279158);CNOOC Institute of Chemicals &Advanced Materials(YJSCZX07956YJ)

摘要/Abstract

摘要：

低碳烯烃(C_2-4⁼)是生产塑料、纤维等化学品的重要原料, 具有广泛的应用和巨大的需求. 传统的低碳烯烃生产工艺需要消耗大量化石资源并排放大量CO₂, 随着未来石油资源的紧缺, 无法满足逐渐增长的低碳烯烃需求和环保要求. 在全球碳排放量不断增加的背景下, 以CO₂为原料, 利用CO₂加氢制低碳烯烃是一条具有经济和社会效益的绿色技术路线. Fe基催化剂被广泛用于CO₂加氢制低碳烯烃. 然而, 实现活性相的精确调控和串联反应之间的高效协同仍存在巨大挑战. 因此, 利用金属相互作用以实现Fe基催化剂的活性相调控和性能提升是本文的主要思路.
本文通过调控还原条件和Fe/Ti比, 成功调节了FeTi相互作用以及Fe₃O₄/Fe₅C₂比. 气氛还原性较弱时, 反应后催化剂主要由FeTi固溶体(Fe₂TiO₅和FeTiO₃)组成; 引入CO还原后, 渗碳作用增强, 促进了Fe₃C相的生成; H₂还原温度为600 °C时出现FeO相, 表明还原性的提高; 升至800 °C时, Fe₂TiO₅和FeTiO₃消失, 出现Fe₃O₄, α-Fe和Fe₅C₂相, 这表明FeTi固溶体影响着Fe物相的还原和碳化. 进一步调控Fe/Ti比, 拉曼光谱及H₂程序升温还原等结果表明, FeTi存在相互作用且在Fe/Ti为4/1时最强. 原位X射线衍射结果进一步验证了FeTi相互作用的存在, 且FeTi强相互作用可以抑制关键活性相Fe₃O₄的形成和还原, 从而调节了Fe₃O₄和Fe₅C₂的含量. 穆斯堡尔谱定量分析显示, 3K/FeTi(4/1)催化剂具有最高的Fe₅C₂/Fe₃O₄比(3.6), 进一步证实了FeTi强相互作用对活性相比例的调控作用. 透射电镜结果表明, FeTi强相互作用促进了Fe₅C₂取向生长为棱柱状结构, 主要暴露(020), (-112)和(311)晶面, 并与Fe₃O₄形成紧密的界面位点, 从而增强了逆水气变换(RWGS)和费托合成(FTS)反应之间的协同耦合. 原位漫反射红外光谱实验表明, 3K/FeTi催化剂遵循RWGS + FTS机理, 对于3K/FeTi(4/1)催化剂的CO₂加氢过程, 在150 °C时出现碳酸氢盐物种(*HCO₃^-)的振动峰, 并随着温度的升高而快速减弱. 而在300 °C时, 甲酸盐物种(*HCOO^-)、乙烯基(*-CH=CH₂)、气态CO、亚甲基(*-CH₂-)和烯烃的*C-H振动峰出现, 并随着反应时间的延长而增强. 而当原料气从H₂/CO₂换成H₂时, 气态CO峰消失, 而*-CH=CH₂强度增加, 这再次证实了CO的强吸附性及其通过C-C偶联促进CO加氢和烯烃生成的作用. 3K/FeTi(4/1)催化剂在优化反应条件后实现了52.2%的CO₂转化率、44.5%的C_2-4⁼选择性、9.5%的CO选择性和4.9的烯烃/烷烃比, 以及高达412.0 mg g_cat^-1 h^-1的C_2-4⁼时空收率.
综上所述, 本文介绍了在CO₂加氢制低碳烯烃过程中调节金属相互作用和优化关键活性相比例的新策略, 为调控催化系统中金属相互作用、活性相比例、晶面和界面提供了见解.

关键词: CO₂加氢, 低碳烯烃, FeTi强相互作用, Fe₅C₂, 活性相调控

Abstract:

Fe-based catalysts are widely used for CO₂ hydrogenation to light olefins (C_2-4⁼); however, precise regulation of active phases and the balance between intermediate reactions remain significant challenges. Herein, we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions, modulating the Fe₃O₄ and Fe₅C₂ contents. Enhanced interaction leads to an increased Fe₅C₂/Fe₃O₄ ratio, which in turn enhances the adsorption of reactants and intermediates, promoting CO hydrogenation to unsaturated alkyl groups and facilitating C-C coupling. Furthermore, the strong Fe-Ti interaction induces the preferential growth of Fe₅C₂ into prismatic structures that expose the (020), (-112), and (311) facets, forming compact active interfacial sites with Fe₃O₄ nanoparticles. These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions. The optimized 3K/FeTi catalyst with the highest Fe₅C₂/Fe₃O₄ ratio of 3.6 achieves a 52.2% CO₂ conversion rate, with 44.5% selectivity for C_2-4⁼ and 9.5% for CO, and the highest space-time yield of 412.0 mg g_cat^-1 h^-1 for C_2-4⁼.

Key words: CO₂ hydrogenation, Light olefins, Strong Fe-Ti interaction, Fe₅C₂, Active phase modulation

梁昊, 张书南, 张若楠, 周浩志, 夏林, 孙予罕, 王慧. FeTi强相互作用促进CO₂高效加氢制低碳烯烃[J]. 催化学报, 2025, 71: 146-157.

Hao Liang, Shunan Zhang, Ruonan Zhang, Haozhi Zhou, Lin Xia, Yuhan Sun, Hui Wang. Strong interaction between Fe and Ti compositions for effective CO₂ hydrogenation to light olefins[J]. Chinese Journal of Catalysis, 2025, 71: 146-157.

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图/表 11

Fig. 1. CO2 conversion, CO selectivity and hydrocarbon distribution over the 3K/FeTi (1/2) catalyst reduced by different atmospheres (a) and temperatures (b). (c) Impact of Fe/Ti ratio on CO2 conversion, hydrocarbon distribution, and STY of C2-4=. (d) Influence of K content for the FeTi (4/1) catalyst. Reaction conditions: H2/CO2 = 3, P = 3 MPa, T = 320 °C and WHSV = 6000 mL gcat-1 h-1. (e) Pressure-dependent CO2 conversion, hydrocarbon distribution, and STY of C2-4= over the 3K/FeTi (4/1) catalyst. Reaction conditions: H2/CO2 = 3, P = 2-4.5 MPa, T = 320 °C, and WHSV = 6000 mL gcat-1 h-1. (f) Temperature-dependent CO2 conversion, hydrocarbon distribution, and STY of C2-4= over the 3K/FeTi (4/1) catalyst. Reaction conditions: H2/CO2 = 3, P = 3.5 MPa, T = 300-380 °C and WHSV = 6000 mL gcat-1 h-1.

Fig. 2. XRD patterns of fresh and spent 3K/FeTi catalysts: (a) Post-reduction in different atmospheres; (b) Post-reduction at different H2 reduction temperatures.

Fig. 3. (a) Phase distribution of the spent 3K/FeTi (1/2) catalyst after the reduction under different conditions. (b) The relationship between phase ratios and reaction rate in the 3K/FeTi (1/2) catalyst.

Fig. 4. XRD patterns (a), XPS spectra of Fe 2p (b), Raman spectra (c), and H2-TPR profiles (d) of fresh 3K/FeTi catalysts with different Fe/Ti ratios.

Fig. 5. In situ XRD patterns of the fresh 3K/FeTi (4/1) (a) and 3K/FeTi (5/1) (b) catalysts. (c) XRD patterns of the spent catalysts with different Fe/Ti ratios.

Fig. 6. EXAFS spectra (a) and corresponding wavelet transform plots (b-d) of the spent catalysts with different Fe/Ti ratios, corresponding wavelet transform plots of the reference materials (e).

Fig. 7. M?ssbauer spectra of the spent catalysts with different Fe/Ti ratios. (a) 3K-FeTi (1/2)-600H2-R; (b) 3K-FeTi (2/1)-600H2-R; (c) 3K-FeTi (4/1)-600H2-R; (d) 3K-FeTi (5/1)-600H2-R.

Fig. 8. (a) Phase distribution of the spent catalysts with different Fe/Ti ratios. (b) Relationship between phase ratios and reaction rates in the spent catalysts with different Fe/Ti ratios.

Fig. 9. (a) H2-TPD profiles of the spent catalysts with different Fe/Ti ratios. (b) CO2-TPD profiles of the spent catalysts with different Fe/Ti ratios. (c) CO-TPD profiles of the spent catalysts with different Fe/Ti ratios.

Fig. 10. (a,b) TEM images of the spent 3K/FeTi (4/1) catalyst. (c,d) HRTEM images of the exposed facets in the 3K/FeTi (4/1) spent catalyst. (e) Model of Fe5C2 nanoprism with triclinic prism structure. (f) HRTEM image of Fe5C2 and Fe3O4 interface.

Fig. 11. In situ DIRFTS analysis during the CO2 hydrogenation over the3K/FeTi (4/1) (a) and 3K/FeTi (5/1) (b) catalysts.

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FeTi强相互作用促进CO₂高效加氢制低碳烯烃

Strong interaction between Fe and Ti compositions for effective CO₂ hydrogenation to light olefins

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