石墨烯层包覆铁钴合金的电子相互作用促进CO2高效加氢制低碳烯烃

doi:10.1016/S1872-2067(24)60188-9

催化学报 ›› 2025, Vol. 68: 366-375.DOI: 10.1016/S1872-2067(24)60188-9

石墨烯层包覆铁钴合金的电子相互作用促进CO₂高效加氢制低碳烯烃

张淼^a, 张莉民^a, 王明瑞^a, 张光辉^a^,^*(), 宋春山^a^,^b, 郭新闻^a^,^*()

^a大连理工大学化工学院, 精细化工国家重点实验室, 智能材料化工前沿科学中心, 宾州-大连联合能源研究中心, 辽宁大连 116024
^b香港中文大学理学院化学系, 香港 999077

收稿日期:2024-08-31 接受日期:2024-10-30 出版日期:2025-01-18 发布日期:2025-01-02
通讯作者: * 电子信箱: gzhang@dlut.edu.cn (张光辉); guoxw@dlut.edu.cn (郭新闻).
基金资助:
国家自然科学基金(22372022);国家自然科学基金(22102016);新疆维吾尔自治区重大科技专项(2022A01002-1);中央高校基本科研业务费专项(DUT22LAB602);辽宁省“兴辽英才计划”项目(XLYC2203126);香港中文大学研究启动基金(4930981)

The electronic interaction of encapsulating graphene layers with FeCo alloy promotes efficient CO₂ Hydrogenation to light olefins

Miao Zhang^a, Limin Zhang^a, Mingrui Wang^a, Guanghui Zhang^a^,^*(), Chunshan Song^a^,^b, Xinwen Guo^a^,^*()

^aState Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^bDepartment of Chemistry, Faculty of Science, the Chinese University of Hong Kong, Hong Kong 999077, China

Received:2024-08-31 Accepted:2024-10-30 Online:2025-01-18 Published:2025-01-02
Contact: * E-mail: gzhang@dlut.edu.cn (G. Zhang),guoxw@dlut.edu.cn (X. Guo).
Supported by:
National Natural Science Foundation of China(22372022);National Natural Science Foundation of China(22102016);Major Science and Technology Special Project of Xinjiang Uygur Autonomous Region(2022A01002-1);Fundamental Research Funds for the Central Universities(DUT22LAB602);Liaoning Revitalization Talent Program(XLYC2203126);CUHK Research Startup Fund(4930981)

摘要/Abstract

摘要：

大气CO₂浓度的增加导致全球变暖速度加快并引发了一系列严峻的环境问题, 威胁着人类的生存和发展. 将捕集到的CO₂与太阳能、风能等可再生能源获得的“绿氢”进行热催化加氢反应可以生成重要的工业生产原料低碳烯烃(C_2‒4⁼), 在减少CO₂排放量的同时, 可以降低对化石能源的消耗与依赖，从而进一步实现碳资源的有效循环. 铁基催化剂由于其较强的C-O活化和C-C偶联能力在CO₂加氢制低碳烯烃中受到青睐, 尤其是引入金属钴得到的活性相铁钴合金碳化物χ-(Fe_xCo_1-_x)₅C₂对高附加值烯烃的生成至关重要. 但目前较低的CO₂转化效率和低碳烯烃生成速率限制了其进一步的发展与应用, 因此设计开发高效稳定的铁基催化剂十分必要. 催化剂通常富含电子和键合位点, 与反应物分子成键以进行吸附和活化, 因此调控催化剂的表面电子结构可有效改善催化剂吸附活化行为, 提升催化活性. 由于内外表面π电子密度差异而具有独特电子性质的弯曲石墨烯层是调控活性相电子结构的良好材料.
本文从调控活性相电子结构出发, 利用弯曲石墨烯层内表面的缺电子性质, 通过溶胶-凝胶法制备了石墨烯层包覆铁钴合金的核壳型催化剂, 用于CO₂加氢制低碳烯烃. X射线粉末衍射、高分辨透射电子显微镜、X射线光电子能谱等表征结果表明了石墨烯层包裹铁钴合金的成功制备以及活性Fe物种向石墨烯层的电子转移. CO₂程序升温脱附实验证明了催化剂表面电子结构的调控改善了反应物分子吸附活化行为, 促进了CO₂分子的中等强度吸附. 在CO₂加氢测试中, 由石墨烯层包裹的铁钴合金催化剂FeCoK@C表现出了52.0%的高CO₂转化率、33.0%的低碳烯烃选择性以及超过100 h的催化稳定性, 低碳烯烃的时空收率是无石墨烯层包覆催化剂的2.3倍, 动力学实验也证实了石墨烯层包覆对活性相电子结构的调控作用促进了CO₂向目标产物低碳烯烃的高效转化. 对反应条件进一步优化后, 催化剂的低碳烯烃收率可达到52.9 mmol_CO2·g^-1·h^-1, 为目前文献报道的高水平. 石墨烯层对金属的分散与隔离还避免了反应过程中碱金属的过度富集. 此外, 通过原位XRD表征分析结果表明, 助剂Co, K的引入对活性相χ-(Fe_xCo_1-_x)₅C₂的形成与稳定起到了重要作用.
综上, 本工作采用了一种简单的活性相电子调控方法制备出了高效的铁钴合金碳化物催化剂, 实现了CO₂向低碳烯烃的高效与稳定转化, 为高性能CO₂加氢催化剂的设计、制备和应用提供了一种简单有效的策略.

关键词: CO₂加氢, 低碳烯烃, 石墨烯层, 钴铁合金碳化物, 电子相互作用

Abstract:

CO₂ hydrogenation to value-added light olefins (C_2-4⁼) is crucial for the utilization and cycling of global carbon resource. Moderate CO₂ activation and carbon chain growth ability are key factors for iron-based catalysts for efficient CO₂ conversion to target C_2-4⁼ products. The electronic interaction and confinement effect of electron-deficient graphene inner surface on the active phase are effective to improve surface chemical properties and enhance the catalytic performance. Here, we report a core-shell FeCo alloy catalyst with graphene layers confinement prepared by a simple sol-gel method. The electron transfer from Fe species to curved graphene inner surface modifies the surface electronic structure of the active phase χ-(Fe_xCo_1-_x)₅C₂ and improves CO₂ adsorption capacity, enhancing the efficient conversion of CO₂ and moderate C-C coupling. Therefore, the catalyst FeCoK@C exhibits C_2-4⁼ selectivity of 33.0% while maintaining high CO₂ conversion of 52.0%. The high stability without obvious deactivation for over 100 h and unprecedented C_2-4⁼ space time yield (STY) up to 52.9 mmol_CO2·g^-1·h^-1 demonstrate its potential for practical application. This work provides an efficient strategy for the development of high-performance CO₂ hydrogenation catalysts.

Key words: CO₂ hydrogenation, Light olefins, Graphene layers, Cobalt-iron alloy carbide, Electronic interaction

张淼, 张莉民, 王明瑞, 张光辉, 宋春山, 郭新闻. 石墨烯层包覆铁钴合金的电子相互作用促进CO₂高效加氢制低碳烯烃[J]. 催化学报, 2025, 68: 366-375.

Miao Zhang, Limin Zhang, Mingrui Wang, Guanghui Zhang, Chunshan Song, Xinwen Guo. The electronic interaction of encapsulating graphene layers with FeCo alloy promotes efficient CO₂ Hydrogenation to light olefins[J]. Chinese Journal of Catalysis, 2025, 68: 366-375.

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https://www.cjcatal.com/CN/Y2025/V68/I1/366

图/表 6

Fig. 1. Synthesis and microscopic analysis of Fe-based catalysts. (A) Schematic illustration of the synthesis of the samples. TEM and HRTEM images of fresh FeCoK@C (B,E), FeCoK-1 (C,F), and FeCoK-2 (D,G) catalysts.

Fig. 2. Structural characterizations of fresh catalysts. (A) XRD patterns of fresh Fe-based catalysts. C 1s (B) and Fe 2p (C) XPS spectra of fresh catalysts.

Fig. 3. Surface chemical properties of activated catalysts. C 1s (A) and Fe 2p (B) XPS spectra of activated FeCoK@C, FeCoK-1 and FeCoK-2. (C) CO2-TPD profiles of all activated Fe-based catalysts.

Fig. 4. Catalytic performances of the catalysts. (A) CO2 conversion and product selectivity over different Fe-based catalysts in CO2 hydrogenation. (B) C2-4= STY, C2-4 O/P, and chain growth factor α of different Fe-based catalysts. (C) Comparison between C2-4= STY over FeCoK@C and other Fe-based catalysts in previous reports. (D) Catalytic performance of FeCoK@C for 100 h stability test. Reaction conditions: 320 °C, 3.0 MPa, space velocity = 18000 mL·g-1·h-1, H2/CO2/N2 = 9/3/2, TOS = 8 h.

Fig. 5. EDS Mapping and HRTEM images of spent catalysts. (A,D) FeCoK@C; (B,E) FeCoK-1; (C,F) FeCoK-2.

Fig. 6. Structural characterizations of spent catalysts and comparison of carburizing rates of catalysts from in-situ XRD during CO2 hydrogenation. (A) XRD patterns of spent catalysts. (B) The intensity ratio of the XRD peaks at 43.5° and 44.7° during CO2 hydrogenation. C 1s (C) and Fe 2p (D) XPS spectra of spent catalysts.

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石墨烯层包覆铁钴合金的电子相互作用促进CO₂高效加氢制低碳烯烃

The electronic interaction of encapsulating graphene layers with FeCo alloy promotes efficient CO₂ Hydrogenation to light olefins

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