界面电子扰动促进的C-H键活化

doi:10.1016/S1872-2067(23)64575-9

催化学报 ›› 2024, Vol. 56: 130-138.DOI: 10.1016/S1872-2067(23)64575-9

界面电子扰动促进的C-H键活化

王哲^a^,^b^,¹, 王春鹏^a^,¹, 陆冰^a, 陈志荣^b, 王勇^a^,^*(), 毛善俊^a^,^*()

^a浙江大学化学系, 催化研究所, 能源高效清洁利用全国重点实验室, 化学前瞻技术研究中心, 先进材料与催化课题组, 浙江杭州310058
^b浙江大学化学工程与生物工程学院, 浙江杭州310058

收稿日期:2023-10-05 接受日期:2023-11-29 出版日期:2024-01-18 发布日期:2024-01-10
通讯作者: *电子信箱: maoshanjun@zju.edu.cn (毛善俊), chemwy@zju.edu.cn (王勇).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2021YFB3801600);国家自然科学基金(22325204);浙江省“尖兵”“领雁”研发攻关计划项目(2023C01108);浙江省“尖兵”“领雁”研发攻关计划项目(2022C01218)

Electronic perturbation-promoted interfacial pathway for facile C-H dissociation

Zhe Wang^a^,^b^,¹, Chunpeng Wang^a^,¹, Bing Lu^a, Zhirong Chen^b, Yong Wang^a^,^*(), Shanjun Mao^a^,^*()

^aAdvanced Materials and Catalysis Group, Center of Chemistry for Frontier Technologies, State Key Laboratory of Clean Energy Utilization, Institute of Catalysis, Department of Chemistry, Zhejiang University, Hangzhou 310058, Zhejiang, China
^bCollege of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, Zhejiang, China

Received:2023-10-05 Accepted:2023-11-29 Online:2024-01-18 Published:2024-01-10
Contact: *E-mail: maoshanjun@zju.edu.cn (S. Mao), chemwy@zju.edu.cn (Y. Wang).
About author:¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2021YFB3801600);National Natural Science Foundation of China(22325204);“Pioneer” and “Leading Goose” R&D Program of Zhejiang(2023C01108);“Pioneer” and “Leading Goose” R&D Program of Zhejiang(2022C01218)

摘要/Abstract

摘要：

丙烯是重要的化工原料, 广泛用于生产聚丙烯、环氧丙烷、丙烯醛、丙烯腈和丙酮等重要化工中间体以及合成树脂、合成橡胶和许多精细化工产品. 目前生产丙烯的方法主要有石脑油裂解、催化流化裂化、丙烷脱氢、烯烃复分解和甲醇制烯烃等. 其中丙烷脱氢因具有较高的丙烯选择性和较低的原料成本而备受关注, 尤其是页岩气在全球的大量发现和开采, 使得丙烷的原料成本持续下降, 丙烷脱氢技术的迅速发展, 但高效催化剂研发成为提升生产效率的关键.

商业Pt基催化剂通常采用合金化的手段优化Pt颗粒的表面结构和中间体的吸附状态, 进而获得较好的催化性能, 但金属助剂的引入在一定程度上会弱化Pt位点的C-H键活化能力. 针对该问题, 本文从惰性C-H键活化角度出发, 揭示了一种新的C-H键界面活化机制. 通过金属-载体强相互作用诱导形成Pt-Ga₂O₃反向界面结构, 密度泛函理论计算结果表明, Pt与Ga₂O₃之间存在强烈的电子扰动现象, 使得界面处O位点表现出类金属的电子特性, 在费米能级附近存在连续的电子态, 这与Ga₂O₃本身离散性电子态呈明显对比, 显示出Pt-Ga₂O₃反向界面结构的独特性质, 使得界面O位点表现出极强的H吸附能和C-H键活化能力, 其催化丙烷分子中亚甲基C-H键断裂的活化能仅为0.21 eV, 远低于Pt(111)晶面的0.64 eV. 原位红外光谱结果表明, 反应过程中该界面结构会产生大量的羟基. 根据过渡态的精细结构可知, 反应位点是通过抓取H原子并随即稳定产生的C自由基完成C-H键的断裂, 分析结果表明, H吸附能与反应能垒有着紧密的关联, 而Pt-Ga₂O₃反向界面结构中, Pt基底赋予界面O位点独特的电子结构, 同时也可以作为电子受体接收H传递的电子, 从而表现出极强的H结合能和C-H键活化能力, 其C-H断裂能垒要远低于各类Pt位点. 进一步的分析表明, 首个C-H键在Pt-O界面位发生断裂后, 所形成的H物种会由O位点溢流至Pt颗粒表面, 最终以H₂形式释放, 留下的2-丙基碎片再经历甲基的C-H键断裂、H溢流、脱氢等步骤形成丙烯分子. 而Pt颗粒表面的Ga₂O₃团簇也起到分割表面位点的作用, 促进丙烯脱附的同时, 有效弱化C-C键的断裂趋势, 减少裂解副产物, 生成丙烯的选择性超过99%.

综上所述, 本文构建的Pt/Ga-Al₂O₃界面位催化剂在丙烷脱氢反应中的性能要明显优于Pt/Al₂O₃以及工业常用的PtSn/Al₂O₃催化剂, 揭示了一种全新的C-H键活化策略, 并探究其中的化学机制, 既可以深化对界面协同催化的理解, 又可以为高性能催化剂的设计提供借鉴和指导.

关键词: 界面催化, 碳氢键活化, 丙烷脱氢, 铂, 电子效应

Abstract:

Interface has often played significant role in the behavior of metal-based catalysts during various heterogeneous reactions. Herein, we reported a novel interfacial pathway for propane dehydrogenation on Pt-GaO_x dual sites. The active ensemble, composing Pt particles and Ga₂O₃ clusters, facilitates the facile dissociation of C‒H bonds (energy barrier < 0.30 eV) through H-abstraction by O sites, coupled with alkyl stabilization on the Pt surface. Notably, the electronic perturbation of the Pt slab induces higher-lying O 2p states at the interface, accompanied by a substantial density of states around fermi level. This is in stark contrast to the O species present in Ga₂O₃ crystals or clusters alone, leading to an exceptionally strong affinity for H and a robust ability for C-H scission. The Pt/Ga-Al₂O₃ catalysts prepared with Pt nanoparticles decorated by Ga oxide exhibit superior performance compared to Pt/Al₂O₃ and PtSn/Al₂O₃ catalysts. This insight into interfacial catalysis contributes to a broader understanding of the origin of the high catalytic efficiency observed in metal-based catalysts.

Key words: Metal-based catalysts, C-H dissociation, Propane dehydrogenation, Electronic perturbation, Interfacial catalysis

王哲, 王春鹏, 陆冰, 陈志荣, 王勇, 毛善俊. 界面电子扰动促进的C-H键活化[J]. 催化学报, 2024, 56: 130-138.

Zhe Wang, Chunpeng Wang, Bing Lu, Zhirong Chen, Yong Wang, Shanjun Mao. Electronic perturbation-promoted interfacial pathway for facile C-H dissociation[J]. Chinese Journal of Catalysis, 2024, 56: 130-138.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64575-9

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图/表 5

Fig. 1. HAADF-STEM images and corresponding particle size distribution of 2% Pt/Al2O3 (a) and 2% Pt/Ga-Al2O3 (b). (c,d) Aberration-corrected TEM image and corresponding EDX mapping of 2% Pt/Ga-Al2O3. (e) Pt 4d XPS spectra of 2% Pt/Al2O3 and 2% Pt/Ga-Al2O3. (f) Ga 2p XPS spectra of 2% Pt/Ga-Al2O3-cal (before reduction) and 2% Pt/Ga-Al2O3. (g) FT-IR of CO adsorbed on 2% Pt/Al2O3 and 2% Pt/Ga-Al2O3 at 30 °C (color code in structure models: cyan, Pt; red, O; grey, C). HRTEM and HAADF-STEM (with EDS line data) images of PtNP/Ga-Al2O3-cal (before reduction) (h,i) and PtNP/Ga-Al2O3 (j,k).

Fig. 2. (a) FT-IR of CO adsorbed on 2% Pt/Ga-Al2O3 reduced at different temperature (2% Pt/Ga-Al2O3-cal were catalysts without reduction; 2% Pt/Ga-Al2O3-cal and 2% Pt/Ga-Al2O3-cal denotes catalysts reduced at 200 °C and 300 °C, respectively; 2% Pt/Ga-Al2O3 means reduction at 550 °C, as shown in methods; color code in structure models: cyan, Pt; red, O; grey, C). (b) Proposed scheme for structure evolution of Ga-containing Pt catalysts during reduction process.

Fig. 3. (a) PDH performance of Pt-based catalysts with 2 wt% Pt loading. (b) HAADF-STEM image of 0.6% Pt/Ga-Al2O3; the scale bar corresponds to 10 nm. (c) FT-IR of adsorbed CO on 0.6% Pt/Al2O3 and 0.6% Pt/Ga-Al2O3 (color code in structure models: cyan, Pt; red, O; grey, C). (d) PDH performance of Pt-based catalysts with 0.6 wt% Pt loading. (e) Regeneration property of 0.6% Pt/Ga-Al2O3.

Fig. 4. The free energy profile along the corresponding pathway of propane dehydrogenation on Pt (111) and Ga2O3-Pt model (reaction pathway on Pt (111) plane was shown in Fig. S12; color code in structure models: cyan, Pt; light brown, Ga; red, O; grey, C; white, H).

Fig. 5. (a) Charge density difference of propane dissociated adsorption on Ga2O3-Pt model (yellow and cyan areas means charge depletion and accumulation, respectively, with 0.003 e/?3 isosurface value; light grey, light green, red, brown and white balls denote Pt, Ga, O, C and H atoms, respectively. According to the charge analysis, H bonded to O site lose about 0.62 electron). (b) The reaction (Er) and activation (Ea) energy of the C-H bond (in methylene) dissociation on various active sites. (c) Bader charge of adsorbed H and C3H7 on Pt-O dual sites of different catalyst models. (d) The relationship between C-H activation energy and adsorption energy of H. (e) O 2p partial density of states (pDOS) of various O sites for H adsorption in C-H dissociation. (f) Charge density difference upon Ga2O3 decoration on Pt (111).

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界面电子扰动促进的C-H键活化

Electronic perturbation-promoted interfacial pathway for facile C-H dissociation

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