乙炔选择加氢反应中碳化钯的动态精细调控: 气氛和氧化锌助剂的作用

doi:10.1016/S1872-2067(24)60033-1

催化学报 ›› 2024, Vol. 60: 190-200.DOI: 10.1016/S1872-2067(24)60033-1

乙炔选择加氢反应中碳化钯的动态精细调控: 气氛和氧化锌助剂的作用

陈欢^a^,^b, 虞周楠^b, 杨冰^b^,^*(), 张亚峰^b, 车春霞^c, 刘晓艳^b, 张峰^c, 韩伟^c, 温翯^c, 王爱琴^b^,^*(), 张涛^a^,^b^,^*()

^a大连理工大学化学学院, 辽宁大连 116024
^b中国科学院大连化学物理研究所, 中国科学院应用催化科学技术重点实验室, 辽宁大连 116023
^c中国石油石油化工研究院兰州化工研究中心, 甘肃兰州 730060

收稿日期:2024-03-04 接受日期:2024-04-03 出版日期:2024-05-18 发布日期:2024-05-20
通讯作者: *电子信箱: byang@dicp.ac.cn (杨冰), aqwang@dicp.ac.cn (王爱琴), taozhang@dicp.ac.cn (张涛)
基金资助:
国家重点研发计划(2023YFA1506603);国家自然科学基金(22132006);国家自然科学基金(22072151);国家自然科学基金委“单原子催化”基础科学中心(22388102);中国博士后科学基金(2023M733452);中国科学院大连化学物理研究所创新基金(DICP I202107);中国石油-大连化物所能源化工联合研发中心科技项目(2017A-1808)

Fine tuning the dynamic PdC_x formation for enhanced acetylene semi-hydrogenation: The role of gas environment and ZnO addition

Huan Chen^a^,^b, Zhounan Yu^b, Bing Yang^b^,^*(), Yafeng Zhang^b, Chunxia Che^c, Xiaoyan Liu^b, Feng Zhang^c, Wei Han^c, He Wen^c, Aiqin Wang^b^,^*(), Tao Zhang^a^,^b^,^*()

^aSchool of Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China
^bCAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cLanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, Lanzhou 730060, Gansu, China

Received:2024-03-04 Accepted:2024-04-03 Online:2024-05-18 Published:2024-05-20
Contact: *E-mail: byang@dicp.ac.cn (B. Yang), aqwang@dicp.ac.cn (A. Wang), taozhang@dicp.ac.cn (T. Zhang).
Supported by:
National Key R&D Program of China(2023YFA1506603);National Natural Science Foundation of China(22132006);National Natural Science Foundation of China(22072151);NSFC Center for Single-Atom Catalysis(22388102);China Postdoctoral Science Foundation(2023M733452);Dalian Institute of Chemical Physics(DICP I202107);CNPC-DICP Joint Project(2017A-1808)

摘要/Abstract

摘要：

碳化钯通常被认为是乙炔选择加氢反应中原位生成的活性相, 其生成有助于抑制次表面非选择性的氢化钯物种, 从而实现高选择性乙炔加氢制乙烯的目标. 次表面上碳化钯和氢化钯物种之间的竞争很大程度上决定了乙炔加氢反应的选择性. 然而, 由于实际反应环境的复杂性, 反应环境下的两种物种之间的动态转化过程和竞争关系尚不清晰. 特别是, 反应环境(比如氢气组分)对碳化钯物种的调控机制仍不明确, 也使得对碳化钯活性物种的精准调控变得困难. 此外, 氧化锌助剂作为乙炔选择加氢反应中最常用的助剂之一, 存在典型的金属-氧化物界面相互作用, 也会对渗碳过程产生重要影响. 因此, 从动态视角理解碳化钯物种的原位形成过程, 对于精准设计和合成高性能乙炔选择加氢钯基催化剂具有重要的科学意义.

近年来, 先进原位表征光谱技术的不断发展使得从原子、分子层面理解原位过程机制成为可能. 本文旨在通过先进的原位表征技术揭示乙炔选择加氢反应中碳化钯物种的动态生成过程, 并进一步探究气氛环境、温度、助催化剂等参数对碳化钯物种的动态调控机制, 从而为高性能乙炔选择加氢催化剂的精准设计和合成提供有力支撑. 原位研究结果表明, 在氢气升温还原条件下, 空气焙烧后新鲜催化剂中氧化钯相首先转变为氢化钯相; 随着还原温度升高, 氢化钯相的含氢量逐渐降低. 当切换至乙炔选择加氢反应原料气时, 氢化钯相迅速分解为金属钯, 并随着恒温碳化时间的延长, 烃类裂解产生的碳原子逐渐渗入钯的体相, 最终形成稳定的碳化钯活性相. 通过移除乙炔加氢反应原料气氛中的氢气, 考察了反应气中的氢气组分对碳化钯形成的调控机制. 实验发现, 在仅有乙炔和乙烯存在时, 碳化过程仍能发生; 而引入少量氢气(体积分数2.2%)后, 碳化程度显著增强, C/Pd原子比从0.136提升至0.154. 相变机理研究表明, 氢气的引入促进了氢化钯物种的形成, 并通过晶格扩张作用促进渗碳过程. 此外, 还研究了氧化锌助剂对原位渗碳过程的影响, 揭示了氧化锌助剂对碳化钯的抑制作用. 结合原位CO吸附漫反射红外光谱、准原位X射线光电子能谱分析发现, 低温氢气还原下Pd-ZnO界面作用促进了微量表面PdZn合金的生成, 从而抑制了碳的渗入. 这种现象在不含氢气的碳化气氛中尤为显著, 碳含量降低一个数量级(C/Pd原子比仅为0.019). 在此基础上, 通过调节反应条件, 实现了对碳化钯物种碳含量的精准调控, 并与反应活性关联, 揭示了碳化钯含量与乙炔选择加氢反应活性之间的线性关系. 电子结构表征和同位素实验进一步表明, Pd-C的电子相互作用促进了向Pd中心原子的电子转移, 从而提高了氢气的活化解离能力和乙炔加氢反应活性.

综上, 本工作原位解析了碳化钯的动态形成过程, 阐明了氢气辅助插碳和ZnO抑制插碳的微观机制, 实现了碳化钯活性物种的精准调控, 揭示了碳化程度与反应活性的线性关系, 为高性能乙炔选择加氢催化剂设计提供了参考.

关键词: 乙炔选择加氢, 碳化钯, 渗碳过程, 原位光谱, 动态机制

Abstract:

Palladium carbide (PdC_x) has been extensively reported as active phase in acetylene semi-hydrogenation that can be dynamically formed during reaction. However, fine tuning of dynamic PdC_x formation towards enhanced acetylene semi-hydrogenation is of great challenge and the dynamic insights remain elusive. In this paper, the state-of-the-art in situ characterizations have been adopted to elucidate the dynamic PdC_x formation for acetylene semi-hydrogenation. The role of hydrogen atmosphere and ZnO addition in tuning the carburization process were clearly identified by in situ spectroscopies. The hydrogen in the gas environment assisted the carbon infiltration via PdH_x hydrides, while the addition of ZnO suppress the carburization by the surface Zn alloy. As a result, the carbon content in PdC_x can be precisely modulated by altering the hydrogen atmosphere and ZnO additives, and exhibits a linear correlation with the activity of acetylene semi-hydrogenation. The carbon insertion enriched the electron state of Pd sites in PdC_x that favors the activation of hydrogen for acetylene semi-hydrogenation. This work thus provides a new route for the design of Pd catalyst for high-performance acetylene semi-hydrogenation by fine tuning the reaction environment and the degree of carburization during dynamic PdC_x formation.

Key words: Acetylene semi-hydrogenation, Palladium carbide, Carburization process, In situ spectroscopy, Dynamic insight

陈欢, 虞周楠, 杨冰, 张亚峰, 车春霞, 刘晓艳, 张峰, 韩伟, 温翯, 王爱琴, 张涛. 乙炔选择加氢反应中碳化钯的动态精细调控: 气氛和氧化锌助剂的作用[J]. 催化学报, 2024, 60: 190-200.

Huan Chen, Zhounan Yu, Bing Yang, Yafeng Zhang, Chunxia Che, Xiaoyan Liu, Feng Zhang, Wei Han, He Wen, Aiqin Wang, Tao Zhang. Fine tuning the dynamic PdC_x formation for enhanced acetylene semi-hydrogenation: The role of gas environment and ZnO addition[J]. Chinese Journal of Catalysis, 2024, 60: 190-200.

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Fig. 1. In situ identification of dynamic PdCx formation. (a) In situ XRD patterns of PdO/Al2O3 sample during the in situ reduction-carburization process. (b?d) BF-STEM images of the typical structure transition of Pd species during in situ reduction-carburization process. The normalized in situ XANES spectra and EXAFS spectra in R-space at Pd K-edge for PdO/Al2O3 sample (e,f), and the evolution of Pd?Pd bond length during the in situ reduction-carburization process (g).

Fig. 2. The role of hydrogen atmosphere and ZnO additives for dynamic PdCx formation. (a) In situ XRD patterns of PdO/Al2O3 and PdO/ZnO/Al2O3 sample under reaction atmosphere with hydrogen or without hydrogen at 120 °C. BF-STEM images of PdZnAl-120 (b) and PdZnAl-N-120 (c) samples were obtained after carburization under reaction atmosphere at 120 °C. The dashed line indicates carbon deposition on particle surface. (d) Carbon content of palladium carbides formed on different samples after carburization at 120 °C. (e) In situ CO-DRIFTS on PdO/Al2O3 sample after treatment under reaction environment with hydrogen (red line) or without hydrogen (black line). (f) In situ CO-DRIFTS on PdO/ZnO/Al2O3 sample after treatment under reaction environment with hydrogen (red line) or without hydrogen (black line). (g) Schematic diagram of hydrogen assisted carbon insertion mechanism.

Fig. 3. Identification of surface Zn and its inhibition effect on carburization. In situ CO-DRIFTS on PdO/Al2O3 sample (a) and PdO/ZnO/Al2O3 sample (b) after in situ reduction-carburization pretreatment under reaction atmosphere with hydrogen at 120 °C. (c) Quasi in situ XPS spectra of Zn LMM of PdO/ZnO/Al2O3 sample under a hydrogen atmosphere. (d) Schematic diagram of in situ reduction-carburization process under different atmospheres and different supports.

Fig. 4. Catalytic performance and the fine tuning of carbon content for acetylene semi-hydrogenation. (a) Acetylene conversion on different catalysts. GHSV are denoted by parentheses in a unit of mL g?1 h?1. T = 80 °C. P = 0.1 MPa. (b) Comparison of acetylene selective hydrogenation mass activity of samples with different degrees of carburization. (c) The linear relationship between mass activity of acetylene semi-hydrogenation and carbon content of catalysts (Activity correction according to ICP results in Table S3). (d) H2-D2 exchange reaction at temperature of 25 °C for PdAl-120 sample carburized at 120 °C (red line) and PdAl-80 sample carburized at 80 °C (marine green line).

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乙炔选择加氢反应中碳化钯的动态精细调控: 气氛和氧化锌助剂的作用

Fine tuning the dynamic PdC_x formation for enhanced acetylene semi-hydrogenation: The role of gas environment and ZnO addition

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乙炔选择加氢反应中碳化钯的动态精细调控: 气氛和氧化锌助剂的作用

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Fine tuning the dynamic PdC_x formation for enhanced acetylene semi-hydrogenation: The role of gas environment and ZnO addition