ZnCr2O4表面CO加氢反应活性位点的探测

doi:10.1016/S1872-2067(21)64008-1

催化学报 ›› 2022, Vol. 43 ›› Issue (8): 2017-2025.DOI: 10.1016/S1872-2067(21)64008-1

• 桥连热、光、电催化的表界面化学专栏 • 上一篇下一篇

ZnCr₂O₄表面CO加氢反应活性位点的探测

凌云健^a^,^b, 冉义华^c, 邵伟鹏^c, 李娜^a^,^b, 焦峰^a, 潘秀莲^a, 傅强^a, 刘志^c, 杨帆^a^,^c^,^d^,^*(), 包信和^a

^a中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连116023
^b中国科学院大学, 北京100039
^c上海科技大学物质科学与技术学院, 上海201210
^d上海科技大学上海市高分辨电子显微学重点实验室, 上海201210

收稿日期:2021-09-19 接受日期:2021-12-20 出版日期:2022-08-18 发布日期:2022-06-20
通讯作者: 杨帆
基金资助:
国家自然科学基金(21972144);国家自然科学基金(92045303);国家自然科学基金(91945302);国家自然科学基金(21991152);上海市科委(20JC1416700);上海市科委(21DZ2260400)

Probing active species for CO hydrogenation over ZnCr₂O₄ catalysts

Yunjian Ling^a^,^b, Yihua Ran^c, Weipeng Shao^c, Na Li^a^,^b, Feng Jiao^a, Xiulian Pan^a, Qiang Fu^a, Zhi Liu^c, Fan Yang^a^,^c^,^d^,^*(), Xinhe Bao^a

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100039, China
^cSchool of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
^dShanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai 201210, China

Received:2021-09-19 Accepted:2021-12-20 Online:2022-08-18 Published:2022-06-20
Contact: Fan Yang
Supported by:
National Natural Science Foundation of China(21972144);National Natural Science Foundation of China(92045303);National Natural Science Foundation of China(91945302);National Natural Science Foundation of China(21991152);Science and Technology Commission of Shanghai Municipality(20JC1416700);Science and Technology Commission of Shanghai Municipality(21DZ2260400)

摘要/Abstract

摘要：

CO加氢转化为高附加值化学品是煤、天然气和生物质等清洁利用的核心过程之一. 近年来, 氧化物催化剂越来越多地被用于加氢反应, 其中ZnCrO_x催化剂广泛应用于C1分子催化加氢反应, 并且是氧化物分子筛(OXZEO)合成气转化催化剂的主要活性组分之一. 由于复合氧化物表面结构的复杂性, 在CO加氢反应中, ZnCrO_x上的活性位点和活化过程尚存在争议.

本文采用原位傅里叶变换红外光谱(FT-IR)和X射线光电子能谱(XPS)研究了不同条件预处理的ZnCr₂O₄尖晶石催化剂在CO/H₂中的原位吸附和反应过程. XPS结果表明, 相较氧化的ZnCr₂O₄, 使用H₂还原的ZnCr₂O₄中Cr⁶⁺的含量会下降, 同时带来更多的表面氧空位或羟基物种. Cr⁶⁺的还原也能由FT-IR谱中位于1013 cm^-1铬酸盐的Cr=O振动峰的消失来证明. 利用CO作为探针分子, FT-IR结果表明还原的ZnCr₂O₄比氧化的ZnCr₂O₄具有更多的CO吸附位点. 通过对比ZnO和Cr₂O₃上的CO吸附波数发现, 这些CO吸附位点并非还原ZnCr₂O₄相分离产生的ZnO和Cr₂O₃, 而是通过直接还原表面Cr位点, 在其周围产生氧空位而产生的新位点. 在室温下, ZnCr₂O₄与CO能反应形成碳酸盐, 还原的ZnCr₂O₄产生碳酸盐的表面吸附量以及结合碳酸盐的稳定性要明显高于氧化的ZnCr₂O₄. 真空室温下, H₂能在还原的ZnCr₂O₄上异裂解离形成氢化物, 并可在373 K稳定存在; 而ZnO表面H₂异裂产生的氢化物在低于室温即已脱附. 还原的ZnCr₂O₄表面形成的氢化物在423 K以上会有部分转化为羟基, 这些羟基具有较高的热稳定性, 在673 K以上才开始脱附. 相比ZnO或Cr₂O₃, 还原的ZnCr₂O₄表面与CO和H₂的作用都要更强.

在CO/H₂ (1:1)混合气氛下, 还原的ZnCr₂O₄表面能发生CO加氢反应, 在373 K发现CO加氢产物甲酸盐形成. 然而, 在只有羟基存在的还原的ZnCr₂O₄表面上, 羟基只能通过水气变换反应氧化CO, 通过羟基含量的减少判断该反应发生在523 K以上; 而ZnCr₂O₄表面H₂异裂形成的氢化物在373-473 K下就能使CO加氢形成甲酰基或甲酸盐. 因此, H₂异裂形成的表面氢化物才是CO加氢的活性物种. 综上, 本文通过探测ZnCr₂O₄上的CO和H₂活化和反应过程, 为复合氧化物表面的CO加氢的基元过程提供了更深入的理解.

关键词: ZnCr₂O₄, 傅里叶变换红外光谱, CO吸附, 氢化物, 羟基

Abstract:

Oxide catalysts are increasingly employed for hydrogenation reactions, among which ZnCrO_x is a major catalyst for the oxide-zeolite (OXZEO) process and for the hydrogenation of C1 molecules in general. Owing to the complex nature of ternary oxides, the surface and catalytic properties of ZnCr₂O₄spinel have remained controversial for CO hydrogenation. Combining in-situ Fourier-transformed infrared spectroscopy and X-ray photoelectron spectroscopy, we examined the adsorption and reaction of CO/H₂ on the ZnCr₂O₄ catalysts, which were pre-treated under oxidative or reductive conditions. The reduced ZnCr₂O₄ catalyst was found to expose more surface sites for CO adsorption/reaction than the oxidized ZnCr₂O₄ catalyst. Exposing the reduced ZnCr₂O₄ to H₂ at room temperature led to the formation of surface hydride species, which would transform into hydroxyl species at elevated temperatures. The reduced ZnCr₂O₄ surface exhibited much stronger interaction with CO and H₂ than ZnO and Cr₂O₃. Exposing the reduced ZnCr₂O₄ to the CO and H₂ (1:1) mixture gas led to the hydrogenation of CO. However, CO was oxidized by the hydroxyl species via the water-gas-shift reaction, whereas the hydrogenation of CO could only be achieved by surface hydride species on the reduced ZnCr₂O₄ to formyl or formate species at 373-473 K. Our study has thus shed light on the active species that control elementary reaction process of CO hydrogenation on complex oxide surfaces.

Key words: ZnCr₂O₄, Fourier-transformed infrared, spectroscopy, CO adsorption, Hydride, Hydroxyl

凌云健, 冉义华, 邵伟鹏, 李娜, 焦峰, 潘秀莲, 傅强, 刘志, 杨帆, 包信和. ZnCr₂O₄表面CO加氢反应活性位点的探测[J]. 催化学报, 2022, 43(8): 2017-2025.

Yunjian Ling, Yihua Ran, Weipeng Shao, Na Li, Feng Jiao, Xiulian Pan, Qiang Fu, Zhi Liu, Fan Yang, Xinhe Bao. Probing active species for CO hydrogenation over ZnCr₂O₄ catalysts[J]. Chinese Journal of Catalysis, 2022, 43(8): 2017-2025.

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图/表 9

Fig. 1. TEM image (a), XRD pattern (b) and quasi-in-situ XPS spectra (c-e) of the ZnCr2O4 catalysts. XPS measurements compared the ZnCr2O4 catalyst pretreated in 1 mbar O2 at 673 K or 10 mbar H2 at 673 K by their Zn 2p (c), Cr 2p3/2 (d) and O 1s (e) spectra, respectively. (f) FT-IR background spectra of the oxidized and reduced ZnCr2O4 catalysts.

Fig. 2. (a) FT-IR spectra of the oxidized and reduced ZnCr2O4 catalysts exposed to 0.001 mbar CO at 120 K. (b) FT-IR spectra of oxidized ZnCr2O4 exposed to 0.001 mbar CO at 117 K, followed by UHV evacuation and the annealing at indicated temperatures from 133 to 313 K in UHV. (c) FT-IR spectra of reduced ZnCr2O4 exposed to 0.001 mbar CO at 114 K, followed by UHV evacuation and the annealing at indicated temperatures from 133 to 333 K in UHV.

Fig. 3. (a) FT-IR spectra of the oxidized and reduced ZnCr2O4 catalysts exposed to 10 mbar CO at room temperature. (b) FT-IR spectra of oxidized ZnCr2O4 exposed to 10 mbar CO at room temperature, followed by UHV evacuation and the annealing at indicated temperatures from 323 to 473 K in UHV. (c) FT-IR spectra of reduced ZnCr2O4 exposed to 10 mbar CO at room temperature, followed by UHV evacuation and the annealing at indicated temperatures from 323 to 873 K in UHV.

Fig. 4. (a) FT-IR spectra of oxidized and reduced ZnCr2O4 catalysts exposed to 12 mbar H2 and 1 bar H2 at room temperature, respectively. (b) FT-IR spectra of oxidized and reduced ZnCr2O4 catalysts exposed to 1 bar D2 at room temperature.

Fig. 5. FT-IR spectra of the reduced ZnCr2O4 catalyst exposed to 1 bar H2 (a) or 1 bar D2 (b) at room temperature, which is followed by UHV evacuation and the annealing at indicated temperatures from 373 to 873 K.

Fig. 6. FT-IR spectra of reduced ZnCr2O4 catalysts exposed to 2 mbar H2/CO (1:1) gas mixture at room temperature, followed by the annealing at 373 and 473 K, respectively.

Fig. 7. FT-IR spectra of reduced ZnCr2O4 and hydroxylated ZnCr2O4 catalysts exposed to 1 bar H2 (a) or 10 mbar CO (b) at room temperature. The hydroxylation was achieved by annealing the reduced ZnCr2O4 in 1 mbar H2 at 623 K.

Fig. 8. FT-IR spectra of hydroxyl-covered ZnCr2O4 catalyst exposed to 1 mbar CO at indicated temperatures from room temperature to 623 K (a,b) and hydride-covered ZnCr2O4 catalyst exposed to 1 mbar CO at indicated temperatures from room temperature to 523 K (c,d). The hydroxyl-covered ZnCr2O4 catalyst was prepared by annealing the reduced ZnCr2O4 in 1 mbar H2 at 623 K. The hydride-covered ZnCr2O4 catalyst was prepared by exposing the reduced ZnCr2O4 in 1 bar H2 at room temperature.

Fig. 9. Schematic diagram on the roles of hydride and hydroxyl species in their reactions with CO on ZnCr2O4.

参考文献

[1]	V. Subramani, S. K. Gangwal, Energy Fuels, 2008, 22, 814-839.
[2]	F. Jiao, J. Li, X. Pan, J. Xiao, H. Li, H. Ma, M. Wei, Y. Pan, Z. Zhou, M. Li, S. Miao, J. Li, Y. Zhu, D. Xiao, T. He, J. Yang, F. Qi, Q. Fu, X. Bao, Science, 2016, 351, 1065-1068.
[3]	S. Kattel, P. J. Ramirez, J. G. Chen, J. A. Rodriguez, P. Liu, Science, 2017, 355, 1296-1299.
[4]	N. Li, F. Jiao, X. L. Pan, Y. Ding, J. Y. Feng, X. H. Bao, ACS Catal., 2019, 9, 960-966.
[5]	M. Behrens, F. Studt, I. Kasatkin, S. Kuhl, M. Havecker, F. Abild-Pedersen, S. Zander, F. Girgsdies, P. Kurr, B. L. Kniep, M. Tovar, R. W. Fischer, J. K. Norskov, R. Schlogl, Science, 2012, 336, 893-897.
[6]	X. Pan, F. Jiao, D. Miao, X. Bao, Chem. Rev., 2021, 121, 6588-6609.
[7]	H. Q. Song, D. Laudenschleger, J. J. Carey, H. Ruland, M. Nolan, M. Muhler, ACS Catal., 2017, 7, 7610-7622.
[8]	X. F. Gao, Y. Q. Wu, G. H. Yang, T. Zhang, X. L. Li, H. J. Xie, J. X. Pan, Y. S. Tan, Appl. Catal. A, 2017, 547, 1-11.
[9]	W. S. Epling, G. B. Hoflund, W. M. Hart, D. M. Minahan, J. Catal., 1997, 169, 438-446.
[10]	G. Delpiero, F. Trifiro, A. Vaccari, J. Chem. Soc., Chem. Commun., 1984, 656-658.
[11]	G. Busca, A. Vaccari, J. Catal., 1987, 108, 491-494.
[12]	A. Riva, F. Trifiro, A. Vaccari, L. Mintchev, G. Busca, J. Chem. Soc., Faraday Trans. 1, 1988, 84, 1423-1435.
[13]	E. Errani, F. Trifiro, A. Vaccari, M. Richter, G. DelPiero, Catal. Lett., 1989, 3, 65-72.
[14]	E. Giamello, B. Fubini, M. Bertoldi, G. Busca, A. Vaccari, J. Chem. Soc., Faraday Trans. 1, 1989, 85, 237-249.
[15]	M. Kurtz, J. Strunk, O. Hinrichsen, M. Muhler, K. Fink, B. Meyer, C. Woll, Angew. Chem. Int. Ed., 2005, 44, 2790-2794.
[16]	S. P. Tian, S. C. Wang, Y. Q. Wu, J. W. Gao, H. J. Xie, X. L. Li, G. H. Yang, Y. Z. Han, Y. S. Tan, RSC Adv., 2015, 5, 89273-89281.
[17]	Y. Cao, J. Luo, W. Huang, Y. Ling, J. Zhu, W. X. Li, F. Yang, X. Bao, J. Chem. Phys., 2020, 152, 074714.
[18]	H. Noei, C. Woll, M. Muhler, Y. M. Wang, Appl. Catal. A, 2011, 391, 31-35.
[19]	M. Buchholz, X. J. Yu, C. W. Yang, S. Heissler, A. Nefedov, Y. M. Wang, C. Woll, Surf. Sci., 2016, 652, 247-252.
[20]	W. Huang, W. W. Zha, D. L. Zhao, S. J. Feng, Solid State Sci., 2019, 87, 49-52.
[21]	J. Q. Zhong, Z. K. Han, K. Werner, X. Y. Li, Y. Gao, S. Shaikhutdinov, H. J. Freund, Angew. Chem. Int. Ed., 2020, 59, 6150-6154.
[22]	D. Klissurski, K. Hadjiivanov, A. Davydov, J. Catal., 1988, 111, 421-424.
[23]	K. Hadjiivanov, G. Busca, Langmuir, 1994, 10, 4534-4541.
[24]	C. Lamberti, E. Groppo, G. Spoto, S. Bordiga, A. Zecchina, Adv. Catal., 2007, 51, 1-74.
[25]	C. Li, Y. Sakata, T. Arai, K. Domen, K.-i. Maruya, T. Onishi, J. Chem. Soc., Faraday Trans. 1, 1989, 85, 929-943.
[26]	Y. Wang, C. Woll, Chem. Soc. Rev., 2017, 46, 1875-1932.
[27]	Y. Y. Li, J. Hu, J. Xu, Y. P. Zheng, M. S. Chen, H. L. Wan, Q. Fu, F. Yang, X. H. Bao, Appl. Surf. Sci., 2019, 494, 353-360.
[28]	H. Noei, H. Qiu, Y. Wang, E. Loffler, C. Woll, M. Muhler, Phys. Chem. Chem. Phys., 2008, 10, 7092-7097.
[29]	G. Busca, J. Mol. Struct., 1990, 218, 363-368.
[30]	F. Boccuzzi, E. Borello, A. Zecchina, A. Bossi, M. Camia, J. Catal., 1978, 51, 150-159.
[31]	Z. Li, K. Werner, L. Chen, A. Jia, K. Qian, J. Q. Zhong, R. You, L. Wu, L. Zhang, H. Pan, X. P. Wu, X. Q. Gong, S. Shaikhutdinov, W. Huang, H. J. Freund, Chem. Eur. J., 2021, 27, 5268-5276.
[32]	Z. Li, K. Werner, K. Qian, R. You, A. Plucienik, A. Jia, L. Wu, L. Zhang, H. Pan, H. Kuhlenbeck, S. Shaikhutdinov, W. Huang, H. J. Freund, Angew. Chem. Int. Ed., 2019, 58, 14686-14693.
[33]	L. Y. Zhang, X. Y. Zhang, K. Qian, Z. R. Li, Y. Q. Cheng, L. L. Daemen, Z. L. Wu, W. X. Huang, J. Energy Chem., 2020, 50, 351-357.
[34]	J. C. Lavalley, J. Saussey, T. Rais, J. Mol. Catal., 1982, 17, 289-298.

ZnCr₂O₄表面CO加氢反应活性位点的探测

Probing active species for CO hydrogenation over ZnCr₂O₄ catalysts

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