双金属氧化物催化CO2加氢制备甲醇: 最新进展和挑战

doi:10.1016/S1872-2067(25)64689-4

催化学报 ›› 2025, Vol. 73: 62-78.DOI: 10.1016/S1872-2067(25)64689-4

双金属氧化物催化CO₂加氢制备甲醇: 最新进展和挑战

吴剑峰^a^,^b^,¹(), 梁丽烨^a^,^b^,¹, 车政^b^,¹, 苗宇婷^b, 丑凌军^a()

^a中国科学院兰州化学物理研究所, 低碳催化与二氧化碳利用全国重点实验室, 甘肃兰州 730000
^b兰州大学化学化工学院, 天然产物化学全国重点实验室, 甘肃省有色金属化学与资源利用重点实验室, 甘肃兰州 730000

收稿日期:2024-12-28 接受日期:2025-03-07 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: wjf@licp.cas.cn (吴剑峰),ljchou@licp.cas.cn (丑凌军).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22472181);甘肃省重点人才项目;甘肃省自然科学基金(24JRRA050);中国北方稀土(集团)高科技股份有限公司企业项目(BFXT-2023-D-0048);秦惠䇹与李政道中国大学生见习进修基金(LZU-JZH2534)

Bimetallic oxide catalysts for CO₂ hydrogenation to methanol: Recent advances and challenges

Jian-Feng Wu^a^,^b^,¹(), Li-Ye Liang^a^,^b^,¹, Zheng Che^b^,¹, Yu-Ting Miao^b, Lingjun Chou^a()

^aState Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
^bState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China

Received:2024-12-28 Accepted:2025-03-07 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: wjf@licp.cas.cn (J.-F. Wu),ljchou@licp.cas.cn (L. Chou).
About author:Jian-Feng Wu, PhD, is an Associate Research Fellow at the State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. He obtained his B.A. degree in 2008 and Ph.D. degree in 2014 from Lanzhou University, China. Following this, he conducted postdoctoral research at the Center for Environmentally Beneficial Catalysis at the University of Kansas, USA, from 2014 to 2017. Wu has held positions at the School of Chemistry and Chemical Engineering, Lanzhou University (2017-2023), and currently at the State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences (since 2023). He was recognized as a beneficiary of the key talent program in Gansu Province in 2024 and the talent introduction program of the Chinese Academy of Sciences in 2025. His research primarily focuses on low carbon catalysis, encompassing CO₂ hydrogenation to methanol and methane conversion to CH₃OH, CH₃COOH, and HCOOH.
Lingjun Chou, PhD, Professor in the State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. Research major field is on catalytic material and catalytic processes related to energy conversion.
¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22472181);Key Talent Project of Gansu Province;Natural Science Foundation of Gansu Province(24JRRA050);enterprise project of China Northern Rare Earth (Group) High-Tech Co., Ltd(BFXT-2023-D-0048);Hui-Chun Chin and Tsung-Dao Lee Chinese Undergraduate Research Endowment(LZU-JZH2534)

摘要/Abstract

摘要：

随着化石能源消耗加剧及CO₂过量排放所导致的全球气候危机日益严重, CO₂催化加氢制甲醇作为实现碳循环经济的关键路径备受关注. 传统铜基催化剂(Cu/ZnO/Al₂O₃)受限于水诱导失活及甲醇选择性不足等问题, 难以满足工业化需求. 双金属氧化物催化剂凭借其优异的协同效应、可调控活性位点及优异稳定性成为突破瓶颈的新方向. 尽管双金属氧化物催化剂相较传统铜基催化剂具有明显优势, 但仍面临活性和成本等挑战. 本文系统综述了2015-2024年之间双金属氧化物催化剂的研究进展, 重点探讨催化剂分类、制备方法、构效关系、反应机理及工业化潜力,旨在为高性能催化剂开发提供理论支撑.

本文系统总结了双金属氧化物在CO₂加氢制备甲醇领域的研究进展. 首先, 阐述了双金属氧化物催化剂的分类体系, 主要包括: (1) Co基氧化物催化剂(如MnO_x/Co₃O₄), 通过界面协同作用提升CO₂转化率, 但甲醇选择性较低(~30%), 需通过硅基载体限域或表面改性抑制C-O断裂; (2) In基氧化物催化剂(如In₂O₃/ZrO₂), 依托氧空位高效活化CO₂和H₂、稳定反应中间体, 甲醇选择性达77.3%-99.8%, 单程转化率最高达17.6%, 且千小时稳定性优异, 但水诱导氧空位消耗及铟团聚问题亟待解决; (3) M_aZrO_x (M_a = Zn, Ga等)固溶体催化剂, 通过Zr与M之间的协同效应和M-O键的极化促进H₂异裂解离, 其中GaZrO_x催化剂时空产率达760 g_CH3OH+DME kg_cat^-1 h^-1. 然后, 探讨了影响催化性能的关键因素: 晶体结构(调控表面酸碱性、活性组分分散度和载体-活性组分相互作用等)、助剂(调控活化CO₂和H₂的能力和反应中间体的吸附性能等)和催化剂制备方法(调控催化剂结构特性、传质和活性位点可接近性等). 其后, 进一步对比了几种催化剂的合成成本(需开发低In、Ga含量体系)以及稳定性(需工业化条件验证). 最后, 总结了双金属氧化物的催化机理. 甲酸盐路径被广泛认为是主要途径, 其中HCOO*和CH₃O*为关键中间体, 氧空位与金属-载体界面(如In-V_O-Zr)协同促进CO₂吸附与HCOO*中间体氢化, 而RWGS路径可通过调控表面酸碱性选择性抑制.

尽管取得显著进展, 该领域仍存在亟待突破的瓶颈: (1) 现有体系低温活性不足; (2)催化剂组成局限, 新型双金属组合开发滞后; (3) ZrO₂基固溶体的构效关系缺乏理论计算支撑等. 未来研究应聚焦于: 提高现有双金属氧化物催化剂的性能, 创建新型催化体系, 对双金属协同作用、活性位点结构、催化反应路径和动力学过程进行广泛的理论研究.

关键词: CO₂加氢, 甲醇, 双金属氧化物, 催化性能, 反应机理

Abstract:

Against the backdrop of global energy and environmental crises, the technology of CO₂ hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution. Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability. The performance of bimetallic oxide catalysts is influenced by multiple factors, including the selection of carrier materials, the addition of promoters, and the synthesis process. Different types of bimetallic oxide catalysts exhibit significant differences in microstructure, surface active sites, and electronic structure, which directly determine the yield and selectivity of methanol. Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts, they still encounter challenges related to activity and cost. In order to enhance catalyst performance, future investigations must delve into microstructure control, surface modification, and reaction kinetics.

Key words: CO₂ hydrogenation, Methanol, Bimetallic oxide catalyst, Catalytic performance, Reaction mechanism

吴剑峰, 梁丽烨, 车政, 苗宇婷, 丑凌军. 双金属氧化物催化CO₂加氢制备甲醇: 最新进展和挑战[J]. 催化学报, 2025, 73: 62-78.

Jian-Feng Wu, Li-Ye Liang, Zheng Che, Yu-Ting Miao, Lingjun Chou. Bimetallic oxide catalysts for CO₂ hydrogenation to methanol: Recent advances and challenges[J]. Chinese Journal of Catalysis, 2025, 73: 62-78.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64689-4

https://www.cjcatal.com/CN/Y2025/V73/I6/62

图/表 13

参考文献

[1]	W. Li, H. Wang, X. Jiang, J. Zhu, Z. Liu, X. Guo, C. Song, RSC Adv., 2018, 8, 7651-7669.
[2]	X. Jiang, X. Nie, X. Guo, C. Song, J. G. Chen, Chem. Rev., 2020, 120, 7984-8034.
[3]	J. Zhong, X. Yang, Z. Wu, B. Liang, Y. Huang, T. Zhang, Chem. Soc. Rev., 2020, 49, 1385-1413.
[4]	M. He, Y. Sun, B. Han, Angew. Chem. Int. Ed., 2022, 61, e202112835.
[5]	W. Wang, S. Wang, X. Ma, J. Gong, Chem. Soc. Rev., 2011, 40, 3703-3027.
[6]	M. Aresta, A. Dibenedetto, A. Angelini, Chem. Rev., 2014, 114, 1709-1742.
[7]	W. Zhou, K. Cheng, J. Kang, C. Zhou, V. Subramanian, Q. Zhang, Y. Wang, Chem. Soc. Rev., 2019, 48, 3193-3228.
[8]	S. Das, J. Pérez-Ramírez, J. Gong, N. Dewangan, K. Hidajat, B. C. Gates, S. Kawi, Chem. Soc. Rev., 2020, 49, 2937-3004.
[9]	G. A. Olah, G. K. Prakash, A. Goeppert, J. Am. Chem. Soc., 2011, 133, 12881-12898.
[10]	C. F. Shih, T. Zhang, J. Li, C. Bai, Joule, 2018, 2, 1925-1949.
[11]	M. Saito, K. Murata, Catal. Surv. Asia, 2004, 8, 285-294.
[12]	O. Martin, J. Pérez-Ramírez, Catal. Sci. Technol., 2013, 3, 3343-3352.
[13]	M. B. Fichtl, D. Schlereth, N. Jacobsen, I. Kasatkin, J. Schumann, M. Behrens, R. Schlögl, O. Hinrichsen, Appl. Catal., A, 2015, 502, 262-270.
[14]	A. Bansode, B. Tidona, P. R. von Rohr, A. Urakawa, Catal. Sci. Technol., 2013, 3, 767-778.
[15]	H. Ban, C. Li, K. Asami, K. Fujimoto, Catal. Commun., 2014, 54, 50-54.
[16]	T. Phongamwong, U. Chantaprasertporn, T. Witoon, T. Numpilai, Y. Poo-arporn, W. Limphirat, W. Donphai, P. Dittanet, M. Chareonpanich, J. Limtrakul, Chem. Eng. J., 2017, 316, 692-703.
[17]	S. Li, L. Guo, T. Ishihara, Catal. Today, 2020, 339, 352-361.
[18]	H. Bahruji, M. Bowker, G. Hutchings, N. Dimitratos, P. Wells, E. Gibson, W. Jones, C. Brookes, D. Morgan, G. Lalev, J. Catal., 2016, 343, 133-146.
[19]	T. Toyao, S. Kayamori, Z. Maeno, S. M. A. H. Siddiki, K.-i. Shimizu, ACS Catal., 2019, 9, 8187-8196.
[20]	F. Jiang, S. Wang, B. Liu, J. Liu, L. Wang, Y. Xiao, Y. Xu, X. Liu, ACS Catal., 2020, 10, 11493-11509.
[21]	C. Shen, K. Sun, Z. Zhang, N. Rui, X. Jia, D. Mei, C.-J. Liu, ACS Catal., 2021, 11, 4036-4046.
[22]	X. Jiang, N. Koizumi, X. Guo, C. Song, Appl. Catal. B, 2015, 170-171, 173-185.
[23]	M. M.-J. Li, Z. Zeng, F. Liao, X. Hong, S. C. E. Tsang, J. Catal., 2016, 343, 157-167.
[24]	A. Ota, E. L. Kunkes, I. Kasatkin, E. Groppo, D. Ferri, B. Poceiro, R. M. Navarro Yerga, M. Behrens, J. Catal., 2012, 293, 27-38.
[25]	Z. Shi, Q. Tan, C. Tian, Y. Pan, X. Sun, J. Zhang, D. Wu, J. Catal., 2019, 379, 78-89.
[26]	Y. Yin, B. Hu, X. Li, X. Zhou, X. Hong, G. Liu, Appl. Catal. B, 2018, 234, 143-152.
[27]	Y. Chen, H. Li, W. Zhao, W. Zhang, J. Li, W. Li, X. Zheng, W. Yan, W. Zhang, J. Zhu, R. Si, J. Zeng, Nat. Commun., 2019, 10, 1885.
[28]	X. Li, G. Liu, D. Xu, X. Hong, S. C. Edman Tsang, J. Mater. Chem. A, 2019, 7, 23878-23885.
[29]	L. Wang, W. Zhang, X. Zheng, Y. Chen, W. Wu, J. Qiu, X. Zhao, X. Zhao, Y. Dai, J. Zeng, Nat. Energy, 2017, 2, 869-876.
[30]	K. Cheng, Y. Li, J. Kang, Q. Zhang, Y. Wang, Acc. Chem. Res., 2024, 57, 714-725.
[31]	T. Liu, Z. Liu, S. Jiang, P. Peng, Z. Liu, A. D. Chowdhury, G. Liu, Chem. Soc. Rev., 2025, 54, 2726-2761.
[32]	F. Sha, Z. Han, S. Tang, J. Wang, C. Li, ChemSusChem, 2020, 13, 6160-6181.
[33]	X. Zhang, G. Zhang, W. Liu, F. Yuan, J. Wang, J. Zhu, X. Jiang, A. Zhang, F. Ding, C. Song, X. Guo, Appl. Catal. B, 2021, 284, 119700.
[34]	M. Wang, L. Zheng, G. Wang, J. Cui, G.-L. Guan, Y.-T. Miao, J.-F. Wu, P. Gao, F. Yang, Y. Ling, X. Luo, Q. Zhang, G. Fu, K. Cheng, Y. Wang, J. Am. Chem. Soc., 2024, 146, 14528-14538.
[35]	H. Yang, Z. Wei, J. Zhang, Y. Dang, S. Li, X. Bu, Z. Zhou, C. Gong, H. Wang, J. Li, Y. Liu, Y. Yang, T. Xiao, C. Liu, Y. Sun, P. Gao, Chem, 2024, 10, 2245-2265.
[36]	J. Wang, G. Li, Z. Li, C. Tang, Z. Feng, H. An, H. Liu, T. Liu, C. Li, Sci. Adv., 2017, 3, e1701290.
[37]	Z. Han, C. Tang, F. Sha, S. Tang, J. Wang, C. Li, J. Catal., 2021, 396, 242-250.
[38]	X. Wang, Y. Wang, C. Yang, Y. Yi, X. Wang, F. Liu, J. Cao, H. Pan, Appl. Catal. A, 2020, 595, 117507.
[39]	C. Temvuttirojn, Y. Poo-arporn, N. Chanlek, C. K. Cheng, C. C. Chong, J. Limtrakul, T. Witoon, Ind. Eng. Chem. Res., 2020, 59, 5525-5535.
[40]	T. Pinheiro Araújo, J. Morales-Vidal, T. Zou, M. Agrachev, S. Verstraeten, P. O. Willi, R. N. Grass, G. Jeschke, S. Mitchell, N. López, J. Pérez-Ramírez, Adv. Energy Mater., 2023, 13, 2204122.
[41]	F. Sha, S. Tang, C. Tang, Z. Feng, J. Wang, C. Li, Chin. J. Catal., 2023, 45, 162-173.
[42]	K. Lee, P. C. D. Mendes, H. Jeon, Y. Song, M. P. Dickieson, U. Anjum, L. Chen, T.-C. Yang, C.-M. Yang, M. Choi, S. M. Kozlov, N. Yan, Nat. Commun., 2023, 14, 819.
[43]	J. Wang, C. Tang, G. Li, Z. Han, Z. Li, H. Liu, F. Cheng, C. Li, ACS Catal., 2019, 9, 10253-10259.
[44]	W.-H. Feng, M.-M. Yu, L.-J. Wang, Y.-T. Miao, M. Shakouri, J. Ran, Y. Hu, Z. Li, R. Huang, Y.-L. Lu, D. Gao, J.-F. Wu, ACS Catal., 2021, 11, 4704-4711.
[45]	W. Li, K. Wang, J. Huang, X. Liu, D. Fu, J. Huang, Q. Li, G. Zhan, ACS Appl. Mater. Interfaces, 2019, 11, 33263-33272.
[46]	J. Zhang, B. An, Z. Li, Y. Cao, Y. Dai, W. Wang, L. Zeng, W. Lin, C. Wang, J. Am. Chem. Soc., 2021, 143, 8829-8837.
[47]	S. Dang, B. Qin, Y. Yang, H. Wang, J. Cai, Y. Han, S. Li, P. Gao, Y. Sun, Sci. Adv., 2020, 6, eaaz2060.
[48]	O. Martin, A. J. Martín, C. Mondelli, S. Mitchell, T. F. Segawa, R. Hauert, C. Drouilly, D. Curulla-Ferré, J. Pérez-Ramírez, Angew. Chem. Int. Ed., 2016, 55, 6261-6265.
[49]	P. Zhang, W. Na, J. Zuo, J. Wen, Z. Huang, H. Huang, W. Gao, X. Qi, M. Zheng, H. Wang, Mol. Catal., 2023, 538, 112977.
[50]	K. Stangeland, D. Y. Kalai, Y. Ding, Z. Yu, J. CO₂ Util., 2019, 32, 146-154.
[51]	F. Sha, C. Z. Tang, S. Tang, Q. N. Wang, Z. Han, J. J. Wang, C. Li, J. Catal., 2021, 404, 383-392.
[52]	C.-S. Li, G. Melaet, W. T. Ralston, K. An, C. Brooks, Y. Ye, Y.-S. Liu, J. Zhu, J. Guo, S. Alayoglu, G. A. Somorjai, Nat. Commun., 2015, 6, 6538.
[53]	L. Wang, E. Guan, Y. Wang, L. Wang, Z. Gong, Y. Cui, X. Meng, B. C. Gates, F. S. Xiao, Nat. Commun., 2020, 11, 1033.
[54]	N. H. M. D. Dostagir, C. R. Tomuschat, K. Oshiro, M. Gao, J.-y. Hasegawa, A. Fukuoka, A. Shrotri, JACS Au, 2024, 4, 1048-1058.
[55]	H. Lorenz, W. Jochum, B. Klötzer, M. Stöger-Pollach, S. Schwarz, K. Pfaller, S. Penner, Appl. Catal. A, 2008, 347, 34-42.
[56]	J. Ye, C. Liu, D. Mei, Q. Ge, ACS Catal., 2013, 3, 1296-1306.
[57]	K. Sun, Z. Fan, J. Ye, J. Yan, Q. Ge, Y. Li, W. He, W. Yang, C.-j. Liu, J. CO₂ Util., 2015, 12, 1-6.
[58]	N. Akkharaphatthawon, N. Chanlek, C. K. Cheng, M. Chareonpanich, J. Limtrakul, T. Witoon, Appl. Surf. Sci., 2019, 489, 278-286.
[59]	J. Zhu, F. Cannizzaro, L. Liu, H. Zhang, N. Kosinov, I. A. W. Filot, J. Rabeah, A. Brückner, E. J. M. Hensen, ACS Catal., 2021, 11, 11371-11384.
[60]	Z. M. Detweiler, J. L. White, S. L. Bernasek, A. B. Bocarsly, Langmuir, 2014, 30, 7593-7600.
[61]	L. B. Hoch, T. E. Wood, P. G. O'Brien, K. Liao, L. M. Reyes, C. A. Mims, G. A. Ozin, Adv. Sci., 2014, 1, 1400013.
[62]	A. Wesner, P. Kampe, N. Herrmann, S. Eller, C. Ruhmlieb, J. Albert, ChemCatChem, 2023, 15, e202301125.
[63]	F. Salomone, E. Sartoretti, S. Ballauri, M. Castellino, C. Novara, F. Giorgis, R. Pirone, S. Bensaid, Catal. Today, 2023, 423, 114023.
[64]	L. Liu, B. Mezari, N. Kosinov, E. J. M. Hensen, ACS Catal., 2023, 13, 15730-15745.
[65]	A. Tsoukalou, P. M. Abdala, D. Stoian, X. Huang, M.-G. Willinger, A. Fedorov, C. R. Müller, J. Am. Chem. Soc., 2019, 141, 13497-13505.
[66]	N. Rui, F. Zhang, K. Sun, Z. Liu, W. Xu, E. Stavitski, S. D. Senanayake, J. A. Rodriguez, C.-J. Liu, ACS Catal., 2020, 10, 11307-11317.
[67]	R. Zou, C. Shen, K. Sun, X. Ma, Z. Li, M. Li, C.-J. Liu, J. Energy Chem., 2024, 93, 135-145.
[68]	K. Sun, Z. Zhang, C. Shen, N. Rui, C.-J. Liu, Green Energy Environ., 2022, 7, 807-817.
[69]	Q. Wu, C. Shen, N. Rui, K. Sun, C.-J. Liu, J. CO₂ Util., 2021, 53, 101720.
[70]	D. Cai, Y. Cai, K. B. Tan, G. Zhan, Materials, 2023, 16, 2803.
[71]	I. U. Din, M. S. Shaharun, M. A. Alotaibi, A. I. Alharthi, A. Naeem, J. CO₂ Util., 2019, 34, 20-33.
[72]	K. Li, J. G. Chen, ACS Catal., 2019, 9, 7840-7861.
[73]	Y.-X. Pan, C.-J. Liu, D. Mei, Q. Ge, Langmuir, 2010, 26, 5551-5558.
[74]	Y.-X. Pan, D. Mei, C.-J. Liu, Q. Ge, J. Phys. Chem. C, 2011, 115, 10140-10146.
[75]	J. Wang, C.-Y. Liu, T. P. Senftle, J. Zhu, G. Zhang, X. Guo, C. Song, ACS Catal., 2020, 10, 3264-3273.
[76]	K. Pokrovski, K. T. Jung, A. T. Bell, Langmuir, 2001, 17, 4297-4303.
[77]	K. Samson, M. Śliwa, R. P. Socha, K. Góra-Marek, D. Mucha, D. Rutkowska-Zbik, J. F. Paul, M. Ruggiero-Mikołajczyk, R. Grabowski, J. Słoczyński, ACS Catal., 2014, 4, 3730-3741.
[78]	K. T. Jung, A. T. Bell, Catal. Lett., 2002, 80, 63-68.
[79]	T. Witoon, J. Chalorngtham, P. Dumrongbunditkul, M. Chareonpanich, J. Limtrakul, Chem. Eng. J., 2016, 293, 327-336.
[80]	M. S. Frei, C. Mondelli, A. Cesarini, F. Krumeich, R. Hauert, J. A. Stewart, D. Curulla Ferré, J. Pérez-Ramírez, ACS Catal., 2020, 10, 1133-1145.
[81]	C. Yang, C. Pei, R. Luo, S. Liu, Y. Wang, Z. Wang, Z. J. Zhao, J. Gong, J. Am. Chem. Soc., 2020, 142, 19523-19531.
[82]	L. Lin, G. Wang, F. Zhao, ChemistrySelect, 2021, 6, 2119-2125.
[83]	X. Zhang, X. Yu, R. G. Mendes, P. Matvija, A. E. M. Melcherts, C. Sun, X. Ye, B. M. Weckhuysen, M. Monai, Angew. Chem. Int. Ed., 2025, 64, e202416899.
[84]	A. Tsoukalou, P. M. Abdala, A. Armutlulu, E. Willinger, A. Fedorov, C. R. Müller, ACS Catal., 2020, 10, 10060-10067.
[85]	A. Tsoukalou, A. I. Serykh, E. Willinger, A. Kierzkowska, P. M. Abdala, A. Fedorov, C. R. Müller, Catal. Today, 2022, 387, 38-46.
[86]	A. Tsoukalou, N. S. Bushkov, S. R. Docherty, D. Mance, A. I. Serykh, P. M. Abdala, C. Copéret, A. Fedorov, C. R. Müller, J. Phys. Chem. C, 2022, 126, 1793-1799.
[87]	X. Zhang, A. V. Kirilin, S. Rozeveld, J. H. Kang, G. Pollefeyt, D. F. Yancey, A. Chojecki, B. Vanchura, M. Blum, ACS Catal., 2022, 12, 3868-3880.
[88]	A. Luo, H. Chang, F. Gao, Y. Liu, H. He, Y. Cao, Chem. Commun., 2023, 59, 12747-12750.
[89]	C.-Y. Chou, R. F. Lobo, Appl. Catal. A, 2019, 583, 117144.
[90]	K. Lee, U. Anjum, T. P. Araújo, C. Mondelli, Q. He, S. Furukawa, J. Pérez-Ramírez, S. M. Kozlov, N. Yan, Appl. Catal. B, 2022, 304, 120994.
[91]	Y. Yang, C. Shen, K. Sun, D. Mei, C.-j. Liu, ACS Catal., 2023, 13, 6154-6168.
[92]	S. Yuan, J.-S. Qin, J. Li, L. Huang, L. Feng, Y. Fang, C. Lollar, J. Pang, L. Zhang, D. Sun, A. Alsalme, T. Cagin, H.-C. Zhou, Nat. Commun., 2018, 9, 808.
[93]	T. Numpilai, P. Kidkhunthod, C. K. Cheng, C. Wattanakit, M. Chareonpanich, J. Limtrakul, T. Witoon, Catal. Today, 2021, 375, 298-306.
[94]	K. Lee, M. P. Dickieson, M. Jung, Y. Yang, N. Yan, ACS Catal., 2024, 14, 3074-3089.
[95]	M. Behrens, F. Studt, I. Kasatkin, S. Kühl, M. Hävecker, F. Abild-Pedersen, S. Zander, F. Girgsdies, P. Kurr, B.-L. Kniep, M. Tovar, R. W. Fischer, J. K. Nørskov, R. Schlögl, Science, 2012, 336, 893-897.
[96]	S. Kattel, P. J. Ramírez, J. G. G. Chen, J. A. Rodriguez, P. Liu, Science, 2017, 355, 1296-1299.
[97]	M. Dou, M. Zhang, Y. Chen, Y. Yu, Surf. Sci., 2018, 672-673, 7-12.
[98]	M. Zhang, M. Dou, Y. Yu, Appl. Surf. Sci., 2018, 433, 780-789.
[99]	J. Ye, C. Liu, Q. Ge, J. Phys. Chem. C, 2012, 116, 7817-7825.
[100]	A. Cao, Z. Wang, H. Li, J. K. Nørskov, ACS Catal., 2021, 11, 1780-1786.
[101]	Z. Wei, S. Li, P. Gao, Phys. Chem. Chem. Phys., 2024, 26, 16449-16453.
[102]	S. Tada, N. Ochiai, H. Kinoshita, M. Yoshida, N. Shimada, T. Joutsuka, M. Nishijima, T. Honma, N. Yamauchi, Y. Kobayashi, K. Iyoki, ACS Catal., 2022, 12, 7748-7759.
[103]	Z. Feng, C. Tang, P. Zhang, K. Li, G. Li, J. Wang, Z. Feng, C. Li, J. Am. Chem. Soc., 2023, 145, 12663-12672.
[104]	J. Wang, S. Li, W. Liu, Y. Xiao, Z. Feng, X. Liang, S. Tang, G. Li, C. Dong, F. Pan, C. Li, CCS Chem., 2024, 6, 2996-3007.
[105]	X. Wang, Z. Yao, X. Guo, Z. Yan, H. Ban, P. Wang, R. Yao, L. Li, C. Li, ACS Catal., 2024, 14, 508-521.
[106]	N. Podrojková, V. Sans, A. Oriňak, R. Oriňaková, ChemCatChem, 2020, 12, 1802-1825.
[107]	S. Zhou, S. Li, J. Phys. Chem. C, 2020, 124, 27467-27478.
[108]	G. H. Graaf, E. J. Stamhuis, A. A. C. M. Beenackers, Chem. Eng. Sci., 1988, 43, 3185-3195.
[109]	C. Tang, S. Tang, F. Sha, Z. Han, Z. Feng, J. Wang, C. Li, J. Phys. Chem. C, 2022, 126, 10399-10407.
[110]	M. S. Frei, M. Capdevila-Cortada, R. García-Muelas, C. Mondelli, N. López, J. A. Stewart, D. Curulla Ferré, J. Pérez-Ramírez, J. Catal., 2018, 361, 313-321.
[111]	C. Cao, T. Chen, X. Ding, H. Huang, J. Xu, Y. Han, CIESC J., 2019, 70, 3985-3993.
[112]	S. Ghosh, J. Sebastian, L. Olsson, D. Creaser, Chem. Eng. J., 2021, 416, 129120.
[113]	W. L. Ng, P. Sripada, S. Biswas, S. Bhattacharya, Appl. Catal. A, 2022, 646, 118885.

Catalyst	Preparation method	n_H2/n_CO2	T (K)	P (MPa)	GHSV ^a mL g_cat^‒1 h^‒1	CO₂ Conv. (%)	Methanol Sel. (%)	STY ^b g_MeOH kg_cat^‒1 h^‒1	Ref.
ZnO-ZrO₂	co-precipitation	3/1	593	5	24000	10	86	737	[36]
ZnO-ZrO₂	co-precipitation	3/1	573	2	24000	3.4	87	250	[36]
ZnO-ZrO₂	EISA^c	3/1	593	2	24000	6.4	78.5	413	[37]
ZnO/t-ZrO₂	microreaction	3/1	593	3	12000	9.2	93.1	350	[38]
ZnO_x/ZrO₂-600	impregnation	3/1	573	2	9000	5.5	75.1	106	[39]
ZnZrO_x	flame spray pyrolysis	4/1	593	5	24000	8.7	78.3	460	[40]
ZnZrO_x	reflux ammonia	6/1	563	5	24000	8.4	95.6	377	[41]
Pd/CNT+ZnZrO_x	mechanical mixed	4/1	593	5	24000	18.1	66.3	900	[42]
CdZrO_x	co-precipitation	3/1	573	2	24000^d	5.5	80	—	[43]
GaZrO_x	co-precipitation	3/1	573	2	24000^d	2.4	75	—	[43]
GaZrO_x	EISA^c	3/1	603	4	24000	10.8	72.9^e	760^f	[44]
ZnO-ZrO₂ (UiO-66)	thermal pyrolysis	3/1	593	3	18000	5.7	70	—	[45]
ZnO-ZrO₂ (MOF-808)	postsynthetic treatment	3/1	523	4	9000^d	2.1	>99	30.4	[46]
h-In₂O₃(104)	hydrothermal	6/1	573	5	9000	17.6	92.4	288	[47]
In₂O₃/ZrO₂	impregnation	4/1	573	5	16000^d	5.2	99.8	295	[48]
In₂O₃/ZrO₂	hydrothermal	3/1	573	3	12000^d	8.83	77.3	269	[49]
20MnO_x-Co₃O₄	sol-gel	3/1	523	1	88800^d	—	30	—	[50]
Ga-ZnZrO_x	co-precipitation	3/1	593	5	24000	8.8	87.5	630	[51]

Catalyst	Preparation method	n_H2/n_CO2	T (K)	P (MPa)	GHSV ^a mL g_cat^‒1 h^‒1	CO₂ Conv. (%)	Methanol Sel. (%)	STY ^b g_MeOH kg_cat^‒1 h^‒1	Ref.
ZnO-ZrO₂	co-precipitation	3/1	593	5	24000	10	86	737	[36]
ZnO-ZrO₂	co-precipitation	3/1	573	2	24000	3.4	87	250	[36]
ZnO-ZrO₂	EISA^c	3/1	593	2	24000	6.4	78.5	413	[37]
ZnO/t-ZrO₂	microreaction	3/1	593	3	12000	9.2	93.1	350	[38]
ZnO_x/ZrO₂-600	impregnation	3/1	573	2	9000	5.5	75.1	106	[39]
ZnZrO_x	flame spray pyrolysis	4/1	593	5	24000	8.7	78.3	460	[40]
ZnZrO_x	reflux ammonia	6/1	563	5	24000	8.4	95.6	377	[41]
Pd/CNT+ZnZrO_x	mechanical mixed	4/1	593	5	24000	18.1	66.3	900	[42]
CdZrO_x	co-precipitation	3/1	573	2	24000^d	5.5	80	—	[43]
GaZrO_x	co-precipitation	3/1	573	2	24000^d	2.4	75	—	[43]
GaZrO_x	EISA^c	3/1	603	4	24000	10.8	72.9^e	760^f	[44]
ZnO-ZrO₂ (UiO-66)	thermal pyrolysis	3/1	593	3	18000	5.7	70	—	[45]
ZnO-ZrO₂ (MOF-808)	postsynthetic treatment	3/1	523	4	9000^d	2.1	>99	30.4	[46]
h-In₂O₃(104)	hydrothermal	6/1	573	5	9000	17.6	92.4	288	[47]
In₂O₃/ZrO₂	impregnation	4/1	573	5	16000^d	5.2	99.8	295	[48]
In₂O₃/ZrO₂	hydrothermal	3/1	573	3	12000^d	8.83	77.3	269	[49]
20MnO_x-Co₃O₄	sol-gel	3/1	523	1	88800^d	—	30	—	[50]
Ga-ZnZrO_x	co-precipitation	3/1	593	5	24000	8.8	87.5	630	[51]

Catalyst type	Price range ($ kg⁻¹)
Cu/ZnO/Al₂O₃	~80 to ~200
ZnO-ZrO₂	~130 to ~275
GaZrO_x	~230 to ~400
In₂O₃/ZrO₂	~300 to ~600

Catalyst type	Price range ($ kg⁻¹)
Cu/ZnO/Al₂O₃	~80 to ~200
ZnO-ZrO₂	~130 to ~275
GaZrO_x	~230 to ~400
In₂O₃/ZrO₂	~300 to ~600

双金属氧化物催化CO₂加氢制备甲醇: 最新进展和挑战

Bimetallic oxide catalysts for CO₂ hydrogenation to methanol: Recent advances and challenges

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 13

参考文献

相关文章 15

编辑推荐

Metrics

[1]	庹杰, 盛振腾, 龚贤晨, 杨琪, 吴鹏, 徐浩. ZnCeZrO_x/MCM-22择形催化二氧化碳加氢耦合甲苯甲基化反应[J]. 催化学报, 2025, 73(6): 174-185.
[2]	胡晓春, 陶龙刚, 雷坤, 孙志强, 谭明务. 揭示TiO₂相效应对Pt单原子催化剂高效CO₂转化的影响[J]. 催化学报, 2025, 73(6): 186-195.
[3]	肖佩佩, 王勇, 唐晓敏, 郑安民, Trees De Baerdemaeker, Andrei-Nicolae Parvulescu, Dirk De Vos, 孟祥举, 肖丰收, Hermann Gies, 横井俊之. 有机结构导向剂的异构体影响AEI沸石中铝的分布及其在甲烷氧化中的催化性能[J]. 催化学报, 2025, 73(6): 252-260.
[4]	石德志, 陈艳艳, 陈晓, 王森, 王强, 王鹏飞, 朱华青, 董梅, 徐君, 邓风, 王建国, 樊卫斌. [Ga(OH)]²⁺负载介孔中空结构H-ZSM-5: 一种高效低碳烷烃芳构化催化剂[J]. 催化学报, 2025, 72(5): 359-375.
[5]	詹钰捷, 钟承钦, 毕明莉, 梁亚飞, 祁玉基, 陈家琪, 刘家旭, 张新党, 张帅, 王业红, 王峰. 催化甲醇选择性氧化制甲醛的铁钒催化剂活性位点的识别[J]. 催化学报, 2025, 72(5): 334-343.
[6]	蔚张茜, 王明秀, 路昕楠, 周紫璇, 唐梓祁, 常春然, 杨永, 李圣刚, 高鹏. CO₂加氢反应诱导过程中In₂O₃催化剂结构演变的实验和理论研究[J]. 催化学报, 2025, 72(5): 301-313.
[7]	张亚楠, 张雯娜, 张成伟, 何林海, 林杉帆, 徐舒涛, 魏迎旭, 刘中民. C1物种在甲醇制烃类反应过程中的作用: 超越反应物角色[J]. 催化学报, 2025, 71(4): 169-178.
[8]	李显泉, 庞纪峰, 赵于嘉, 李林, 于文广, 徐斐斐, 苏扬, 杨小峰, 罗文豪, 郑明远. 乙醇乙醛催化转化制丁二烯的双分子协同吸附机制研究[J]. 催化学报, 2025, 71(4): 297-307.
[9]	王一潮, 张磊磊, 潘晓丽, 王爱琴, 张涛. 碳化铁催化氢气气氛下苯甲醇脱氧偶联制备联苄类化学品[J]. 催化学报, 2025, 71(4): 179-186.
[10]	陈瑶, 戈钧. 固定化催化剂合成5-羟甲基糠醛及其氧化衍生物: 高效的绿色可持续技术[J]. 催化学报, 2025, 71(4): 5-24.
[11]	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(4): 146-157.
[12]	蔡子国, 于学峰, 王鹏龙, 吴慧芳, 种瑞峰, 任利敏, 胡涛, 王翔. CO₂加氢制甲醇Cu/ZnO/Y₂O₃催化剂中Y₂O₃的作用[J]. 催化学报, 2025, 70(3): 410-419.
[13]	班涛, 王建伟, 余希阳, 田海阔, 高新, 黄正清, 常春然. 机器学习辅助筛选SA-FLP双活性位催化剂用于甲烷与水共转化制甲醇反应[J]. 催化学报, 2025, 70(3): 311-321.
[14]	李爽, 林海莉, 贾雪梅, 金昕, 汪钱龙, 李馨悦, 陈士夫, 曹静. 双金属Ni_xFe₂₋_xP修饰的RP用于增强光催化苯甲醇氧化耦合产H₂[J]. 催化学报, 2025, 70(3): 363-377.
[15]	李兴娟, 郭昱昊, 管勤辉, 李晓, 张璐璐, 冉维广, 李娜, 颜廷江. 高密度Au-O_V协同位点促进串联光催化CO₂加氢制CH₃OH[J]. 催化学报, 2025, 69(2): 303-314.