CeO2载体在CO2加氢制甲醇中的应用和研究进展

doi:10.16085/j.issn.1000-6613.2023-2207

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2723-2738.DOI: 10.16085/j.issn.1000-6613.2023-2207

• 二氧化碳捕集与资源化利用 • 上一篇

CeO₂载体在CO₂加氢制甲醇中的应用和研究进展

周运桃¹^,²(), 王洪星¹^,², 李新刚¹(), 崔丽凤²()

^1.化学工程联合国家重点实验室，天津化学化工协同创新中心，天津市应用催化科学与工程重点实验室，天津大学化工学院，天津 300354
^2.山东华鲁恒升化工股份有限公司，山东德州 253024

收稿日期:2023-12-15 修回日期:2024-03-01 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 李新刚,崔丽凤
作者简介:周运桃（1988—），男，博士，研究方向为催化反应。E-mail：zhouyuntao1005@163.com。
基金资助:
国家重点研发计划(2022YFB4101800)

Application and research progress of CeO₂ support in CO₂hydrogenation to methanol

ZHOU Yuntao¹^,²(), WANG Hongxing¹^,², LI Xingang¹(), CUI Lifeng²()

^1.State Key Laboratory of Chemical Engineering, Collaborative Innovation Center of Chemical Science and Engineering, Tianjin Key Laboratory of Applied Catalysis Science and Engineering, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354, China
^2.Shandong Hualu Hengsheng Chemical Co. , Ltd. , Dezhou 253024, Shandong, China

Received:2023-12-15 Revised:2024-03-01 Online:2024-05-15 Published:2024-06-15
Contact: LI Xingang, CUI Lifeng

摘要/Abstract

摘要：

随着经济的快速发展，CO₂排放导致的温室效应日益严峻，通过与绿氢反应将其转化为甲醇等有价值的化工产品是减少CO₂排放、缓解全球气候变暖的有效途径。近年来，CeO₂负载金属催化剂在CO₂加氢制甲醇反应中得到了广泛关注。本文主要综述了CeO₂表面氧空位和碱性位点、Ce³⁺/Ce⁴⁺可逆氧化还原能力、几何形貌等特性在CO₂/H₂吸附活化和甲醇形成过程中所起到的重要作用，比较了CeO₂与ZrO₂、ZnO以及复合金属氧化物等载体在反应中的差异，提出了CeO₂载体催化剂在确认活性关键中间体、兼顾CO₂转化率和甲醇选择性、提高催化活性与稳定性等方面的不足和挑战，以期为新型CO₂加氢制甲醇催化剂的设计提供有益参考。

关键词: 二氧化碳, 加氢, 催化剂, CeO₂载体, 甲醇, 活性

Abstract:

The urgency of addressing the greenhouse effect produced by CO₂ emissions is growing due to the economy’s rapid development. Reducing CO₂ emissions and slowing down global warming can be accomplished by reacting CO₂ with green hydrogen to produce value-added chemical compounds like methanol. Recently, CeO₂-supported metal catalysts for CO₂ hydrogenation to methanol have received extensive attentions. In this review, the importance of CeO₂ surface oxygen vacancy, basic sites, Ce³⁺/Ce⁴⁺ reversible redox ability, and unique geometric morphology were highlighted in the processes of CO₂/H₂ adsorption and activation and methanol formation. Moreover, the catalytic activities between CeO₂ and ZrO₂, ZnO and composite metal oxides supports were compared. Finally, the shortcomings and challenges in identifying active key intermediates, compromising between CO₂ conversion and methanol selectivity, and improving the catalytic activity and stability of CeO₂-based catalysts were highlighted. This work could provide useful advises for further design of CO₂ hydrogenation to methanol catalysts.

Key words: carbon dioxide, hydrogenation, catalyst, CeO₂ support, methanol, activation

中图分类号:

TQ426

周运桃, 王洪星, 李新刚, 崔丽凤. CeO₂载体在CO₂加氢制甲醇中的应用和研究进展[J]. 化工进展, 2024, 43(5): 2723-2738.

ZHOU Yuntao, WANG Hongxing, LI Xingang, CUI Lifeng. Application and research progress of CeO₂ support in CO₂hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2723-2738.

图/表 17

参考文献 102

1	FORSTER Piers M, SMITH Christopher J, WALSH Tristram, et al. Indicators of global climate change 2022: Annual update of large-scale indicators of the state of the climate system and human influence[J]. Earth System Science Data, 2023, 15(6): 2295-2327.
2	CHENG Lijing, ABRAHAM John, TRENBERTH Kevin E, et al. Another year of record heat for the oceans[J]. Advances in Atmospheric Sciences, 2023, 40(6): 963-974.
3	LAN Xin, TANS Pieter, KIRK Thoning. Trends in globally-averaged CO₂ determined from NOAA Global Monitoring Laboratory measurements[EB/OL]. (2023-11-30) [2023-12-10]. .
4	LIN Qingyang, ZHANG Xiao, WANG Tao, et al. Technical perspective of carbon capture, utilization, and storage[J]. Engineering, 2022, 14: 27-32.
5	DE Sudipta, DOKANIA Abhay, RAMIREZ Adrian, et al. Advances in the design of heterogeneous catalysts and thermocatalytic processes for CO₂ utilization[J]. ACS Catalysis, 2020, 10(23): 14147-14185.
6	KUMARAVEL Vignesh, BARTLETT John, PILLAI Suresh C. Photoelectrochemical conversion of carbon dioxide (CO₂) into fuels and value-added products[J]. ACS Energy Letters, 2020, 5(2): 486-519.
7	GAO Peng, ZHANG Lina, LI Shenggang, et al. Novel heterogeneous catalysts for CO₂ hydrogenation to liquid fuels[J]. ACS Central Science, 2020, 6(10): 1657-1670.
8	KALIYAPERUMAL Alamelu, GUPTA Pooja, PRASAD Yadavalli Satya Sivaram, et al. Recent progress and perspective of the electrochemical conversion of carbon dioxide to alcohols[J]. ACS Engineering Au, 2023, 3(6): 403-425.
9	GANJI Parameswaram, CHOWDARI Ramesh Kumar, LIKOZAR Blaž. Photocatalytic reduction of carbon dioxide to methanol: Carbonaceous materials, kinetics, industrial feasibility, and future directions[J]. Energy & Fuels, 2023, 37(11): 7577-7602.
10	MINYUKOVA Tatyana P, DOKUCHITS Eugene V. Hydrogen for CO₂ processing in heterogeneous catalytic reactions[J]. International Journal of Hydrogen Energy, 2023, 48(59): 22462-22483.
11	SHIH Choon Fong, ZHANG Tao, LI Jinghai, et al. Powering the future with liquid sunshine[J]. Joule, 2018, 2(10): 1925-1949.
12	DANG Shanshan, YANG Haiyan, GAO Peng, et al. A review of research progress on heterogeneous catalysts for methanol synthesis from carbon dioxide hydrogenation[J]. Catalysis Today, 2019, 330: 61-75.
13	ZHONG Jiawei, YANG Xiaofeng, WU Zhilian, et al. State of the art and perspectives in heterogeneous catalysis of CO₂ hydrogenation to methanol[J]. Chemical Society Reviews, 2020, 49(5): 1385-1413.
14	ROY Soumyabrata, CHEREVOTAN Arjun, PETER Sebastian C. Thermochemical CO₂ hydrogenation to single carbon products: Scientific and technological challenges[J]. ACS Energy Letters, 2018, 3(8): 1938-1966.
15	BAI Shaotao, DE SMET Gilles, LIAO Yuhe, et al. Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions[J]. Chemical Society Reviews, 2021, 50(7): 4259-4298.
16	MURTHY Pradeep S, LIANG Weibin, JIANG Yijiao, et al. Cu-based nanocatalysts for CO₂ hydrogenation to methanol[J]. Energy & Fuels, 2021, 35(10): 8558-8584.
17	VIEIRA Luiz H, RASTEIRO Letícia F, SANTANA Cássia S, et al. Noble metals in recent developments of heterogeneous catalysts for CO₂ conversion processes[J]. ChemCatChem, 2023, 15(14): e202300493.
18	LIANG Binglian, MA Junguo, SU Xiong, et al. Investigation on deactivation of Cu/ZnO/Al₂O₃ catalyst for CO₂ hydrogenation to methanol[J]. Industrial & Engineering Chemistry Research, 2019, 58(21): 9030-9037.
19	WANG Jijie, LI Guanna, LI Zelong, et al. A highly selective and stable ZnO-ZrO₂ solid solution catalyst for CO₂ hydrogenation to methanol[J]. Science Advances, 2017, 3(10): e1701290.
20	YANG Chengsheng, PEI Chunlei, LUO Ran, et al. Strong electronic oxide-support interaction over In₂O₃/ZrO₂ for highly selective CO₂ hydrogenation to methanol[J]. Journal of the American Chemical Society, 2020, 142(46): 19523-19531.
21	MARTIN Oliver, MARTÍN Antonio J, MONDELLI Cecilia, et al. Indium oxide as a superior catalyst for methanol synthesis by CO₂ hydrogenation[J]. Angewandte Chemie International Edition, 2016, 55(21): 6261-6265.
22	LI Huazheng, QIU Chenglong, REN Shoujie, et al. Na⁺-gated water-conducting nanochannels for boosting CO₂ conversion to liquid fuels[J]. Science, 2020, 367(6478): 667-671.
23	SONOWAL Karanika, NANDAL Neha, BASYACH Purashri, et al. Photocatalytic reduction of CO₂ to methanol using Zr(Ⅳ)-based MOF composite with g-C₃N₄ quantum dots under visible light irradiation[J]. Journal of CO₂ Utilization, 2022, 57: 101905.
24	WANG Fei, WEI Min, EVANS David G, et al. CeO₂-based heterogeneous catalysts toward catalytic conversion of CO₂ [J]. Journal of Materials Chemistry A, 2016, 4(16): 5773-5783.
25	CHANG Kuan, ZHANG Haochen, CHENG Mu-jeng, et al. Application of ceria in CO₂ conversion catalysis[J]. ACS Catalysis, 2020, 10(1): 613-631.
26	ZHANG Sai, TIAN Zhimin, MA Yuanyuan, et al. Adsorption of molecules on defective CeO₂ for advanced catalysis[J]. ACS Catalysis, 2023, 13(7): 4629-4645.
27	GRACIANI Jesús, MUDIYANSELAGE Kumudu, XU Fang, et al. Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO₂ [J]. Science, 2014, 345(6196): 546-550.
28	HUANG Weixin, GAO Yuxian. Morphology-dependent surface chemistry and catalysis of CeO₂ nanocrystals[J]. Catalysis Science & Technology, 2014, 4(11): 3772-3784.
29	TROVARELLI Alessandro, LLORCA Jordi. Ceria catalysts at nanoscale: How do crystal shapes shape catalysis?[J]. ACS Catalysis, 2017, 7(7): 4716-4735.
30	MA Yuanyuan, GAO Wei, ZHANG Zhiyun, et al. Regulating the surface of nanoceria and its applications in heterogeneous catalysis[J]. Surface Science Reports, 2018, 73(1): 1-36.
31	LI Ping, CHEN Xiaoyin, LI Yongdan, et al. A review on oxygen storage capacity of CeO₂-based materials: Influence factors, measurement techniques, and applications in reactions related to catalytic automotive emissions control[J]. Catalysis Today, 2019, 327: 90-115.
32	HUANG Xiubing, ZHANG Kaiyue, PENG Baoxiang, et al. Ceria-based materials for thermocatalytic and photocatalytic organic synthesis[J]. ACS Catalysis, 2021, 11(15): 9618-9678.
33	VIVIER Laurence, DUPREZ Daniel. Ceria-based solid catalysts for organic chemistry[J]. ChemSusChem, 2010, 3(6): 654-678.
34	LI Ge, WANG Ping, HE Miao, et al. Cerium-based nanomaterials for photo/electrocatalysis[J]. Science China Chemistry, 2023, 66(8): 2204-2220.
35	CAI Jun, LI Danyang, JIANG Lei, et al. Review on CeO₂-based photocatalysts for photocatalytic reduction of CO₂: Progresses and perspectives[J]. Energy & Fuels, 2023, 37(7): 4878-4897.
36	WANG Jianda, XIAO Xiao, LIU Yong, et al. The application of CeO₂-based materials in electrocatalysis[J]. Journal of Materials Chemistry A, 2019, 7(30): 17675-17702.
37	YU Jun, DU Xinjuan, LIU Hongzhi, et al. Mini review on active sites in Ce-based electrocatalysts for alkaline water splitting[J]. Energy & Fuels, 2021, 35(23): 19000-19011.
38	MONTINI Tiziano, MELCHIONNA Michele, MONAI Matteo, et al. Fundamentals and catalytic applications of CeO₂-based materials[J]. Chemical Reviews, 2016, 116(10): 5987-6041.
39	SINGH Rajan, PANDEY Vaibhav, PANT Kamal Kishore. Promotional role of oxygen vacancy defects and Cu-Ce interfacial sites on the activity of Cu/CeO₂ catalyst for CO₂ hydrogenation to methanol[J]. ChemCatChem, 2022, 14(24): e202201053.
40	GAO Peng, LI Feng, ZHAO Ning, et al. Influence of modifier (Mn, La, Ce, Zr and Y) on the performance of Cu/Zn/Al catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Applied Catalysis A: General, 2013, 468: 442-452.
41	SINGH Rajan, TRIPATHI Komal, PANT Kamal Kishore. Investigating the role of oxygen vacancies and basic site density in tuning methanol selectivity over Cu/CeO₂ catalyst during CO₂ hydrogenation[J]. Fuel, 2021, 303: 121289.
42	WANG Weiwei, QU Zhenping, SONG Lixin, et al. CO₂ hydrogenation to methanol over Cu/CeO₂ and Cu/ZrO₂ catalysts: Tuning methanol selectivity via metal-support interaction[J]. Journal of Energy Chemistry, 2020, 40: 22-30.
43	FAN Liping, ZHANG Jing, MA Kexin, et al. Ceria morphology-dependent Pd-CeO₂ interaction and catalysis in CO₂ hydrogenation into formate[J]. Journal of Catalysis, 2021, 397: 116-127.
44	XIE Yu, CHEN Jianjun, WU Xi, et al. Frustrated Lewis pairs boosting low-temperature CO₂ methanation performance over Ni/CeO₂ nanocatalysts[J]. ACS Catalysis, 2022, 12(17): 10587-10602.
45	ZHANG Sai, XIA Zhaoming, ZOU Yong, et al. Interfacial frustrated Lewis pairs of CeO₂ activate CO₂ for selective tandem transformation of olefins and CO₂ into cyclic carbonates[J]. Journal of the American Chemical Society, 2019, 141(29): 11353-11357.
46	LIU Bin, LI Congming, ZHANG Guoqiang, et al. Oxygen vacancy promoting dimethyl carbonate synthesis from CO₂ and methanol over Zr-doped CeO₂ nanorods[J]. ACS Catalysis, 2018, 8(11): 10446-10456.
47	ZHANG Wei, MA Xuelu, XIAO Hai, et al. Mechanistic investigations on thermal hydrogenation of CO₂ to methanol by nanostructured CeO₂(100): The crystal-plane effect on catalytic reactivity[J]. The Journal of Physical Chemistry C, 2019, 123(18): 11763-11771.
48	KUMARI Neetu, HAIDER M ALI, AGARWAL Manish, et al. Role of reduced CeO₂(110) surface for CO₂ reduction to CO and methanol[J]. The Journal of Physical Chemistry C, 2016, 120(30): 16626-16635.
49	SCHMITT Rafael, NENNING Andreas, KRAYNIS Olga, et al. A review of defect structure and chemistry in ceria and its solid solutions[J]. Chemical Society Reviews, 2020, 49(2): 554-592.
50	GUO Chen, WEI Shuxian, ZHOU Sainan, et al. Initial reduction of CO₂ on Pd-, Ru-, and Cu-doped CeO₂(111) surfaces: Effects of surface modification on catalytic activity and selectivity[J]. ACS Applied Materials & Interfaces, 2017, 9(31): 26107-26117.
51	Marçal CAPDEVILA-CORTADA, Gianvito VILÉ, TESCHNER Detre, et al. Reactivity descriptors for ceria in catalysis[J]. Applied Catalysis B: Environmental, 2016, 197: 299-312.
52	ZHANG Yang, ZHAO Shuna, FENG Jing, et al. Unraveling the physical chemistry and materials science of CeO₂-based nanostructures[J]. Chem., 2021, 7(8): 2022-2059.
53	JIANG Feng, WANG Shanshan, LIU Bing, et al. Insights into the influence of CeO₂crystal facet on CO₂hydrogenation to methanol over Pd/CeO₂catalysts[J]. ACS Catalysis, 2020, 10(19): 11493-11509.
54	OUYANG Bi, TAN Weiling, LIU Bing. Morphology effect of nanostructure ceria on the Cu/CeO₂ catalysts for synthesis of methanol from CO₂ hydrogenation[J]. Catalysis Communications, 2017, 95: 36-39.
55	WEI Yuechang, ZHANG Yilin, ZHANG Peng, et al. Boosting the removal of diesel soot particles by the optimal exposed crystal facet of CeO₂ in Au/CeO₂ catalysts[J]. Environmental Science & Technology, 2020, 54(3): 2002-2011.
56	WANG Zheng, HUANG Zhenpeng, BROSNAHAN John T, et al. Ru/CeO₂ catalyst with optimized CeO₂ support morphology and surface facets for propane combustion[J]. Environmental Science & Technology, 2019, 53(9): 5349-5358.
57	WERNER Kristin, WENG Xuefei, CALAZA Florencia, et al. Toward an understanding of selective alkyne hydrogenation on ceria: On the impact of O vacancies on H₂ interaction with CeO₂(111)[J]. Journal of the American Chemical Society, 2017, 139(48): 17608-17616.
58	WANG Zhiqiang, CHU Deren, ZHOU Hui, et al. Role of low-coordinated Ce in hydride formation and selective hydrogenation reactions on CeO₂ surfaces[J]. ACS Catalysis, 2022, 12(1): 624-632.
59	WANG Zhiqiang, LIU Huihui, WU Xinping, et al. Hydride generation on the Cu-doped CeO₂(111) surface and its role in CO₂ hydrogenation reactions[J]. Catalysts, 2022, 12(9): 963.
60	LEE Jaeha, TIEU Peter, FINZEL Jordan, et al. How Pt influences H₂ reactions on high surface-area Pt/CeO₂ powder catalyst surfaces[J]. JACS Au, 2023, 3(8): 2299-2313.
61	AZHARI Noerma J, ERIKA Denanti, MARDIANA St, et al. Methanol synthesis from CO₂: A mechanistic overview[J]. Results in Engineering, 2022, 16: 100711.
62	ZHAO Yafan, YANG Yong, MIMS Charles, et al. Insight into methanol synthesis from CO₂ hydrogenation on Cu(111): Complex reaction network and the effects of H₂O[J]. Journal of Catalysis, 2011, 281(2): 199-211.
63	LIU Lingna, YAO Hedan, JIANG Zhao, et al. Theoretical study of methanol synthesis from CO₂ hydrogenation on PdCu₃(111) surface[J]. Applied Surface Science, 2018, 451: 333-345.
64	NIE Xiaowa, JIANG Xiao, WANG Haozhi, et al. Mechanistic understanding of alloy effect and water promotion for Pd-Cu bimetallic catalysts in CO₂ hydrogenation to methanol[J]. ACS Catalysis, 2018, 8(6): 4873-4892.
65	WU Wenlong, WANG Yanan, LUO Lei, et al. CO₂ hydrogenation over copper/ZnO single-atom catalysts: Water-promoted transient synthesis of methanol[J]. Angewandte Chemie, 2022, 134(48): e202213024.
66	JIANG Lei, LI Kongzhai, PORTER William N, et al. Role of H₂O in catalytic conversion of C₁ molecules[J]. Journal of the American Chemical Society, 2024, 146(5): 2857-2875.
67	WANG Hao, ZHANG Guangcheng, FAN Guoli, et al. Fabrication of Zr-Ce oxide solid solution surrounded Cu-based catalyst assisted by a microliquid film reactor for efficient CO₂ hydrogenation to produce methanol[J]. Industrial & Engineering Chemistry Research, 2021, 60(45): 16188-16200.
68	NIE Mengdong, CUI Aixin, WU Man, et al. CuO/LaCeO _x catalysts with enhanced metal-support interactions for CO₂ methanolization[J]. Journal of CO₂ Utilization, 2023, 75: 102579.
69	MALIK Ali Shan, ZAMAN Sharif F, AL-ZAHRANI Abdulrahim A, et al. Development of highly selective PdZn/CeO₂ and Ca-doped PdZn/CeO₂ catalysts for methanol synthesis from CO₂ hydrogenation[J]. Applied Catalysis A: General, 2018, 560: 42-53.
70	REZVANI Azita, ABDEL-MAGEED Ali M, ISHIDA Tamao, et al. CO₂reduction to methanol on Au/CeO₂catalysts: Mechanistic insights from activation/deactivation and SSITKA measurements[J]. ACS Catalysis, 2020, 10(6): 3580-3594.
71	TAN Qingqing, SHI Zhisheng, WU Dongfang. CO₂ hydrogenation over differently morphological CeO₂-supported Cu-Ni catalysts[J]. International Journal of Energy Research, 2019, 43(10): 5392-5404.
72	PASUPULETY Nagaraju, DRISS Hafedh, RAFIQUI Mohammed Raoof A, et al. Methanol synthesis using CO₂ and H₂ on nano silver-ceria zirconia catalysts: Influence of preparation method[J]. Journal of Nanoscience and Nanotechnology, 2019, 19(6): 3197-3204.
73	CHENG Zhuo, SHERMAN Brent J, Cynthia S LO. Carbon dioxide activation and dissociation on ceria(110): A density functional theory study[J]. The Journal of Chemical Physics, 2013, 138(1): 014702.
74	MURAVEV Valery, PARASTAEV Alexander, VAN DEN BOSCH Yannis, et al. Size of cerium dioxide support nanocrystals dictates reactivity of highly dispersed palladium catalysts[J]. Science, 2023, 380(6650): 1174-1179.
75	CHOI Eun Jeong, LEE Yong Hee, LEE Dae-Won, et al. Hydrogenation of CO₂ to methanol over Pd-Cu/CeO₂ catalysts[J]. Molecular Catalysis, 2017, 434: 146-153.
76	OJELADE Opeyemi A, ZAMAN Sharif F, DAOUS Muhammad A, et al. Optimizing Pd: Zn molar ratio in PdZn/CeO₂ for CO₂ hydrogenation to methanol[J]. Applied Catalysis A: General, 2019, 584: 117185.
77	TAN Qingqing, SHI Zhisheng, WU Dongfang. CO₂ hydrogenation to methanol over a highly active Cu-Ni/CeO₂-nanotube catalyst[J]. Industrial & Engineering Chemistry Research, 2018, 57(31): 10148-10158.
78	WU Congyi, CHENG Danyang, WANG Meng, et al. Understanding and application of strong metal-support interactions in conversion of CO₂ to methanol: A review[J]. Energy & Fuels, 2021, 35(23): 19012-19023.
79	ZHU Jiadong, SU Yaqiong, CHAI Jiachun, et al. Mechanism and nature of active sites for methanol synthesis from CO/CO₂ on Cu/CeO₂ [J]. ACS Catalysis, 2020, 10(19): 11532-11544.
80	VOURROS A, GARAGOUNIS I, KYRIAKOU V, et al. Carbon dioxide hydrogenation over supported Au nanoparticles: Effect of the support[J]. Journal of CO₂ Utilization, 2017, 19: 247-256.
81	RASTEIRO Letícia F, DE SOUSA Rafael A, VIEIRA Luiz H, et al. Insights into the alloy-support synergistic effects for the CO₂ hydrogenation towards methanol on oxide-supported Ni₅Ga₃ catalysts: An experimental and DFT study[J]. Applied Catalysis B: Environmental, 2022, 302: 120842.
82	YANG Xiaofang, KATTEL Shyam, SENANAYAKE Sanjaya D, et al. Low pressure CO₂ hydrogenation to methanol over gold nanoparticles activated on a CeO _x /TiO₂ interface[J]. Journal of the American Chemical Society, 2015, 137(32): 10104-10107.
83	ABDEL-MAGEED Ali M, KLYUSHIN Alexander, REZVANI Azita, et al. Negative charging of Au nanoparticles during methanol synthesis from CO₂/H₂ on a Au/ZnO catalyst: Insights from operando IR and near-ambient-pressure XPS and XAS measurements[J]. Angewandte Chemie International Edition, 2019, 58(30): 10325-10329.
84	CHANG Shuai, NA Wei, ZHANG Jiaqi, et al. Effect of the Zn/Ce ratio in Cu/ZnO-CeO₂ catalysts on CO₂ hydrogenation for methanol synthesis[J]. New Journal of Chemistry, 2021, 45(48): 22814-22823.
85	LI Shaozhong, GUO Limin, ISHIHARA Tatsumi. Hydrogenation of CO₂ to methanol over Cu/AlCeO catalyst[J]. Catalysis Today, 2020, 339: 352-361.
86	ZHANG Jingpeng, SUN Xiaohang, WU Congyi, et al. Engineering Cu⁺/CeZrO _x interfaces to promote CO₂ hydrogenation to methanol[J]. Journal of Energy Chemistry, 2023, 77: 45-53.
87	SHI Zhisheng, TAN Qingqing, WU Dongfang. Ternary copper-cerium-zirconium mixed metal oxide catalyst for direct CO₂ hydrogenation to methanol[J]. Materials Chemistry and Physics, 2018, 219: 263-272.
88	ZABILSKIY Maxim, MA Kaibo, BECK Arik, et al. Methanol synthesis over Cu/CeO₂-ZrO₂ catalysts: The key role of multiple active components[J]. Catalysis Science & Technology, 2021, 11(1): 349-358.
89	WANG Weiwei, QU Zhenping, SONG Lixin, et al. An investigation of Zr/Ce ratio influencing the catalytic performance of CuO/Ce_1- _x Zr _x O₂ catalyst for CO₂ hydrogenation to CH₃OH[J]. Journal of Energy Chemistry, 2020, 47: 18-28.
90	NIE Mengdong, GUO Tuo, QIANG Fangyuan, et al. Effect of Mn content in CuO/MnCeO _x catalysts on CO₂ hydrogenation for methanol synthesis[J]. Reaction Chemistry & Engineering, 2023, 8(6): 1383-1394.
91	YAN Yong, WONG Roong Jien, MA Zhirui, et al. CO₂ hydrogenation to methanol on tungsten-doped Cu/CeO₂ catalysts[J]. Applied Catalysis B: Environmental, 2022, 306: 121098.
92	LI Shaozhong, WANG Yu, YANG Bin, et al. A highly active and selective mesostructured Cu/AlCeO catalyst for CO₂ hydrogenation to methanol[J]. Applied Catalysis A: General, 2019, 571: 51-60.
93	ATTADA Yerrayya, VELISOJU Vijay Kumar, MOHAMED Hend Omar, et al. Dual experimental and computational approach to elucidate the effect of Ga on Cu/CeO₂-ZrO₂ catalyst for CO₂ hydrogenation[J]. Journal of CO₂ Utilization, 2022, 65: 102251.
94	MA Nana, CHENG Weiyi, WEI Changgeng, et al. Mechanism of methanol synthesis from CO₂ on Cu/CeO₂ and Cu/W-CeO₂: A DFT investigation into the nature of W-doping[J]. Journal of Materials Chemistry A, 2024, 12(4): 2323-2334.
95	RODRIGUEZ José A, LIU Ping, GRACIANI Jesús, et al. Inverse oxide/metal catalysts in fundamental studies and practical applications: A perspective of recent developments[J]. The Journal of Physical Chemistry Letters, 2016, 7(13): 2627-2639.
96	SENANAYAKE Sanjaya D, STACCHIOLA Dario, RODRIGUEZ Jose A. Unique properties of ceria nanoparticles supported on metals: Novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction[J]. Accounts of Chemical Research, 2013, 46(8): 1702-1711.
97	KAPIAMBA Kashala Fabrice, OTOR Hope O, VIAMAJALA Sridhar, et al. Inverse oxide/metal catalysts for CO₂ hydrogenation to methanol[J]. Energy & Fuels, 2022, 36(19): 11691-11711.
98	SENANAYAKE Sanjaya D, RAMÍREZ Pedro J, WALUYO Iradwikanari, et al. Hydrogenation of CO₂ to methanol on CeO _x /Cu(111) and ZnO/Cu(111) catalysts: Role of the metal-oxide interface and importance of Ce³⁺ sites[J]. The Journal of Physical Chemistry C, 2016, 120(3): 1778-1784.
99	MONCADA Jorge, CHEN Xiaobo, DENG Kaixi, et al. Structural and chemical evolution of an inverse CeO _x /Cu catalyst under CO₂ hydrogenation: Tunning oxide morphology to improve activity and selectivity[J]. ACS Catalysis, 2023, 13(23): 15248-15258.
100	LOU Yang, JIANG Feng, ZHU Wen, et al. CeO₂ supported Pd dimers boosting CO₂ hydrogenation to ethanol[J]. Applied Catalysis B: Environmental, 2021, 291: 120122.
101	ZHENG Ke, LI Yufeng, LIU Bing, et al. Ti-doped CeO₂ stabilized single-atom rhodium catalyst for selective and stable CO₂ hydrogenation to ethanol[J]. Angewandte Chemie International Edition, 2022, 61(44): e202210991.
102	CHEN Jie, ZHA Yajun, LIU Bing, et al. Rationally designed water enriched nano reactor for stable CO₂ hydrogenation with near 100% ethanol selectivity over diatomic palladium active sites[J]. ACS Catalysis, 2023, 13(10): 7110-7121.

催化剂	H₂/CO₂	温度/℃，压力/MPa	GHSV/WHSV	CO₂转化率/%	甲醇选择性/%	STY/g·kg_cat^-1·h^-1
2Pd/CeO₂-R^[53]	3	240，3.0	2.0L/(g_cat·h)	约6.2^①	约30^①	12.0
2Pd/CeO₂-P^[53]	3	240，3.0	2.0L/(g_cat·h)	—	约29^①	9.5
2Pd/CeO₂-C^[53]	3	240，3.0	2.0L/(g_cat·h)	—	约25^①	5.0
2Pd/CeO₂-O^[53]	3	240，3.0	2.0L/(g_cat·h)	约6.3^①	约26^①	2.5
Cu/CeO₂-R^[54]	3	240，2.0	3.0L/(g_cat·h)	约2.2^①	89.5	21.1
Cu/CeO₂-C^[54]	3	240，2.0	3.0L/(g_cat·h)	约1.5^①	84	13.5
Cu/CeO₂-S^[54]	3	240，2.0	3.0L/(g_cat·h)	约0.6^①	89	5.7
1Cu2Ni/CeO₂-R^[71]	3	260，3.0	6.0L/h	18.3	73.3	230.2
1Cu2Ni/CeO₂-S^[71]	3	260，3.0	6.0L/h	约17.5^①	约69.5^①	208.8
1Cu2Ni/CeO₂-P^[71]	3	260，3.0	6.0L/h	约14.0^①	约68.5^①	164.6
Cu/CeO₂-SG^[39]	3	240，3.0	2.4L/(g_cat·h)	6.4	89.1	48.9
Cu/CeO₂-SCP^[39]	3	240，3.0	2.4L/(g_cat·h)	5.9	84.6	42.8
Cu/CeO₂-CP^[39]	3	240，3.0	2.4L/(g_cat·h)	3.8	80.5	26.2
Cu-CF^[67]	3	260，3.0	18.0L/(g_cat·h)	约9.8^①	约41.0^①	249.0
Cu-CP^[67]	3	260，3.0	18.0L·/(g_cat·h)	约9.0^①	约35.0^①	197.0
Cu-IM^[67]	3	260，3.0	18.0L/(g_cat·h)	约5.1^①	约42.5^①	143.0
5Ag/ZrCeO _x-IM^[72]	3	250，2.0	1.8L/h	7	70	31.9
5Ag/ZrCeO _x-CH^[72]	3	250，2.0	1.8L/h	8	60	30.9

催化剂	H₂/CO₂	温度/℃，压力/MPa	GHSV/WHSV	CO₂转化率/%	甲醇选择性/%	STY/g·kg_cat^-1·h^-1
2Pd/CeO₂-R^[53]	3	240，3.0	2.0L/(g_cat·h)	约6.2^①	约30^①	12.0
2Pd/CeO₂-P^[53]	3	240，3.0	2.0L/(g_cat·h)	—	约29^①	9.5
2Pd/CeO₂-C^[53]	3	240，3.0	2.0L/(g_cat·h)	—	约25^①	5.0
2Pd/CeO₂-O^[53]	3	240，3.0	2.0L/(g_cat·h)	约6.3^①	约26^①	2.5
Cu/CeO₂-R^[54]	3	240，2.0	3.0L/(g_cat·h)	约2.2^①	89.5	21.1
Cu/CeO₂-C^[54]	3	240，2.0	3.0L/(g_cat·h)	约1.5^①	84	13.5
Cu/CeO₂-S^[54]	3	240，2.0	3.0L/(g_cat·h)	约0.6^①	89	5.7
1Cu2Ni/CeO₂-R^[71]	3	260，3.0	6.0L/h	18.3	73.3	230.2
1Cu2Ni/CeO₂-S^[71]	3	260，3.0	6.0L/h	约17.5^①	约69.5^①	208.8
1Cu2Ni/CeO₂-P^[71]	3	260，3.0	6.0L/h	约14.0^①	约68.5^①	164.6
Cu/CeO₂-SG^[39]	3	240，3.0	2.4L/(g_cat·h)	6.4	89.1	48.9
Cu/CeO₂-SCP^[39]	3	240，3.0	2.4L/(g_cat·h)	5.9	84.6	42.8
Cu/CeO₂-CP^[39]	3	240，3.0	2.4L/(g_cat·h)	3.8	80.5	26.2
Cu-CF^[67]	3	260，3.0	18.0L/(g_cat·h)	约9.8^①	约41.0^①	249.0
Cu-CP^[67]	3	260，3.0	18.0L·/(g_cat·h)	约9.0^①	约35.0^①	197.0
Cu-IM^[67]	3	260，3.0	18.0L/(g_cat·h)	约5.1^①	约42.5^①	143.0
5Ag/ZrCeO _x-IM^[72]	3	250，2.0	1.8L/h	7	70	31.9
5Ag/ZrCeO _x-CH^[72]	3	250，2.0	1.8L/h	8	60	30.9

催化剂	H₂/CO₂	温度/℃，压力/MPa	GHSV/WHSV	CO₂转化率/%	甲醇选择性/%	STY/g·kg_cat^-1·h^-1
1Pd-10Cu/CeO₂^[75]	3	250，3.0	3.0L/(g_cat·h)	16.1	26.7	28.3
5Pd5Zn/CeO₂^[69]	3	220，3.0	2.4L/(g_cat·h)	6.3	100	54.1
0.5Ca5Pd5Zn/CeO₂^[69]	3	220，3.0	2.4L/(g_cat·h)	7.7	100	66.1
PdZn/CeO₂^[76]	3	220，2.0	2.4L/(g_cat·h)	14.1	94.5	114.3
CuNi₂/CeO₂-NT^[77]	3	260，3.0	6.0L/h	17.8	78.8	579.9

催化剂	H₂/CO₂	温度/℃，压力/MPa	GHSV/WHSV	CO₂转化率/%	甲醇选择性/%	STY/g·kg_cat^-1·h^-1
1Pd-10Cu/CeO₂^[75]	3	250，3.0	3.0L/(g_cat·h)	16.1	26.7	28.3
5Pd5Zn/CeO₂^[69]	3	220，3.0	2.4L/(g_cat·h)	6.3	100	54.1
0.5Ca5Pd5Zn/CeO₂^[69]	3	220，3.0	2.4L/(g_cat·h)	7.7	100	66.1
PdZn/CeO₂^[76]	3	220，2.0	2.4L/(g_cat·h)	14.1	94.5	114.3
CuNi₂/CeO₂-NT^[77]	3	260，3.0	6.0L/h	17.8	78.8	579.9

催化剂	H₂/CO₂	温度/℃，压力/MPa	GHSV/WHSV	CO₂转化率/%	甲醇选择性/%	STY/g·kg_cat^-1·h^-1
Cu/CeO₂^[41]	3	220，3.0	2.4L/(g_cat·h)	约2.5^①	91	19.5
Cu/ZrO₂^[41]	3	220，3.0	2.4L/(g_cat·h)	约3.0^①	80	20.6
Cu/ZnO^[41]	3	220，3.0	2.4L/(g_cat·h)	约3.5^①	74	22.2
Cu/CeO₂^[42]	3	220，3.0	10L/h	4.5	约85^①	136.8
Cu/ZrO₂^[42]	3	220，3.0	10L/h	6.5	约77^①	179.0
Cu/CeO₂^[79]	3	250，3.0	30L/(g_cat·h)	1.0	53	45.5
Cu/SiO₂^[79]	3	250，3.0	60L/(g_cat·h)	1.1	16	30.2
Au/CeO₂^[80]	9	225，0.1	20L/h	—	62.2	—
Au/ZnO^[80]	9	225，0.1	20L/h	—	88.9	—
Ni₅Ga₃/SiO₂^[81]	3	270，1.0	8.0L/(g_cat·h)	1.5	12.5	50.0
Ni₅Ga₃/ZrO₂^[81]	3	270，1.0	8.0L/(g_cat·h)	3.5	18.0	160.0
Ni₅Ga₃/CeO₂^[81]	3	270，1.0	8.0L/(g_cat·h)	6.1	3.4	54.0

CeO₂载体在CO₂加氢制甲醇中的应用和研究进展

Application and research progress of CeO₂ support in CO₂hydrogenation to methanol

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催化剂	H₂/CO₂	温度/℃，压力/MPa	GHSV/WHSV	CO₂转化率/%	甲醇选择性/%	STY/g·kg_cat^-1·h^-1
Cu/ZnO-CeO₂^[84]	3	280，3.0	12.0L/h	15.6	64.5	431.7
Cu/AlCeO-7^[85]	3	260，3.0	14.4L/(g_cat·h)	约17^①	约45^①	381.3
Cu_0.3Zr_0.3Ce_0.7^[86]	3	240，3.0	30.0L/(g_cat·h)	4.1	55.3	192.0
Cu₃₀Ce₃₅Zr₃₅O^[87]	3	250，3.0	7.5L/(g_cat·h)	14.3	53.8	165.0
5-Cu-CeO₂/ZrO₂^[88]	3	260，5.0	60.0L/(g_cat·h)	1.7	42	147.1
CuO/Ce_0.4Zr_0.6O₂^[89]	3	280，3.0	10.0L/h	13.2	71.8	338.9
CuO/Mn_0.2CeO _x^[90]	3	260，1.5	6.0L/(g_cat·h)	14.2	82.3	250.0
CuO/La_0.25CeO _x^[68]	3	260，1.5	6.0L/(g_cat·h)	15.7	83.3	281.0
Cu/CeO₂^[91]	3	250，3.5	15.0L/(g_cat·h)	1.3	51	40.4
Cu/CeW_0.25O _x^[91]	3	250，3.5	15.0L/(g_cat·h)	13	87	394.7

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