Application and research progress of CeO2 support in CO2 hydrogenation to methanol

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

Abstract

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

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

CLC Number:

TQ426

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.

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.

Figures/Tables 17

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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
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

Application and research progress of CeO₂ support in CO₂hydrogenation to methanol

CeO₂载体在CO₂加氢制甲醇中的应用和研究进展

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Figures/Tables 17

References 102

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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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