Research Progress on the Design, Preparation and Properties of Catalysts for CO2 Hydrogenation to Alcohols

doi:10.6023/A23040126

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (8): 1081-1100.DOI: 10.6023/A23040126 Previous Articles

Review

CO₂加氢制醇类催化剂的设计制备及性能研究进展

崔国庆^*(), 胡溢玚, 娄颖洁, 周明霞, 李宇明, 王雅君, 姜桂元, 徐春明^*()

中国石油大学(北京) 重质油全国重点实验室北京 102249

投稿日期:2023-04-10 发布日期:2023-09-14

作者简介:

崔国庆, 博士, 硕士生导师, 2020年6月在北京化工大学获得化学工程与技术博士学位, 师从段雪教授和卫敏教授. 2020年至今在中国石油大学(北京)重质油全国重点实验室从事能源催化方面的研究工作, 目前, 已在Nat. Commun.、Angew. Chem. Int. Ed.、ACS Catal.、Appl. Catal. B: Environ.、J. Catal.和《化工学报》等期刊发表研究论文20余篇, 获2021年中国分析测试协会科学技术奖(CAIA奖)一等奖1项等.

胡溢玚, 中国石油大学(北京)在读研究生, 2021年6月于中国石油大学(北京)化学工程与环境学院获得能源化学工程学士学位, 主要研究方向为二氧化碳的热催化转化与高效利用.

徐春明, 教授, 博士生导师, 中国科学院院士, 重质油全国重点实验室主任, 碳中和未来技术学院院长, 山东石油化工学院院长, 国家杰出青年基金获得者, “全国优秀教师”称号获得者, 国家“万人计划”百千万工程领军人才, 国家自然科学基金创新研究群体项目负责人, 全国优秀教师, 北京市教学名师, 北京市课程思政教学名师, 国家级教学团队负责人, 中国化工学会副理事长. 主要致力于重油高效转化和清洁油品生产、新能源技术等研究, 主持国家重点研发、国家基金委创新研究群体、重点基金等20余个项目, 获国家技术发明二等奖1项, 国家科技进步二等奖2项, 中国石油和化学工业联合会技术发明特等奖1项, 省部级一等奖8项等, 发表高水平论文300余篇, 撰写专著4部, 授权国际发明专利36件、中国发明专利102件, 其中实施转化48件等.

基金资助:
项目受国家自然科学基金(22109177); 中央高校基本科研业务费专项资金(2462020BJRC008)

Research Progress on the Design, Preparation and Properties of Catalysts for CO₂ Hydrogenation to Alcohols

Guoqing Cui(), Yiyang Hu, Yingjie Lou, Mingxia Zhou, Yuming Li, Yajun Wang, Guiyuan Jiang, Chunming Xu()

State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249

Received:2023-04-10 Published:2023-09-14
Contact: *E-mail: cui@cup.edu.cn; xcm@cup.edu.cn
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22109177); Fundamental Research Funds for the Central Universities(2462020BJRC008)

CO₂, as one of the most important renewable C₁ resource and oxygen resource, has the advantages of abundant reserves, low price, safe and non-toxic, etc. CO₂ can be converted into high-value chemicals and fuels such as alcohols with the help of the heterogeneous thermal-catalytic technologies, which have attracted widespread attention and developed rapidly in both academic research and industrial applications. In particular, the design and preparation of the catalysts with satisfactory catalytic CO₂ hydrogenation performance (high activity, selectivity and stability) at mild condition still remain a huge challenge. In recent years, the structural design of catalysts for CO₂ hydrogenation to alcohols has been widely reported, in which great advances have been achieved in the metal-based and metal oxide-based catalysts. In this review, the basic reaction steps and reaction mechanism for the hydrogenation reaction of carbon dioxide to methanol, ethanol and other C₂₊ alcohols are overviewed in details. The structural characteristic, catalytic performance and structure-activity relationship are analyzed and categorized from the perspective of metals, metal oxide, metal carbide and metal sulfide components. Finally, the challenges and potential research directions of CO₂ hydrogenation to alcohols are elucidated and prospected in the future.

Key words: CO₂ hydrogenation, alcohols, catalyst, structure design, reaction mechanism

Cite this article

Guoqing Cui, Yiyang Hu, Yingjie Lou, Mingxia Zhou, Yuming Li, Yajun Wang, Guiyuan Jiang, Chunming Xu. Research Progress on the Design, Preparation and Properties of Catalysts for CO₂ Hydrogenation to Alcohols[J]. Acta Chimica Sinica, 2023, 81(8): 1081-1100.

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反应名称	反应式	$\Delta H_{\operatorname{san}}^{n}$/(kJ•mol⁻¹)
CO₂加氢制甲醇	CO₂＋3H₂ → CH₃OH＋H₂O	－49.5
逆水汽变换反应	CO_2＋H₂ → CO＋H₂O	＋41.2
CO加氢制甲醇	CO＋2H₂ → CH₃OH	－90.4

反应名称	反应式	$\Delta H_{\operatorname{san}}^{n}$/(kJ•mol⁻¹)
CO₂加氢制甲醇	CO₂＋3H₂ → CH₃OH＋H₂O	－49.5
逆水汽变换反应	CO_2＋H₂ → CO＋H₂O	＋41.2
CO加氢制甲醇	CO＋2H₂ → CH₃OH	－90.4

催化剂	温度/℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	甲醇选择性^a/%	甲醇STY/ (mg•g_cat⁻¹•h⁻¹)	参考文献
CuZnAl-C-1.0	240	3.0	3600	3	14.6	63.6	120	[49]
CuZnAl-O-1.0	240	3.0	3600	3	12.1	62.6	100	[49]
CuZnAl-U-1.0	240	3.0	3600	3	3.2	53.9	22	[49]
AE-Cu/SiO₂	190	3.0	2040	3	1.4	52.8	30 (mg•g_Cu⁻¹•h⁻¹)	[50]
FSP-Cu/SiO₂	190	3.0	2040	3	5.2	79.3	168 (mg•g_Cu⁻¹•h⁻¹)	[50]
Cu/ZnO/Al₂O₃	250	2.0	2000	3	13.4	13	9.28 (mg•mL_cat⁻¹•h⁻¹)	[51]
CuZnGa-LDH	270	4.5	18000	3	—	—	590	[52]
CuZnGa-LDH-ww	270	4.5	18000	3	—	—	320	[52]
CZG5Ga	270	4.5	18000	3	—	—	370	[52]
CuZn/Al-M	280	0.5	36000	3	3.1	28.6	105	[53]
CuZn/Al-N	280	0.5	36000	3	2.8	24.5	83	[53]
Cu/Al-M	280	0.5	36000	3	0.2	8.4	2	[53]
2CuZnAl-In3	250	3.0	30000	3	—	35	134.4	[54]
Cu_0.5Zn_0.4Ce_0.1/SBA-15	260	3.0	1200	3	6.5	—	—	[55]
Cu_0.5Zn_0.4Ce_0.1/MCM-41	260	3.0	1200	3	2.2	—	—	[55]
Cu_0.5Zn_0.4Ce_0.1/SiO₂	260	3.0	1200	3	2.8	—	—	[55]
Cu_0.5Zn_0.4Ce_0.1	260	3.0	1200	3	13.9		—	[55]
CuZnAlZr	250	3.0	54000	3	14.2	57.2	1376	[57]
Cu-ZnO/Al₂O₃-ZrO₂	200	5.0	7800	3	8.4	94	201.6	[58]
CuZnZr-1	180	3.0	—	3	1.61	100.0	—	[59]
CuZnZr-1.5	180	3.0	—	3	2.42	100.0	—	[59]
CuZnZr-2	180	3.0	—	3	2.75	100.0	—	[59]
CuZnZr-2.5	180	3.0	—	3	3.87	100.0	—	[59]
CuZnZr-4	180	3.0	—	3	4.37	89.22	—	[59]
CuZnZr-8	180	3.0	—	3	6.26	83.41	—	[59]
CuZnZr-12	180	3.0	—	3	6.67	82.74	—	[59]
CuZnZr-15	180	3.0	—	3	6.50	82.97	—	[59]
Cu-SiO_2P	225	3.0	—	3	3.5	77	140	[60]
Cu/SiO_2−2h	230	2.5	—	3	—	45	0.41 (g•g_Cu⁻¹•h⁻¹)	[61]
Cu/Mo₂CT_x/SiO_2-2h	230	2.5	—	3	—	54	1.5 (g•g_Cu⁻¹•h⁻¹)	[61]
Cu/Mo₂CT_x/SiO_2-6h	230	2.5	—	3	—	52	2.5 (g•g_Cu⁻¹•h⁻¹)	[61]
CuZnO-MOF-74-350	190	4.0	4000	3	7.5	78.2	80	[63]
CuZnO-MOF-74-350	210	4.0	16000	3	6.3	79.6	290	[63]
CuZnO-MOF-74-350	240	4.0	16000	3	14.5	54.0	450	[63]
Cu-ZnO@UiO-bpy	250	4.0	18000	3	3.3	100	2.59 (g_MeOH•kg_Cu⁻¹•h⁻¹)	[64]
Cu/ZnO/Al₂O₃	250	4.0	4000	3	≈22	43.7	—	[66]
Cu-La/ZnO/Al₂O₃	250	4.0	4000	3	≈25	43.3	—	[66]
Cu-Sm/ZnO/Al₂O₃	250	4.0	4000	3	≈22	41.4	—	[66]
Cu/ZnO/Al₂O₃	270	3.0	—	3	—	93.5^b	490	[67]
Cu/ZnO/Al₂O₃-Mg	270	3.0	—	3	—	78.5^b	—	[67]
Cu/ZnO/Al₂O₃-Mg-Cr1	270	3.0	—	3	—	97.7^b	520	[67]
Cu/ZnO/Al₂O₃-Mg-Cr2	270	3.0	—	3	—	98.3^b	530	[67]
CuZnGa	270	3.0	—	3	15.9	—	135.7	[68]
CuZnFe	270	3.0	—	3	13.2	—	46.4	[68]

催化剂	温度/℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	甲醇选择性^a/%	甲醇STY/ (mg•g_cat⁻¹•h⁻¹)	参考文献
CuZnAl-C-1.0	240	3.0	3600	3	14.6	63.6	120	[49]
CuZnAl-O-1.0	240	3.0	3600	3	12.1	62.6	100	[49]
CuZnAl-U-1.0	240	3.0	3600	3	3.2	53.9	22	[49]
AE-Cu/SiO₂	190	3.0	2040	3	1.4	52.8	30 (mg•g_Cu⁻¹•h⁻¹)	[50]
FSP-Cu/SiO₂	190	3.0	2040	3	5.2	79.3	168 (mg•g_Cu⁻¹•h⁻¹)	[50]
Cu/ZnO/Al₂O₃	250	2.0	2000	3	13.4	13	9.28 (mg•mL_cat⁻¹•h⁻¹)	[51]
CuZnGa-LDH	270	4.5	18000	3	—	—	590	[52]
CuZnGa-LDH-ww	270	4.5	18000	3	—	—	320	[52]
CZG5Ga	270	4.5	18000	3	—	—	370	[52]
CuZn/Al-M	280	0.5	36000	3	3.1	28.6	105	[53]
CuZn/Al-N	280	0.5	36000	3	2.8	24.5	83	[53]
Cu/Al-M	280	0.5	36000	3	0.2	8.4	2	[53]
2CuZnAl-In3	250	3.0	30000	3	—	35	134.4	[54]
Cu_0.5Zn_0.4Ce_0.1/SBA-15	260	3.0	1200	3	6.5	—	—	[55]
Cu_0.5Zn_0.4Ce_0.1/MCM-41	260	3.0	1200	3	2.2	—	—	[55]
Cu_0.5Zn_0.4Ce_0.1/SiO₂	260	3.0	1200	3	2.8	—	—	[55]
Cu_0.5Zn_0.4Ce_0.1	260	3.0	1200	3	13.9		—	[55]
CuZnAlZr	250	3.0	54000	3	14.2	57.2	1376	[57]
Cu-ZnO/Al₂O₃-ZrO₂	200	5.0	7800	3	8.4	94	201.6	[58]
CuZnZr-1	180	3.0	—	3	1.61	100.0	—	[59]
CuZnZr-1.5	180	3.0	—	3	2.42	100.0	—	[59]
CuZnZr-2	180	3.0	—	3	2.75	100.0	—	[59]
CuZnZr-2.5	180	3.0	—	3	3.87	100.0	—	[59]
CuZnZr-4	180	3.0	—	3	4.37	89.22	—	[59]
CuZnZr-8	180	3.0	—	3	6.26	83.41	—	[59]
CuZnZr-12	180	3.0	—	3	6.67	82.74	—	[59]
CuZnZr-15	180	3.0	—	3	6.50	82.97	—	[59]
Cu-SiO_2P	225	3.0	—	3	3.5	77	140	[60]
Cu/SiO_2−2h	230	2.5	—	3	—	45	0.41 (g•g_Cu⁻¹•h⁻¹)	[61]
Cu/Mo₂CT_x/SiO_2-2h	230	2.5	—	3	—	54	1.5 (g•g_Cu⁻¹•h⁻¹)	[61]
Cu/Mo₂CT_x/SiO_2-6h	230	2.5	—	3	—	52	2.5 (g•g_Cu⁻¹•h⁻¹)	[61]
CuZnO-MOF-74-350	190	4.0	4000	3	7.5	78.2	80	[63]
CuZnO-MOF-74-350	210	4.0	16000	3	6.3	79.6	290	[63]
CuZnO-MOF-74-350	240	4.0	16000	3	14.5	54.0	450	[63]
Cu-ZnO@UiO-bpy	250	4.0	18000	3	3.3	100	2.59 (g_MeOH•kg_Cu⁻¹•h⁻¹)	[64]
Cu/ZnO/Al₂O₃	250	4.0	4000	3	≈22	43.7	—	[66]
Cu-La/ZnO/Al₂O₃	250	4.0	4000	3	≈25	43.3	—	[66]
Cu-Sm/ZnO/Al₂O₃	250	4.0	4000	3	≈22	41.4	—	[66]
Cu/ZnO/Al₂O₃	270	3.0	—	3	—	93.5^b	490	[67]
Cu/ZnO/Al₂O₃-Mg	270	3.0	—	3	—	78.5^b	—	[67]
Cu/ZnO/Al₂O₃-Mg-Cr1	270	3.0	—	3	—	97.7^b	520	[67]
Cu/ZnO/Al₂O₃-Mg-Cr2	270	3.0	—	3	—	98.3^b	530	[67]
CuZnGa	270	3.0	—	3	15.9	—	135.7	[68]
CuZnFe	270	3.0	—	3	13.2	—	46.4	[68]

催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	C₂₊醇选择性^a/%	C₂₊醇STY/ (mg•g_cat⁻¹•h⁻¹)	C₂₊OH/ROH (w/%)	参考文献
Cs-Cu_0.2Fe_1.0Zn_1.0	330	5.0	4500	3	—	13.8	36.2	—	[42]
Cs-Cu_0.5Fe_1.0Zn_1.0	330	5.0	4500	3	—	17.9	64.5	—	[42]
Cs-Cu_0.8Fe_1.0Zn_1.0	330	5.0	4500	3	36.6	19.8	73.4	93.8	[42]
Cs-Cu_0.9Fe_1.0Zn_1.0	330	5.0	4500	3	—	17.2	51.7	—	[42]
Cs-Cu_0.9Fe_1.0Zn_1.0	310	5.0	4500	3	23.7	17.4	36.6	82.1	[42]
Cu@Na-Beta	300	1.3	12000	3	7.9	≈100^b	258	—	[46]
CuZnK_0.15	300	6.0	5000	3	25.1	10.91(总醇)	0.04 (g•mL⁻¹•h⁻¹)	36.3	[69]
CuZnFe_0.25K_0.15	300	6.0	5000	3	33.6	23.64(总醇)	0.10 (g•mL⁻¹•h⁻¹)	77.7	[69]
CuZnFe_0.5K_0.15	300	6.0	5000	3	42.3	36.67(总醇)	0.17 (g•mL⁻¹•h⁻¹)	87.1	[69]
CuZnFe_0.75K_0.15	300	6.0	5000	3	45.1	27.11(总醇)	0.14 (g•mL⁻¹•h⁻¹)	85.6	[69]
CuZnFe_1.0K_0.15	300	6.0	5000	3	36.1	26.76(总醇)	0.11 (g•mL⁻¹•h⁻¹)	84.3	[69]
CuZnFe_1.5K_0.15	300	6.0	5000	3	33.8	22.44(总醇)	0.06 (g•mL⁻¹•h⁻¹)	82.3	[69]

CO₂加氢制醇类催化剂的设计制备及性能研究进展

Research Progress on the Design, Preparation and Properties of Catalysts for CO₂ Hydrogenation to Alcohols

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催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	甲醇选择性^a/%	甲醇STY/ (mg•g_cat⁻¹•h⁻¹)	参考文献
Pd/SiO₂	220	0.8	—	3	—	3	—	[76]
Pd-Ga/SiO₂	220	0.8	—	3	—	12	—	[76]
Pd-Zn/SiO₂	220	0.8	—	3	—	30	—	[76]
2%Pd/CeO₂-R	240	3.0	6000	3	4.6	25.9	22.8	[70]
2%Pd/CeO₂-R	240	5.0	2000	3	5.9	47.7	17.9	[70]
2%Pd/CeO₂-P	240	3.0	2000	3	—	—	9.5	[70]
2%Pd/CeO₂-C	240	3.0	2000	3	—	—	5.0	[70]
2%Pd/CeO₂-O	240	3.0	2000	3	—	—	2.5	[70]
PdZn/SiO₂	260	3.0	30000	3	2.6	11.2	30	[77]
PdZn/Al₂O₃	260	3.0	30000	3	4.4	6.0	27	[77]
PdZn/ZnO/SiO₂	260	3.0	30000	3	3.6	49.8	184	[77]
PdZn/ZnO/SiO₂	260	3.0	30000	3	3.3	65.3	443	[77]
Pd-ZnO@ZIF-8	250	4.5	19200	3	6.6	79	360	[78]
Pd-ZnO@ZIF-8	270	4.5	19200	3	9.3	74	470	[78]
Pt(3)/Mo22x(30)/TiO₂	150	6.0	—	5	—	66	—	[82]
UiO-67-Pt(2.7wt%)	170	0.8	—	6	1.5	19	—	[71]
Rh/In₂O₃	250	5.0	21000	4	4.0	82.0	188.2	[86]
Rh/In₂O₃	275	5.0	21000	4	9.3	72.6	385.3	[86]
Rh/In₂O₃	300	5.0	21000	4	17.1	56.1	544.8	[86]

催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	C₂₊醇选择性^a/%	C₂₊醇STY/ (mg•g_cat⁻¹•h⁻¹)	参考文献
0.43%Pd₂Cu NPs/P25	200	3.2	—	3	—	78.7(乙醇)^b	13.5 (mmol•g⁻¹•h⁻¹)	[80]
1.23%Pd₂Cu NPs/P25	200	3.2	—	3	—	92.0(乙醇)^b	41.5 (mmol•g⁻¹•h⁻¹)	[80]
2.45%Pd₂Cu NPs/P25	200	3.2	—	3	—	96.1(乙醇)^b	86.7 (mmol•g⁻¹•h⁻¹)	[80]
4.91%Pd₂Cu NPs/P25	200	3.2	—	3	—	95.9(乙醇)^b	103.5 (mmol•g⁻¹•h⁻¹)	[80]
RhFeLi/TiO₂NRs-400 ̊C	250	3.0	6000	3	21.4	14.6	—	[72]
RhFeLi/TiO₂NRs-500 ̊C	250	3.0	6000	3	15.7	31.3	—	[72]
RhFeLi/TiO₂NRs-600 ̊C	250	3.0	6000	3	6.6	12.6	—	[72]
RhFeLi/TiO₂ Com	250	3.0	6000	3	4.5	15.7	—	[72]
Rh₁/CeTiO_x	250	3.0	—	3	6.32	99.1	5.75 (mmol•g_Rh⁻¹•h⁻¹)	[88]
Au/TiO₂	200	6.0	—	3	—	—	282.5 (mmol•g_Au⁻¹•h⁻¹)	[73]

催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	C₂₊醇选择性^b/%	C₂₊OH/ROH (w/%)	参考文献
CoAlO_x-600	140	4.0	—	3	—	92.1	95.6	[43]
Mo/SiO₂	250	1.6	—	1	—	34	70.6	[92]
CoMoS	340	10.4	0.43 (kg•kg_cat⁻¹•h⁻¹)	3	32	6.0^a	—	[95]
Mo₁Co₁K_0.6	320	5.0	3000	3	23.5	8.9	11	[96]
Mo₁Co₁K_0.6-AC-18%	320	5.0	3000	3	8.1	12.9	27	[96]
Mo₁Co₁K_0.6-AC-9%	320	5.0	3000	3	8.1	1.2	6	[96]
Mo₁Co₁K_0.6-AC-9%	320	5.0	3000	3	23.4	5.8	8	[96]
Mo₁Co_0.3K_0.9-AC-12%	320	5.0	3000	3	23.7	10.0	12	[96]
Mo₁Co_0.3K_0.9-AC-15%	320	5.0	3000	3	24.2	6.7	8	[96]

催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	甲醇选择性^a/%	甲醇STY/ (mg•g_cat⁻¹•h⁻¹)	参考文献
In₂O₃/ZrO₂	300	5.0	16000	4	—	100	—	[99]
In₂O₃/m-ZrO₂	280	5.0	24000	4	4.8	84	270	[101]
In₂O₃/t-ZrO₂	280	5.0	24000	4	0.5	82	40	[101]
In₂O₃/Al₂O₃	280	5.0	24000	4	0.5	80	40	[101]
In₂O₃/CeO₂	280	5.0	24000	4	0.4	82	30	[101]
In₂O₃/Al₂O₃/Al-fiber	325	4.0	21600	3	4.4	67.6	200	[103]
In₂O₃-IWI/Al₂O₃/Al-fiber	325	4.0	21600	3	4.3	36.8	110	[103]
In_0.1/ZrO₂	280	5.0	24000	4	1.1	21.3	14	[104]
In_0.25/ZrO₂	280	5.0	24000	4	1.2	27.0	17	[104]
In_0.5/ZrO₂	280	5.0	24000	4	1.9	38.7	42	[104]
In₁/ZrO₂	280	5.0	24000	4	2.0	49.3	50	[104]
In_2.5/ZrO₂	280	5.0	24000	4	2.5	60.0	87	[104]
In₅/ZrO₂	280	5.0	24000	4	1.8	68.2	71	[104]
In₁₀/ZrO₂	280	5.0	24000	4	1.4	66.0	56	[104]
c-In₂O₃-S	300	5.0	9000	3	12.0	71.9	265.6	[29]
h-In₂O₃-R	300	5.0	20000	3	5.1	95.1	332.8	[29]
h-In2O3-R	300	5.0	9000	6	17.6	92.4	—	[29]
h-In₂O₃/Pd	235	3.0	19200	3	—	100	170	[105]
h-In₂O₃/Pd	295	3.0	19200	3	—	72.4	530	[105]
h-In₂O₃/Pd	295	3.0	24000	3	—	74	570	[105]
In₂O₃	300	5.0	21000	4	8.9	61	326	[74]
Ir/In₂O₃-1	300	5.0	21000	4	11.6	73	512	[74]
Ir/In₂O₃-5	300	5.0	21000	4	14.2	71	608	[74]
Ir/In₂O₃-10	300	5.0	21000	4	17.7	71	765	[74]
Pt/film/In₂O₃	30	0.1	—	3	37.0	62.6	354.88	[106]
Cu_0.25-In_0.75-Zr_0.5-O	250	2.5	18000	3	1.48	79.7	—	[107]
Au/ZrO₂	300	5.0	21000	4	14.8	70.1	590	[108]
Au/In₂O₃-ZrO₂	300	5.0	21000	4	26.0	13.3	200	[108]
In₂O₃/SiO₂	300	5.0	7500	4	—	24	—	[109]
In:Pd(2:1)/SiO₂	300	5.0	7500	4	—	61	—	[109]
In:Pd(1:1)/SiO₂	300	5.0	7500	4	—	42	—	[109]
In:Pd(1:2)/SiO₂	300	5.0	7500	4	—	23	—	[109]

催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	甲醇选择性^a/%	甲醇STY/ (mg•g_cat⁻¹•h⁻¹)	参考文献
13%ZnO-ZrO₂	300	2.0	24000	3	3.4	87	248	[113]
11.5%CdZrO_x	300	2.0	24000	3	5.5	≈80	—	[114]
11.5%GaZrO_x	300	2.0	24000	3	2.4	≈80	—	[114]
CP-PdZnZr	320	5.0	30000	3	8.1	87.5	735	[119]
3Al-C-ZnO-ZrO₂	320	3.0	—	—	11.4	81.3	—	[118]
3Cr-C-ZnO-ZrO₂	320	3.0	—	—	10.7	73.2	—	[118]
3Fe-C-ZnO-ZrO₂	320	3.0	—	—	10.8	77.0	—	[118]
3Mg-C-ZnO-ZrO₂	320	3.0	—	—	12.9	81.5	—	[118]
Rh/ZrO₂	300	5.0	21000 (cm³•g_cat^-1•h^-1)	—	65.5	0.2	6	[87]
Rh/In₂O₃-ZrO₂	275	5.0	21000 (cm³•g_cat⁻¹•h⁻¹)		11.9	80.9	550	[87]
Rh/In₂O₃-ZrO₂	300	5.0	21000 (cm³•g_cat⁻¹•h⁻¹)	—	18.1	66.5	684	[87]

催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	甲醇选择性^a/%	甲醇STY/ (mg•g_cat⁻¹•h⁻¹)	参考文献
FL-MoS₂	180	5.0	3000	3	12.5	94.3	—	[121]
FL-MoS₂	180	5.0	15000	3	2.5	96.4	130	[121]
FL-MoS₂	240	5.0	15000	3	11.0	81.4	490	[121]
FL-MoS₂	260	5.0	15000	3	15.3	70.1	600	[121]
h-MoS₂/ZnS	240	5.0	15000	4	7.2	74.6	220	[122]
h-MoS₂/ZnS	260	5.0	15000	4	9.0	67.3	250	[122]
MoS₂	180	4.0	1200	—	0.3	54	0.64	[37]
MoS_x/NaZSM-5	180	4.0	1200	—	0.4	63	1	[37]
Mo₃S₄@NaZSM-5	180	4.0	1200		10.2	98	39.5	[37]
β-Mo₂C	220	3.0	7500	3	8.4	9.7	0.2	[127]
Mo₂C@NSC-700	220	3.0	7500	3	16.0	62.0	266	[127]
Mo₂C@NSC-800	220	3.0	7500	3	16.7	90.5	405	[127]
Mo₂C@NSC-900	220	3.0	7500	3	17.0	84.2	383	[127]
β-Mo₂C	150	2.0	7200	3	3.25	60	—	[130]
Cu/Mo₂C	150	2.0	7200	3	5	70	—	[130]
Cs/Mo₂C	150	2.0	7200	3	3	50	—	[130]
Cu/Cs-Mo₂C	150	2.0	7200	3	4	55	—	[130]

催化剂	温度/ ℃	压力/ MPa	GHSV/ (mL•g_cat⁻¹•h⁻¹)	H₂/CO₂	CO₂ 转化率/%	C₂₊醇选择性^a/%	C₂₊OH/ROH (w/%)	参考文献
Na-Co/SiO₂	250	5.0	4000	3	18.82	9.54(总醇)	62.81	[124]
Na-Co/Si₃N₄	250	5.0	4000	3	17.75	9.19(总醇)	62.43	[124]
0.5%Na-Co/SiO₂	250	5.0	6000	3	40.0	0.1(总醇)	—	[126]
1%Na-Co/SiO₂	250	5.0	6000	3	33.7	3.4(总醇)	—	[126]
2%Na-Co/SiO₂	250	5.0	6000	3	21.5	12.5(总醇)	—	[126]
5%Na-Co/SiO₂	250	5.0	6000	3	16.5	9.9(总醇)	—	[126]
Mo₂C	200	4.0	—	3	—	16		[128]
Co/Mo₂C	200	4.0	—	3	—	25	—	[128]
Pd/Mo₂C	200	4.0	—	3	—	11	—	[128]
Cu/Mo₂C	200	4.0	—	3	—	14	—	[128]
Fe/Mo₂C	200	4.0	—	3	—	16	—	[128]

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CO2加氢制醇类催化剂的设计制备及性能研究进展