二氧化碳加氢制高级醇Fe基催化剂研究进展

doi:10.16085/j.issn.1000-6613.2024-0066

摘要/Abstract

摘要：

高级醇（HA）可作为重要的能源化工基础原料。CO₂加氢制备高级醇（CO₂-HAS）具有流程短、效率高、操作简便等特点，该技术兼具碳减排和高附加值利用的双重意义。Fe基催化剂的低成本和高活性优势使其具备工业应用潜力，但仍存在反应网络复杂、C—C键生成难控制、高级醇收率不理想等问题。本文从热力学角度分析了CO₂-HAS的固有限制和适宜的工艺条件，简述了高级醇生成的转化路径和Fe物种演变。进一步阐述了反应条件、助剂、制备方法和载体等因素对Fe基催化剂反应性能的影响，并揭示了Fe基多功能催化反应偶联的构建策略以及对性能的促进机制。基于此，指出中间物种的定向转化和C—C偶联的精准调控是Fe基催化剂设计的关键考量。预测3D打印自催化技术将助力Fe基催化剂的大规模制备，多元化的技术整合可能是CO₂-HAS产业化开发的可行方式之一。廉价的绿氢制备技术与CO₂捕集技术的突破与耦合将推动CO₂-HAS的高质量发展并成为主流趋势。

关键词: 二氧化碳加氢, 高级醇, Fe基催化剂, C—C耦合

Abstract:

Higher alcohols (HA) are important basic raw materials of energy and chemical industry. Higher alcohols synthesis via CO₂ hydrogenation (CO₂-HAS) possesses the characteristics of short process, high efficiency, and easy operation, which exhibits the great significance for both emission reduction and high value-added utilization of CO₂. Fe-based catalysts show great potential for industrial application due to their low cost and high activity, but they still faces some problems such as complex reaction network, difficult control of C—C bond formation and unsatisfactory yield of HA. Herein, the inherent limitation and suitable process conditions of CO₂-HAS were analyzed from the thermodynamic point of view, and the transformation path of HA and the evolution of Fe species were described. The effects of reaction conditions, promoters, preparation methods and supports on the performance of Fe-based catalysts were further discussed. The construction strategy of Fe-based multifunction catalytic reaction-coupling and its promoting mechanism were also revealed. The directed conversion of intermediate species and the precise regulation of C—C coupling are the key considerations in the design of Fe-based catalysts. 3D printing self-catalytic technology is expected to accelerate the large-scale preparation of Fe-based catalysts. Integration of various technologies may be one of the feasible ways for the industrial exploration of CO₂-HAS. The breakthrough of cheap green hydrogen production technology and its coupling with CO₂ capture technology will promote high quality development of CO₂-HAS and will be the mainstream trend in the future.

Key words: CO₂ hydrogenation, higher alcohols, Fe-based catalysts, C—C coupling

中图分类号:

TQ426

秦婷婷, 牛强. 二氧化碳加氢制高级醇Fe基催化剂研究进展[J]. 化工进展, 2025, 44(1): 253-265.

QIN Tingting, NIU Qiang. Research progress on Fe-based catalysts for CO₂ hydrogenation to higher alcohols[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 253-265.

图/表 10

图1 CO2加氢催化剂及产物[2]

表1 CO2加氢过程的主要反应

序号	反应方程	ΔG_298K/kJ·mol^-1	ΔH_298K/kJ·mol^-1	K_298K
(1)	CO₂+H₂ $\overset{}{⇌}$ CO+H₂O	28.6	41.1	9.67×10^-6
(2)	CO+3H₂ $\overset{}{⇌}$ CH₄+H₂O	-141.9	-206.0	—
(3)	CO₂+4H₂ $\overset{}{⇌}$ CO+2H₂O	-113.5	-165.0	7.79×10¹⁹
(4)	CO+2H₂ $\overset{}{⇌}$ CH₃OH	—	-90.4	—
(5)	CO₂+3H₂ $\overset{}{⇌}$ CH₃OH+H₂O	3.5	-49.3	2.45×10^-1
(6)	2CH₃OH $\overset{}{⇌}$ CH₃OCH₃+H₂O	—	-24.52	—
(7)	CH₃OCH₃+CO $\overset{}{⇌}$ CH₃COOCH₃	—	—	—
(8)	CH₃COOCH₃+2H₂ $\overset{}{⇌}$ C₂H₅OH+CH₃OH	—	—	—
(9)	CH₃OH+CO+2H₂ $\overset{}{⇌}$ C₂H₅OH+H₂O	-97.0	-165.1	—
(10)	2CH₄+H₂O $\overset{}{⇌}$ C₂H₅OH+2H₂	—	—	—
(11)	C₂H₅OH→CH₃CHO+H₂ $\overset{}{⇌}$ CH₄+CO+H₂	—	—	—
(12)	2CO+4H₂ $\overset{}{⇌}$ C₂H₅OH+H₂O	-221.1	-253.6	—
(13)	2CO₂+6H₂ $\overset{}{⇌}$ C₂H₅OH+3H₂O	-32.4	-86.7	4.70×10⁵
(14)	C₂H₅OH+3H₂O $\overset{}{⇌}$ CH₃COOH+2H₂	—	—	—
(15)	2CO₂+7H₂ $\overset{}{⇌}$ C₂H₆+4H₂O	-78.7	-132.1	6.26×10¹³
(16)	3CO₂+10H₂ $\overset{}{⇌}$ C₃H₈+6H₂O	-70.9	-125.0	2.64×10¹²
(17)	CH₄ $\overset{}{⇌}$ C+2H₂	—	74.9	—
(18)	2CO $\overset{}{⇌}$ CO₂+C	—	-172.5	—

表1 CO2加氢过程的主要反应

序号	反应方程	ΔG_298K/kJ·mol^-1	ΔH_298K/kJ·mol^-1	K_298K
(1)	CO₂+H₂ $\overset{}{⇌}$ CO+H₂O	28.6	41.1	9.67×10^-6
(2)	CO+3H₂ $\overset{}{⇌}$ CH₄+H₂O	-141.9	-206.0	—
(3)	CO₂+4H₂ $\overset{}{⇌}$ CO+2H₂O	-113.5	-165.0	7.79×10¹⁹
(4)	CO+2H₂ $\overset{}{⇌}$ CH₃OH	—	-90.4	—
(5)	CO₂+3H₂ $\overset{}{⇌}$ CH₃OH+H₂O	3.5	-49.3	2.45×10^-1
(6)	2CH₃OH $\overset{}{⇌}$ CH₃OCH₃+H₂O	—	-24.52	—
(7)	CH₃OCH₃+CO $\overset{}{⇌}$ CH₃COOCH₃	—	—	—
(8)	CH₃COOCH₃+2H₂ $\overset{}{⇌}$ C₂H₅OH+CH₃OH	—	—	—
(9)	CH₃OH+CO+2H₂ $\overset{}{⇌}$ C₂H₅OH+H₂O	-97.0	-165.1	—
(10)	2CH₄+H₂O $\overset{}{⇌}$ C₂H₅OH+2H₂	—	—	—
(11)	C₂H₅OH→CH₃CHO+H₂ $\overset{}{⇌}$ CH₄+CO+H₂	—	—	—
(12)	2CO+4H₂ $\overset{}{⇌}$ C₂H₅OH+H₂O	-221.1	-253.6	—
(13)	2CO₂+6H₂ $\overset{}{⇌}$ C₂H₅OH+3H₂O	-32.4	-86.7	4.70×10⁵
(14)	C₂H₅OH+3H₂O $\overset{}{⇌}$ CH₃COOH+2H₂	—	—	—
(15)	2CO₂+7H₂ $\overset{}{⇌}$ C₂H₆+4H₂O	-78.7	-132.1	6.26×10¹³
(16)	3CO₂+10H₂ $\overset{}{⇌}$ C₃H₈+6H₂O	-70.9	-125.0	2.64×10¹²
(17)	CH₄ $\overset{}{⇌}$ C+2H₂	—	74.9	—
(18)	2CO $\overset{}{⇌}$ CO₂+C	—	-172.5	—

图2 CO2-HAS过程的中间体及反应路径[15]

图3 各种铁碳化物的相变条件[47]

表2 Fe基CO2加氢制备高级醇性能汇总

序号	催化剂	制备/混合方法	温度/℃	压力/MPa	H₂/CO₂	GHSV	CO₂转化率/%	C₂₊OH选择性/%	C₂₊OH收率	参考文献
1	K-CuMgZnFe	共沉淀	320	5	3	6000mL/(g·h)	30.4	15.8	70.6mg/(g·h)	[48]
2	K/S-CuFeZn	共沉淀+浸渍	320	5	3	3000mL/(g·h)	36.1	20.2	50.7mg/(g·h)	[49]
3	10Mn1K-FeC	热分解	300	3	3	6000mL/(g·h)	40.5	10.7	4.3%^①	[50]
4	MnCuK-FeC	热分解	300	3	3	6000mL/(g·h)	40.8	13.5	5.6%^①	[51]
5	K-CuMgZnFe	共沉淀	320	5	3	6000mL/(g·h)	28.1	约15.7	69.6mg/(g·h)	[52]
6	CuZnFe_0.5K_0.15	共沉淀+浸渍	300	6	3	5000mL/(g·h)	42.3	36.7	170mg/(mL·h)	[39]
7	K/Cu-Zn-Fe	共沉淀	300	7	3	5000h^-1	44.2	26.9	11.9%^①	[30]
8	K/Cu-Zn-Fe	共沉淀+浸渍	300	7	3	5000mL/(g·h)	45.0	19.0	8.6%^①	[53]
9	PDA/CuFeZn-N450	共沉淀	320	4	3	7200mL/(g·h)	约7.0	41.5	55.9mg/(mL·h)	[54]
10	CuFeZn-0.7PDA	共沉淀	310	4	3	7200mL/(g·h)	10.6	33.1	58.2mg/(mL·h)	[55]
11	KFeCu/a-ZrO₂	分步沉淀+浸渍	320	4	3	12000mL/(g·h)	25.7	26.1	125.0mg/(g·h)	[56]
12	K-0.82-FeIn/Ce-ZrO₂	浸渍	300	10	3	4500mL/(g·h)	29.6	28.7	8.5%^①	[57]
13	(K₂O)_5%/CuZnFeZrO₂	共沉淀+浸渍	320	3	3	3600mL/(g·h)	25.5	11.0	2.55mmol/(mL·h)	[58]
14	Fe-Cu-Al-K	均匀凝胶法	330	8	3	20000h^-1	41.4	11.4	4.7%^①	[30-31]
15	sp-CuNaFe	物理溅射	310	3	3	28800mL/(g·h)	32.3	约10.0	153.0mg/(g·h)	[59]
16	Na-Fe@C	水热+浸渍+碳化	320	5	3	9000mL/(g·h)	25.5	12.0（乙醇）	52.3mg/(g·h)	[43]
17	Na-ZnFe@C	水热+浸渍+碳化	320	5	3	9000mL/(g·h)	38.4	20.3（乙醇）	158.1mg/(g·h)	[43]
18	2%Na-Fe@C	水热+热解+浸渍	320	5	3	9000mL/(g·h)	32.8	16.3	5.3%^①	[60]
19	Cr(1%)-CuFe	溶胶-凝胶法	320	4	3	6000mL/(g·h)	38.4	29.2	104.1mg/(g·h)	[61]
20	1%Na-50Co50Fe	草酸盐分解	270	0.92	2.5	2.0nL/(g·h)	22.7	5.3	1.2%^①	[40]
21	90Fe10Co1.0K	草酸盐分解	240	1.2	3	1.5nL/(g·h)	14.5	5.9	0.85%^①	[41]
22	Cs-Cu_0.8Fe_1.0Zn_1.0	共沉淀	330	5	3	4500h^-1	36.6	19.8	73.4mg/(g·h)	[62]
23	FeNaS-0.6	沉淀	320	3	3	8000mL/(g·h)	32.0	16.1	78.5mg/(g·h)	[63]
24	NaS-Fe	沉淀/洗涤	320	3	3	8000mL/(g·h)	32.0	15.9	78.5mg/(g·h)	[64]
25	Fe/Al₂O₃	浸渍	300	2	3	4000mL/(g·h)	22.6	3.3	0.7%^①	[65]
26	Fe/K-Al₂O₃	浸渍	300	2	3	4000mL/(g·h)	34.4	27.3	9.4%^①	[65]
27	In_2_Fe/K-Al₂O₃	浸渍	300	2	3	4000mL/(g·h)	36.7	42.0	15.4%^①	[65]
28	CuZnFe_1.0K/ATP-CZO	浸渍	320	6	3	5000mL/(g·h)	14.3	35.1（混合醇ROH）	5.0%^①	[66]
29	Rh-Fe/SiO₂	浸渍	260	5	3	6000mL/(g·h)	26.7	16.0	4.3%^①	[33]
30	2.5%Fe/TiO₂	浸渍	270	2	1	8000mL/(g·h)	2.7	2.8	0.07%^①	[36]
31	2%Rh-2.5%Fe/TiO₂	浸渍	270	2	1	8000mL/(g·h)	9.2	6.4	0.6%^①	[36]
32	2.5%RhFeLi/TiO₂	浸渍	250	3	3	6000h^-1	15.7	31.4	4.9%^①	[34]
33	2.0K20Fe5Rh-SiO₂	浸渍	250	5	3	7000mL/(g·h)	18.4	15.9	2.9%^①	[35]
34	0.1Pd/Fe₃O₄	浸渍	300	0.1	4	60000mL/(g·h)	0.3	97.5	0.41mmol/(g·h)	[38]
35	PdFe	水热+浸渍	300	5	3	6000mL/(g·h)	33.3	19.1	86.5mg/(g·h)	[67]
36	0.3K-1Pd/Fe₂O₃	浸渍	320	4	3	6000mL/(g·h)	30.0	13.4	52.2mg/(g·h)	[68]
37	Cu₂₅Fe₂₂Co₃K₃	浸渍	350	6	3	5000h^-1	20.0	6.4（混合醇ROH）	1.3%^①	[69]
38	CuZn_1.0K_0.15/Cu₂₅Fe₂₂Co₃K₃	共沉淀+浸渍	350	6	3	5000h^-1	32.4	11.8（混合醇ROH）	3.8%^①	[69]
39	CuZnAl/K-CuMgZnFe	共沉淀	320	5	3	6000mL/(g·h)	42.3	17.4	106.5mg/(g·h)	[48]
40	4.7KCuFeZn/CuZnAlZr	共沉淀+粉末混合	300	5	3	3000mL/(g·h)	27.0	24.6	42.0mg/(g·h)	[70]
41	0.6S-KCFZ+CuZnAlZr	共沉淀+浸渍+粉末混合	320	5	3	12000mL/(g·h)	36.6	18.2	173.9mg/(g·h)	[49]
42	Na-Fe@C/K-CuZnAl	水热+热解+ 浸渍+共沉淀	320	5	3	4500mL/(g·h)	39.2	35.0	12.4%^①	[60]
43	FeCuAlK+CuZnAlK	均匀凝胶法+物理混合	330	8	3	20000h^-1	39.5	15.8	6.2%^①	[30-31]
44	MnCuK-FeC(1)/CuZnAlZr(1)	热分解+共沉淀	300	3	3	6000mL/(g·h)	42.1	15.5	6.5%^①	[51]
45	ZnFe₂O₄/Fe-Zn-Na^#	有机物燃烧+共沉淀+浸渍	320	5	3	2000mL/(g·h)	38.8	30.0	55.5mg/(g·h)	[71]

表2 Fe基CO2加氢制备高级醇性能汇总

序号	催化剂	制备/混合方法	温度/℃	压力/MPa	H₂/CO₂	GHSV	CO₂转化率/%	C₂₊OH选择性/%	C₂₊OH收率	参考文献
1	K-CuMgZnFe	共沉淀	320	5	3	6000mL/(g·h)	30.4	15.8	70.6mg/(g·h)	[48]
2	K/S-CuFeZn	共沉淀+浸渍	320	5	3	3000mL/(g·h)	36.1	20.2	50.7mg/(g·h)	[49]
3	10Mn1K-FeC	热分解	300	3	3	6000mL/(g·h)	40.5	10.7	4.3%^①	[50]
4	MnCuK-FeC	热分解	300	3	3	6000mL/(g·h)	40.8	13.5	5.6%^①	[51]
5	K-CuMgZnFe	共沉淀	320	5	3	6000mL/(g·h)	28.1	约15.7	69.6mg/(g·h)	[52]
6	CuZnFe_0.5K_0.15	共沉淀+浸渍	300	6	3	5000mL/(g·h)	42.3	36.7	170mg/(mL·h)	[39]
7	K/Cu-Zn-Fe	共沉淀	300	7	3	5000h^-1	44.2	26.9	11.9%^①	[30]
8	K/Cu-Zn-Fe	共沉淀+浸渍	300	7	3	5000mL/(g·h)	45.0	19.0	8.6%^①	[53]
9	PDA/CuFeZn-N450	共沉淀	320	4	3	7200mL/(g·h)	约7.0	41.5	55.9mg/(mL·h)	[54]
10	CuFeZn-0.7PDA	共沉淀	310	4	3	7200mL/(g·h)	10.6	33.1	58.2mg/(mL·h)	[55]
11	KFeCu/a-ZrO₂	分步沉淀+浸渍	320	4	3	12000mL/(g·h)	25.7	26.1	125.0mg/(g·h)	[56]
12	K-0.82-FeIn/Ce-ZrO₂	浸渍	300	10	3	4500mL/(g·h)	29.6	28.7	8.5%^①	[57]
13	(K₂O)_5%/CuZnFeZrO₂	共沉淀+浸渍	320	3	3	3600mL/(g·h)	25.5	11.0	2.55mmol/(mL·h)	[58]
14	Fe-Cu-Al-K	均匀凝胶法	330	8	3	20000h^-1	41.4	11.4	4.7%^①	[30-31]
15	sp-CuNaFe	物理溅射	310	3	3	28800mL/(g·h)	32.3	约10.0	153.0mg/(g·h)	[59]
16	Na-Fe@C	水热+浸渍+碳化	320	5	3	9000mL/(g·h)	25.5	12.0（乙醇）	52.3mg/(g·h)	[43]
17	Na-ZnFe@C	水热+浸渍+碳化	320	5	3	9000mL/(g·h)	38.4	20.3（乙醇）	158.1mg/(g·h)	[43]
18	2%Na-Fe@C	水热+热解+浸渍	320	5	3	9000mL/(g·h)	32.8	16.3	5.3%^①	[60]
19	Cr(1%)-CuFe	溶胶-凝胶法	320	4	3	6000mL/(g·h)	38.4	29.2	104.1mg/(g·h)	[61]
20	1%Na-50Co50Fe	草酸盐分解	270	0.92	2.5	2.0nL/(g·h)	22.7	5.3	1.2%^①	[40]
21	90Fe10Co1.0K	草酸盐分解	240	1.2	3	1.5nL/(g·h)	14.5	5.9	0.85%^①	[41]
22	Cs-Cu_0.8Fe_1.0Zn_1.0	共沉淀	330	5	3	4500h^-1	36.6	19.8	73.4mg/(g·h)	[62]
23	FeNaS-0.6	沉淀	320	3	3	8000mL/(g·h)	32.0	16.1	78.5mg/(g·h)	[63]
24	NaS-Fe	沉淀/洗涤	320	3	3	8000mL/(g·h)	32.0	15.9	78.5mg/(g·h)	[64]
25	Fe/Al₂O₃	浸渍	300	2	3	4000mL/(g·h)	22.6	3.3	0.7%^①	[65]
26	Fe/K-Al₂O₃	浸渍	300	2	3	4000mL/(g·h)	34.4	27.3	9.4%^①	[65]
27	In_2_Fe/K-Al₂O₃	浸渍	300	2	3	4000mL/(g·h)	36.7	42.0	15.4%^①	[65]
28	CuZnFe_1.0K/ATP-CZO	浸渍	320	6	3	5000mL/(g·h)	14.3	35.1（混合醇ROH）	5.0%^①	[66]
29	Rh-Fe/SiO₂	浸渍	260	5	3	6000mL/(g·h)	26.7	16.0	4.3%^①	[33]
30	2.5%Fe/TiO₂	浸渍	270	2	1	8000mL/(g·h)	2.7	2.8	0.07%^①	[36]
31	2%Rh-2.5%Fe/TiO₂	浸渍	270	2	1	8000mL/(g·h)	9.2	6.4	0.6%^①	[36]
32	2.5%RhFeLi/TiO₂	浸渍	250	3	3	6000h^-1	15.7	31.4	4.9%^①	[34]
33	2.0K20Fe5Rh-SiO₂	浸渍	250	5	3	7000mL/(g·h)	18.4	15.9	2.9%^①	[35]
34	0.1Pd/Fe₃O₄	浸渍	300	0.1	4	60000mL/(g·h)	0.3	97.5	0.41mmol/(g·h)	[38]
35	PdFe	水热+浸渍	300	5	3	6000mL/(g·h)	33.3	19.1	86.5mg/(g·h)	[67]
36	0.3K-1Pd/Fe₂O₃	浸渍	320	4	3	6000mL/(g·h)	30.0	13.4	52.2mg/(g·h)	[68]
37	Cu₂₅Fe₂₂Co₃K₃	浸渍	350	6	3	5000h^-1	20.0	6.4（混合醇ROH）	1.3%^①	[69]
38	CuZn_1.0K_0.15/Cu₂₅Fe₂₂Co₃K₃	共沉淀+浸渍	350	6	3	5000h^-1	32.4	11.8（混合醇ROH）	3.8%^①	[69]
39	CuZnAl/K-CuMgZnFe	共沉淀	320	5	3	6000mL/(g·h)	42.3	17.4	106.5mg/(g·h)	[48]
40	4.7KCuFeZn/CuZnAlZr	共沉淀+粉末混合	300	5	3	3000mL/(g·h)	27.0	24.6	42.0mg/(g·h)	[70]
41	0.6S-KCFZ+CuZnAlZr	共沉淀+浸渍+粉末混合	320	5	3	12000mL/(g·h)	36.6	18.2	173.9mg/(g·h)	[49]
42	Na-Fe@C/K-CuZnAl	水热+热解+ 浸渍+共沉淀	320	5	3	4500mL/(g·h)	39.2	35.0	12.4%^①	[60]
43	FeCuAlK+CuZnAlK	均匀凝胶法+物理混合	330	8	3	20000h^-1	39.5	15.8	6.2%^①	[30-31]
44	MnCuK-FeC(1)/CuZnAlZr(1)	热分解+共沉淀	300	3	3	6000mL/(g·h)	42.1	15.5	6.5%^①	[51]
45	ZnFe₂O₄/Fe-Zn-Na^#	有机物燃烧+共沉淀+浸渍	320	5	3	2000mL/(g·h)	38.8	30.0	55.5mg/(g·h)	[71]

图4 碱金属（Li、Na、K）和S共改性Fe基催化剂上CO2加氢制高级醇[64]

图5 CO2加氢转化为高级醇的不同路径[32]

图6 CuZnAl/K-CuMgZnFe多功能催化剂上CO2加氢制高级醇的反应路径[48]

图7 Na-Fe@C/K-CuZnAl多功能催化剂上CO2加氢制乙醇的反应[60]

图8 两种催化剂的混合模式[32]

参考文献 87

1	PETER Sebastian C. Reduction of CO₂ to chemicals and fuels: A solution to global warming and energy crisis[J]. ACS Energy Letters, 2018, 3(7): 1557-1561.
2	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.
3	JIANG Xiao, NIE Xiaowa, GUO Xinwen, et al. Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis[J]. Chemical Reviews, 2020, 120(15): 7984-8034.
4	YE Runping, DING Jie, GONG Weibo, et al. CO₂ hydrogenation to high-value products via heterogeneous catalysis[J]. Nature Communications, 2019, 10(1): 5698.
5	ZHANG Shunan, WU Zhaoxuan, LIU Xiufang, et al. A short review of recent advances in direct CO₂ hydrogenation to alcohols[J]. Topics in Catalysis, 2021, 64(5): 371-394.
6	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.
7	BOWKER Michael. Methanol synthesis from CO₂ hydrogenation[J]. ChemCatChem, 2019, 11(17): 4238-4246.
8	LI Zelong, WANG Jijie, QU Yuanzhi, et al. Highly selective conversion of carbon dioxide to lower olefins[J]. ACS Catalysis, 2017, 7(12): 8544-8548.
9	LI Zelong, QU Yuanzhi, WANG Jijie, et al. Highly selective conversion of carbon dioxide to aromatics over tandem catalysts[J]. Joule, 2019, 3(2): 570-583.
10	CUI Xu, GAO Peng, LI Shenggang, et al. Selective production of aromatics directly from carbon dioxide hydrogenation[J]. ACS Catalysis, 2019, 9(5): 3866-3876.
11	NI Youming, CHEN Zhiyang, FU Yi, et al. Selective conversion of CO₂ and H₂ into aromatics[J]. Nature Communications, 2018, 9(1): 3457.
12	WEI Jian, GE Qingjie, YAO Ruwei, et al. Directly converting CO₂ into a gasoline fuel[J]. Nature Communications, 2017, 8: 15174.
13	PRIETO Gonzalo. Carbon dioxide hydrogenation into higher hydrocarbons and oxygenates: Thermodynamic and kinetic bounds and progress with heterogeneous and homogeneous catalysis[J]. ChemSusChem, 2017, 10(6): 1056-1070.
14	GAO Peng, LI Shenggang, BU Xianni, et al. Direct conversion of CO₂ into liquid fuels with high selectivity over a bifunctional catalyst[J]. Nature Chemistry, 2017, 9(10): 1019-1024.
15	ZENG Feng, MEBRAHTU Chalachew, XI Xiaoying, et al. Catalysts design for higher alcohols synthesis by CO₂ hydrogenation: Trends and future perspectives[J]. Applied Catalysis B: Environmental, 2021, 291: 120073.
16	LATSIOU Angeliki I, CHARISIOU Nikolaos D, FRONTISTIS Zacharias, et al. CO₂ hydrogenation for the production of higher alcohols: Trends in catalyst developments, challenges and opportunities[J]. Catalysis Today, 2023, 420: 114179.
17	XU Di, WANG Yanqiu, DING Mingyue, et al. Advances in higher alcohol synthesis from CO₂ hydrogenation[J]. Chem, 2021, 7(4): 849-881.
18	LI Jiachen, WANG Liguo, CAO Yan, et al. Recent advances on the reduction of CO₂ to important C₂₊ oxygenated chemicals and fuels[J]. Chinese Journal of Chemical Engineering, 2018, 26(11): 2266-2279.
19	DELUGA G A, SALGE J R, SCHMIDT L D, et al. Renewable hydrogen from ethanol by autothermal reforming[J]. Science, 2004, 303(5660): 993-997.
20	LATIF Mohd Nor, WAN ISAHAK Wan Nor Roslam, SAMSURI Alinda, et al. Recent advances in the technologies and catalytic processes of ethanol production[J]. Catalysts, 2023, 13(7): 1093.
21	LAN Ethan I, LIAO James C. Microbial synthesis of n-butanol, isobutanol, and other higher alcohols from diverse resources[J]. Bioresource Technology, 2013, 135: 339-349.
22	BAI F W, ANDERSON W A, MOO-YOUNG M. Ethanol fermentation technologies from sugar and starch feedstocks[J]. Biotechnology Advances, 2008, 26(1): 89-105.
23	HE Xinyi. CO₂ hydrogenation for ethanol production: A thermodynamic analysis[J]. International Journal of Oil, Gas and Coal Engineering, 2017, 5(6): 145-152.
24	AZIZ M A A, JALIL A A, TRIWAHYONO S, et al. CO₂ methanation over heterogeneous catalysts: Recent progress and future prospects[J]. Green Chemistry, 2015, 17(5): 2647-2663.
25	JIANG Yongjun, WANG Kangzhou, WANG Yuan, et al. Recent advances in thermocatalytic hydrogenation of carbon dioxide to light olefins and liquid fuels via modified Fischer-Tropsch pathway[J]. Journal of CO₂Utilization, 2023, 67: 102321.
26	NIE Xiaowa, LI Wenhui, JIANG Xiao, et al. Recent advances in catalytic CO₂ hydrogenation to alcohols and hydrocarbons[M]// Advances in Catalysis. Amsterdam: Elsevier, 2019, 65: 121-233.
27	LI Xiaopeng, KE Jucang, LI Rui, et al. Research progress of hydrogenation of carbon dioxide to ethanol[J]. Chemical Engineering Science, 2023, 282: 119226.
28	STANGELAND Kristian, LI Hailong, YU Zhixin. Thermodynamic analysis of chemical and phase equilibria in CO₂ hydrogenation to methanol, dimethyl ether, and higher alcohols[J]. Industrial & Engineering Chemistry Research, 2018, 57(11): 4081-4094.
29	KANGVANSURA Praewpilin, CHEW Ly May, SAENGSUI Worasarit, et al. Product distribution of CO₂ hydrogenation by K- and Mn-promoted Fe catalysts supported on N-functionalized carbon nanotubes[J]. Catalysis Today, 2016, 275: 59-65.
30	TAKAGAWA Makoto, OKAMOTO Atsushi, FUJIMURA Hiromitsu, et al. Ethanol synthesis from carbon dioxide and hydrogen[J]. Studies in Surface Science and Catalysis, 1998, 114: 525-528.
31	INUI Tomoyuki, YAMAMOTO Tetsuo, INOUE Masahito, et al. Highly effective synthesis of ethanol by CO₂-hydrogenation on well balanced multi-functional FT-type composite catalysts[J]. Applied Catalysis A: General, 1999, 186(1/2): 395-406.
32	HE Yiming, MÜLLER Fabian H, PALKOVITS Regina, et al. Tandem catalysis for CO₂ conversion to higher alcohols: A review[J]. Applied Catalysis B: Environment and Energy, 2024, 345: 123663.
33	KUSAMA Hitoshi, OKABE Kiyomi, SAYAMA Kazuhiro, et al. Ethanol synthesis by catalytic hydrogenation of CO₂ over Rh-Fe/SiO₂ catalysts[J]. Energy, 1997, 22(2/3): 343-348.
34	YANG Chengsheng, MU Rentao, WANG Guishuo, et al. Hydroxyl-mediated ethanol selectivity of CO₂ hydrogenation[J]. Chemical Science, 2019, 10(11): 3161-3167.
35	GORYACHEV Andrey, PUSTOVARENKO Alexey, SHTERK Genrikh, et al. A multi-parametric catalyst screening for CO₂ hydrogenation to ethanol[J]. ChemCatChem, 2021, 13(14): 3324-3332.
36	GOGATE Makarand R, DAVIS Robert J. Comparative study of CO and CO₂ hydrogenation over supported Rh-Fe catalysts[J]. Catalysis Communications, 2010, 11(10): 901-906.
37	CHEN Yuan, CHOI Saemin, THOMPSON Levi T. Low temperature CO₂ hydrogenation to alcohols and hydrocarbons over Mo₂C supported metal catalysts[J]. Journal of Catalysis, 2016, 343: 147-156.
38	CAPARRÓS Francisco J, SOLER Lluís, ROSSELL Marta D, et al. Remarkable carbon dioxide hydrogenation to ethanol on a palladium/iron oxide single-atom catalyst[J]. ChemCatChem, 2018, 10(11): 2365-2369.
39	LI Shanggui, GUO Haijun, LUO Cairong, et al. Effect of iron promoter on structure and performance of K/Cu-Zn catalyst for higher alcohols synthesis from CO₂ hydrogenation[J]. Catalysis Letters, 2013, 143(4): 345-355.
40	GNANAMANI Muthu Kumaran, JACOBS Gary, HAMDEH Hussein H, et al. Hydrogenation of carbon dioxide over Co-Fe bimetallic catalysts[J]. ACS Catalysis, 2016, 6(2): 913-927.
41	GNANAMANI Muthu Kumaran, HAMDEH Hussein H, JACOBS Gary, et al. Hydrogenation of carbon dioxide over K-promoted FeCo bimetallic catalysts prepared from mixed metal oxalates[J]. ChemCatChem, 2017, 9(7): 1303-1312.
42	DING Fanshu, ZHANG Anfeng, LIU Min, et al. CO₂hydrogenation to hydrocarbons over iron-based catalyst: Effects of physicochemical properties of Al₂O₃ supports[J]. Industrial & Engineering Chemistry Research, 2014, 53(45): 17563-17569.
43	WANG Yang, WANG Wenhang, HE Ruosong, et al. Carbon-based electron buffer layer on ZnO _x -Fe₅C₂-Fe₃O₄ boosts ethanol synthesis from CO₂ hydrogenation[J]. Angewandte Chemie International Edition, 2023, 62(46): e202311786.
44	LU Fangxu, CHEN Xin, WANG Wen, et al. Adjusting the CO₂ hydrogenation pathway via the synergic effects of iron carbides and iron oxides[J]. Catalysis Science & Technology, 2021, 11(23): 7694-7703.
45	VISCONTI Carlo Giorgio, MARTINELLI Michela, FALBO Leonardo, et al. CO₂ hydrogenation to lower olefins on a high surface area K-promoted bulk Fe-catalyst[J]. Applied Catalysis B: Environmental, 2017, 200: 530-542.
46	LIU Junhui, ZHANG Guanghui, JIANG Xiao, et al. Insight into the role of Fe₅C₂ in CO₂ catalytic hydrogenation to hydrocarbons[J]. Catalysis Today, 2021, 371: 162-170.
47	DE SMIT Emiel, CINQUINI Fabrizio, BEALE Andrew M., et al. Stability and reactivity of ε-χ-θ iron carbide catalyst phases in Fischer-Tropsch synthesis: Controlling μ_C [J]. Journal of the American Chemical Society, 2010, 132(42): 14928-14941.
48	XU Di, YANG Hengquan, HONG Xinlin, et al. Tandem catalysis of direct CO₂ hydrogenation to higher alcohols[J]. ACS Catalysis, 2021, 11(15): 8978-8984.
49	WANG Yanqiu, ZHANG Xinxin, HONG Xinlin, et al. Sulfate-promoted higher alcohol synthesis from CO₂ hydrogenation[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(27): 8980-8987.
50	HUANG Jiamin, ZHANG Guanghui, ZHU Jie, et al. Boosting the production of higher alcohols from CO₂ and H₂ over Mn- and K-modified iron carbide[J]. Industrial & Engineering Chemistry Research, 2022, 61(21): 7266-7274.
51	HUANG Jiamin, ZHANG Guanghui, WANG Mingrui, et al. The synthesis of higher alcohols from CO₂ hydrogenation over Mn-Cu-K modified Fe₅C₂ and CuZnAlZr tandem catalysts[J]. Frontiers in Energy Research, 2023, 10: 995800.
52	XU Di, DING Mingyue, HONG Xinlin, et al. Mechanistic aspects of the role of K promotion on Cu-Fe-based catalysts for higher alcohol synthesis from CO₂ hydrogenation[J]. ACS Catalysis, 2020, 10(24): 14516-14526.
53	HIGUCHI Katsumi, HANEDA Yoko, TABATA Kenji, et al. A study for the durability of catalysts in ethanol synthesis by hydrogenation of carbon dioxide[J]. Studies in Surface Science and Catalysis, 1998, 114: 517-520.
54	JIA Yazhen, WANG Bin, WEN Yueli, et al. Mechanism of stability and deactivation of N-doped CuFeZn catalysts for C₂₊ alcohols synthesis by hydrogenation of CO₂ [J]. Fuel Processing Technology, 2023, 250: 107901.
55	YANG Chen, WANG Bin, WEN Yueli, et al. Composition control of CuFeZn catalyst derived by PDA and its effect on synthesis of C₂₊ alcohols from CO₂ [J]. Fuel, 2022, 327: 125055.
56	LIU Tangkang, XU Di, SONG Mengyang, et al. K-ZrO₂ interfaces boost CO₂ hydrogenation to higher alcohols[J]. ACS Catalysis, 2023, 13(7): 4667-4674.
57	XI Xiaoying, ZENG Feng, ZHANG Heng, et al. CO₂ hydrogenation to higher alcohols over K-promoted bimetallic Fe-In catalysts on a Ce-ZrO₂ support[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(18): 6235-6249.
58	GUO Wei, GAO Wengui, WANG Hua, et al. Higher alcohols synthesis from CO₂ hydrogenation over K₂O-modified CuZnFeZrO₂ catalysts[J]. Advanced Materials Research, 2013, 827: 20-24.
59	SI Zhiyan, WANG Linkai, HAN Yu, et al. Synthesis of alkene and ethanol in CO₂ hydrogenation on a highly active sputtering CuNaFe catalyst[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(45): 14972-14979.
60	WANG Yang, WANG Kangzhou, ZHANG Baizhang, et al. Direct conversion of CO₂ to ethanol boosted by intimacy-sensitive multifunctional catalysts[J]. ACS Catalysis, 2021, 11(18): 11742-11753.
61	ZHANG Qian, WANG Sen, GENG Rui, et al. Hydrogenation of CO₂ to higher alcohols on an efficient Cr-modified CuFe catalyst[J]. Applied Catalysis B: Environmental, 2023, 337: 123013.
62	XU Di, DING Mingyue, HONG Xinlin, et al. Selective C₂₊ alcohol synthesis from direct CO₂ hydrogenation over a Cs-promoted Cu-Fe-Zn catalyst[J]. ACS Catalysis, 2020, 10(9): 5250-5260.
63	YAO Ruwei, WEI Jian, GE Qingjie, et al. Monometallic iron catalysts with synergistic Na and S for higher alcohols synthesis via CO₂ hydrogenation[J]. Applied Catalysis B: Environmental, 2021, 298: 120556.
64	YAO Ruwei, WU Bin, YU Yang, et al. Regulating the electronic property of iron catalysts for higher alcohols synthesis from CO₂ hydrogenation[J]. Applied Catalysis B: Environment and Energy, 2024, 355: 124159.
65	GOUD Devender, CHURIPARD Sathyapal R, BAGCHI Debabrata, et al. Strain-enhanced phase transformation of iron oxide for higher alcohol production from CO₂ [J]. ACS Catalysis, 2022, 12(18): 11118-11128.
66	GUO Haijun, DING Shuai, ZHANG Hairong, et al. Promotion effect of iron addition on the structure and CO₂ hydrogenation performance of attapulgite/Ce_0.75Zr_0.25O₂ nanocomposite supported Cu-ZnO based catalyst[J]. Molecular Catalysis, 2021, 513: 111820.
67	WANG Yanqiu, ZHOU Ying, ZHANG Xinxin, et al. PdFe alloy-Fe₅C₂ interfaces for efficient CO₂ hydrogenation to higher alcohols[J]. Applied Catalysis B: Environmental and Energy, 2024, 345: 123691.
68	ZHOU Ying, WANG Yanqiu, LU Hanjun, et al. Highly dispersed K- and Pd-comodified Fe catalyst for CO₂ hydrogenation to higher alcohols[J]. ACS Sustainable Chemistry & Engineering, 2024, 12(8): 3322-3330.
69	GUO Haijun, LI Shanggui, PENG Fen, et al. Roles investigation of promoters in K/Cu-Zn catalyst and higher alcohols synthesis from CO₂ hydrogenation over a novel two-stage bed catalyst combination system[J]. Catalysis Letters, 2014, 145(2): 620-630.
70	WANG Yanqiu, XU Di, ZHANG Xinxin, et al. Selective C₂₊ alcohol synthesis by CO₂hydrogenation via a reaction-coupling strategy[J]. Catalysis Science & Technology, 2022, 12(5): 1539-1550.
71	YANG Haiyan, WEI Zhangqian, ZHANG Jian, et al. Tuning the selectivity of CO₂ hydrogenation to alcohols by crystal structure engineering[J]. Chem, 2024, 10: 2245-2265.
72	KIM Jun-Sik, LEE Sunmook, LEE Sang-Bong, et al. Performance of catalytic reactors for the hydrogenation of CO₂ to hydrocarbons[J]. Catalysis Today, 2006, 115(1/2/3/4): 228-234.
73	DING Mingyue, TU Junling, QIU Minghuang, et al. Impact of potassium promoter on Cu-Fe based mixed alcohols synthesis catalyst[J]. Applied Energy, 2015, 138: 584-589.
74	SHOLEHA Novia Amalia, HOLILAH Holilah, BAHRUJI Hasliza, et al. Recent trend of metal promoter role for CO₂ hydrogenation to C₁ and C₂₊ products[J]. South African Journal of Chemical Engineering, 2023, 44: 14-30.
75	GNANAMANI Muthu Kumaran, JACOBS Gary, KEOGH Robert A, et al. Fischer-Tropsch synthesis: Effect of pretreatment conditions of cobalt on activity and selectivity for hydrogenation of carbon dioxide[J]. Applied Catalysis A: General, 2015, 499: 39-46.
76	INUI Tomoyuki, YAMAMOTO Tetsuo. Effective synthesis of ethanol from CO₂ on polyfunctional composite catalysts[J]. Catalysis Today, 1998, 45(1/2/3/4): 209-214.
77	ZHANG Shunan, HUANG Chaojie, SHAO Zilong, et al. Revealing and regulating the complex reaction mechanism of CO₂ hydrogenation to higher alcohols on multifunctional tandem catalysts[J]. ACS Catalysis, 2023, 13(5): 3055-3065.
78	BEDIAKO Bernard Baffour Asare, QIAN Qingli, HAN Buxin. Synthesis of C₂₊ chemicals from CO₂ and H₂ via C—C bond formation[J]. Accounts of Chemical Research, 2021, 54(10): 2467-2476.
79	潞安集团CO2重整利用工业尾气生产20万吨乙醇项目预计 9月试车[EB/OL]. .
80	“ 5万吨/年乙烯多相氢甲酰化及其加氢制正丙醇工业化技术”通过科技成果鉴定[EB/OL]. .
81	JI Lei, LI Lei, JI Xuqiang, et al. Highly selective electrochemical reduction of CO₂ to alcohols on an FeP nanoarray[J]. Angewandte Chemie International Edition, 2020, 59(2): 758-762.
82	JI Lei, CHANG Le, ZHANG Ya, et al. Electrocatalytic CO₂ reduction to alcohols with high selectivity over a two-dimensional Fe₂P₂S₆ nanosheet[J]. ACS Catalysis, 2019, 9(11): 9721-9725.
83	AMPELLI C, GENOVESE C, PASSALACQUA R, et al. The use of a solar photoelectrochemical reactor for sustainable production of energy[J]. Theoretical Foundations of Chemical Engineering, 2012, 46(6): 651-657.
84	ARRIGO Rosa, SCHUSTER Manfred E, WRABETZ Sabine, et al. New insights from microcalorimetry on the FeO _x /CNT-based electrocatalysts active in the conversion of CO₂ to fuels[J]. ChemSusChem, 2012, 5(3): 577-586.
85	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.
86	LU Peng, CHEN Qingjun, YANG Guohui, et al. Space-confined self-regulation mechanism from a capsule catalyst to realize an ethanol direct synthesis strategy[J]. ACS Catalysis, 2020, 10(2): 1366-1374.
87	CHEN Jie, ZHA Yajun, LIU Bing, et al. Rationally designed water enriched nano reactor for stable CO₂hydrogenation with near 100% ethanol selectivity over diatomic palladium active sites[J]. ACS Catalysis, 2023, 13(10): 7110-7121.

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