负载型多相金属催化剂用于二氧化碳辅助低碳烷烃氧化脱氢反应

doi:10.1016/S1872-2067(24)60094-X

催化学报 ›› 2024, Vol. 65: 40-69.DOI: 10.1016/S1872-2067(24)60094-X

负载型多相金属催化剂用于二氧化碳辅助低碳烷烃氧化脱氢反应

郑颖滨^a^,^b^,¹, 张新宝^a^,¹, 李俊杰^a, 安杰^a, 徐龙伢^a, 李秀杰^a^,^*(), 朱向学^a^,^*()

^a中国科学院大连化学物理研究所, 能源催化转化全国重点实验室, 辽宁大连116023
^b中国科学院大学, 北京100049

收稿日期:2024-06-03 接受日期:2024-07-09 出版日期:2024-10-18 发布日期:2024-10-15
通讯作者: *电子信箱: xiujieli@dicp.ac.cn (李秀杰), zhuxx@dicp.ac.cn (朱向学).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22078312);大连市重点领域创新团队(2020RT06);中国科学院“西部之光-西部交叉团队”重点实验室专项(xbzg-zdsys-202318)

CO₂-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts

Yingbin Zheng^a^,^b^,¹, Xinbao Zhang^a^,¹, Junjie Li^a, Jie An^a, Longya Xu^a, Xiujie Li^a^,^*(), Xiangxue Zhu^a^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-06-03 Accepted:2024-07-09 Online:2024-10-18 Published:2024-10-15
Contact: *E-mail: xiujieli@dicp.ac.cn (X. Li), zhuxx@dicp.ac.cn (X. Zhu).
About author:Xiujie Li, Professor at the Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (CAS). Prof. Li received her Ph.D. in Physical Chemistry from DICP, CAS in 2008 and has been working in the Division of Fossil Conversion and Applied Catalysis at DICP since then. Her research interests primarily focus on the synthesis and applications of zeolites for heterogeneous catalysis and VOCs removal, CO₂-assisted oxidative dehydrogenation of light alkanes, and developing new routes for value-added olefin on basis of fossil energy and renewable energy. She has published more than 80 peer-reviewed papers.
Xiangxue Zhu, Chair Professor at the Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (CAS). Prof. Zhu received his Ph.D. in Industrial Catalysis from DICP, CAS in 2006 and has been working in the Division of Fossil Conversion and Applied Catalysis at DICP since then. His research interests primarily focus on zeolite synthesis and catalysis, shape-selective catalysis, catalysis and catalytic materials for chemicals, and CO₂-assisted oxidative dehydrogenation of light alkanes. Numerous catalytic processes developed by him and his research team have been implemented in over 30 industrial units.
¹ These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22078312);Dalian Innovation Team in Key Areas(2020RT06);West Light Foundation of the Chinese Academy of Sciences and the Liaoning Key Laboratory(xbzg-zdsys-202318)

摘要/Abstract

摘要：

低碳烯烃(C2-C4)是石油化工产业链中的重要原料, 其需求量随着全球经济的稳步增长而持续攀升. 近年来, 页岩气革命在全球范围内兴起, 促进了低碳烷烃脱氢技术的蓬勃发展, 使之成为低碳烯烃供给的关键路线之一. 同时, 全球CO₂排放量与日俱增, 引发的温室效应等环境问题威胁着人类社会的健康发展. 为有效利用CO₂中的碳氧资源, 研究者们将CO₂引入低碳烷烃脱氢体系中, 一方面可有效避免直接脱氢反应中活性金属组分易烧结的问题; 另一方面, 可解决强氧化剂易深度氧化低碳烯烃引起的目标产品选择性低和副产大量CO_x的难题, 并减少反应体系易燃易爆的风险; 同时, 该过程还可副产CO, H₂等基础化工原料, 对于优化能源结构和促进化学工业的可持续发展具有重要意义.

近年来, 用于CO₂辅助低碳烷烃氧化脱氢反应的催化技术取得显著进展. 各类金属基催化剂因其独特性质展现出优异的催化性能, 但不同催化剂也面临着各自的挑战. 例如Pt基催化剂因高活性而受到广泛关注,但环境有害的氯化再生技术仍然是亟待解决的难题; Cr基催化剂因潜在的环境毒性问题而面临挑战. 此外, 氧化还原型金属 (如V, Fe等) 和主族金属 (如Ga, In等) 催化剂也展现出了良好的脱氢能力, 但其性能仍有待进一步提升. 通过调控催化剂的组成、结构或反应条件, 有望进一步提升这些催化剂的脱氢效率和选择性. 为进一步促进低碳烷烃和CO₂资源的高值化利用, 并为高效催化剂的开发设计提供指导, 本文综述了各类金属基 (包括贵金属、过渡金属、金属氧化物以及高熵合金体系) 催化剂在CO₂辅助低碳烷烃 (乙烷、丙烷、丁烷) 氧化脱氢反应中的最新研究成果, 旨在为相关领域的研究人员提供有益的参考和启示, 推动CO₂辅助低碳烷烃氧化脱氢技术向更高效、更环保的方向发展. 聚焦于活性金属的种类和数量、活性位点的化学价态和配位环境、助剂的功能以及载体的效应, 本文系统归纳了CO₂在低碳烷烃脱氢反应中的多重正面作用, 包括促进氢物种消耗、有效清除积碳、补充晶格氧以及稳定金属价态等. 同时, 深入探讨了引入CO₂所伴随的负面效应, 如竞争吸附现象、反应能耗与产物分离成本的增加, 以及可能引发的重整反应等不利因素. 进一步地, 详细分析了不同活性位点在微观结构层面的特性以及它们在低碳烷烃与CO₂活化中的协同作用机制. 详细讨论了催化剂的物化性质和催化性能之间的构-效关系以及提升催化性能的策略. 系统综述揭示, 当前研究面临的主要挑战在于高温条件下烷烃C-H键的选择性活化难题及催化剂因积碳而导致的失活问题. 为解决这些问题, 催化剂的研发工作应聚焦于开发能够协同活化C=O和C-H键的双功能或多功能复合催化材料.

展望未来, 实现多功能位点的精准控制, 结合活性位点动力学行为的原位解析技术, 同时确保催化剂的高效性、环保性以及转化路线的多元化发展, 将是推动非均相金属催化剂在CO₂耦合轻质烷烃脱氢领域取得突破性进展的关键路径. 这一方向不仅为催化剂设计提供了新的思路, 也为实现低碳资源的高效、高值化利用奠定基础.

关键词: 烷烃脱氢, CO₂利用, 金属催化剂, 低碳烯烃, 耦合反应

Abstract:

Light olefins are important platform feedstocks in the petrochemical industry, and the ongoing global economic development has driven sustained growth in demand for these compounds. The dehydrogenation of alkanes, derived from shale gas, serves as an alternative olefins production route. Concurrently, the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas. The integrated process of light alkanes dehydrogenation and carbon dioxide reduction (CO₂-ODH) can produce light olefins and realize resource utilization of CO₂, which has gained wide popularity. With the introduction of CO₂, coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed. CO₂-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O₂-oxidative dehydrogenation reactions. Recent investigations into various metal-based catalysts including mono- and bi-metallic alloys and oxides have displayed promising performances due to their unique properties. This paper provides the comprehensive review and critical analysis of advancements in the CO₂-assisted oxidative dehydrogenation of light alkanes (C2-C4) on metal-based catalysts developed in recent years. Moreover, it offers a comparative summary of the structural properties, catalytic activities, and reaction mechanisms over various active sites, providing valuable insights for the future design of dehydrogenation catalysts.

Key words: Light alkanes dehydrogenation, CO₂ utilization, Metal-based catalysts, Light olefins, Coupling reaction

郑颖滨, 张新宝, 李俊杰, 安杰, 徐龙伢, 李秀杰, 朱向学. 负载型多相金属催化剂用于二氧化碳辅助低碳烷烃氧化脱氢反应[J]. 催化学报, 2024, 65: 40-69.

Yingbin Zheng, Xinbao Zhang, Junjie Li, Jie An, Longya Xu, Xiujie Li, Xiangxue Zhu. CO₂-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts[J]. Chinese Journal of Catalysis, 2024, 65: 40-69.

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	Chemical equation	$ \Delta H_{298 \mathrm{~K}}^{\ominus}$(kJ/mol)	Reaction type
1-1	C₂H₆ → C₂H₄ + H₂	137	DDH
1-2	C₃H₈ → C₃H₆ + H₂	125
1-3	i-C₄H₁₀ → i-C₄H₈ + H₂	138
1-4	n-C₄H₁₀ → n-C₄H₈ + H₂	148
1-5	n-C₄H₁₀ → cis-2-C₄H₈ + H₂	142
1-6	n-C₄H₁₀ → trans-2-C₄H₈ + H₂	138
1-7	n-C₄H₁₀ → 1,3-C₄H₆ + 2H₂	258
1-8	n-C₄H₈ → 1,3-C₄H₆ + H₂	110
2-1	2C₂H₆ + O₂ → 2C₂H₄ + 2H₂O	‒209	O₂-ODH
2-2	2C₃H₈ + O₂ → 2C₃H₆ + 2H₂O	‒234
2-3	2n-C₄H₁₀ + O₂ → 2 n-C₄H₈ + 2H₂O	‒187
2-4	2n-C₄H₈ + O₂ → 2 1,3-C₄H₆ + 2H₂O	‒264
3-1	C₂H₆ + CO₂ → C₂H₄ + CO + H₂O	178	CO₂-ODH
3-2	C₃H₈ + CO₂ → C₃H₆ + CO + H₂O	166
3-3	n-C₄H₁₀ + CO₂ → n-C₄H₈ + CO + H₂O	189
3-4	n-C₄H₁₀ + 2CO₂ → 1,3-C₄H₆ + 2CO + 2H₂O	399
4	H₂ + CO₂ → CO + H₂O	41	RWGS
5	C + CO₂ → 2CO	172	Reverse Boudouard
6-1	C₂H₆ + 2CO₂ → 4CO + 3H₂	430	Dry-reforming
6-2	C₃H₈ + 3CO₂ → 6CO + 4H₂	637
6-3	n-C₄H₁₀ + 4CO₂ → 8CO + 5H₂	838

	Chemical equation	$ \Delta H_{298 \mathrm{~K}}^{\ominus}$(kJ/mol)	Reaction type
1-1	C₂H₆ → C₂H₄ + H₂	137	DDH
1-2	C₃H₈ → C₃H₆ + H₂	125
1-3	i-C₄H₁₀ → i-C₄H₈ + H₂	138
1-4	n-C₄H₁₀ → n-C₄H₈ + H₂	148
1-5	n-C₄H₁₀ → cis-2-C₄H₈ + H₂	142
1-6	n-C₄H₁₀ → trans-2-C₄H₈ + H₂	138
1-7	n-C₄H₁₀ → 1,3-C₄H₆ + 2H₂	258
1-8	n-C₄H₈ → 1,3-C₄H₆ + H₂	110
2-1	2C₂H₆ + O₂ → 2C₂H₄ + 2H₂O	‒209	O₂-ODH
2-2	2C₃H₈ + O₂ → 2C₃H₆ + 2H₂O	‒234
2-3	2n-C₄H₁₀ + O₂ → 2 n-C₄H₈ + 2H₂O	‒187
2-4	2n-C₄H₈ + O₂ → 2 1,3-C₄H₆ + 2H₂O	‒264
3-1	C₂H₆ + CO₂ → C₂H₄ + CO + H₂O	178	CO₂-ODH
3-2	C₃H₈ + CO₂ → C₃H₆ + CO + H₂O	166
3-3	n-C₄H₁₀ + CO₂ → n-C₄H₈ + CO + H₂O	189
3-4	n-C₄H₁₀ + 2CO₂ → 1,3-C₄H₆ + 2CO + 2H₂O	399
4	H₂ + CO₂ → CO + H₂O	41	RWGS
5	C + CO₂ → 2CO	172	Reverse Boudouard
6-1	C₂H₆ + 2CO₂ → 4CO + 3H₂	430	Dry-reforming
6-2	C₃H₈ + 3CO₂ → 6CO + 4H₂	637
6-3	n-C₄H₁₀ + 4CO₂ → 8CO + 5H₂	838

Catalyst	Feed ratio (C₂:CO₂:inert gas)	Temp. (°C)	WHSV (L/g/h)	X_C2 (%)	S_C2 (%)	X_CO2 (%)	Ref.
1.0% Pd(1:0)/CeO₂	1:01:02	600	24	4.6	59.6	8.6	[44]
1.0% PdFe(1:3)/CeO₂	1:01:02	600	24	6.1	86.4	7.1
1.0% PdFe(1:9)/CeO₂	1:01:02	600	24	6.6	85.8	8.3
0.5% PdFe(1:3)/CeO₂	1:01:02	600	24	4.9	87.2	6.7
0.1% PdFe(1:3)/CeO₂	1:01:02	600	24	3.2	93.1	3.7
1.4% Fe(0:3)/CeO₂	1:01:02	600	24	0.9	40	2.5
1%PdCo₃/CeO₂	1:01:02	600	24	8.3	10.6	21.6	[48]
1%PdIn₃/CeO₂	1:01:02	600	24	3.1	89	4.5
1%PdGa₃/CeO₂	1:01:02	600	24	0.4	95.5	0.8
1%PdSn₃/CeO₂	1:01:02	600	24	2.8	88.9	2.9
1%PdFe₃/CeO₂	1:01:02	600	24	4.9	81.7	5.7
1%PdAg₃/CeO₂	1:01:02	600	24	3.6	65.5	5.6
1%PdAu₃/CeO₂	1:01:02	600	24	3.1	56.9	6.7
1%PdCu₃/CeO₂	1:01:02	600	24	2.4	39.4	5.3
1%PdNi₃/CeO₂	1:01:02	600	24	9.4	5.7	23.4
1%PdPt₃/CeO₂	1:01:02	600	24	16.1	2.2	37.8
1%PdRh₃/CeO₂	1:01:02	600	24	27.7	0.8	56.1
1%PdRu₃/CeO₂	1:01:02	600	24	31.3	0.3	63.4
1%PdIr₃/CeO₂	1:01:02	600	24	33.5	0.7	61.1
Pd-Fe₆/CeO₂	1:02:03	650	18	9.9	80.4	9.3	[49]
Pd-Co₆/CeO₂	1:02:03	650	18	24.9	4.4	34.2
Pd-Ni₉/CeO₂	1:02:03	650	18	74.9	2	62.2
Au/CeR	0.136365741	650	9	16.9	97.6	—	[50]
Au/Ce_0.9Y_0.1	0.136365741	650	9	20.9	99.5	—	[51]
PtCe@MZ	2:01:17	600	15	34	94	35*	[53]
1Pt@ZNS	2:01:07	600	15	9.5	54	48*	[54]
1Pt-1La@ZNS	2:01:07	600	15	37.2	78	68
1Pt-1Y@ZNS	2:01:07	600	15	38	83	22*
1Pt-1Sc@ZNS	2:01:07	600	15	34.6	84	40*
GaPt MWFB 450	3:03:04	450	8.6	42*	83*	8*	[56]
Cr-10%/SiO₂	1:02:01	650	—	30.5	98.6	21	[60]
Fe-10%/SiO₂	1:02:01	650	—	18.9	99	8.27
Co-10%/SiO₂	1:02:01	650	—	20.5	19.6	36.4
Cr/SBA-15@4	1:01:00	650	7.2	18	76.3	9*	[63]
Cr/SBA-15@5	1:01:00	650	7.2	21.5	80.5	10*
Cr/SBA-15@7	1:01:00	650	7.2	25.8	81	14*
Cr/SBA-15@8	1:01:00	650	7.2	21.8	78.4	12*
Cr/ZSM-5-S-0.15	0.136365741	650	9	48.9	87.4	—	[64]
8Cr-Cr-TEOS	1:05:04	700	15	58	91*	—	[66]
Cr/Silicalite-1	0.136365741	650	9	40.2	93.8	—	[67]
5 wt% CrO_x/D-ERB-1	5:15:30	600	6	35.6	94.5	-	[68]
0.5Cr/NaM	0.136365741	650	9	5	95.7	2.5	[70]
0.5Cr/NaM-d1	0.136365741	650	9	23	95	5.5
0.5Cr/NaM-d2	0.136365741	650	9	23.9	94.8	6.1
3Cr/NaM	0.136365741	650	9	7.1	89.7	2.8
3Cr/NaM-d1	0.136365741	650	9	36.1	88.9	9.8
3Cr/NaM-d2	0.136365741	650	9	38.2	86.2	11.1
8 wt% Cr/Al₂O₃	1:02:07	600	7.5	25*	83*	12*	[71]
8 wt% Cr/Al₂O₃	1:02:07	625	7.5	35*	83*	18*
8 wt% Cr/Al₂O₃	1:02:07	650	7.5	50*	80*	24*
8 wt% Cr/Al₂O₃	1:02:07	675	7.5	62*	69*	32*
Cr-TUD-1	1:05	650	24	37.5	92.5	6.8	[72]
Cr/CZ	1:01:03	700	6	31.7	52.6	33.7	[73]
0.6KCr/CZ	1:01:03	700	6	39.8	56.1	41.5
1KCr/CZ	1:01:03	700	6	43.1	68.6	42.8
5KCr/CZ	1:01:03	700	6	32	82.5	27.3
10KCr/CZ	1:01:03	700	6	28	79	25.7
Cr₂O₃(5%)/HZSM-5-ZrO₂(10%)	1:05:04	700	6	64.6	87*	—	[74]
Cr/Ce-MCM-41(Si/Ce=25)-p	1:05:04	700	9	64*	97*	—	[75]
Cr/MgO(50)-CeO₂(50)	1:04:05	700	6000 h^‒1	68.28	61.97	—	[76]
5%Cr /ZSM-5	1:01:08	800	12	70*	64*	55*	[77]
5%Ce/ZSM-5	1:01:08	800	12	57*	80*	18*
5%Cr-5%Ce/ZSM-5	1:01:08	800	12	71*	64*	65*
10%Cr-5%Ce/ZSM-5	1:01:08	800	12	72*	53*	82*
15%Cr-5%Ce/ZSM-5	1:01:08	800	12	70*	65*	70*
5%Cr-10%Ce/ZSM-5	1:01:08	800	12	67*	75*	53*
5%Cr-15%Ce/ZSM-5	1:01:08	800	12	62*	75*	54*
Fe/0Mg10Al	1:01:08	650	6	12	96	9	[82]
Fe/3Mg7Al	1:01:08	650	6	21	84	20
Fe/5Mg5Al	1:01:08	650	6	14	87	16
Fe/10Mg0Al	1:01:08	650	6	9	73	14
Fe/S1-EDA	1:01:08	650	6	15	90	10
Fe/SiO₂	1:01:08	650	6	4	90	2
Fe/S1	1:01:08	650	6	10	94	9
Fe/commercial MgO	1:01:08	650	6	7	73	13
Fe/ZrO₂	1:01:08	650	6	30	55	37
1FeZr	1:01:03	650	12	9	85	8	[83]
3FeZr	1:01:03	650	12	21	71	25
5FeZr	1:01:03	650	12	25	60	29
10FeZr	1:01:03	650	12	19	61	24
5Fe-10Co/Al₂O₃	1:01:02	700	7.2	16	55	—	[84]
Fe/NiMgZr	01:01.2	600	1.4	30*	68*	33*	[85]
5Fe/10NiMgZr	1:01	650	5.4	23.3	90	25.5	[87]
Fe₃Ni₁/SiO₂	1:01:02	600	24	0.4	75*	0.9	[89]
Fe₃Ni₁/ZrO₂	1:01:02	600	24	2.6	61.7	5.6
Fe₃Ni₁/CeO₂	1:01:02	600	24	3.5	82	6.9
Fe_0.75Ni_0.25/CeO₂	1:01:02	600	24	2.2	76.7	4.7
Fe_1.5Ni_0.5/CeO₂	1:01:02	600	24	3.1	79.2	6.2
Fe₆Ni₂/CeO₂	1:01:02	600	24	3.4	67.4	8.7
Fe₁₂Ni₄/CeO₂	1:01:02	600	24	3.5	31.9	13.1
Ni₁Fe₃/CeO₂	1:01:02	600	24	3.5	77.5	5.9	[90]
NiFe/CeO₂-C1	1:01:02	600	24	4.6	83	6.2	[91]
NiFe/CeO₂-C2	1:01:02	600	24	3.9	47	8
NiFe/CeO₂-C3	1:01:02	600	24	2.6	40	7.9
NiFe/CeO₂-S	1:01:02	600	24	1.9	48	5.5
Fe_1.5Ni_0.5/ZrO₂-T	1:01:01	650	9	3.2	22.3	3.8	[92]
Fe_1.5Ni_0.5/ZrO₂-Mix	1:01:01	650	9	9.9	68.9	15.3
Fe_1.5Ni_0.5/ZrO₂-M	1:01:01	650	9	21.8	80.5	25.2
FeNi@CNTs	4:04:02	500	60	2.3	41.6	—	[93]
1 wt% Co/S-1	1:01:03	650	12	20	84	8	[97]
CoZ-IM	0.130219907	650	9	74.6	3.6	81.8	[111]
CoZ-IE	0.130219907	650	9	26.5	96.7	4.3
0.75Co/SiO₂	1:02	700	6	46	85	12*	[112]
1%Co-HMS	1:01:02	650	6	24.4	86.7	—	[113]
1%Co-HMS (1 h)	1:01:02	650	6	26	92.6	—	[114]
CoZ5-C	0.130219907	650	9	51.3	90.3	—	[115]
Mo₂C/SiO₂-WI	1:01:02	600	15	5.8	57*	5*	[122]
Mo₂C/SiO₂-SG	1:01:02	600	15	4.7	64*	1*
Mo₂C/SiO₂-HNC	1:01:02	600	15	2	60*	4*
Mo/5CeTi	0.212847222	600	15	15*	72	—	[127]
VO_x/ZrO₂(25)-MgO(75)-A	1:05:04	700	600 s^‒1	67.14	90*	—	[129]
V₂O₅/MgO-ZrO₂(S1)	1:04:05	700	6000 h^‒1	79	61*	—	[130]
VO_x/Mg-Zr-MCM-41	1:04:05	700	6000 h^‒1	55*	76*	—	[131]
Ga₂O₃	0.136365741	650	9	13	87.4	5.2	[136]
MgGa₂O₄	0.136365741	650	9	35.2	81.8	8.3
MgGa_1.5Al_0.5O₄	0.136365741	650	9	44.3	87.1	6.1
MgGa₁Al₁O₄	0.136365741	650	9	42.7	91.7	9.3
MgGa_0.5Al_1.5O₄	0.136365741	650	9	21.2	99.6	4.1
Ga/ZSM-5-S	0.136365741	650	9	25.3	91.7	—	[137]
Ga/meso-TiO₂	1:05:04	550	4	12*	73*	—	[138]
Ga/TiSi-3	0.136365741	650	9	31.6	86.6	—	[139]
CoZ	0.136365741	650	9	36	93.5	1.1	[140]
Zn/HZ	0.136365741	650	9	41.1	85.6	7.5
Zn/CoZ	0.136365741	650	9	49.4	84.9	7.8
Zn_8.35/NaS-U	1:01:18	650	3.6	37.3	88.1	19.4	[141]
Zn_8.67/NaS-N	1:01:18	650	3.6	65.9	59	36
Zn_9.18K_0.74/NaS-N	1:01:18	650	3.6	61.9	68.6	35.4
Zn_8.95K_1.36/NaS-N	1:01:18	650	3.6	56.5	78.9	30
Zn_8.80K_1.96/NaS-N	1:01:18	650	3.6	42.5	89.1	13.9
Zn_2.92/NaS50	1:01:18	550	3.6	68*	94*	58*	[142]
Zn_2.92/NaS50	1:01:18	580	3.6	55*	89*	44*
Zn_2.92/NaS50	1:01:18	600	3.6	44*	84*	31*
Zn_2.92/NaS50	1:01:18	625	3.6	34*	75*	21*
Zn_2.92/NaS50	1:01:18	650	3.6	23*	64*	12*
5%Zn-ZSM-5(11.5)	1:05	500	3.2	16.4	47.8	1.4	[143]
5%Zn-ZSM-5(25)	1:05	500	3.2	10.5	59.3	0.6
5%Zn-silicalite-1	1:05	500	3.2	1.8	61	0.13
Si_0.1CeO₂	2:02:06	700	6	41.4	64.9	46.2	[144]
CeO₂	2:02:06	700	6	39	24	45.4
3CT1Z1	1:02:17	650	9	33.8	73*	18	[145]

Catalyst	Feed ratio (C₂:CO₂:inert gas)	Temp. (°C)	WHSV (L/g/h)	X_C2 (%)	S_C2 (%)	X_CO2 (%)	Ref.
1.0% Pd(1:0)/CeO₂	1:01:02	600	24	4.6	59.6	8.6	[44]
1.0% PdFe(1:3)/CeO₂	1:01:02	600	24	6.1	86.4	7.1
1.0% PdFe(1:9)/CeO₂	1:01:02	600	24	6.6	85.8	8.3
0.5% PdFe(1:3)/CeO₂	1:01:02	600	24	4.9	87.2	6.7
0.1% PdFe(1:3)/CeO₂	1:01:02	600	24	3.2	93.1	3.7
1.4% Fe(0:3)/CeO₂	1:01:02	600	24	0.9	40	2.5
1%PdCo₃/CeO₂	1:01:02	600	24	8.3	10.6	21.6	[48]
1%PdIn₃/CeO₂	1:01:02	600	24	3.1	89	4.5
1%PdGa₃/CeO₂	1:01:02	600	24	0.4	95.5	0.8
1%PdSn₃/CeO₂	1:01:02	600	24	2.8	88.9	2.9
1%PdFe₃/CeO₂	1:01:02	600	24	4.9	81.7	5.7
1%PdAg₃/CeO₂	1:01:02	600	24	3.6	65.5	5.6
1%PdAu₃/CeO₂	1:01:02	600	24	3.1	56.9	6.7
1%PdCu₃/CeO₂	1:01:02	600	24	2.4	39.4	5.3
1%PdNi₃/CeO₂	1:01:02	600	24	9.4	5.7	23.4
1%PdPt₃/CeO₂	1:01:02	600	24	16.1	2.2	37.8
1%PdRh₃/CeO₂	1:01:02	600	24	27.7	0.8	56.1
1%PdRu₃/CeO₂	1:01:02	600	24	31.3	0.3	63.4
1%PdIr₃/CeO₂	1:01:02	600	24	33.5	0.7	61.1
Pd-Fe₆/CeO₂	1:02:03	650	18	9.9	80.4	9.3	[49]
Pd-Co₆/CeO₂	1:02:03	650	18	24.9	4.4	34.2
Pd-Ni₉/CeO₂	1:02:03	650	18	74.9	2	62.2
Au/CeR	0.136365741	650	9	16.9	97.6	—	[50]
Au/Ce_0.9Y_0.1	0.136365741	650	9	20.9	99.5	—	[51]
PtCe@MZ	2:01:17	600	15	34	94	35*	[53]
1Pt@ZNS	2:01:07	600	15	9.5	54	48*	[54]
1Pt-1La@ZNS	2:01:07	600	15	37.2	78	68
1Pt-1Y@ZNS	2:01:07	600	15	38	83	22*
1Pt-1Sc@ZNS	2:01:07	600	15	34.6	84	40*
GaPt MWFB 450	3:03:04	450	8.6	42*	83*	8*	[56]
Cr-10%/SiO₂	1:02:01	650	—	30.5	98.6	21	[60]
Fe-10%/SiO₂	1:02:01	650	—	18.9	99	8.27
Co-10%/SiO₂	1:02:01	650	—	20.5	19.6	36.4
Cr/SBA-15@4	1:01:00	650	7.2	18	76.3	9*	[63]
Cr/SBA-15@5	1:01:00	650	7.2	21.5	80.5	10*
Cr/SBA-15@7	1:01:00	650	7.2	25.8	81	14*
Cr/SBA-15@8	1:01:00	650	7.2	21.8	78.4	12*
Cr/ZSM-5-S-0.15	0.136365741	650	9	48.9	87.4	—	[64]
8Cr-Cr-TEOS	1:05:04	700	15	58	91*	—	[66]
Cr/Silicalite-1	0.136365741	650	9	40.2	93.8	—	[67]
5 wt% CrO_x/D-ERB-1	5:15:30	600	6	35.6	94.5	-	[68]
0.5Cr/NaM	0.136365741	650	9	5	95.7	2.5	[70]
0.5Cr/NaM-d1	0.136365741	650	9	23	95	5.5
0.5Cr/NaM-d2	0.136365741	650	9	23.9	94.8	6.1
3Cr/NaM	0.136365741	650	9	7.1	89.7	2.8
3Cr/NaM-d1	0.136365741	650	9	36.1	88.9	9.8
3Cr/NaM-d2	0.136365741	650	9	38.2	86.2	11.1
8 wt% Cr/Al₂O₃	1:02:07	600	7.5	25*	83*	12*	[71]
8 wt% Cr/Al₂O₃	1:02:07	625	7.5	35*	83*	18*
8 wt% Cr/Al₂O₃	1:02:07	650	7.5	50*	80*	24*
8 wt% Cr/Al₂O₃	1:02:07	675	7.5	62*	69*	32*
Cr-TUD-1	1:05	650	24	37.5	92.5	6.8	[72]
Cr/CZ	1:01:03	700	6	31.7	52.6	33.7	[73]
0.6KCr/CZ	1:01:03	700	6	39.8	56.1	41.5
1KCr/CZ	1:01:03	700	6	43.1	68.6	42.8
5KCr/CZ	1:01:03	700	6	32	82.5	27.3
10KCr/CZ	1:01:03	700	6	28	79	25.7
Cr₂O₃(5%)/HZSM-5-ZrO₂(10%)	1:05:04	700	6	64.6	87*	—	[74]
Cr/Ce-MCM-41(Si/Ce=25)-p	1:05:04	700	9	64*	97*	—	[75]
Cr/MgO(50)-CeO₂(50)	1:04:05	700	6000 h^‒1	68.28	61.97	—	[76]
5%Cr /ZSM-5	1:01:08	800	12	70*	64*	55*	[77]
5%Ce/ZSM-5	1:01:08	800	12	57*	80*	18*
5%Cr-5%Ce/ZSM-5	1:01:08	800	12	71*	64*	65*
10%Cr-5%Ce/ZSM-5	1:01:08	800	12	72*	53*	82*
15%Cr-5%Ce/ZSM-5	1:01:08	800	12	70*	65*	70*
5%Cr-10%Ce/ZSM-5	1:01:08	800	12	67*	75*	53*
5%Cr-15%Ce/ZSM-5	1:01:08	800	12	62*	75*	54*
Fe/0Mg10Al	1:01:08	650	6	12	96	9	[82]
Fe/3Mg7Al	1:01:08	650	6	21	84	20
Fe/5Mg5Al	1:01:08	650	6	14	87	16
Fe/10Mg0Al	1:01:08	650	6	9	73	14
Fe/S1-EDA	1:01:08	650	6	15	90	10
Fe/SiO₂	1:01:08	650	6	4	90	2
Fe/S1	1:01:08	650	6	10	94	9
Fe/commercial MgO	1:01:08	650	6	7	73	13
Fe/ZrO₂	1:01:08	650	6	30	55	37
1FeZr	1:01:03	650	12	9	85	8	[83]
3FeZr	1:01:03	650	12	21	71	25
5FeZr	1:01:03	650	12	25	60	29
10FeZr	1:01:03	650	12	19	61	24
5Fe-10Co/Al₂O₃	1:01:02	700	7.2	16	55	—	[84]
Fe/NiMgZr	01:01.2	600	1.4	30*	68*	33*	[85]
5Fe/10NiMgZr	1:01	650	5.4	23.3	90	25.5	[87]
Fe₃Ni₁/SiO₂	1:01:02	600	24	0.4	75*	0.9	[89]
Fe₃Ni₁/ZrO₂	1:01:02	600	24	2.6	61.7	5.6
Fe₃Ni₁/CeO₂	1:01:02	600	24	3.5	82	6.9
Fe_0.75Ni_0.25/CeO₂	1:01:02	600	24	2.2	76.7	4.7
Fe_1.5Ni_0.5/CeO₂	1:01:02	600	24	3.1	79.2	6.2
Fe₆Ni₂/CeO₂	1:01:02	600	24	3.4	67.4	8.7
Fe₁₂Ni₄/CeO₂	1:01:02	600	24	3.5	31.9	13.1
Ni₁Fe₃/CeO₂	1:01:02	600	24	3.5	77.5	5.9	[90]
NiFe/CeO₂-C1	1:01:02	600	24	4.6	83	6.2	[91]
NiFe/CeO₂-C2	1:01:02	600	24	3.9	47	8
NiFe/CeO₂-C3	1:01:02	600	24	2.6	40	7.9
NiFe/CeO₂-S	1:01:02	600	24	1.9	48	5.5
Fe_1.5Ni_0.5/ZrO₂-T	1:01:01	650	9	3.2	22.3	3.8	[92]
Fe_1.5Ni_0.5/ZrO₂-Mix	1:01:01	650	9	9.9	68.9	15.3
Fe_1.5Ni_0.5/ZrO₂-M	1:01:01	650	9	21.8	80.5	25.2
FeNi@CNTs	4:04:02	500	60	2.3	41.6	—	[93]
1 wt% Co/S-1	1:01:03	650	12	20	84	8	[97]
CoZ-IM	0.130219907	650	9	74.6	3.6	81.8	[111]
CoZ-IE	0.130219907	650	9	26.5	96.7	4.3
0.75Co/SiO₂	1:02	700	6	46	85	12*	[112]
1%Co-HMS	1:01:02	650	6	24.4	86.7	—	[113]
1%Co-HMS (1 h)	1:01:02	650	6	26	92.6	—	[114]
CoZ5-C	0.130219907	650	9	51.3	90.3	—	[115]
Mo₂C/SiO₂-WI	1:01:02	600	15	5.8	57*	5*	[122]
Mo₂C/SiO₂-SG	1:01:02	600	15	4.7	64*	1*
Mo₂C/SiO₂-HNC	1:01:02	600	15	2	60*	4*
Mo/5CeTi	0.212847222	600	15	15*	72	—	[127]
VO_x/ZrO₂(25)-MgO(75)-A	1:05:04	700	600 s^‒1	67.14	90*	—	[129]
V₂O₅/MgO-ZrO₂(S1)	1:04:05	700	6000 h^‒1	79	61*	—	[130]
VO_x/Mg-Zr-MCM-41	1:04:05	700	6000 h^‒1	55*	76*	—	[131]
Ga₂O₃	0.136365741	650	9	13	87.4	5.2	[136]
MgGa₂O₄	0.136365741	650	9	35.2	81.8	8.3
MgGa_1.5Al_0.5O₄	0.136365741	650	9	44.3	87.1	6.1
MgGa₁Al₁O₄	0.136365741	650	9	42.7	91.7	9.3
MgGa_0.5Al_1.5O₄	0.136365741	650	9	21.2	99.6	4.1
Ga/ZSM-5-S	0.136365741	650	9	25.3	91.7	—	[137]
Ga/meso-TiO₂	1:05:04	550	4	12*	73*	—	[138]
Ga/TiSi-3	0.136365741	650	9	31.6	86.6	—	[139]
CoZ	0.136365741	650	9	36	93.5	1.1	[140]
Zn/HZ	0.136365741	650	9	41.1	85.6	7.5
Zn/CoZ	0.136365741	650	9	49.4	84.9	7.8
Zn_8.35/NaS-U	1:01:18	650	3.6	37.3	88.1	19.4	[141]
Zn_8.67/NaS-N	1:01:18	650	3.6	65.9	59	36
Zn_9.18K_0.74/NaS-N	1:01:18	650	3.6	61.9	68.6	35.4
Zn_8.95K_1.36/NaS-N	1:01:18	650	3.6	56.5	78.9	30
Zn_8.80K_1.96/NaS-N	1:01:18	650	3.6	42.5	89.1	13.9
Zn_2.92/NaS50	1:01:18	550	3.6	68*	94*	58*	[142]
Zn_2.92/NaS50	1:01:18	580	3.6	55*	89*	44*
Zn_2.92/NaS50	1:01:18	600	3.6	44*	84*	31*
Zn_2.92/NaS50	1:01:18	625	3.6	34*	75*	21*
Zn_2.92/NaS50	1:01:18	650	3.6	23*	64*	12*
5%Zn-ZSM-5(11.5)	1:05	500	3.2	16.4	47.8	1.4	[143]
5%Zn-ZSM-5(25)	1:05	500	3.2	10.5	59.3	0.6
5%Zn-silicalite-1	1:05	500	3.2	1.8	61	0.13
Si_0.1CeO₂	2:02:06	700	6	41.4	64.9	46.2	[144]
CeO₂	2:02:06	700	6	39	24	45.4
3CT1Z1	1:02:17	650	9	33.8	73*	18	[145]

Catalyst	Feed ratio (C₃:CO₂:inert gas)	Temp. (°C)	WHSV (L g^‒1 h^‒1)	X_C3 (%)	S_C3 (%)	X_CO2 (%)	Ref.
5%Pd/CeZrAlO_x	37:37:26	500	6000 h^‒1	9.5	93	—	[37]
Pd₁	1:01:02	550	24	0.4	44.4	3.2	[147]
Fe₃Pd₁	1:01:02	550	24	0.4	57.6	0.1
Co₃Pd₁	1:01:02	550	24	2.8	25.2	8.4
Ni₃Pd₁	1:01:02	550	24	5.3	11.2	17.6
Pt₁	1:01:02	550	24	1.6	21.4	4
Fe₃Pt₁	1:01:02	550	24	1.1	32	2.6
Co₃Pt₁	1:01:02	550	24	5.6	10.1	20.3
dCo₃Pt₁	1:01:02	550	24	3.4	27.3	9.5
Ni₃Pt₁	1:01:02	550	24	11.6	2.8	39.4
Fe₁Co₃	1:01:02	550	24	0.9	43.8	1.5
Fe₃Co₁	1:01:02	550	24	0.27	57.1	0.23
Fe₃Ni₁	1:01:02	550	24	2.7	58.2	4
Fe₁Ni₃	1:01:02	550	24	7.4	2.9	26.9
Fe₃Ni₃	1:01:02	550	24	5	20.4	16.1
Fe₉Ni₃	1:01:02	550	24	3.4	22.5	10.9
1Pt5Sn/CeO₂	4:20:01	500	6	21*	79*	—	[150]
0.1 wt% Pt/1.0 wt% Sn-CeO₂	2.4:4.8:10	550	1	15.1	63.9	22*	[151]
Pt₁Fe₇/S-1	5:05:30	550	16	25*	95*	14*	[153]
1Pt-1Zn/SiNS	1:01	600	2.4	46.7	80	—	[154]
0.25%Rh0.50%Pt@Zn-MFI	6:06:18	600	3.6	48*	60*	23*	[156]
Pt₁Co₁-SiBeta	1:01:03	550	12	51.8	91.8	30.6	[156]
Pt₂-SiBeta	1:01:03	550	12	3.6	85.1	0.4
Pt_1.5Co_0.5-SiBeta	1:01:03	550	12	21.8	86.3	6.3
Pt_0.5Co_1.5-SiBeta	1:01:03	550	12	23.5	73.8	22.9
Co₂-SiBeta	1:01:03	550	12	26.4	93.1	14.8
Pt-Co-In/CeO₂	1:01:02	550	12	52	95	57	[157]
HEI/CeO₂	1:01:02	600	12	30	94	53	[158]
Ru₁Cr₁₀O_x/SiO₂	1:01:01	496	12	9	85	5*	[160]
7Cr/SiO₂-5	1:02	650	3.6	80	20	—	[162]
CrO_x/silicalite-1-0.15	4:20:01	550	3	36*	86*	4*	[164]
Cr/GNFp	1:02	600	3.6	21	56.2	—	[165]
Cr_0.5SiBeta	1:05:09	550	9	11	94.7	0.6	[166]
Cr_1.0SiBeta	1:05:09	550	9	17.6	90.8	1.2
Cr_2.0SiBeta	1:05:09	550	9	24.8	87.1	4
Cr_5.0SiBeta	1:05:09	550	9	27.6	84.4	5.5
Cr_7.0SiBeta	1:05:09	550	9	33.3	81.6	7
Cr_2.0AlBeta	1:05:09	550	9	4.5	45.1	0.8
ALD-Cr 0.72%	1:05:14	600	4.5	34*	88*	—	[167]
7% Cr-TUD-1	10.5:2.55	550	1020 h^‒1	45	75	—	[168]
Cr/MSS-1	2:08:08	600	5.4	30*	88*	4.7	[169]
Cr/MSS-2	2:08:08	600	5.4	32*	89*	5.3
Cr/MSS-3	2:08:08	600	5.4	29*	88*	4.3
Cr/MSS-4	2:08:08	600	5.4	27*	88*	2.6
5СrO_y/Сe_0.5Zr_0.5O₂/SiO₂_wet	1:02	675	3.6	38	77	—	[170]
1Cr-Ca/ZrO₂	1:03:06	550	5	3.6	87.9	1.5	[171]
2Cr-Ca/ZrO₂	1:03:06	550	5	20.2	93.5	4.1
3Cr-Ca/ZrO₂	1:03:06	550	5	12.1	90.1	3.3
2Cr-ZrO₂	1:03:06	550	5	17	88.2	6
2Cr/10Fe-CeO₂	0.212847222	510	60	2.9*	80*	—	[172]
7Cr-ZrO₂	1:02:37	550	6	68	60*	37*	[173]
c-2.5CZ	2.5:6.5:91	550	6	26	69*	13	[174]
m-2.5CZ	2.5:6.5:91	550	6	42	60*	23
c-5CZ	2.5:6.5:91	550	6	41	63*	24
m-5CZ	2.5:6.5:91	550	6	58	52*	42
c-10CZ	2.5:6.5:91	550	6	38	68*	17
m-10CZ	2.5:6.5:91	550	6	36	59*	21
c-15CZ	2.5:6.5:91	550	6	59	58*	33
m-15CZ	2.5:6.5:91	550	6	58	59*	35
5Cr/ZrO₂	1:02:37	600	6	79.8	57.6	42.7	[175]
5Cr/Ce_0.1Zr_0.9O₂	1:02:37	600	6	75	66.7	41.6
5Cr/Ce_0.2Zr_0.8O₂	1:02:37	600	6	62.6	79.4	31.2
5Cr/Ce_0.3Zr_0.7O₂	1:02:37	600	6	57.9	82.4	33.8
5Cr/Ce_0.5Zr_0.5O₂	1:02:37	600	6	9.7	92.9	7.9
5Cr/CeO₂	1:02:37	600	6	20.8	79.8	11.9
5 wt% Cr/Al₂O₃	0.085833333	600	60	13.6	90	—	[176]
12 Fe₂O₃/ZrO₂	1:02:37	600	6	32	73	—	[178]
Fe₂O₃-19ZrO₂	01:01.5	550	1.8	10.2	89.2	7.35	[179]
Fe₂O₃-9ZrO₂	01:01.5	550	1.8	17.6	87.8	12.5
Fe₂O₃-4ZrO₂	01:01.5	550	1.8	38.7	85.7	27.5
Fe₂O₃-3ZrO₂	01:01.5	550	1.8	39.9	83.7	28.2
Fe₂O₃-2ZrO₂	01:01.5	550	1.8	40.8	85.1	30.8
Fe₂O₃-1ZrO₂	01:01.5	550	1.8	36.3	88.5	25.7
Fe₂O₃	01:01.5	550	1.8	29.3	90.5	24.2
FeCr50	37:37:26	550	4.5	14.2	71	—	[180]
Fe_0.67Ce_0.5O₂	2:02:06	700	6	42.2	37.4	51.3	[181]
15FeCeO₂	0.212847222	550	6	21.5	45*	28*	[182]
FeNi/Ceria-Vo-R	2.4:4.8:10	550	1	25.2	49	—	[183]
ZnFe₂O_x/S-1	1:01:04	580	7.2	38*	97*	19*	[185]
2V-Fe/KIT-6	1:04:05	580	6	37.8	87	18.5	[186]
5Fe-5V-Al₂O₃	0.636226852	600	7.5	41.3	84.4	31*	[187]
7 Ga/SiO₂(A)	1:02	600	1.8	33	84	—	[188]
5% Ga/HZSM-5	1:01:08	600	90	25*	50*	—	[189]
8Ga₂O₃/SiO₂	2.5:2.5:60	600	3.9	37*	93*	—	[191]
ALD-3C (2.9%Ga)	0.22650463	600	4.5	38	82	—	[195]
Ga_4.0SiBEA	2.5:15:82.5	600	9	57.5	64	—	[196]
5-GaN/Q-3	1:02:07	600	9	31	93	—	[197]
5GaN/NaZSM-5(470)	1:02:07	600	9	45	63*	—	[198]
5GaN/KIT-6	1:02:07	600	9	24*	95*	5*	[199]
5GaN/2000-Fe-silicalite-1	1.5:3:25.5	600	9	45*	78*	6*	[200]
V-La-MSNS	1:02:07	550	6	37*	79*	—	[202]
0.5Cu-10VO_x/S-1	01:01.5	600	1.8	36	90	22	[203]
AlVO7B	1:01	650	18	62*	55*	22*	[204]
20 CeVO₄/AC	1:01:01	550	6	8.5	57	—	[205]
3.4V/In	2.5:2.5:95	540	18	4.2*	67*	—	[206]
3.4V/In-S	2.5:2.5:95	540	18	6.5*	65*	—	[207]
5.2V-MSNSs	1:04:04	600	4.5	58*	83*	—	[208]
6.8V-MCM-41	1:04:04	600	4.5	57*	90*	—	[209]
VO_x/SiO₂	1:01:06	600	16	5.8*	99*	—	[211]
Co/S-1-HTS	2.5:2.5:95	550	24	60*	98*	—	[212]
20%ZnO-ZrO₂	4:20:01	550	6	18*	76*	—	[213]
Zn/Mo-Zr-10	1:02	550	7.2 h^‒1	29.5	80	12	[214]
12% In/HZSM-5	1:04	580	6	13.3	78.9	6.34	[217]

负载型多相金属催化剂用于二氧化碳辅助低碳烷烃氧化脱氢反应

CO₂-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts

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Metrics

Catalyst	Feed ratio (C₄:CO₂:inert gas)	Temp. (°C)	WHSV (L g^-1 h^-1)	X_C4 (%)	S_C4 (%)	X_CO2 (%)	Ref.
Fe/S-1-H	1:1:1	600	2.1	18.7	53.4	11.7	[222]
Fe/S-1-E	1:1:1	600	2.1	17.8	52.5	11.2
Fe/S-1-E-EDA	1:1:1	600	2.1	21.3	53.4	17.9
Fe/S-1-H-EDA	1:1:1	600	2.1	16.6	48.4	7.3
Li-Fe₂O₃/Al₂O₃	1:9	600	18	52*	29*	—	[224]
15MFO/N-C	1:3	580	6000 h^-1	20*	90*	—	[223]
Fe₂O₃	1:4:15	550	9.6	14*	52*	14*	[225]
Fe₄/CeO₂	1:2:17	600	24	7.0	13.5	10.5	[226]
Ni₁Fe₃/CeO₂	1:2:17	600	24	11.9	21.4	18.7
Ni₃Fe₁/CeO₂	1:2:17	600	24	30.9	0.3	59.3
Ni₁Fe₃/ZrO₂	1:2:17	600	24	15.8	3.7	35.1
Ni₁Fe₃/CeO₂-ZrO₂	1:2:17	600	24	13.9	27.4	21.7
Ni₁Fe₃/CeO₂+Ni₁Fe₃/ZrO₂	1:2:17	600	24	14.5	7.5	28.3
FeVCrO_x/10%ZnCl₂/Al₂O₃	1:9	600	18	81.1	49	10.2	[228]
Fe₂O₃/Meso-CeAl-100	1:9	600	18	85	51	14	[239]
Meso-FeAl	1:9	600	18	73*	24*	1.8*	[230]
20 wt% FeCaAlO_x	1:9	600	18	82	34	7	[231]
20 wt% FeCrAlO_x	1:9	600	18	80	34	10
PtMn/SiO₂	1:1:8	500	24	36	99*	—	[232]
Ni-Mo/Al₂O₃	1:2	450	6000 h^-1	7.5	45	—	[233]
5%Cr-SiO₂	1:6	600	12.6	82.2	41.9	—	[234]
3Cr-3Ce/SBA	1:5	570	2.3	35.4	89.6	7.1	[235]
10%CrO_x/Ce_0.5Zr_0.5O₂	1:2:7	550	6	37*	65*	—	[236]
ZnO/S-1-0.08	1:1	570	3.5	44.3	81.7	5.5	[239]
ZnO/S-1-0.35	1:1	570	3.5	49.0	79.4	7.2
ZnO/S-1-1	1:1	570	3.5	41.4	82.6	4.6
ZnO/S-1-1.7	1:1	570	3.5	36.4	83.0	2.7
1%ZnO/S-1	1:1	570	3.5	22.6	78.3	2.7	[240]
2%ZnO/S-1	1:1	570	3.5	37.7	80.4	3.8
3%ZnO/S-1	1:1	570	3.5	44.1	80.7	4.2
5%ZnO/S-1	1:1	570	3.5	49.0	79.4	7.2
9%ZnO/S-1	1:1	570	3.5	50.7	77.1	7.3
5%ZnO/SBA	1:1	570	3.5	17.6	72.7	2.0

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负载型多相金属催化剂用于二氧化碳辅助低碳烷烃氧化脱氢反应

CO2-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts

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CO₂-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts