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

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

Chinese Journal of Catalysis ›› 2024, Vol. 65: 40-69.DOI: 10.1016/S1872-2067(24)60094-X

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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)

Abstract

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

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]

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

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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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