光热催化甲烷干重整研究进展

doi:10.3866/PKU.WHXB202212060

摘要/Abstract

摘要：

随着工业化的推进，化石能源的消耗产生大量温室气体，其中CH₄和CO₂占据温室气体排放的98%以上。将CH₄和CO₂转化为高附加值化学品具有重要的意义，一直受到工业界和学术界广泛关注。传统的热催化甲烷干重整(DRM)可实现将CH₄和CO₂转化为合成气，但该反应过程受热力学限制，需要很高的能量输入，并且由于反应温度较高，催化剂易发生积碳而失活。绿色环保的光催化技术可以使甲烷干重整反应在温和条件下进行，但是存在太阳光利用率和反应转化率较低等问题。最近光热协同催化受到学术界广泛关注。许多研究结果表明，在相对温和的条件下，光热催化DRM可以获得良好的催化效果，可有效实现太阳能转化为化学能。本文简要介绍近期光热催化甲烷干重整反应的研究进展，总结不同金属催化剂在光热催化甲烷干重整中的应用，同时提出了光热催化甲烷干重整存在的一些挑战及展望。

关键词: 甲烷干重整, 光热催化, LSPR, 金属基催化剂

Abstract:

During the development of traditional industries, large amounts of greenhouse gases have been emitted due to the increasing consumption of fossil energy. CH₄ and CO₂ account for more than 98% of greenhouse gas emissions, and the conversion of CH₄ and CO₂ into high value-added chemicals has attracted extensive attention from both industry and academia. Dry reforming of methane (DRM) can co-convert CH₄ and CO₂ into syngas, which can be further converted into various value-added fuels and chemicals through Fischer-Tropsch synthesis. The dry reforming of methane into syngas by thermal catalysis provides an effective strategy for the consumption of both CH₄ and CO₂, which is beneficial for alleviating environmental problems such as global warming. However, a high-intensity energy input is needed at high temperatures owing to the thermodynamic limitations of the DRM reaction and catalyst instability caused by coke formation. Environmentally friendly photocatalytic technology can make the DRM reaction proceed under mild conditions. However, its development is greatly restricted owing to the low utilization rate of sunlight and low reaction conversion rate. Recently, photothermocatalysis has been widely used in various fields. Many studies have shown that under relatively mild conditions, photothermocatalysis of DRM can achieve promising catalytic performance and effectively convert solar energy into chemical energy. Photothermocatalysis can greatly increase the reaction rate of photocatalytic DRM without a high energy input. In addition, the introduction of light is beneficial for the thermal catalysis of DRM by reducing the reaction activation energy, inhibiting coke formation, and reversing the water-gas shift reaction. In this paper, the advantages and disadvantages of thermal catalysis, photocatalysis, and photothermal catalysis of DRM are first discussed. Then, recent research progress in photothermocatalysis of the DRM reaction, especially the application of different metal-based catalysts (Ni, Pt, Rh, Ru, and Co) is summarized. Localized surface plasmon resonance effects, types of carriers, elimination of coke formation, and suppression of the reverse water-gas shift reaction are briefly mentioned. Finally, the future challenges and new perspectives on the photothermocatalysis of DRM are highlighted, including high utilization of sunlight, catalyst long-term stability, reactor optimization, and the photothermocatalytic mechanism.

Key words: Dry reforming of methane, Photothermal catalysis, LSPR, Metal-based catalysts

何展军, 黄敏, 林铁军, 钟良枢. 光热催化甲烷干重整研究进展[J]. 物理化学学报, 2023, 39(9), 2212060. doi: 10.3866/PKU.WHXB202212060

Zhanjun He, Min Huang, Tiejun Lin, Liangshu Zhong. Recent Advances in Dry Reforming of Methane via Photothermocatalysis[J]. Acta Phys. -Chim. Sin. 2023, 39(9), 2212060. doi: 10.3866/PKU.WHXB202212060

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202212060

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I9/2212060

图/表 14

图1

图2

表1

表2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

参考文献 56

1	Noor, Z. Z.; Yusuf, R. O.; Abba, A. H.; Abu Hassan, M. A.; Din, M. F. M. Renew. Sustain. Energy Rev. 2013, 20, 378. doi: 10.1016/j.rser.2012.11.050
2	Yusuf, R. O.; Noor, Z. Z.; Abba, A. H.; Abu Hassan, M. A.; Din, M. F. M. Renew. Sustain. Energy Rev. 2012, 16, 5059. doi: 10.1016/j.rser.2012.04.008
3	Jiao, F.; Li, J. J.; Pan, X. L.; Xiao, J. P.; Li, H. B.; Ma, H.; Wei, M. M.; Pan, Y.; Zhou, Z. Y.; Li, M. R.; et al. Science 2016, 351, 1065. doi: 10.1126/science.aaf1835
4	Zhong, L. S.; Yu, F.; An, Y. L.; Zhao, Y. H.; Sun, Y. H.; Li, Z. J.; Lin, T. J.; Lin, Y. J.; Qi, X. Z.; Dai, Y. Y.; et al. Nature 2016, 538, 84. doi: 10.1038/nature19786
5	Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507. doi: 10.1038/417507a
6	Kroll, V. C. H.; Swaan, H. M.; Mirodatos, C. J. Catal. 1996, 161, 409. doi: 10.1006/jcat.1996.0199
7	He, C.; Wu, S.; Wang, L.; Zhang, J. J. Photochem. Photobiol. C 2022, 51, 100468. doi: 10.1016/j.jphotochemrev.2021.100468
8	Li, M.; Sun, Z.; Hu, Y. H. Chem. Eng. J. 2022, 428, 131222. doi: 10.1016/j.cej.2021.131222
9	Wu, S.; Li, Y.; Hu, Q.; Wu, J.; Zhang, Q. ACS Sustain. Chem. Eng. 2021, 9, 11635. doi: 10.1021/acssuschemeng.1c03692
10	Wang, C.; Su, Y.; Tavasoli, A.; Sun, W.; Wang, L.; Ozin, G. A.; Yang, D. Mater. Today Nano 2021, 14, 100113. doi: 10.1016/j.mtnano.2021.100113
11	Ning, S.; Sun, Y.; Ouyang, S.; Qi, Y.; Ye, J. Appl. Catal. B 2022, 310, 121063. doi: 10.1016/j.apcatb.2022.121063
12	Aramouni, N. A. K.; Touma, J. G.; Abu Tarboush, B.; Zeaiter, J.; Ahmad, M. N. Renew. Sustain. Energy Rev. 2018, 82, 2570. doi: 10.1016/j.rser.2017.09.076
13	Theofanidis, S. A.; Galvita, V. V.; Poelman, H.; Marin, G. B. ACS Catal. 2015, 5, 3028. doi: 10.1021/acscatal.5b00357
14	Zhang, S. R.; Nguyen, L.; Liang, J. X.; Shan, J. J.; Liu, J. Y.; Frenkel, A. I.; Patlolla, A.; Huang, W. X.; Li, J.; Tao, F. Nat. Commun. 2015, 6, 1. doi: 10.1038/ncomms8938
15	Bian, Z. F.; Das, S.; Wai, M. H.; Hongmanorom, P.; Kawi, S. ChemPhysChem 2017, 18, 3117. doi: 10.1002/cphc.201700529
16	Zubenko, D.; Singh, S.; Rosen, B. Appl. Catal. B 2017, 209, 711. doi: 10.1016/j.apcatb.2017.03.047
17	Song, Y.; Ozdemir, E.; Ramesh, S.; Adishev, A.; Subramanian, S.; Harale, A.; Albuali, M.; Fadhel, B.; Jamal, A.; Moon, D.; et al. Science 2020, 367, 777. doi: 10.1126/science.aav2412
18	Naeem, M. A.; Abdala, P. M.; Armutlulu, A.; Kim, S. M.; Fedorov, A.; Mueller, C. R. ACS Catal. 2020, 10, 1923. doi: 10.1021/acscatal.9b04555
19	Das, S.; Perez-Ramirez, J.; Gong, J.; Dewangan, N.; Hidajat, K.; Gates, B. C.; Kawi, S. Chem. Soc. Rev. 2020, 49, 2937. doi: 10.1039/c9cs00713j
20	Li, Z.; Li, M.; Bian, Z.; Kathiraser, Y.; Kawi, S. Appl. Catal. B 2016, 188, 324. doi: 10.1016/j.apcatb.2016.01.067
21	Fujishima, A.; Honda, K. Nature 1972, 238, 37. doi: 10.1038/238037a0
22	Liu, J.; Liu, Y.; Liu, N. Y.; Han, Y. Z.; Zhang, X.; Huang, H.; Lifshitz, Y.; Lee, S. T.; Zhong, J.; Kang, Z. H. Science 2015, 347, 970. doi: 10.1126/science.aaa3145
23	Hisatomi, T.; Kubota, J.; Domen, K. Chem. Soc. Rev. 2014, 43, 7520. doi: 10.1039/c3cs60378d
24	Han, F.; Kambala, V. S. R.; Srinivasan, M.; Rajarathnam, D.; Naidu, R. Appl. Catal. A 2009, 359, 25. doi: 10.1016/j.apcata.2009.02.043
25	Byrne, C.; Subramanian, G.; Pillai, S. C. J. Environ. Chem. Eng. 2018, 6, 3531. doi: 10.1016/j.jece.2017.07.080
26	Li, X.; Yu, J. G.; Jaroniec, M.; Chen, X. B. Chem. Rev. 2019, 119, 3962. doi: 10.1021/acs.chemrev.8b00400
27	Ding, M.; Flaig, R. W.; Jiang, H.-L.; Yaghi, O. M. Chem. Soc. Rev. 2019, 48, 2783. doi: 10.1039/c8cs00829a
28	Tahir, B.; Tahir, M.; Amin, N. A. S. Appl. Surf. Sci. 2017, 419, 875. doi: 10.1016/j.apsusc.2017.05.117
29	Tahir, M.; Tahir, B.; Zakaria, Z. Y.; Muhammad, A. J. Cleaner Prod. 2019, 213, 451. doi: 10.1016/j.jclepro.2018.12.169
30	Yang, Y.; Tan, H. Y.; Cheng, B.; Fan, J. J.; Yu, J. G.; Ho, W. K. Small Methods 2021, 5, 2001042. doi: 10.1002/smtd.202001042
31	Liu, H.; Meng, X.; Thang Duy, D.; Liu, L.; Li, P.; Zhao, G.; Nagao, T.; Yang, L.; Ye, J. J. Mater. Chem. A 2017, 5, 10567. doi: 10.1039/c7ta00704c
32	Liu, H.; Thang Duy, D.; Liu, L.; Meng, X.; Nagaoa, T.; Ye, J. Appl. Catal. B 2017, 209, 183. doi: 10.1016/j.apcatb.2017.02.080
33	Zhang, Q.; Mao, M.; Li, Y.; Yang, Y.; Huang, H.; Jiang, Z.; Hu, Q.; Wu, S.; Zhao, X. Appl. Catal. B 2018, 239, 555. doi: 10.1016/j.apcatb.2018.08.052
34	Liu, H.; Song, H.; Meng, X.; Yang, L.; Ye, J. Catal. Today 2019, 335, 187. doi: 10.1016/j.cattod.2018.11.005
35	Zhang, Q.; Jiang, Z.; Li, Y.; Zhang, Q.; Yang, Y.; Wu, S.; Wu, J.; Zhao, X. J. Mater. Chem. A 2019, 7, 4881. doi: 10.1039/c9ta00259f
36	Zhang, Q.; Li, Y.; Wu, S.; Wu, J.; Jiang, Z.; Yang, Y.; Ren, L.; Zhao, X. J. Mater. Chem. A 2019, 7, 19800. doi: 10.1039/c9ta06923b
37	Takeda, K.; Yamaguchi, A.; Cho, Y.; Anjaneyulu, O.; Fujita, T.; Abe, H.; Miyauchi, M. Global Chall. 2020, 4, 1900067. doi: 10.1002/gch2.201900067
38	Rao, Z.; Cao, Y.; Huang, Z.; Yin, Z.; Wan, W.; Ma, M.; Wu, Y.; Wang, J.; Yang, G.; Cui, Y.; et al. ACS Catal. 2021, 11, 4730. doi: 10.1021/acscatal.0c04826
39	Han, K.; Wang, Y.; Wang, S.; Liu, Q.; Deng, Z.; Wang, F. Chem. Eng. J. 2021, 421, 129989. doi: 10.1016/j.cej.2021.129989
40	Tan, X.; Wu, S.; Li, Y.; Zhang, Q.; Hu, Q.; Wu, J.; Zhang, A.; Zhang, Y. Energy Environ. Mater. 2022, 5, 582. doi: 10.1002/eem2.12193
41	Lorber, K.; Zavasnik, J.; Sancho-Parramon, J.; Bubas, M.; Mazaj, M.; Djinovic, P. Appl. Catal. B 2022, 301, 120745. doi: 10.1016/j.apcatb.2021.120745
42	Zhao, J.; Guo, X.; Shi, R.; Waterhouse, G. I. N.; Zhang, X.; Dai, Q.; Zhang, T. Adv. Funct. Mater. 2022, 32, 2204056. doi: 10.1002/adfm.202204056
43	Du, Z.; Pan, F.; Yang, X.; Fang, L.; Gang, Y.; Fang, S.; Li, T.; Hu, Y. H.; Li, Y. Catal. Today 2023, 409, 31. doi: 10.1016/j.cattod.2022.05.014
44	Xie, T.; Zhang, Z.-Y.; Zheng, H.-Y.; Xu, K.-D.; Hu, Z.; Lei, Y. Chem. Eng. J. 2022, 429, 132507. doi: 10.1016/j.cej.2021.132507
45	Han, B.; Wei, W.; Chang, L.; Cheng, P. F.; Hu, Y. H. ACS Catal. 2016, 6, 494. doi: 10.1021/acscatal.5b02653
46	Liu, H.; Song, H.; Zhou, W.; Meng, X.; Ye, J. Angew. Chem. Int. Ed. 2018, 57, 16781. doi: 10.1002/anie.201810886
47	Song, H.; Meng, X.; Dao, T. D.; Zhou, W.; Liu, H.; Shi, L.; Zhang, H.; Nagao, T.; Kako, T.; Ye, J. ACS Appl. Mater. Interfaces 2018, 10, 408. doi: 10.1021/acsami.7b13043
48	Liu, H.; Meng, X.; Thang Duy, D.; Zhang, H.; Li, P.; Chang, K.; Wang, T.; Li, M.; Nagao, T.; Ye, J. Angew. Chem. Int. Ed. 2015, 54, 11545. doi: 10.1002/anie.201504933
49	hoji, S.; Peng, X.; Yamaguchi, A.; Watanabe, R.; Fukuhara, C.; Cho, Y.; Yamamoto, T.; Matsumura, S.; Yu, M. -W.; Ishii, S.; et al. Nat. Catal. 2020, 3, 148. doi: 10.1038/s41929-019-0419-z
50	Cho, Y.; Shoji, S.; Yamaguchi, A.; Hoshina, T.; Fujita, T.; Abe, H.; Miyauchi, M. Chem. Commun. 2020, 56, 4611. doi: 10.1039/d0cc00729c
51	Liu, H.; Li, M.; Thang Duy, D.; Liu, Y.; Zhou, W.; Liu, L.; Meng, X.; Nagao, T.; Ye, J. Nano Energy 2016, 26, 398. doi: 10.1016/j.nanoen.2016.05.045
52	Zhou, L.; Martirez, J. M. P.; Finzel, J.; Zhang, C.; Swearer, D. F.; Tian, S.; Robatjazi, H.; Lou, M.; Dong, L.; Henderson, L.; et al. Nat. Energy 2020, 5, 61. doi: 10.1038/s41560-019-0517-9
53	Wu, S.; Li, Y.; Zhang, Q.; Jiang, Z.; Yang, Y.; Wu, J.; Zhao, X. Energy Environ. Sci. 2019, 12, 2581. doi: 10.1039/c9ee01484e
54	He, K.; Shen, R.; Hao, L.; Li, Y.; Zhang, P.; Jiang, J.; Li, X. Acta Phys. -Chim. Sin. 2022, 38, 2201021.
	何科林, 沈荣晨, 郝磊, 李佑稷, 张鹏, 江吉周, 李鑫. 物理化学学报, 2022, 38, 2201021. doi: 10.3866/PKU.WHXB202201021
55	Ma, J.; Long, R.; Liu, D.; Low, J. X.; Xiong, Y. J. Small Struct. 2022, 3, 2100147. doi: 10.1002/sstr.202100147
56	Liu, Y.; Duan, Z.; Li, J.; Chan, C. 2021 Phys. -Chim. Sin. 2018, 37, 2011012.
	刘源, 段增晖, 李隽, 常春然. 物理化学学报, 2018, 37, 2011012. doi: 10.3866/PKU.WHXB202011012

Different methane dry reforming technologies	Advantages	Disadvantages
Thermocatalytic dry reforming of methane	High conversion and yield, low investment cost, pilot-scale plant	Non-Renewable energy input, high energy consumption, high operation cost, low flexibility, high coke formation, high operating temperature
Photocatalytic dry reforming of methane	Renewable energy input, green technology, low operating cost, low investment cost, low coke formation, tunable operating temperature	Low conversion and yield, Non-commercial
Photothermocatalytic dry reforming of methane	Renewable energy input, green technology, low operating cost, low coke formation, high flexibility	Non-commercial, High operating temperature, high investment cost

Entry	Catalyst	Reaction conditions			Catalytic performance	Ref.
Entry	Catalyst	T/℃	Light intensity (kW∙m⁻²)	External heating	Catalytic performance	Ref.
1	Ni@SiO₂-Core	550	10.7	Yes	r_H₂ ≈ 19.50 μmol∙min⁻¹, r_CO ≈ 23.40 μmol∙min⁻¹	31
1	Ni@SiO₂-Yolk	550	10.7	Yes	r_H₂ ≈ 21.00 μmol∙min⁻¹, r_CO ≈ 23.40 μmol∙min⁻¹	31
2	Ni/Al₂O₃	550	10.7	Yes	r_H₂ ≈ 6.25 μmol∙min⁻¹, r_CO ≈ 6.50 μmol∙min⁻¹	32
3	Ni/CeO₂	807	363.4	No	r_H₂ = 6.53 mmol∙min⁻¹∙g⁻¹, r_CO = 6.27 mmol∙min⁻¹∙g⁻¹	33
4	Ni/Al₂O₃	550	10.7	Yes	r_H₂ = 4 mmol∙min⁻¹∙g⁻¹, r_CO = 4.5 mmol∙min⁻¹∙g⁻¹	34
5	Ni-CeO₂/SiO₂	678	385.2	No	r_H₂ = 33.42 mmol∙min⁻¹∙g⁻¹, r_CO = 41.53 mmol∙min⁻¹∙g⁻¹	35
6	Ni/Ni-Al₂O₃	771	333.8	No	r_H₂ = 27.02 mmol∙min⁻¹∙g⁻¹, r_CO = 28.71 mmol∙min⁻¹∙g⁻¹	36
7	Ni/TaC	500	150	Yes	CO yield ~40%, H₂ yield ~35%	37
8	Ni/Ga₂O₃	391	27	Yes	r_H₂ ≈ 200 μmol∙min⁻¹∙g⁻¹, r_CO = 210 μmol∙min⁻¹∙g⁻¹	38
9	(Ni/CeO₂)@SiO₂	750	NA	Yes	C_CH₄ = 74%, C_CO₂ = 82%	39
10	Ni/Mg-Al₂O₃	NA	NA	No	r_H₂ = 69.71 mmol∙min⁻¹∙g⁻¹, r_CO = 74.57 mmol∙min⁻¹∙g⁻¹	40
11	Ni/CeO_2−x	400	7.9	No	r_CH₄ = 0.21 mmol∙min⁻¹∙g⁻¹, r_CO₂ = 0.75 mmol∙min⁻¹∙g⁻¹	41
12	Ni₃Fe₁Al-LDH	350	36.2	No	r_H₂ + r_CO = 0.96 mol∙g⁻¹∙h⁻¹	42
13	Ni-CeO₂/ZrO₂	700	30	Yes	r_H₂ = 713 mmol∙h⁻¹∙g⁻¹, r_CO = 693 mmol∙h⁻¹∙g⁻¹	43
14	Ni/mesoporous TiO₂	600	NA	Yes	r_H₂ = 95.34 mmol∙h⁻¹∙g⁻¹, r_CO = 131.72 mmol∙h⁻¹∙g⁻¹	44

[1]	张城城, 吴之怡, 沈家辉, 何乐, 孙威. 硅纳米结构阵列：光热CO₂催化的新兴平台[J]. 物理化学学报, 2024, 40(1): 2304004 - .
[2]	宋千伟, 何观朝, 费慧龙. 基于单原子催化剂的光热催化转化：原理和应用[J]. 物理化学学报, 2023, 39(9): 2212038 -0 .
[3]	尹倩, 宋慧婷, 徐明, 鄢红, 赵宇飞, 段雪. 碳酸盐炼制共热耦合甲烷干重整制高附加值化学品发展展望[J]. 物理化学学报, 2023, 39(3): 2210026 -0 .
[4]	徐军科;李兆静;汪吉辉;周伟;马建新. 甲烷干重整催化剂Ni/Al₂O₃表面积炭表征与分析[J]. 物理化学学报, 2009, 25(02): 253 -260 .