有机液体储氢中全氢化乙基咔唑催化脱氢研究进展

doi:10.11949/0438-1157.20231253

摘要/Abstract

摘要：

在碳达峰碳中和的背景下，能源结构转型势在必行。氢能是以非化石能源为主体的新型能源系统的重要能量载体。目前氢能的发展瓶颈在于氢气的储运。以乙基咔唑/全氢化乙基咔唑为代表的有机液体储氢技术提供了一个安全、高效的储氢方式。全氢化乙基咔唑脱氢温度高、催化剂稳定性差等问题是限制该技术大规模应用的主要挑战。基于此，本文介绍了全氢化乙基咔唑催化脱氢过程的反应机理，阐述其反应路径、反应动力学、催化反应过程；综述了目前脱氢催化剂的研究进展，对脱氢催化剂的循环性能进行总结，并总结了失活机理；结合脱氢反应的特点提出反应器设计的挑战，并介绍目前典型的脱氢反应器。最后，针对现阶段全氢化乙基咔唑脱氢反应的潜在挑战，对该技术在储氢领域的应用进行了展望。

关键词: 有机液体储氢, 全氢化乙基咔唑, 脱氢反应, 动力学, 催化剂, 反应器

Abstract:

To achieve the goal of carbon peaking and carbon neutrality, it is necessary to adjust energy consumption structure. The new energy system is mainly based on non-fossil energy and hydrogen energy is an essential energy carrier. At present, hydrogen storage and transportation are the main challenges for its application. Liquid organic hydrogen carrier is a promising alternative for safe and efficient hydrogen storage method. N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NEC/12H-NEC) is a good choice for hydrogen carrier. The high dehydrogenation temperature of 12H-NEC and poor stability of catalysts are the main challenges limiting the large-scale application. Therefore, this paper introduced the dehydrogenation reaction mechanism of 12H-NEC and described its reaction pathway, kinetics and catalytic reaction process. And then, the activity, stability and deactivation mechanism of dehydrogenation catalysts were concluded. The challenges of reactor design were discussed based on the characteristics of the dehydrogenation reaction and typical dehydrogenation reactors were described. Finally, in view of the potential challenges of 12H-NEC dehydrogenation reaction, a prospect for the future application of this technology in the field of hydrogen storage is put forward.

Key words: liquid organic hydrogen carrier, dodecahydro-N-ethylcarbazole, dehydrogenation reaction, kinetics, catalyst, reactors

中图分类号:

TK91

范以薇, 刘威, 李盈盈, 王培霞, 张吉松. 有机液体储氢中全氢化乙基咔唑催化脱氢研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20231253.

Yiwei FAN, Wei LIU, Yingying LI, Peixia WANG, Jisong ZHANG. Research progress on catalytic dehydrogenation of dodecahydro-N-ethylcarbazole as liquid organic hydrogen carrier[J]. CIESC Journal, DOI: 10.11949/0438-1157.20231253.

图/表 9

表1 乙基咔唑、全氢化乙基咔唑的理化性质［41-42］

Table 1 Physicochemical properties of NEC and 12H-NEC［41-42］

性质	NEC	12H-NEC
熔点	68 ℃	＜20 ℃
沸点	270 ℃	280 ℃
密度（25 ℃）	1.10 g/cm³	0.94 g/cm³
动力黏度（20 ℃）	121 mPa∙s	5.9 mPa∙s
比热容（25 ℃）	221.6 J/K/mol	352.3 J/K/mol
标准摩尔生成焓（ $∆ f H m ° g, 25 ℃$ ）	167.7±2.8 kJ/mol	-151.4±4.4 kJ/mol
危险等级	08	/

表1 乙基咔唑、全氢化乙基咔唑的理化性质［41-42］

Table 1 Physicochemical properties of NEC and 12H-NEC［41-42］

性质	NEC	12H-NEC
熔点	68 ℃	＜20 ℃
沸点	270 ℃	280 ℃
密度（25 ℃）	1.10 g/cm³	0.94 g/cm³
动力黏度（20 ℃）	121 mPa∙s	5.9 mPa∙s
比热容（25 ℃）	221.6 J/K/mol	352.3 J/K/mol
标准摩尔生成焓（ $∆ f H m ° g, 25 ℃$ ）	167.7±2.8 kJ/mol	-151.4±4.4 kJ/mol
危险等级	08	/

图1 基于乙基咔唑体系储氢示意图

Fig.1 Schematic of hydrogen storage utilizing N-ethylcarbazole/dodecahydro-N-ethylcarbazole

图2 12H-NEC脱氢反应路径

Fig.2 Reaction pathway of 12H-NEC dehydrogenation

图3 12H-NEC在Pd/Al2O3/NiAl{110}催化剂上吸附反应机理示意图[51]

Fig.3 Schematic of the adsorption and reaction mechanism of 12H-NEC in the Pd/Al2O3/NiAl{110} catalyst[51]

图4 不同平均配位数的钯催化剂脱氢活性[58]

Fig.4 Dehydrogenation activity for supported palladium species with different average Pd-Pd coordination numbers[58]

图5 Pd/rGO晶面影响脱氢活性[59]

Fig.5 Facet-dependent dehydrogenation activities of Pd/rGO[59]

图6 Cu的掺杂对脱氢速率常数的影响[46]

Fig.6 Effect of Cu doping on dehydrogenation rate constant[46]

表2 12H-NEC脱氢催化剂稳定性

Table 2 Stability of 12H-NEC dehydrogenation catalysts

Entry	催化剂	反应条件	循环次数	稳定性	参考文献
1	PdCoO_x/Zr-C₃N₄	50 %^①, 140 ℃	3	98%^②	^[45]
2	Pd/rGO_-EG	15.5 %, 180 ℃	5	85%^②	^[61]
3	Pd-EU/K6	15 %, 190 ℃	11	93%^③	^[62]
4	Pd/rGO	7 %, 180 ℃	5	86%^②	^[54]
5	Pd-IP/S15	20 %, 180 ℃	8	77%^③	^[68]
6	Pd/MgAl₂O₄	6.7 %, 180 ℃	3	98%^②	^[49]
7	Pd/LDHs-us	7 %, 180 ℃	6	95%^③	^[69]
8	Pt/S-Ti₃C₂T_x	6.7 %, 180 ℃	6	98%^③	^[70]

图7 结构化反应器示意图[76]

Fig.7 Schematic of structured reactor[76]

参考文献 83

1	Ummenhofer C C, Meehl G A. Extreme weather and climate events with ecological relevance: a review[J]. Philosophical Transactions of the Royal Society of London. Series B, Biological Sciences, 2017, 372(1723): 20160135.
2	Wu X H, Tian Z Q, Guo J. A review of the theoretical research and practical progress of carbon neutrality[J]. Sustainable Operations and Computers, 2022, 3: 54-66.
3	解振华, 何建坤, 王海林, 等. «中国长期低碳发展战略与转型路径研究»综合报告[J]. 中国人口·资源与环境, 2020, 30(11): 1-25.
	Xie Z H, He J K, Wang H L, et al. Comprehensive report on China's long-term low-carbon development strategy and transformation path[J]. China Population, Resources and Environment, 2020, 30(11): 1-25.
4	何建坤. 碳达峰碳中和目标导向下能源和经济的低碳转型[J]. 环境经济研究, 2021, 6(1): 1-9.
	He J K. Low carbon transformation of energy and economy aiming for the peaking of carbon emission and carbon neutrality[J]. Journal of Environmental Economics, 2021, 6(1): 1-9.
5	Xie Y C, Qi J G, Zhang R, et al. Toward a carbon-neutral state: a carbon–energy–water nexus perspective of China's coal power industry[J]. Energies, 2022, 15(12): 4466.
6	周孝信, 赵强, 张玉琼. "双碳"目标下我国能源电力系统发展前景和关键技术[J]. 中国电力企业管理, 2021, 31: 14-17.
	Zhou X X, Zhao Q, Zhang Y Q. Development prospect and key technologies of China's energy and power system under the carbon peaking and carbon neutrality goals[J]. China Power Enterprise Management, 2021, 31: 14-17.
7	Shi X F, Qian Y, Yang S Y. Fluctuation analysis of a complementary wind–solar energy system and integration for large scale hydrogen production[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(18): 7097-7110.
8	Albertus P, Manser J S, Litzelman S. Long-duration electricity storage applications, economics, and technologies[J]. Joule, 2020, 4(1): 21-32.
9	Liu F, Shi C X, Guo X L, et al. Rational design of better hydrogen evolution electrocatalysts for water splitting: a review[J]. Advanced Science, 2022, 9(18): e2200307.
10	Sharma S, Ghoshal S K. Hydrogen the future transportation fuel: from production to applications[J]. Renewable and Sustainable Energy Reviews, 2015, 43: 1151-1158.
11	Liu W G, Zuo H B, Wang J S, et al. The production and application of hydrogen in steel industry[J]. International Journal of Hydrogen Energy, 2021, 46(17): 10548-10569.
12	Meda U S, Bhat N, Pandey A, et al. Challenges associated with hydrogen storage systems due to the hydrogen embrittlement of high strength steels[J]. International Journal of Hydrogen Energy, 2023, 48(47): 17894-17913.
13	Abe J O, Popoola A P I, Ajenifuja E, et al. Hydrogen energy, economy and storage: review and recommendation[J]. International Journal of Hydrogen Energy, 2019, 44(29): 15072-15086.
14	Salman M S, Rambhujun N, Pratthana C, et al. Catalysis in liquid organic hydrogen storage: recent advances, challenges, and perspectives[J]. Industrial & Engineering Chemistry Research, 2022, 61(18): 6067-6105.
15	Xu Z, Zhao N, Hillmansen S, et al. Techno-economic analysis of hydrogen storage technologies for railway engineering: a review[J]. Energies, 2022, 15(17): 6467.
16	Laureys A, Depraetere R, Cauwels M, et al. Use of existing steel pipeline infrastructure for gaseous hydrogen storage and transport: a review of factors affecting hydrogen induced degradation[J]. Journal of Natural Gas Science and Engineering, 2022, 101: 104534.
17	王鑫, 陈叔平, 朱鸣. 液氢储运技术发展现状与展望[J]. 太阳能学报, 2024, 45(01): 500-514.
	Wang X, Chen S P, Zhu M. Development status and prospect of liquid hydrogen storage and transportation technology[J]. Acta Energiae Solaris Sinica, 2024, 45(01): 500-514.
18	Qiu Y N, Yang H, Tong L G, et al. Research progress of cryogenic materials for storage and transportation of liquid hydrogen[J]. Metals, 2021, 11(7): 1101.
19	应强, 李建立, 段秉言, 等. 金属氢化物储放氢反应器研究进展[J]. 北京石油化工学院学报, 2023, 31(4): 12-21.
	Ying Q, Li J L, Duan B Y, et al. Recent developments in metal hydride hydrogen storage and desorption reactor[J]. Journal of Beijing Institute of Petrochemical Technology, 2023, 31(4): 12-21.
20	Sreeraj R, Aadhithiyan A K, Anbarasu S. Integration of thermal augmentation methods in hydride beds for metal hydride based hydrogen storage systems: review and recommendation[J]. Journal of Energy Storage, 2022, 52: 105039.
21	Anshul G, Baron Gino V, Patrice P, et al. Hydrogen clathrates: next generation hydrogen storage materials[J]. Energy Storage Materials, 2021, 41: 69-107.
22	Sekine Y, Higo T. Recent trends on the dehydrogenation catalysis of liquid organic hydrogen carrier (LOHC): a review[J]. Topics in Catalysis, 2021, 64(7): 470-480.
23	Ge L X, Qiu M H, Zhu Y F, et al. Synergistic catalysis of Ru single-atoms and zeolite boosts high-efficiency hydrogen storage[J]. Applied Catalysis B: Environmental, 2022, 319: 121958.
24	Modisha P, Bessarabov D. Aromatic liquid organic hydrogen carriers for hydrogen storage and release[J]. Current Opinion in Green and Sustainable Chemistry, 2023, 42: 100820.
25	Ratnakar R R, Gupta N, Zhang K, et al. Hydrogen supply chain and challenges in large-scale LH2 storage and transportation[J]. International Journal of Hydrogen Energy, 2021, 46(47): 24149-24168.
26	Liu J J, Ma Y, Yang J G, et al. Recent advance of metal borohydrides for hydrogen storage[J]. Frontiers in Chemistry, 2022, 10: 945208.
27	闫光龙, 郭克星, 赵苗苗. 储氢技术的研究现状及进展[J]. 天然气与石油, 2023, 41(5): 1-9.
	Yan G L, Guo K X, Zhao M M. Status and progress on hydrogen storage technology research[J]. Natural Gas and Oil, 2023, 41(5): 1-9.
28	Zhu Q L, Xu Q. Liquid organic and inorganic chemical hydrides for high-capacity hydrogen storage[J]. Energy & Environmental Science, 2015, 8(2): 478-512.
29	Wang C L, Astruc D. Recent developments of nanocatalyzed liquid-phase hydrogen generation[J]. Chemical Society Reviews, 2021, 50(5): 3437-3484.
30	Imada T, Chiku M, Higuchi E, et al. Effect of rhodium modification on activity of platinum nanoparticle-loaded carbon catalysts for electrochemical toluene hydrogenation[J]. ACS Catalysis, 2020, 10(22): 13718-13728.
31	Oda A, Fujita T, Yamamoto Y, et al. Breaking the structure–activity relationship in toluene hydrogenation catalysis by designing heteroatom ensembles based on a single-atom alloying approach[J]. ACS Catalysis, 2023, 13(15): 10026-10040.
32	Meng J C, Zhou F, Ma H X, et al. A review of catalysts for methylcyclohexane dehydrogenation[J]. Topics in Catalysis, 2021, 64(7): 509-520.
33	Jorschick H, Preuster P, Dürr S, et al. Hydrogen storage using a hot pressure swing reactor[J]. Energy & Environmental Science, 2017, 10(7): 1652-1659.
34	Shi L B, Zhou Y M, Qi S T, et al. Pt catalysts supported on H₂ and O₂ plasma-treated Al₂O₃ for hydrogenation and dehydrogenation of the liquid organic hydrogen carrier pair dibenzyltoluene and perhydrodibenzyltoluene[J]. ACS Catalysis, 2020, 10(18): 10661-10671.
35	Modisha P, Gqogqa P, Garidzirai R, et al. Evaluation of catalyst activity for release of hydrogen from liquid organic hydrogen carriers[J]. International Journal of Hydrogen Energy, 2019, 44(39): 21926-21935.
36	Zhou L, Sun L, Xu L X, et al. Recent developments of effective catalysts for hydrogen storage technology using N-ethylcarbazole[J]. Catalysts, 2020, 10(6): 648.
37	Singh R, Singh M, Gautam S. Hydrogen economy, energy, and liquid organic carriers for its mobility[J]. Materials Today: Proceedings, 2021, 46: 5420-5427.
38	Wei D, Shi X Z, Qu R Y, et al. Toward a hydrogen economy: development of heterogeneous catalysts for chemical hydrogen storage and release reactions[J]. ACS Energy Letters, 2022, 7(10): 3734-3752.[LinkOut]
39	Byun M, Lee A, Cheon S, et al. Preliminary feasibility study for hydrogen storage using several promising liquid organic hydrogen carriers: technical, economic, and environmental perspectives[J]. Energy Conversion and Management, 2022, 268: 116001.
40	Yang M, Han C Q, Ni G, et al. Temperature controlled three-stage catalytic dehydrogenation and cycle performance of perhydro-9-ethylcarbazole[J]. International Journal of Hydrogen Energy, 2012, 37(17): 12839-12845.
41	Niermann M, Beckendorff A, Kaltschmitt M, et al. Liquid Organic Hydrogen Carrier (LOHC)–Assessment based on chemical and economicproperties[J]. International Journal of Hydrogen Energy, 2019, 44(13): 6631-6654.
42	Stark K, Emel'yanenko V N, Zhabina A A, et al. Liquid organic hydrogen carriers: thermophysical and thermochemical studies of carbazole partly and fully hydrogenated derivatives[J]. Industrial & Engineering Chemistry Research, 2015, 54(32): 7953-7966.
43	Pei Q J, Yu J F, Qiu G H, et al. Fabrication of ultrafine metastable Ru-B alloy for catalytic hydrogenation of NEC at room temperature[J]. Applied Catalysis B: Environmental, 2023, 336: 122947.
44	Wu Y, Yu H E, Guo Y R, et al. A rare earth hydride supported ruthenium catalyst for the hydrogenation of N-heterocycles: boosting the activity via a new hydrogen transfer path and controlling the stereoselectivity[J]. Chemical Science, 2019, 10(45): 10459-10465.
45	Li X X, Wu F, Zhou W H, et al. Low-temperature dehydrogenation of dodecahydro-N-ethylcarbazole catalyzed by PdCo bimetallic oxide[J]. Chemical Engineering Science, 2023, 273: 118650.
46	Wang B, Chang T Y, Jiang Z, et al. Component controlled synthesis of bimetallic PdCu nanoparticles supported on reduced graphene oxide for dehydrogenation of dodecahydro-N-ethylcarbazole[J]. Applied Catalysis B: Environmental, 2019, 251(15): 261-272.
47	Li J J, Tong F Y, Li Y, et al. Dehydrogenation of dodecahydro-N-ethylcarbazole over spinel supporting catalyst in a continuous flow fixed bed reactor[J]. Fuel, 2022, 321: 124034.
48	Dong Y, Yang M, Mei P, et al. Dehydrogenation kinetics study of perhydro-N-ethylcarbazole over a supported Pd catalyst for hydrogen storage application[J]. International Journal of Hydrogen Energy, 2016, 41(20): 8498-8505.
49	Wang B, Li P Y, Wang S Y, et al. Tuning the interaction between Pd and MgAl₂O₄ to enhance the dehydrogenation activity and selectivity of dodecahydro-N-ethylcarbazole[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(14): 5485-5494.
50	Sotoodeh F, Smith K J. Kinetics of hydrogen uptake and release from heteroaromatic compounds for hydrogen storage[J]. Industrial & Engineering Chemistry Research, 2010, 49(3): 1018-1026.
51	Sobota M, Nikiforidis I, Amende M, et al. Dehydrogenation of dodecahydro-N-ethylcarbazole on Pd/Al₂O₃ model catalysts[J]. Chemistry, 2011, 17(41): 11542-11552.
52	Amende M, Schernich S, Sobota M, et al. Dehydrogenation mechanism of liquid organic hydrogen carriers: dodecahydro-N-ethylcarbazole on Pd(111)[J]. Chemistry, 2013, 19(33): 10854-10865.
53	Yang M, Dong Y, Fei S X, et al. A comparative study of catalytic dehydrogenation of perhydro-N-ethylcarbazole over noble metal catalysts[J]. International Journal of Hydrogen Energy, 2014, 39: 18976-18983.
54	Wang B, Chang T Y, Jiang Z, et al. Catalytic dehydrogenation study of dodecahydro-N-ethylcarbazole by noble metal supported on reduced graphene oxide[J]. International Journal of Hydrogen Energy, 2018, 43(15): 7317-7325.
55	Peters W, Seidel A, Herzog S, et al. Macrokinetic effects in perhydro-N-ethylcarbazole dehydrogenation and H₂ productivity optimization by using egg-shell catalysts[J]. Energy & Environmental Science, 2015, 8(10): 3013-3021.
56	Feng Z L, Chen X M, Bai X F. Hydrogen production from the catalytic dehydrogenation of dodecahydro-N-ethylcarbazole: effect of Pd precursor on the catalytic performance of Pd/C catalysts[J]. Environmental Science and Pollution Research, 2021, 28(43): 61623-61635.
57	Guo Y, Wang M L, Zhu Q J, et al. Ensemble effect for single-atom, small cluster and nanoparticle catalysts[J]. Nature Catalysis, 2022, 5: 766-776.
58	Dong C Y, Gao Z R, Li Y L, et al. Fully exposed palladium cluster catalysts enable hydrogen production from nitrogen heterocycles[J]. Nature Catalysis, 2022, 5: 485-493.
59	Wang B, Chen Y T, Chang T Y, et al. Facet-dependent catalytic activities of Pd/rGO: exploring dehydrogenation mechanism of dodecahydro-N-ethylcarbazole[J]. Applied Catalysis B: Environmental, 2020, 266: 118658.
60	Feng Z L, Chen X M, Bai X F. Catalytic dehydrogenation of liquid organic hydrogen carrier dodecahydro-N-ethylcarbazole over palladium catalysts supported on different supports[J]. Environmental Science and Pollution Research, 2020, 27(29): 36172-36185.
61	Wang B, Yan T, Chang T Y, et al. Palladium supported on reduced graphene oxide as a high-performance catalyst for the dehydrogenation of dodecahydro-N-ethylcarbazole[J]. Carbon, 2017, 122: 9-18.
62	Feng Z L, Bai X F. 3D-mesoporous KIT-6 supported highly dispersed Pd nanocatalyst for dodecahydro-N-ethylcarbazole dehydrogenation[J]. Microporous and Mesoporous Materials, 2022, 335: 111789.
63	Yang Z W, Gong X, Li L S, et al. Strengthening the metal-support interaction over Pt/SiO₂-TiO(OH)₂ by defect engineering for efficient dehydrogenation of dodecahydro-N-ethylcarbazole[J]. Fuel, 2023, 334: 126733.
64	Jiang Z, Gong X, Guo S Y, et al. Engineering PdCu and PdNi bimetallic catalysts with adjustable alloying degree for the dehydrogenation reaction of dodecahydro-N-ethylcarbazole[J]. International Journal of Hydrogen Energy, 2021, 46(2): 2376-2389.
65	Feng Z L, Liu Z T, Bai X F. Preparation of Ni@Pd Core–Shell Nanoparticles Supported on KIT-6 by Ultrasound-Assisted Galvanic Replacement for Dodecahydro-N-ethylcarbazole Dehydrogenation[J]. Inorganic Chemistry, 2023, 62(35): 14355-14367.
66	Forberg D, Schwob T, Zaheer M, et al. Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia[J]. Nature Communications, 2016, 7: 13201.
67	Xue W J, Liu H X, Mao B H, et al. Reversible hydrogenation and dehydrogenation of N-ethylcarbazole over bimetallic Pd-Rh catalyst for hydrogen storage[J]. Chemical Engineering Journal, 2021, 421: 127781.
68	Feng Z L, Wang Y D, Bai X F. Preparation of highly dispersed Pd/SBA-15 catalysts for dodecahydro-N-ethylcarbazole dehydrogenation reaction by ion exchange-glow discharge[J]. Environmental Science and Pollution Research, 2022, 29(26): 39266-39280.
69	Wu Y P, Liu X R, Bai X F, et al. Ultrasonic-assisted preparation of ultrafine Pd nanocatalysts loaded on Cl--intercalated MgAl layered double hydroxides for the catalytic dehydrogenation of dodecahydro-N-ethylcarbazole[J]. Ultrasonics Sonochemistry, 2022, 88: 106097.
70	Li L S, Gong X, Yang Z W, et al. Boosting the dehydrogenation efficiency of dodecahydro-N-ethylcarbazole by assembling Pt nanoparticles on the single-layer Ti3C2Tx MXene[J]. International Journal of Hydrogen Energy, 2023, 48(51): 19633-19645.
71	Stephan K, Daniel L, Andreas B, et al. Dehydrogenation of perhydro-N-ethylcarbazole under reduced total pressure[J]. International Journal of Hydrogen Energy, 2021, 46(29): 15660-15670.
72	Heublein N, Stelzner M, Sattelmayer T. Hydrogen storage using liquid organic carriers: equilibrium simulation and dehydrogenation reactor design[J]. International Journal of Hydrogen Energy, 2020, 45(46): 24902-24916.
73	Wan C, An Y, Xu G H, et al. Study of catalytic hydrogenation of N-ethylcarbazole over ruthenium catalyst[J]. International Journal of Hydrogen Energy, 2012, 37(17): 13092-13096.
74	薛景文, 于鹏飞, 张彦康, 等. 液态有机氢载体储氢系统脱氢反应器研究进展[J]. 热力发电, 2022, 51(11): 1-10.
	Xue J W, Yu P F, Zhang Y K, et al. Review on advances of dehydrogenation reactor for hydrogen storage system using liquid organic hydrogen carrier[J]. Thermal Power Generation, 2022, 51(11): 1-10.
75	Wild J V, Friedrich T, Cooper A, et al. Liquid organic hydrogen carriers (LOHC): an auspicious alternative to conventional hydrogen storage technologies[C]//Stolten D, Thomas G. 18th World Hydrogen Energy Conference 2010. Storage systems/policy perspectives, initiatives and cooperations. Essen, Germany: Forschungszentrum Jülich GmbH, Zentralbibliothek, 2010: 189-197.
76	Peters W, Eypasch M, Frank T, et al. Efficient hydrogen release from perhydro-N-ethylcarbazole using catalyst-coated metallic structures produced by selective electron beam melting[J]. Energy & Environmental Science, 2015, 8(2): 641-649.
77	Gora A, Tanaka D A P, Mizukami F, et al. Lower temperature dehydrogenation of methylcyclohexane by membrane-assisted equilibrium shift[J]. Chemistry Letters, 2006, 35(12): 1372-1373.
78	Kreuder H, Boeltken T, Cholewa M, et al. Heat storage by the dehydrogenation of methylcyclohexane–Experimental studies for the design of a microstructured membrane reactor[J]. International Journal of Hydrogen Energy, 2016, 41(28): 12082-12092.
79	Shukla A, Pande J V, Biniwale R B. Dehydrogenation of methylcyclohexane over Pt/V₂O₅ and Pt/Y₂O₃ for hydrogen delivery applications[J]. International Journal of Hydrogen Energy, 2012, 37(4): 3350-3357.
80	Santacesaria E, Tesser R, Di Serio M, et al. A new simple microchannel device to test process intensification[J]. Industrial & Engineering Chemistry Research, 2011, 50(5): 2569-2575.
81	武汉氢阳能源有限公司. 氢能利用整体解决方案[EB/OL]. [2024-03-07]. .
82	高蒙. 推动绿色低碳转型发展打造氢能科创之都产业聚集高地[EB/OL]. (2024-02-20) [2024-03-07]. .
83	辛友. 有机液态储氢商业化"升温"[EB/OL]. (2023-12-22) [2024-03-07]. .

[1]	张家琳, 徐大为, 高越, 李新刚. 泡沫镍负载CeO₂改性CuO催化剂的碳烟燃烧性能研究[J]. 化工学报, 2024, 75(1): 312-321.
[2]	赵文琪, 邓燕君, 朱春英, 付涛涛, 马友光. 纳米粒子稳定的Pickering乳液及其液滴聚并动力学研究进展[J]. 化工学报, 2024, 75(1): 33-46.
[3]	王雪杰, 崔国庆, 王文涵, 杨扬, 王淙恺, 姜桂元, 徐春明. 电内加热Pt/NPC催化剂高效催化甲基环己烷脱氢反应研究[J]. 化工学报, 2024, 75(1): 292-301.
[4]	李亚婷, 王忠东, 董艳鹏, 朱春英, 马友光, 付涛涛. 微通道中毛细流动及其工程应用的研究进展[J]. 化工学报, 2024, 75(1): 159-170.
[5]	张强, 王宪飞, 王凯, 骆广生, 路忠凯. 非金属催化剂在环氧化物和环状酸酐共聚中的研究进展[J]. 化工学报, 2024, 75(1): 60-73.
[6]	王欣雨, 王永涛, 姚加, 李浩然. 电子顺磁共振技术在化工基础研究中的应用进展[J]. 化工学报, 2024, 75(1): 74-82.
[7]	麻雪怡, 刘克勤, 胡激江, 姚臻. POE溶液聚合反应器内混合与反应过程的CFD研究[J]. 化工学报, 2024, 75(1): 322-337.
[8]	王婷, 王忠东, 项星宇, 何呈祥, 朱春英, 马友光, 付涛涛. 微反应器内环酯类锂电池添加剂合成研究进展[J]. 化工学报, 2024, 75(1): 95-109.
[9]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[10]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[11]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[12]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[13]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[14]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[15]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.