含氮有机液体储放氢催化体系研究进展

doi:10.16085/j.issn.1000-6613.2023-0089

摘要/Abstract

摘要：

氢能源作为重要的二次能源，能量密度大、环境友好且用途广泛，是人类战略能源发展的重要方向。然而，氢气储运仍面临较大的成本和安全难题，有机液体储氢化合物（LOHCs）储放氢技术以其储氢密度较高、储存条件温和、运输方便等优势成为氢气储运可供选择的技术之一。相比稠环芳烃类化合物，含氮有机储氢化合物具有更温和的催化加氢和脱氢条件，可有效提高储放氢鲁棒性和反应能效。基于此，本文系统综述了含氮有机储氢化合物加氢及脱氢反应研究进展，阐述了两类反应的路径和催化作用机制，从催化剂活性中心和载体、双金属协同效应、反应条件、催化剂稳定性等方面系统分析了加氢/脱氢催化剂，并详细总结了基于连串反应、反应网络等模型的反应动力学。介绍了含氮有机储氢化合物储氢技术目前面临的挑战并提出未来的研究思路及展望。但是该技术仍存在较多问题，应在有机储氢化合物配方体系、储放氢连续反应系统、催化剂设计与制备、催化剂构效关系、精准反应动力学和全面理化性质数据库等方面进行深入研究。

关键词: 氢, 含氮有机液体储氢化合物, 反应机理, 催化剂, 反应动力学

Abstract:

As an important secondary energy, hydrogen is of high energy density, environmental friendliness and wide use, which is an important direction of human strategic energy development. However, hydrogen storage and transportation are still facing problems of high cost and safety. The hydrogen storage and release technology based on liquid organic hydrogen carriers (LOHCs) has become one of the available technologies with its advantages of relatively high hydrogen storage density, mild storage conditions and convenient transportation. Compared with polycyclic aromatic hydrocarbons, nitrogen-containing LOHCs is milder in catalytic hydrogenation and dehydrogenation, which can effectively improve the robustness of hydrogen storage and release and the reaction efficiency. Based on this, this paper systematically reviewed the progress in hydrogenation and dehydrogenation of nitrogen-containing LOHCs, and revealed the reaction pathway and catalytic mechanism of these two kinds of reactions. Then, the hydrogenation/ dehydrogenation catalysts were systematically summarized from the aspects of active center, support, bimetallic synergistic effect, reaction conditions, catalyst stability, etc. After that, the reaction kinetics models based on the series reactions and reaction network were analyzed in detail. At last, the current challenges of nitrogen-containing LOHCs were introduced, as well as the perspectives of LOHCs systems. However, there are still many problems for this technology, and further in-depth research should be conducted in the aspects of formulation system of organic hydrogen carriers, continuous hydrogen storage and release reaction system, catalyst design and preparation, structure-activity relationship of catalysts, precise reaction kinetics, and comprehensive physicochemical properties database.

Key words: hydrogen, nitrogen-containing LOHCs, reaction mechanism, catalyst, reaction kinetics

中图分类号:

TK91

李佳豪, 杨锦, 潘伦, 钟勇斌, 王志敏, 王锦生, 张香文, 邹吉军. 含氮有机液体储放氢催化体系研究进展[J]. 化工进展, 2023, 42(12): 6325-6344.

LI Jiahao, YANG Jin, PAN Lun, ZHONG Yongbin, WANG Zhimin, WANG Jinsheng, ZHANG Xiangwen, ZOU Jijun. Research progress in catalytic system for hydrogen storage and release from nitrogen-containing liquid organic carriers[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6325-6344.

图/表 14

图1 基于LOHCs的氢气储存和释放循环过程示意图

表1 典型的含氮LOHCs的转化及其理化性质[46,62-65]

LOHCs的转化	储氢量（质量分数） /%	脱氢反应焓 /kJ $∙$ mol H₂^-1	熔点（0.1MPa）/℃		沸点（0.1MPa）/℃
LOHCs的转化	储氢量（质量分数） /%	脱氢反应焓 /kJ $∙$ mol H₂^-1	富氢分子	贫氢分子	富氢分子	贫氢分子
12H-NEC $→$ NEC	5.8	50.6	-85	68	280	190
8H-1-甲基吲哚 $→$ 1-甲基吲哚	5.76	51.9	<-25	<-20	>230	238
8H-2-甲基吲哚 $→$ 2-甲基吲哚	5.76	—	25	57	205	272
8H-7-乙基吲哚 $→$ 7-乙基吲哚	5.23	—	< -20	-14	> 230	230
8H-2,3-二甲基吲哚 $→$ 2,3-二甲基吲哚	5.23	—	<-10	105	≥285	285
10H-喹啉 $→$ 喹啉	7.2	61.9	-45	-17	200	237

表1 典型的含氮LOHCs的转化及其理化性质[46,62-65]

LOHCs的转化	储氢量（质量分数） /%	脱氢反应焓 /kJ $∙$ mol H₂^-1	熔点（0.1MPa）/℃		沸点（0.1MPa）/℃
LOHCs的转化	储氢量（质量分数） /%	脱氢反应焓 /kJ $∙$ mol H₂^-1	富氢分子	贫氢分子	富氢分子	贫氢分子
12H-NEC $→$ NEC	5.8	50.6	-85	68	280	190
8H-1-甲基吲哚 $→$ 1-甲基吲哚	5.76	51.9	<-25	<-20	>230	238
8H-2-甲基吲哚 $→$ 2-甲基吲哚	5.76	—	25	57	205	272
8H-7-乙基吲哚 $→$ 7-乙基吲哚	5.23	—	< -20	-14	> 230	230
8H-2,3-二甲基吲哚 $→$ 2,3-二甲基吲哚	5.23	—	<-10	105	≥285	285
10H-喹啉 $→$ 喹啉	7.2	61.9	-45	-17	200	237

图2 含氮贫氢分子加氢反应路径[46,57-58,60-61]

图3 气相中最稳定反应中间体/产物与NEC之间的自由能比较[56]

图4 NEC和8H-NEC在Ru{001}和Ru{109}位点上的吸附结构及其吸附能[18]

图5 含氮富氢分子脱氢反应路径[46,57,67-68]

图6 Pd{111}和Pd{110}表面上12H-NEC、8H-NEC和4H-NEC的吸附结构[73]（1Å=0.1nm)

图7 不同金属上NEC加氢反应速率常数对比[60]

图8 12H-NEC脱氢过程中Pd与MoO3的协同作用机理[105]

图9 12H-NEC在180℃下Pd{100}、{110}和{111}晶面上脱氢反应的Gibbs自由能[78]

图10 不同催化剂在180℃、1h下12H-NEC脱氢性能[22]

表2 含氮有机储氢化合物脱氢催化剂重复性

序号	底物	催化剂	循环次数	储氢性能^①/%	参考文献
1	12H-NEC	1%Pd-IP/S15	7	94.6	[40]
2		1%Pd₁Ni₁/K₆	6	87	[115]
3		2.5%Pd/LDHs-us	6	93	[5]
4		1%PdRh_0.6/γ-Al₂O₃	5	97.7	[42]
5		5%Pd₂Co₁/NGC	6	95.6	[24]
6		2.5%Pd/LDHs-c	6	86	[5]
7		Pd₃Cu₁/SiO₂	5	95.85	[75]
8		Pd₃Ni₁/SiO₂	5	92.4	[75]
9		1%Pd-IP/S15	7	97	[40]
10		5%Pd/Al₂O₃-YH₃	3	97	[86]
11		5%Pd/C	4	92.2	[22]
12		Au₁Pd_1.3/rGO	5	98	[79]
13		3.0%Pd/CNTs	5	90	[81]
14		5%Pd/Al₂O₃	10	98	[118]

表3 含氮LOHCs贫氢分子加氢反应动力学参数

序号	底物	反应级数	催化剂	温度范围/℃	压力/MPa	表观活化能/kJ·mol^-1	参考文献
1	NPC	1^C	70%Ni/AlSiO-1/1	130~160	7	10.88	[25]
2	NPC	1^C	0.5%Ru/WO₃	100~130	6	70.19	[123]
3	NPC	1^C	5%Ru_2.5Ni_2.5/Al₂O₃	150~180	4	12.95	[124]
4	NPC	1^C	5%Ru/Al₂O₃^①	120~150	7	18.4	[125]
5	NEC	1^C	0.5%Ru/Beta	90~120	6	45.7	[93]
6	NEC	1^C	0.5%Ru/Al₂O₃	90~120	6	88.3	[93]
7	NEC	1^C	5%Ru/Al₂O₃	140~170	7	67.6	[21]
8	NEC	1^P	Ni_0.5Ru_4.5/pg-BC	110~140	6	57.3	[82]
9	NEC	1^P	Ru₄Pd₁/LDH	110~140	6	56.1	[83]
10	NEC	1^P	5.89%Ru/pg-BC	110~140	6	55.9	[97]
11	NEC	1^P	5%Ru/NiFe-LDH	110~130	6	25.15	[90]
12	NEC	1^P	5%Ru/LDH	110~140	6	35.78	[80]
13	NEC	1^C	Raney-Ni	120~180	5	115	[59]
14	NEC	1^C	5%Ru/Al₂O₃^①	150~180	8	71.2	[121]
15	NEC	1^P	5%Ru/γ-Al₂O₃^①	120~160	6	30.94	[119]
16	NEC	1^P	5%Ru/γ-Al₂O₃^①	95~160	6	27.01	[120]
17	NEC	1^C	5%Ru, Rh, Pd/AC^①	130	7	—	[126]
18	NEC	1^P	Raney-Ni	120~200	5	65.17	[91]
19	NEC	1^C	5%Ru/Al₂O₃^①	120~170	7	58	[56]
20	NEC	1^C	5%Ru/Al₂O₃^①	130~150	7	99.5	[57]
21	咔唑	1^C	Raney-Ni	170~230	5	90	[59]
22	1,2-DMID	1^C	5%Ru/Al₂O₃^①	130~170	7	85.1	[64]
23	7-EID	1^C	5%Ru/Al₂O₃^①	130~160	7	51.5	[46]
24	1-EID	1^C	5%Ru/Al₂O₃^①	160~190	9	62.4	[122]
25	2-MID	1^C	5%Ru/Al₂O₃^①	120~170	7	21	[61]
26	NEC	1^C	钌黑^① 铂黑^① 钯黑^① 65%Ni/SiO₂-Al₂O₃^①	130	7	—	[60]
27	NEC	1^C	5%Ru/Al₂O₃^① 钌黑^① 5%Ru/SiO₂-Al₂O₃	130	7	—	[18]
28	NEC	1^C	5%Ru/Al₂O₃^①	150~170	7	NEC $→$ 4H-NEC 107.6 NEC $→$ 8H-NEC 97.9 4H-NEC $→$ 6H-NEC 134.9 6H-NEC $→$ 8H-NEC 208 8H-NEC $→$ 10H-NEC 98.2 8H-NEC $→$ 12H-NEC 75.8 10H-NEC $→$ 12H-NEC 240.9	[58]

表3 含氮LOHCs贫氢分子加氢反应动力学参数

序号	底物	反应级数	催化剂	温度范围/℃	压力/MPa	表观活化能/kJ·mol^-1	参考文献
1	NPC	1^C	70%Ni/AlSiO-1/1	130~160	7	10.88	[25]
2	NPC	1^C	0.5%Ru/WO₃	100~130	6	70.19	[123]
3	NPC	1^C	5%Ru_2.5Ni_2.5/Al₂O₃	150~180	4	12.95	[124]
4	NPC	1^C	5%Ru/Al₂O₃^①	120~150	7	18.4	[125]
5	NEC	1^C	0.5%Ru/Beta	90~120	6	45.7	[93]
6	NEC	1^C	0.5%Ru/Al₂O₃	90~120	6	88.3	[93]
7	NEC	1^C	5%Ru/Al₂O₃	140~170	7	67.6	[21]
8	NEC	1^P	Ni_0.5Ru_4.5/pg-BC	110~140	6	57.3	[82]
9	NEC	1^P	Ru₄Pd₁/LDH	110~140	6	56.1	[83]
10	NEC	1^P	5.89%Ru/pg-BC	110~140	6	55.9	[97]
11	NEC	1^P	5%Ru/NiFe-LDH	110~130	6	25.15	[90]
12	NEC	1^P	5%Ru/LDH	110~140	6	35.78	[80]
13	NEC	1^C	Raney-Ni	120~180	5	115	[59]
14	NEC	1^C	5%Ru/Al₂O₃^①	150~180	8	71.2	[121]
15	NEC	1^P	5%Ru/γ-Al₂O₃^①	120~160	6	30.94	[119]
16	NEC	1^P	5%Ru/γ-Al₂O₃^①	95~160	6	27.01	[120]
17	NEC	1^C	5%Ru, Rh, Pd/AC^①	130	7	—	[126]
18	NEC	1^P	Raney-Ni	120~200	5	65.17	[91]
19	NEC	1^C	5%Ru/Al₂O₃^①	120~170	7	58	[56]
20	NEC	1^C	5%Ru/Al₂O₃^①	130~150	7	99.5	[57]
21	咔唑	1^C	Raney-Ni	170~230	5	90	[59]
22	1,2-DMID	1^C	5%Ru/Al₂O₃^①	130~170	7	85.1	[64]
23	7-EID	1^C	5%Ru/Al₂O₃^①	130~160	7	51.5	[46]
24	1-EID	1^C	5%Ru/Al₂O₃^①	160~190	9	62.4	[122]
25	2-MID	1^C	5%Ru/Al₂O₃^①	120~170	7	21	[61]
26	NEC	1^C	钌黑^① 铂黑^① 钯黑^① 65%Ni/SiO₂-Al₂O₃^①	130	7	—	[60]
27	NEC	1^C	5%Ru/Al₂O₃^① 钌黑^① 5%Ru/SiO₂-Al₂O₃	130	7	—	[18]
28	NEC	1^C	5%Ru/Al₂O₃^①	150~170	7	NEC $→$ 4H-NEC 107.6 NEC $→$ 8H-NEC 97.9 4H-NEC $→$ 6H-NEC 134.9 6H-NEC $→$ 8H-NEC 208 8H-NEC $→$ 10H-NEC 98.2 8H-NEC $→$ 12H-NEC 75.8 10H-NEC $→$ 12H-NEC 240.9	[58]

表4 含氮LOHCs富氢分子脱氢反应动力学参数

序号	底物	反应级数	催化剂	表观活化能/kJ·mol^-1	参考文献
1	12H-NPC	1^C	3%Pd/MIL-101	12H-NPC $→$ 8H-NPC 94.8 8H-NPC $→$ 4H-NPC 95.9 4H-NPC $→$ NPC 98.8	[44]
2		1^C	5%Pd/Al₂O₃^①	12H-NPC $→$ 8H-NPC 90.0 8H-NPC $→$ 4H-NPC 90.6 4H-NPC $→$ NPC 96.4	[127]
3	12H-NEC	1^C	1%Pt/TiO₂	12H-NEC $→$ 8H-NEC 50.44 8H-NEC $→$ 4H-NEC 53.88 4H-NEC $→$ NEC 69.46	[77]
4		1^C	5%Pd/Al₂O₃	12H-NEC $→$ 8H-NEC 56.3 8H-NEC $→$ 4H-NEC 59.2 4H-NEC $→$ NEC 73.1	[128]
5		1^C	5%Pd/SiO₂	126.7	[57]
5		1^C	5%Pd/SiO₂	12H-NEC $→$ 8H-NEC 67.1 12H-NEC $→$ 4H-NEC 144.3	[57]
6		1^C	2.5%Pd/LDHs-us	90.97	[5]
7		1^C	PdCo/NGC	67.2	[24]
8		1^C	5%Pd/MoO₃	55.19	[105]
9		1^C	1%Pd₄Ni₁/KIT-6	84.8	[115]
10		1^C	Pd-M (M=Cu, Ni)/SiO₂	—	[75]
11		1^C	Pd-M (M=Co, Ni, Cu)/Al₂O₃	—	[99]
12	12H-NPC	1^C	5%Pd-Ni/Al₂O₃	72.03	[98]
13	12H-NEC	1^C	5%Pd/C, Al₂O₃, TiO₂, SiO₂^①	—	[22]
14		1^C	5%M (M=Pt, Pd, Ru, Rh, Au)/TiO₂ and Pd/Al₂O₃^①	—	[76]
15		1^C	5%Pd₃Au₁/SiO₂	—	[109]
16		1^C	2.32%Pd/rGO	—	[101]
17		1^C	3%Pd/CNTs	43.8	[81]
18		1^C	Pt/γ-Al₂O₃	203 (本征活化能)	[129]
19		1^C	钳形Ir	115	[130]
20		1^C	5%Pd (Pt, Ru, Rh)/Al₂O₃^①	—	[53]
22		1^C	5%Pd/SiO₂	—	[131]
22	12H-咔唑	1^C	5%Pd/C^①	208.9	[132]
23	4H-咔唑	0^C	5%Pd/SiO₂	67.7	[57]
24	8H-2,3-DMID	1^C	5%Pd/Al₂O₃^①	39.6	[63]
25	8H-1,2-DMID	1^C	5%Pd/Al₂O₃^①	111.9	[64]
26	8H-1-MID	1^C	5%Pd/Al₂O₃^①	122.99	[67]
27		1^C	钳形Ir	142	[130]
28	1-丁基吡咯烷	1^C	钳形Ir	166	[130]
29	8H-7-EID	1^C	5%Pd/Al₂O₃	101.9	[46]
30	8H-2-MID	1^C	5%Pd/Al₂O₃^①	27.1	[61]

表4 含氮LOHCs富氢分子脱氢反应动力学参数

序号	底物	反应级数	催化剂	表观活化能/kJ·mol^-1	参考文献
1	12H-NPC	1^C	3%Pd/MIL-101	12H-NPC $→$ 8H-NPC 94.8 8H-NPC $→$ 4H-NPC 95.9 4H-NPC $→$ NPC 98.8	[44]
2		1^C	5%Pd/Al₂O₃^①	12H-NPC $→$ 8H-NPC 90.0 8H-NPC $→$ 4H-NPC 90.6 4H-NPC $→$ NPC 96.4	[127]
3	12H-NEC	1^C	1%Pt/TiO₂	12H-NEC $→$ 8H-NEC 50.44 8H-NEC $→$ 4H-NEC 53.88 4H-NEC $→$ NEC 69.46	[77]
4		1^C	5%Pd/Al₂O₃	12H-NEC $→$ 8H-NEC 56.3 8H-NEC $→$ 4H-NEC 59.2 4H-NEC $→$ NEC 73.1	[128]
5		1^C	5%Pd/SiO₂	126.7	[57]
5		1^C	5%Pd/SiO₂	12H-NEC $→$ 8H-NEC 67.1 12H-NEC $→$ 4H-NEC 144.3	[57]
6		1^C	2.5%Pd/LDHs-us	90.97	[5]
7		1^C	PdCo/NGC	67.2	[24]
8		1^C	5%Pd/MoO₃	55.19	[105]
9		1^C	1%Pd₄Ni₁/KIT-6	84.8	[115]
10		1^C	Pd-M (M=Cu, Ni)/SiO₂	—	[75]
11		1^C	Pd-M (M=Co, Ni, Cu)/Al₂O₃	—	[99]
12	12H-NPC	1^C	5%Pd-Ni/Al₂O₃	72.03	[98]
13	12H-NEC	1^C	5%Pd/C, Al₂O₃, TiO₂, SiO₂^①	—	[22]
14		1^C	5%M (M=Pt, Pd, Ru, Rh, Au)/TiO₂ and Pd/Al₂O₃^①	—	[76]
15		1^C	5%Pd₃Au₁/SiO₂	—	[109]
16		1^C	2.32%Pd/rGO	—	[101]
17		1^C	3%Pd/CNTs	43.8	[81]
18		1^C	Pt/γ-Al₂O₃	203 (本征活化能)	[129]
19		1^C	钳形Ir	115	[130]
20		1^C	5%Pd (Pt, Ru, Rh)/Al₂O₃^①	—	[53]
22		1^C	5%Pd/SiO₂	—	[131]
22	12H-咔唑	1^C	5%Pd/C^①	208.9	[132]
23	4H-咔唑	0^C	5%Pd/SiO₂	67.7	[57]
24	8H-2,3-DMID	1^C	5%Pd/Al₂O₃^①	39.6	[63]
25	8H-1,2-DMID	1^C	5%Pd/Al₂O₃^①	111.9	[64]
26	8H-1-MID	1^C	5%Pd/Al₂O₃^①	122.99	[67]
27		1^C	钳形Ir	142	[130]
28	1-丁基吡咯烷	1^C	钳形Ir	166	[130]
29	8H-7-EID	1^C	5%Pd/Al₂O₃	101.9	[46]
30	8H-2-MID	1^C	5%Pd/Al₂O₃^①	27.1	[61]

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