静电纺丝技术在氨硼烷水解脱氢催化剂制备中的应用

doi:10.16085/j.issn.1000-6613.2018-1606

摘要/Abstract

摘要：

氨硼烷由于其氢质量分数高达19.6%，在环境条件下稳定性高，无毒，在普通溶剂中溶解度高，因此被视为是一种极具潜力的固体储氢材料。但是传统纳米金属催化剂颗粒容易出现团聚、损失、二次污染、难回收的问题。高压静电纺丝技术将微纳米纤维作为纳米金属颗粒的载体，制备出的催化剂可以有效弥补传统纳米金属催化剂的缺点。本文从静电纺丝技术、纳米纤维的分类、催化剂的分类3个角度重点介绍了静电纺丝法制备应用于氨硼烷水解的纳米催化剂。在纳米纤维的分类中详细介绍了应用电纺技术制备不同种类纤维的制作步骤和关键技术点；在催化剂的分类中全面详细介绍了贵金属以及非贵金属催化剂的制备工艺，对比两种催化剂制备的优缺点，总结出了催化剂颗粒以及载体的选择依据。最后分别提出通过技术设备的升级优化、催化颗粒与载体的合理设计、“三步”化学反应的方法来解决电纺技术效率低、催化性能差、氨硼烷再生难的问题。

关键词: 静电纺丝技术, 氨硼烷, 催化剂载体, 纳米材料, 制氢

Abstract:

Ammonia borane is considered as a potential solid hydrogen storage material due to its high hydrogen content of 19.6%, high stability, non- toxicity and high solubility in ordinary solvents. The catalysts with micro-nano fibers as carriers prepared by electrospinning technology can effectively overcome the shortcomings of traditional nano-metal catalysts such as agglomeration, loss, pollution and difficult recovery. This paper focuses on the preparation of nano-catalysts for hydrolysis of ammonia borane from three aspects of electrospinning technology, the classification of nanofibers and catalysts. Regarding nanofibers, the steps and key technical points for the preparation of different kinds of fibers by electrospinning were discussed in detail. As for the catalysts, the preparation processes of precious metals and non-noble metal catalysts as well as their advantages were reviewed, and the selection principles of catalyst particles and carriers was summarized. Finally, the methods of upgrading and optimizing both the process and the equipment, rational design of the catalytic particles and the carriers, and the “three-step” chemical reaction are put forward respectively to solve the problems of low electrospinning efficiency, poor catalytic performance and difficult for the regeneration of ammonia borane.

Key words: electrospinning techniques, ammonia borane, catalyst support, nanomaterials, hydrogen production

中图分类号:

TQ530.44

张帅, 王斯瑶, 姜召, 方涛. 静电纺丝技术在氨硼烷水解脱氢催化剂制备中的应用[J]. 化工进展, 2019, 38(07): 3194-3206.

Shuai ZHANG, Siyao WANG, Zhao JIANG, Tao FANG. Application of electrospinning technology in the preparation of dehydrogenation catalysts for ammonia borane hydrolysis[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3194-3206.

图/表 14

参考文献 95

1	ZHAN W , ZHU Q L , XU Q ．Dehydrogenation of ammonia borane by metal nanoparticle catalysts[J]．ACS Catalysis, 2016, 6(10): 6892-6905.
2	SUH M P, PARK H J , PRASAD T K , et al ．Hydrogen storage in in metal-organic frameworks[J]. Chemical Reviews, 2011, 112(2): 782-835.
3	BULUT A , YURDERI M , ERTAS I E , et al ．Carbon dispersed copper-cobalt alloy nanoparticles: a cost-effective heterogeneous catalyst with exceptional performance in the hydrolytic dehydrogenation of ammonia-borane[J]. Applied Catalysis B: Environmental, 2016, 180(3): 121-129.
4	JAIN I P , JAIN P , JAIN A ．Novel hydrogen storage materials: a review of lightweight complex hydrides[J]．Journal of Alloys & Compounds, 2010, 503(2): 303-339.
5	AKBAYRAK S , TANEROĞLU O , ÖZKAR S ．Nanoceria supported cobalt(0) nanoparticles: a magnetically separable and reusable catalyst in hydrogen generation from the hydrolysis of ammonia borane[J]．New Journal of Chemistry, 2017, 41(14): 6546-6552.
6	TAMBOLI A H , CHAUGULE A A , SHEIKH F A , et al ．Synthesis and application of CeO₂–NiO loaded TiO₂ nanofiber as novel catalyst for hydrogen production from sodium borohydride hydrolysis[J]．Energy, 2015, 89: 568-575.
7	ZHONG D C , ARANISHI K , SINGH A K , et al ．The synergistic effect of Rh-Ni catalysts on the highly-efficient dehydrogenation of aqueous hydrazine borane for chemical hydrogen storage[J]. Chemical Communications, 2012, 48(98): 11945-11947.
8	YANG L , SU J , MENG X , et al ． In situ synthesis of graphene supported Ag@CoNi core-shell nanoparticles as highly efficient catalysts for hydrogen generation from hydrolysis of ammonia borane and methylamine borane[J]．Journal of Materials Chemistry A, 2013, 1(34): 10016-10023.
9	YAN J M , ZHANG X B , HAN S , et al ．Magnetically recyclable Fe-Ni alloy catalyzed dehydrogenation of ammonia borane in aqueous solution under ambient atmosphere[J]．Journal of Power Sources, 2009, 194(1):478-481.
10	YOUSEF A , BARAKAT N A M , EL-NEWEHY M H , et al ．Catalytic hydrolysis of ammonia borane for hydrogen generation using Cu(0) nanoparticles supported on TiO₂ nanofibers[J]．Colloids & Surfaces A:Physicochemical & Engineering Aspects, 2015, 470: 194-201.
11	BROCKMAN A , ZHENG Y , GORE J ．A study of catalytic hydrolysis of concentrated ammonia borane solutions[J]．International Journal of Hydrogen Energy, 2010, 35(14): 7350-7356.
12	SUN W , LU X , TONG Y , et al ．A one-pot synthesis of a highly dispersed palladium/polypyrrole/polyacrylonitrile nanofiber membrane and its recyclable catalysis in hydrogen generation from ammonia borane[J]．Journal of Materials Chemistry A, 2014, 19(2): 6740-6746.
13	NADAGOUDA M N , VARMA R S ．A greener synthesis of core (Fe, Cu)-Shell (Au, Pt, Pd, and Ag) nanocrystals using aqueous vitamin C[J]．Crystal Growth & Design, 2007, 7(12): 2582-2587.
14	TONBUL Y , AKBAYRAK S , ÖZKAR S ．Palladium(0) nanoparticles supported on ceria: highly active and reusable catalyst in hydrogen generation from the hydrolysis of ammonia borane[J]．International Journal of Hydrogen Energy, 2016, 41(26): 11154-11162.
15	XU Q , CHANDRA M ．A portable hydrogen generation system: catalytic hydrolysis of ammonia-borane[J]．Journal of Alloys & Compounds, 2007, 446/447(22): 729-732.
16	CHANDRA M , XU Q ．Room temperature hydrogen generation from aqueous ammonia-borane using noble metal nano-clusters as highly active catalysts[J]．Journal of Power Sources, 2007, 168(1): 135-142.
17	SHINJOH H ．Noble metal sintering suppression technology in three-way catalyst: automotive three-way catalysts with the noble metal sintering suppression technology based on the support anchoring effect[J]．Catalysis Surveys from Asia, 2009, 13(3): 184-190.
18	WANG Z Z , ZHAI S R , ZHAI B , et al ．One-step green synthesis of multifunctional Fe₃O₄/Cu nanocomposites toward efficient reduction of organic dyes[J]．European Journal of Inorganic Chemistry, 2015(10): 1692-1699.
19	ZHAO D , FENG J , HUO Q , et al ．Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J]．Science, 1998, 279(5350): 548-552.
20	AND D L, XIA Y ．Fabrication of titania nanofibers by electrospinning[J]．Proceedings of SPIE:The International Society for Optical Engineering, 2003, 3(4): 555-560.
21	丁源维, 王騊, 姚菊明, 等．静电纺制备TiO₂/PVA复合纳米纤维及其光催化性能研究[J]．浙江理工大学学报, 2013, 30(1): 31-35.
	DING Yuanwei , WANG Tao , YAO Juming , et al ．Photocatalytic performance investigation of TiO₂/PVA nanofibers prepared by electrospinning[J]. Journal of Zhejiang Institute of Science and Technology, 2013, 30(1): 31-35.
22	MAO Z , XIE R , FU D , et al ．PAN supported Ag-AgBr@Bi₂₀ TiO₃₂ electrospun fiber mats with efficient visible light photocatalytic activity and antibacterial capability[J]．Separation & Purification Technology, 2017, 176: 277-286.
23	ZHANG L , ZHANG Q , XIE H , et al ．Electrospun titania nanofibers segregated by graphene oxide for improved visible light photocatalysis[J]．Applied Catalysis B: Environmental, 2016, 201: 470-478.
24	HONG S , HOU M , ZHANG H , et al ．A high-performance PEM fuel cell with ultralow platinum electrode via electrospinning and underpotential deposition[J]. Electrochimica Acta, 2017, 245: 403-409.
25	CHANDRAWATI R , MTJ O, TCC M, et al ．Enzyme prodrug therapy engineered into electrospun fibers with embedded liposomes for controlled, localized synthesis of therapeutics[J]. Advanced Healthcare Materials, 2017, 6(17): 1700385.
26	WU D , FENG Q , XU T , et al ．Electrospun blend nanofiber membrane consisting of polyurethane, amidoxime polyarcylonitrile, and β-cyclodextrin as high-performance carrier/support for efficient and reusable immobilization of laccase[J]. Chemical Engineering Journal, 2018, 331: 517-526.
27	YU D , BAI J , WANG J , et al ．Assembling formation of highly dispersed Pd nanoparticles supported 1D carbon fiber electrospun with excellent catalytic active and recyclable performance for Suzuki reaction[J]．Applied Surface Science, 2017, 399: 185-191.
28	DEITZEL J M , KLEINMEYER J D , HIRVONEN J K , et al ．Controlled deposition of electrospun poly(ethylene oxide) fibers[J]．Polymer, 2001, 42(19): 8163-8170.
29	RENEKER D H , YARIN A L , FONG H , et al ．Bending instability of electrically charged liquid jets of polymer solutions in electrospinning[J]．J. Appl. Phys., 2000, 87(9): 4531-4547.
30	汪成伟, 邵珠帅, 王飞龙, 等．静电纺丝纤维应用的研究进展[J]．微纳电子技术, 2014, 51(12): 770-775.
	WANG Chengwei , SHAO Zhushuai , WANG Feilong , et al ．Research progress of the application of the electrostatic spinning fiber[J]．Micronanoelectronic Technology, 2014, 51(12): 770-775.
31	THERON S A , YARIN A L , ZUSSMAN E , et al ．Multiple jets in electrospinning: experiment and modeling[J]．Polymer, 2005, 46(9):2889-2899.
32	KIM G H, CHO Y S, WAN D K ．Stability analysis for multi-jets electrospinning process modified with a cylindrical electrode[J]．European Polymer Journal, 2006, 42(9): 2031-2038.
33	TOMASZEWSKI W , SZADKOWSKI M ．Investigation of electrospinning with the use of a multi-jet electrospinning head[J]．Fibres & Textiles in Eastern Europe, 2005, 13(4):22-26.
34	贾志东, 杨颖, 关志成, 等．高效多针静电纺丝喷丝装置: CN 1962966A[P]. 2007-05-16．
	JIA Zhidong , YANG Ying , GUAN Zhicheng , et al . High efficiency multi needle electrostatic spinning device: CN1962966A[P]. 2007-05-16.
35	杨恩龙, 史晶晶．多喷头静电纺丝研究进展[J]．产业用纺织品, 2009, 27(9): 1-4.
	YANG Enlong, SHI Jingjing, Presentation of research on electrospinning with multiple nozzles[J]．Technical Textiles, 2009, 27(9): 1-4.
36	JIRSAK O , SANETRNIK F , LUKAS D , et al ．A method of nanofibres production from a polymer solution using electrostatic spinning and a device for carrying out the method: EP 1673493 B1[P]．2009-07-08.
37	DEITZEL J M , KLEINMEYER J D , HIRVONEN J K , et al ．Controlled deposition of electrospun poly(ethylene oxide) fibers[J]．Polymer, 2001, 42(19): 8163-8170.
38	THERON A , ZUSSMAN E , YARIN A L ．Electrostatic field-assisted alignment of electrospun nanofibres[J]．Nanotechnology, 2001, 12(3): 384.
39	HUANG Z M , ZHANG Y Z , KOTAKI M , et al ．A review on polymer nanofibers by electrospinning and their applications in nanocomposites[J]．Composites Science & Technology, 2003, 63(15): 2223-2253.
40	LI D , WANG Y , XIA Y ．Electrospinning of polymeric and ceramic nanofibers as uniaxially aligned arrays[J]．Nano Letters, 2003, 3(8): 1167-1171.
41	KIM J S, RENEKER D H ．Polybenzimidazole nanofiber produced by electrospinning[J]. Polymer Engineering & Science,1999, 39(5): 849-854.
42	SMIT E , BŰTTNER U , SANDERSON R D ．Continuous yarns from electrospun fibers[J]．Polymer, 2005, 46(8): 2419-2423.
43	DALTON P D , KLEE D , MÖLLER M ．Electrospinning with dual collection rings[J]．Polymer, 2005, 46(3): 611-614.
44	YOUSEF A , BARAKAT N A M , EL-NEWEHY M H , et al ．Catalytic hydrolysis of ammonia borane for hydrogen generation using Cu(0) nanoparticles supported on TiO₂ nanofibers[J]．Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2015, 470: 194-201.
45	YOUSEF A , BARAKAT N A M , EL-NEWEHY M , et al ．Chemically stable electrospun NiCu nanorods@carbon nanofibers for highly efficient dehydrogenation of ammonia borane[J]．International Journal of Hydrogen Energy, 2012, 37(23): 17715-17723.
46	BARAKAT N A M ．Effective Co-Mn-O nanofibers for ammonia borane hydrolysis[J]．Materials Letters, 2013, 106: 229-232.
47	AL-ENIZI A M , BROOKS R M , ABUTALEB A , et al ．Electrospun carbon nanofibers containing Co-TiC nanoparticles-like superficial protrusions as a catalyst for H₂ gas production from ammonia borane complex[J]．Ceramics International, 2017, 43(17): 15735-15742.
48	YOUSEF A , BROOKS R M , EL-HALWANY M M , et al ．Electrospun CoCr₇ C₃-supported C nanofibers: effective, durable, and chemically stable catalyst for H₂ gas generation from ammonia borane[J]．Molecular Catalysis, 2017, 434: 32-38.
49	LI Z Y , ZHANG H N , ZHENG W , et al ．Highly sensitive and stable humidity nanosensors based on LiCl doped TiO₂ electrospun nanofibers[J]．Journal of the American Chemical Society, 2008, 130(15): 5036-5037.
50	FILIZ B C , FIGEN A K ．Fabrication of electrospun nanofiber catalysts and ammonia borane hydrogen release efficiency[J]．International Journal of Hydrogen Energy, 2016, 41(34): 15433-15442.
51	NIRMALA R , KIM H Y, YI C , et al ．Electrospun nickel doped titanium dioxide nanofibers as an effective photocatalyst for the hydrolytic dehydrogenation of ammonia borane[J]．International Journal of Hydrogen Energy, 2012, 37(13):10036-10045.
52	YOUSEF A , BARAKAT N A M , KIM H Y ．Electrospun Cu-doped titania nanofibers for photocatalytic hydrolysis of ammonia borane[J]．Applied Catalysis A: General, 2013, 467: 98-106.
53	BARAKAT N A M , MOTLAK M , TAHA A , et al ．Super effective Zn-Fe-doped TiO₂ nanofibers as photocatalyst for ammonia borane hydrolysis[J]．International Journal of Green Energy, 2015, 13(7): 642-649.
54	TONG Y , LU X , SUN W , et al ．Electrospun polyacrylonitrile nanofibers supported Ag/Pd nanoparticles for hydrogen generation from the hydrolysis of ammonia borane[J]．Journal of Power Sources, 2014, 261: 221-226.
55	ZHANG Z , JIANG Y , CHI M , et al ．Electrospun polyacrylonitrile nanofibers supported alloyed Pd-Pt nanoparticles as recyclable catalysts for hydrogen generation from the hydrolysis of ammonia borane[J]．RSC Advances, 2015, 5(114): 94456-94461.
56	SUN D , MAZUMDER V , Ö METIN , et al . Catalytic hydrolysis of ammonia borane via cobalt palladium nanoparticles[J]. ACS Nano, 2011, 5(8): 6458-6464.
57	PANTHI G , BARAKAT N A M , ABDELRAZEK K K , et al ．Encapsulation of CoS nanoparticles in PAN electrospun nanofibers: effective and reusable catalyst for ammonia borane hydrolysis and dyes photodegradation[J]．Ceramics International, 2013, 39(2): 1469-1476.
58	RYSCHKEWITSCH G E . Amine borane I．kinetics of acid hydrolysis of trimethylamine borane[J]. Journal of the American Chemical Society, 1960, 82(13): 3290-3294.
59	KELLY H C , MARCHELLI F R , GIUSTO M B . The kinetics and mechanism of solvolysis of amineboranes[J]．Inorganic Chemistry, 1964, 3(3): 431-437.
60	CHIRIAC R , TOCHE F , DEMIRCI U B , et al ．Ammonia borane decomposition in the presence of cobalt halides[J]．International Journal of Hydrogen Energy, 2011, 36(20): 12955-12964.
61	TOCHE F , CHIRIAC R , DEMIRCI U B , et al ．Ammonia borane thermolytic decomposition in the presence of metal (Ⅱ) chlorides[J]．International Journal of Hydrogen Energy, 2012, 37(8): 6749-6755.
62	LI Y , FANG F , SONG Y , et al ．Enhanced dehydrogenation of ammonia borane by reaction with alkaline earth metal chlorides[J]．International Journal of Hydrogen Energy, 2012, 37(5): 4274-4279.
63	AKBAYRAK S , TONBUL Y , ÖZKAR S ．Ceria supported rhodium nanoparticles: superb catalytic activity in hydrogen generation from the hydrolysis of ammonia borane[J]．Applied Catalysis B: Environmental, 2016, 198: 162-170.
64	FAN G , LIU Q , TANG D , et al ．Nanodiamond supported Ru nanoparticles as an effective catalyst for hydrogen evolution from hydrolysis of ammonia borane[J]. International Journal of Hydrogen Energy, 2016, 41(3):1542-1549.
65	MANNA J , AKBAYRAK S , ÖZKAR S ．Palladium(0) nanoparticles supported on polydopamine coated Fe₃O₄ as magnetically isolable, highly active and reusable catalysts for hydrolytic dehydrogenation of ammonia borane[J]．RSC Advances, 2016, 6(104): 102035-102042.
66	MANNA J , AKBAYRAK S , ÖZKAR S ．Palladium(0) nanoparticles supported on polydopamine coated CoFe₂O₄ as highly active, magnetically isolable and reusable catalyst for hydrogen generation from the hydrolysis of ammonia borane[J]. Applied Catalysis B: Environmental, 2017, 208: 104-115.
67	AKBAYRAK S , KAYA M , VOLKAN M , et al . Palladium(0) nanoparticles supported on silica-coated cobalt ferrite: a highly active, magnetically isolable and reusable catalyst for hydrolytic dehydrogenation of ammonia borane[J]. Applied Catalysis B: Environmental, 2014, 147(8): 387-393.
68	DAI H , SU J , KAI H, et al . Pd nanoparticles supported on MIL-101 as high-performance catalysts for catalytic hydrolysis of ammonia borane[J]. International Journal of Hydrogen Energy, 2014, 39(10): 4947-4953.
69	TONBUL Y , AKBAYRAK S , ÖZKAR S ．Palladium(0) nanoparticles supported on ceria: highly active and reusable catalyst in hydrogen generation from the hydrolysis of ammonia borane[J]．International Journal of Hydrogen Energy, 2016, 41(26): 11154-11162.
70	KILIÇ B ， ŞENCANLI S ， Ö METIN ．Hydrolytic dehydrogenation of ammonia borane catalyzed by reduced graphene oxide supported monodisperse palladium nanoparticles: high activity and detailed reaction kinetics[J]．Journal of Molecular Catalysis A: Chemical, 2012, 361/362: 104-110.
71	RAKAP M , ÖZKAR S ．Hydroxyapatite-supported palladium(0) nanoclusters as effective and reusable catalyst for hydrogen generation from the hydrolysis of ammonia-borane[J]．International Journal of Hydrogen Energy, 2011, 36(12): 7019-7027.
72	XI P , CHEN F , XIE G , et al ．Surfactant free RGO/Pd nanocomposites as highly active heterogeneous catalysts for the hydrolytic dehydrogenation of ammonia borane for chemical hydrogen storage[J]．Nanoscale, 2012, 4(18): 5597-5601.
73	AKBAYRAK S , ERDEK P , ÖZKAR S ．Hydroxyapatite supported ruthenium(0) nanoparticles catalyst in hydrolytic dehydrogenation of ammonia borane: insight to the nanoparticles formation and hydrogen evolution kinetics[J]．Applied Catalysis B: Environmental, 2013, 142: 187-195.
74	AKBAYRAK S , OZKAR S ．Ruthenium(0) nanoparticles supported on xonotlite nanowire: a long-lived catalyst for hydrolytic dehydrogenation of ammonia-borane[J]．Dalton Trans, 2013, 43(4): 1797-1805.
75	DURAP F , ZAHMAKıRAN M , ÖZKAR S ．Water soluble laurate-stabilized rhodium(0) nanoclusters catalyst with unprecedented catalytic lifetime in the hydrolytic dehydrogenation of ammonia-borane[J]．Applied Catalysis A: General, 2009, 369(1/2): 53-59.
76	YOUSEF A , BROOKS R M , EL-HALWANY M M , et al ．A novel and chemical stable Co-B nanoflakes-like structure supported over titanium dioxide nanofibers used as catalyst for hydrogen generation from ammonia borane complex[J]．International Journal of Hydrogen Energy, 2016, 41(1): 285-293.
77	LIU P , GU X , KANG K , et al ．Highly efficient catalytic hydrogen evolution from ammonia borane using the synergistic effect of crystallinity and size of noble-metal-free nanoparticles supported by porous metal-organic frameworks[J]．ACS Applied Materials & Interfaces, 2017, 9(12): 10759-10767.
78	HU J , CHEN Z , LI M , et al ．Amine-capped Co nanoparticles for highly efficient dehydrogenation of ammonia borane[J]．ACS Applied Materials & Interfaces, 2014, 6(15): 13191.
79	MANNA J , AKBAYRAK S , ÖZKAR S ．Nickel(0) nanoparticles supported on bare or coated cobalt ferrite as highly active, magnetically isolable and reusable catalyst for hydrolytic dehydrogenation of ammonia borane[J]．J. Colloid Interface Sci., 2017, 508: 359-368.
80	LI P Z , AIJAZ A , XU Q ．Highly dispersed surfactant-free nickel nanoparticles and their remarkable catalytic activity in the hydrolysis of ammonia borane for hydrogen generation[J]．Angewandte Chemie, 2012, 51(27): 6753.
81	ZHANG J , CHEN C , YAN W , et al ．Ni nanoparticles supported on CNTs with excellent activity produced by atomic layer deposition for hydrogen generation from hydrolysis of ammonia borane[J]．Catalysis Science & Technology, 2016, 6(7): 2112-2119.
82	LU H , LI M , HU J ．A stable, efficient 3D cobalt-graphene composite catalyst for the hydrolysis of ammonia borane[J].Catalysis Science & Technology, 2016, 6(19): 7186-7192.
83	YANG L , CAO N , CHENG D , et al ．Graphene supported cobalt(0) nanoparticles for hydrolysis of ammonia borane[J]．Materials Letters, 2014, 115(2): 113-116.
84	METIN O , MAZUMDER V , OZKAR S , et al .Monodisperse nickel nanoparticles and their catalysis in hydrolytic dehydrogenation of ammonia borane[J]．Journal of the American Chemical Society, 2010, 132(5): 1468-1469.
85	ZHOU L , MENG J , LI P , et al .Ultrasmall cobalt nanoparticles supported on nitrogen-doped porous carbon nanowires for hydrogen evolution from ammonia borane[J].Materials Horizons, 2017, 4(2): 268-273.
86	WANG H , ZHAO Y , CHENG F , et al . Cobalt nanoparticles embedded in porous N-doped carbon as long-life catalysts for hydrolysis of ammonia borane[J]．Catalysis Science & Technology, 2016, 6(10): 3443-3448.
87	ZAHMAKIRAN M , AYVALI T , AKBAYRAK S , et al .Zeolite framework stabilized nickel(0) nanoparticles: active and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia-borane and sodium borohydride[J].Catalysis Today, 2011, 170(1): 76-84.
88	YANG Y , LU Z H , HU Y , et al ．Facile in situ synthesis of copper nanoparticles supported on reduced graphene oxide for hydrolytic dehydrogenation of ammonia borane[J]. RSC Advances, 2014, 4(27):13749-13752.
89	YAO Q , LU Z H , ZHANG Z , et al ．One-pot synthesis of core-shell Cu@SiO₂ nanospheres and their catalysis for hydrolytic dehydrogenation of ammonia borane and hydrazine borane[J]．Scientific Reports, 2014, 4(4): 7597.
90	BARAKAT N A M ．Catalytic and photo hydrolysis of ammonia borane complex using Pd-doped Co nanofibers[J].Applied Catalysis A: General, 2013, 451: 21-27.
91	YOUSEF A , BROOKS R M , EL-HALWANY M M , et al .CuO /S-doped TiO₂ nanoparticles-decorated carbon nanofibers as novel and efficient photocatalyst for hydrogen generation from ammonia borane[J]. Ceramics International, 2016, 42(1): 1507-1512.
92	MU J , SHAO C , GUO Z , et al ．High photocatalytic activity of ZnO-carbon nanofiber heteroarchitectures[J].ACS Applied Materials & Interfaces, 2011, 3(2): 590-596.
93	SUTTON A D , BURRELL A K , DIXON D A , et al . Regeneration of ammonia borane spent fuel by direct reaction with hydrazine and liquid ammonia[J]．Science, 2011, 331(6023): 1426-1429.
94	SUMMERSCALES O T , GORDON J C . Regeneration of ammonia borane from spent fuel materials[J].Dalton Transactions, 2013, 42(28): 10075-10084.
95	Christian RELLER , MERTENS Florian O . A self-contained regeneration scheme for spent ammonia borane based on the catalytic hydrodechlorination of BCl₃ [J]. Angewandte Chemie International Edition, 2012, 51(47): 11731-11735.

序号	催化剂	TOF/mol H₂·min ^-1·mol（贵金属）^-1	E _a/kJ·mol	颗粒尺寸/nm	参考文献
1	Rh/CeO₂	2010	42.6	—	[63]
2	Ru/纳金刚石	229	50.7	3.7	[64]
3	Ru/HAp	137	58	4.7±0.7	[73]
4	Ru⁰/X-NW	135	77	4.4±0.4	[74]
5	Rh/g-Al₂O₃	128.2	21	2.5	[16]
6	Rh⁰/纳米SiO₂	112	—	—	[63]
7	Pt/C	111	—	1.9	[15]
8	PAN/Pd-Pt	51.9	—	—	[55]
9	Pd/MIL-101	45	—	1.8±0.4	[68]
10	Pd/CeO₂	29	68	—	[14]
11	RGO-Pd	26.3	40	—	[70]
12	Pd-HAP	8.3	55	3.3±0.8	[71]
13	Pd/纳米TiO₂	7.1	—	—	[14]
14	Pd/纳米SiO₂	6.6	—	—	[14]
15	Ag/Pd@PAN NFs	6.29	—	5~20	[54]
16	RGO/Pd	6.25	51	4	[72]
17	Pd/PPy@PAN NFs	3.9	33.5	5	[12]
18	Pd/纳米Al₂O₃	3.5	—	—	[14]

序号	催化剂	TOF/mol H₂·min ^-1·mol（贵金属）^-1	E _a/kJ·mol	颗粒尺寸/nm	参考文献
1	Rh/CeO₂	2010	42.6	—	[63]
2	Ru/纳金刚石	229	50.7	3.7	[64]
3	Ru/HAp	137	58	4.7±0.7	[73]
4	Ru⁰/X-NW	135	77	4.4±0.4	[74]
5	Rh/g-Al₂O₃	128.2	21	2.5	[16]
6	Rh⁰/纳米SiO₂	112	—	—	[63]
7	Pt/C	111	—	1.9	[15]
8	PAN/Pd-Pt	51.9	—	—	[55]
9	Pd/MIL-101	45	—	1.8±0.4	[68]
10	Pd/CeO₂	29	68	—	[14]
11	RGO-Pd	26.3	40	—	[70]
12	Pd-HAP	8.3	55	3.3±0.8	[71]
13	Pd/纳米TiO₂	7.1	—	—	[14]
14	Pd/纳米SiO₂	6.6	—	—	[14]
15	Ag/Pd@PAN NFs	6.29	—	5~20	[54]
16	RGO/Pd	6.25	51	4	[72]
17	Pd/PPy@PAN NFs	3.9	33.5	5	[12]
18	Pd/纳米Al₂O₃	3.5	—	—	[14]

序号	催化剂	TOF/mol H₂·min ^-1·mol（贵金属）^-1	E _a/kJ·mol	颗粒尺寸/nm	参考文献
1	Co-NF	147	41.59	32~46	[50]
2	Co/MIL-101-1-U	51.4	31.3	—	[77]
3	Co/PEI-GO	39.9	28.2	2.6	[78]
4	Ni⁰/CoFe₂O₄	38.3	62.7	—	[79]
5	Co-TiC@CNFs	32	26.19	10~40	[47]
6	Ni@MSC-30	30.7	—	6.3	[80]
7	200 ALD cycle Ni/CNT	26.2	32.3	5.6	[81]
8	Co-CrC/CNFs	25.78	24.2	—	[48]
9	PEI-GO3D/Co	18.5	27.4	—	[82]
10	Co/石墨烯	13.9	37.72	—	[83]
11	Cu-NF	11	36.7	—	[50]
12	Ni/C	8.8	28	3.2	[84]
13	Ni-NF	8	35.54	—	[50]
14	Ni⁰/PDA-CoFe₂O₄	7.6	50.8	12.3	[79]
15	Co/NPCNW	7.29	25.4	3.5	[85]
16	Co⁰/CeO₂	7	43	—	[5]
17	Co@NC700	5.6	31	9	[86]
18	NiO/SiO₂ -CoFe₂O₄	5.3	68.2	21.7	[79]
19	Ni/分子筛	5	54.4	3.9±0.9	[87]
20	RGO-Cu	3.61	38.2	—	[88]
21	Cu/SiO₂	3.24	36	2	[89]
22	Cu⁰/CeO₂	1.5	—	—	[5]
23	Co-B@ TiO₂	—	16.54		[76]
24	NiCu @ CNFs	—	28.9		[45]

序号	催化剂	TOF/mol H₂·min ^-1·mol（贵金属）^-1	E _a/kJ·mol	颗粒尺寸/nm	参考文献
1	Co-NF	147	41.59	32~46	[50]
2	Co/MIL-101-1-U	51.4	31.3	—	[77]
3	Co/PEI-GO	39.9	28.2	2.6	[78]
4	Ni⁰/CoFe₂O₄	38.3	62.7	—	[79]
5	Co-TiC@CNFs	32	26.19	10~40	[47]
6	Ni@MSC-30	30.7	—	6.3	[80]
7	200 ALD cycle Ni/CNT	26.2	32.3	5.6	[81]
8	Co-CrC/CNFs	25.78	24.2	—	[48]
9	PEI-GO3D/Co	18.5	27.4	—	[82]
10	Co/石墨烯	13.9	37.72	—	[83]
11	Cu-NF	11	36.7	—	[50]
12	Ni/C	8.8	28	3.2	[84]
13	Ni-NF	8	35.54	—	[50]
14	Ni⁰/PDA-CoFe₂O₄	7.6	50.8	12.3	[79]
15	Co/NPCNW	7.29	25.4	3.5	[85]
16	Co⁰/CeO₂	7	43	—	[5]
17	Co@NC700	5.6	31	9	[86]
18	NiO/SiO₂ -CoFe₂O₄	5.3	68.2	21.7	[79]
19	Ni/分子筛	5	54.4	3.9±0.9	[87]
20	RGO-Cu	3.61	38.2	—	[88]
21	Cu/SiO₂	3.24	36	2	[89]
22	Cu⁰/CeO₂	1.5	—	—	[5]
23	Co-B@ TiO₂	—	16.54		[76]
24	NiCu @ CNFs	—	28.9		[45]

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