Recent Progress on Materials for Hydrogen Generation via Hydrolysis

doi:10.15541/jim20200215

Abstract

Abstract:

Hydrolysis is a unique method for hydrogen generation at ambient condition. Widespread attentions have been paid to materials for hydrogen generation via hydrolysis due to several advantages: high theoretical hydrogen capacity, moderate storage and operation condition, safety, etc. In this paper, recent progress and development in this area were reviewed. Three types of materials including borohydride (NaBH₄, NH₃·BH₃), metal (Mg, Al), and metal hydride (MgH₂) were introduced. Several issues about them were discussed specifically: mechanism, main problems, designments of catalysts and materials, etc. Based on these discussions, we compared the different materials mentioned above, commented their current performances and practical difficulties. At last, prospects in this field were presented.

Key words: hydrogen generation, hydrolysis, metal, metal hydride, borohydride, cost of hydrogen

CLC Number:

TQ174

DENG Jifeng, CHEN Shunpeng, WU Xiaojuan, ZHENG Jie, LI Xingguo. Recent Progress on Materials for Hydrogen Generation via Hydrolysis[J]. Journal of Inorganic Materials, 2021, 36(1): 1-8.

Figures/Tables 10

References 64

[1]	EBERLE U, FELDERHOFF M, SCHUTH F . Chemical and physical solutions for hydrogen storage. Angew. Chemie. Int. Ed., 2009,48(36):6608-6630.
[2]	HE T, PACHFULE P, WU H , et al. Hydrogen carriers. Nat. Rev. Mater., 2016,1:16059.
[3]	SCHLAPBACH L, ZÜTTEL A. Hydrogen-storage materials for mobile applications. Nature, 2001,414:353-358.
[4]	GÜR T M . Review of electrical energy storage technologies, materials and systems: challenges and prospects for large-scale grid storage. Energy & Environ. Sci., 2018,11(10):2696-2767.
[5]	STAMENKOVIC V R, STRMCNIK D, LOPES P P , et al. Energy and fuels from electrochemical interfaces. Nat. Mater., 2016,16:57-69.
[6]	DEAN J A. Lange's Handbook of Chemistry, 13th Edition. Beijing: Sci. Press, 1991,9:1-172.
[7]	KIM H, OH T H, KWON S J . Simple catalyst bed sizing of a NaBH₄ hydrogen generator with fast startup for small unmanned aerial vehicles. Int. J. Hydrogen Energy, 2016,41(2):1018-1026.
[8]	KIM T . NaBH₄ (sodium borohydride) hydrogen generator with a volume-exchange fuel tank for small unmanned aerial vehicles powered by a PEM (proton exchange membrane) fuel cell. Energy, 2014,69:721-727.
[9]	LI H W, LI D P, ZHANG X D . Research and development of foreign submarine sodium borohydride hydrolysis hydrogen generation. Ship Sci. Technol., 2012,34(7):135-143.
[10]	OH T K . Conceptual design of small unmanned aerial vehicle with proton exchange membrane fuel cell system for long endurance mission. Energy Convers. Manag., 2018,176:349-356.
[11]	CHEN K, OUYANG L Z, ZHONG H , et al. Converting H + from coordinated water into H - enables super facile synthesis of LiBH₄. Green Chem., 2019,21(16):4380-4387.
[12]	SEN B, ŞAVK A, KUYULDAR E , et al. Hydrogen liberation from the hydrolytic dehydrogenation of hydrazine borane in acidic media. Int. J. Hydrogen Energy, 2018,43(38):17978-17983.
[13]	KAUFMAN C M, SEN B . Hydrogen generation by hydrolysis of sodium tetrahydroborate: effects of acids and transition metals and their salts. Dalton Trans., 1984, ( 2):307-313.
[14]	LIU B H, LI Z P . A review: hydrogen generation from borohydride hydrolysis reaction. J. Power Sources, 2009,187(2):527-534.
[15]	BOZKURT G, ÖZER A, YURTCAN A B . Development of effective catalysts for hydrogen generation from sodium borohydride: Ru, Pt, Pd nanoparticles supported on Co₃O₄. Energy, 2019,180:702-713.
[16]	GENÇ A E¸ AKÇA A, KUTLU B . The catalytic effect of the Au(111) and Pt(111) surfaces to the sodium borohydride hydrolysis reaction mechanism: a DFT study. Int. J. Hydrogen Energy, 2018,43(31):14347-14359.
[17]	SEMIZ L, ABDULLAYEVA N, SANKIR M . Nanoporous Pt and Ru catalysts by chemical dealloying of Pt-Al and Ru-Al alloys for ultrafast hydrogen generation. J. Alloys Compd., 2018,744(5):110-115.
[18]	TUAN D D, LIN K Y A. Ruthenium supported on ZIF-67 as an enhanced catalyst for hydrogen generation from hydrolysis of sodium borohydride. Chem. Eng. J., 2018,351:48-55.
[19]	LI Y H, ZHANG X, ZHANG Q , et al. Activity and kinetics of ruthenium supported catalysts for sodium borohydride hydrolysis to hydrogen. RSC Adv., 2016,6(35):29371-29377.
[20]	HAO S, YANG L B, CUI L , et al. Self-supported spinel FeCo₂O₄ nanowire array: an efficient non-noble-metal catalyst for the hydrolysis of NaBH₄ toward on-demand hydrogen generation. Nanotechnology, 2016,27(46):0957-4484.
[21]	CAI H, LIU L, CHEN Q , et al. Ni-polymer nanogel hybrid particles: a new strategy for hydrogen production from the hydrolysis of dimethylamine-borane and sodium borohydride. Energy, 2016,99:129-135.
[22]	LUO C, FU F Y, YANG X J , et al. Highly efficient and selective Co@ZIF-8 nanocatalyst for hydrogen release from sodium borohydride hydrolysis. ChemCatChem, 2019,11(6):1643-1649.
[23]	MAHMOOD J, JUNG S M, KIM S J , et al.Cobalt oxide encapsulated in C₂N-h2D network polymer as a catalyst for hydrogen evolution. Chem. Mater., 2015,27(13):4860-4864.
[24]	LIN K Y A, CHANG H A, CHEN B J . Multi-functional MOF-derived magnetic carbon sponge. J. Mater. Chem. A, 2016,4(35):13611-13625.
[25]	GUO S Q, WU Q Q, SUN J , et al. Highly stable and controllable CoB/Ni-foam catalysts for hydrogen generation from alkaline NaBH₄ solution. Int. J. Hydrogen Energy, 2017,42(33):21063-21072.
[26]	CUI L, SUN X P, XU Y H , et al. Cobalt carbonate hydroxide nanowire array on Ti mesh: an efficient and robust 3D catalyst for on-demand hydrogen generation from alkaline NaBH₄ solution. Chem. Eur. J., 2016,22(42):14831-14835.
[27]	PATEL N, MIOTELLO A . Progress in Co-B related catalyst for hydrogen production by hydrolysis of boron-hydrides: a review and the perspectives to substitute noble metals. Int. J. Hydrogen Energy, 2015,40(3):1429-1464.
[28]	GUO M S, CHENG Y, YU Y N , et al. Ni-Co nanoparticles immobilized on a 3D Ni foam template as a highly efficient catalyst for borohydride electrooxidation in alkaline medium. Appl. Surf. Sci., 2017,416:439-445.
[29]	MARCHIONNI A, BEVILACQUA M, FILIPPI J , et al. High volume hydrogen production from the hydrolysis of sodium borohydride using a cobalt catalyst supported on a honeycomb matrix. J. Power Sources, 2015,299(20):391-397.
[30]	ZHUANG D W, DAI H B, ZHONG Y J , et al. A new reactivation method towards deactivation of honeycomb ceramic monolith supported cobalt-molybdenum-boron catalyst in hydrolysis of sodium borohydride. Int. J. Hydrogen Energy, 2015,40(30):9373-9381.
[31]	SAHINER N . Soft and flexible hydrogel templates of different sizes and various functionalities for metal nanoparticle preparation and their use in catalysis. Prog. Polym. Sci., 2013,38(9):1329-1356.
[32]	Ai L H, GAO X Y, JIANG J . In situ synthesis of cobalt stabilized on macroscopic biopolymer hydrogel as economical and recyclable catalyst for hydrogen generation from sodium borohydride hydrolysis. J. Power Sources, 2014,257(1):213-220.
[33]	PRASAD D, PATIL K N, CHAITRA C R , et al. Sulfonic acid functionalized PVA/PVDF composite hollow microcapsules: highly phenomenal & recyclable catalysts for sustainable hydrogen production. Appl. Surf. Sci., 2019,488:714-727.
[34]	LI Q M, CHEN Y B, LEE D J , et al. Preparation of Y-zeolite/CoCl₂ doped PVDF composite nanofiber and its application in hydrogen production. Energy, 2012,38(1):144-150.
[35]	ZHAO L W, LI Q, SU Y , et al. A novel enteromorpha based hydrogel for copper and nickel nanoparticle preparation and their use in hydrogen production as catalysts. Int. J. Hydrogen Energy, 2017,42(10):6746-6756.
[36]	SCHLESINGER H I, BROWN H C, FINHOLT A E . The preparation of sodium borohydride by the high temperature reaction of sodium hydride with borate esters. J. Am. Chem. Soc., 1953,75:205-209.
[37]	KOJIMA Y, HAGA T . Recycling process of sodium metaborate to sodium borohydride. Int. J. Hydrogen Energy, 2003,28:989-993.
[38]	LANG C G, JIA Y, LIU J W , et al. NaBH₄ regeneration from NaBO₂ by high-energy ball milling and its plausible mechanism.Int. J. Hydrogen Energy, 2017,42(18):13127-13135.
[39]	OUYANG L Z, CHEN W, LIU J W , et al.Enhancing the regeneration process of consumed NaBH₄ for hydrogen storage. Adv. Energy Mater., 2017,7(19):1700299.
[40]	SANYAL U, DEMIRCI U B, JAGIRDAR B R , et al. Hydrolysis of ammonia borane as a hydrogen source: fundamental issues and potential solutions towards implementation. ChemSusChem, 2011,4(12):1731-1739.
[41]	DEMIRCI U B . Ammonia borane, a material with exceptional properties for chemical hydrogen storage. Int. J. Hydrogen Energy, 2017,42(15):9978-10013.
[42]	WANG L B, LI H L, ZHANG W B , et al. Supported rhodium catalysts for ammonia-borane hydrolysis: dependence of the catalytic activity on the highest occupied state of the single rhodium atoms. Angew. Chemie. Int. Ed., 2017,56(17):4712-4718.
[43]	HOU C C, LI Q, WANG C J , et al. Ternary Ni-Co-P to boost the hydrolytic dehydrogenation of ammonia-borane. Energy & Environ. Sci., 2017,10(8):1770-1776.
[44]	PIGHIN S A, URRETAVIZCAYA G, BOBET J L . Nanostructured Mg for hydrogen production by hydrolysis obtained by MgH₂ milling and dehydriding. J. Alloys Compd., 2020,827:154000.
[45]	TAN Z H, OUYANG L Z, LIU J W , et al. Hydrogen generation by hydrolysis of Mg-Mg₂Si composite and enhanced kinetics performance from introducing of MgCl₂ and Si. Int. J. Hydrogen Energy, 2018,43(5):2903-2912.
[46]	JIANG J, OUYANG L Z, WANG H , et al. Controllable hydrolysis performance of MgLi alloys and their hydrides. ChemPhysChem, 2019,20(10):1316-1324.
[47]	GAN D Y, LIU Y N, ZHANG J G , et al. Kinetic performance of hydrogen generation enhanced by AlCl₃ via hydrolysis of MgH₂ prepared by hydriding combustion synthesis. Int. J. Hydrogen Energy, 2018,43(22):10232-10239.
[48]	ZHAO Z L, ZHU Y F, LI L Q . Efficient catalysis by MgCl₂ in hydrogen generation via hydrolysis of Mg-based hydride prepared by hydriding combustion synthesis. Chem. Comm., 2012,48(44):5509-5511.
[49]	ZHENG J, YANG D C, LI W , et al. Promoting H₂ generation from the reaction of Mg nanoparticles and water using cations. Chem. Comm., 2013,49(82):9437-9439.
[50]	HUANG X N, GAO T, PAN X L , et al. A review: feasibility of hydrogen generation from the reaction between aluminum and water for fuel cell applications. J. Power Sources, 2013,229:133-140.
[51]	DENG Z Y, FERREIRA J M F, TANAKA Y, et al. Physicochemical mechanism for the continuous reaction of γ-Al₂O₃-modified aluminum powder with water. J. Am. Chem. Soc., 2007,90(5):1521-1526.
[52]	LIU Y A, WANG X H, LIU H Z , et al. Improved hydrogen generation from the hydrolysis of aluminum ball milled with hydride. Energy, 2014,72:421-426.
[53]	FAN M Q, WANG Y, TIAN G L , et al. Hydrolysis of AlLi/NaBH₄ system promoted by Co powder with different particle size and amount as synergistic hydrogen generation for portable fuel cell. Int. J. Hydrogen Energy, 2013,38(25):10857-10863.
[54]	FAN M Q, LIU S, SUN W Q , et al. Controllable hydrogen generation and hydrolysis mechanism of AlLi/NaBH₄ system activated by CoCl₂ solution. Renew. Energ., 2012,46:203-209.
[55]	FAN M Q, LIU S, SUN W Q , et al.Hydrogen generation from Al/NaBH₄ hydrolysis promoted by Li-NiCl₂ additives. Int. J. Hydrogen Energy, 2011,36(24):15673-15680.
[56]	FAN M Q, WANG Y, TANG R , et al. Hydrogen generation from Al/NaBH₄ hydrolysis promoted by Co nanoparticles and NaAlO₂ solution. Renew. Energ., 2013,60:637-642.
[57]	HUANG X N, LV C J, HUANG Y X , et al. Effects of amalgam on hydrogen generation by hydrolysis of aluminum with water. Int. J. Hydrogen Energy, 2011,36(23):15119-15124.
[58]	REN R M, ORTIZ A L, MARKMAITREE T , et al. Stability of lithium hydride in argon and air. J. Phys. Chem. B, 2006,110(21):10567-10575.
[59]	DUAN C W, HU L X, MA J L . Ionic liquids as an efficient medium for the mechanochemical synthesis of α-AlH₃ nano-composites. J. Mater. Chem. A, 2018,6(15):6309-6318.
[60]	CHEN J, FU H, XIONG Y F , et al.MgCl₂ promoted hydrolysis of MgH₂ nanoparticles for highly efficient H₂ generation.Nano Energy, 2014,10:337-343.
[61]	HUANG M H, OUYANG L Z, WANG H , et al. Hydrogen generation by hydrolysis of MgH₂ and enhanced kinetics performance of ammonium chloride introducing. Int. J. Hydrogen Energy, 2015,40(18):6145-6150.
[62]	TEGEL M, SCHÖNE S, KIEBACK B, et al. An efficient hydrolysis of MgH₂-based materials. Int. J. Hydrogen Energy, 2017,42(4):2167-2176.
[63]	LU C, MA Y L, LI F , et al.Visualization of fast “hydrogen pump” in core-shell nanostructured Mg@Pt through hydrogen-stabilized Mg₃Pt. J. Mater. Chem. A, 2019,7(24):14629-14637.
[64]	SIFER N, GARDNER K . An analysis of hydrogen production from ammonia hydride hydrogen generators for use in military fuel cell environments. J. Power Sources, 2004,132:135-138.

Material	Molar mass/(g·mol^-1)	Density/(g·cm^-3)	∆H^[6]/(kJ·mol^-1_H2)	C_M(H2)*/wt%	C_M(H2)(H₂O)^#/wt%	C_V(H2)^†/(g_H2·L^-1)
NaBH₄	37.83	1.07	-47.15	21.32	7.34	228.09
NH₃·BH₃	30.86	0.78	-75.67	19.50	7.05	151.60
Mg	24.31	1.74	-352.90	8.29	3.34	144.16
Ca	40.08	1.55	-413.60	5.03	2.65	77.97
Al	26.98	2.70	-284.40	11.21	3.73	302.62
LiH	7.95	0.82	-111.20	25.36	7.06	207.97
NaH	24.00	1.40	-83.70	8.40	4.80	117.60
KH	40.02	1.43	-81.10	5.04	3.47	72.04
MgH₂	26.32	1.45	-138.80	15.32	6.47	222.12
CaH₂	42.09	1.70	-116.05	9.58	5.16	162.84
AlH₃	30.00	1.49	-126.87	20.16	7.20	300.34

Material	Molar mass/(g·mol^-1)	Density/(g·cm^-3)	∆H^[6]/(kJ·mol^-1_H2)	C_M(H2)*/wt%	C_M(H2)(H₂O)^#/wt%	C_V(H2)^†/(g_H2·L^-1)
NaBH₄	37.83	1.07	-47.15	21.32	7.34	228.09
NH₃·BH₃	30.86	0.78	-75.67	19.50	7.05	151.60
Mg	24.31	1.74	-352.90	8.29	3.34	144.16
Ca	40.08	1.55	-413.60	5.03	2.65	77.97
Al	26.98	2.70	-284.40	11.21	3.73	302.62
LiH	7.95	0.82	-111.20	25.36	7.06	207.97
NaH	24.00	1.40	-83.70	8.40	4.80	117.60
KH	40.02	1.43	-81.10	5.04	3.47	72.04
MgH₂	26.32	1.45	-138.80	15.32	6.47	222.12
CaH₂	42.09	1.70	-116.05	9.58	5.16	162.84
AlH₃	30.00	1.49	-126.87	20.16	7.20	300.34

Performance	Metal	Metal hydride	Borohydride
Hydrogen capacity of hydrolysis	Low	High	High (affected by dissolution)
Cost	Low	High	High
Complexities of system	Complex	Complex	Relatively simple
Degree of study on hydrolysis	Modest	Rare	Extensive
Storage condition	H₂O & O₂ free	H₂O & O₂ free	H₂O free

Performance	Metal	Metal hydride	Borohydride
Hydrogen capacity of hydrolysis	Low	High	High (affected by dissolution)
Cost	Low	High	High
Complexities of system	Complex	Complex	Relatively simple
Degree of study on hydrolysis	Modest	Rare	Extensive
Storage condition	H₂O & O₂ free	H₂O & O₂ free	H₂O free

Prices	Mg	Al	MgH₂	LiH	NaBH₄	NH₃·BH₃
Price of material /(yuan∙kg^-1)	120	80	800	4300	700	60000
Price of H₂ /(yuan∙kg^-1)	1450	710	5200	16960	3280	307700