海绵负载Co-B催化剂催化硼氢化钠水解制氢性能研究

doi:10.19964/j.issn.1006-4990.2023-0137

摘要/Abstract

摘要：

采用浸渍-还原法制备了聚乙烯醇缩甲醛（PVFM）海绵负载的Co-B/PVFM催化剂，考察了硼氢化钠浓度、氢氧化钠浓度及反应温度对其催化硼氢化钠水解制氢性能的影响。结果表明，制氢速率随硼氢化钠的浓度及反应温度的升高而增大，随氢氧化钠浓度的升高呈先增大后减小的趋势，反应活化能为29.02 kJ/mol。在连续式反应器中Co-B/PVFM催化剂催化硼氢化钠水解制氢速率可达12.0 L/min，可为1 kW的燃料电池供应氢气，并且催化活性持续100 min没有发生衰减，表现出极大的实际应用潜力。

关键词: Co-B催化剂, 硼氢化钠, 水解, 制氢

Abstract:

Polyvinyl formal（PVFM） sponge supported Co-B/PVFM catalyst was prepared by impregnation-reduction method，and the effects of sodium borohydride concentration，sodium hydroxide concentration and reaction temperature on the catalytic hydrolysis of sodium borohydride were investigated.The results showed that the hydrogen production rate was increased with the increase of sodium borohydride concentration and reaction temperature，and with the increase of sodium hydroxide concentration，the hydrogen production rate was firstly increased and then decreased.The activation energy of the hydrolysis reaction was 29.02 kJ/mol.In the continuous reactor，Co-B/PVFM catalyst could catalyze hydrolysis of sodium borohydride to produce hydrogen at a rate of 12.0 L/min，which could supply hydrogen for 1 kW fuel cell，and the catalytic activity did not decay for 100 min，showing great practical application potential.

Key words: Co-B catalyst, NaBH₄, hydrolysis, hydrogen generation

中图分类号:

TQ138.12

刘啸, 谢镭, 邓霁峰, 时雨, 郑捷. 海绵负载Co-B催化剂催化硼氢化钠水解制氢性能研究[J]. 无机盐工业, 2023, 55(12): 146-151.

LIU Xiao, XIE Lei, DENG Jifeng, SHI Yu, ZHENG Jie. Study on performance of sponge supported Co-B catalyst for hydrogen generation from catalytic hydrolysis of sodium borohydride[J]. Inorganic Chemicals Industry, 2023, 55(12): 146-151.

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参考文献 22

1	UZUNDURUKAN A， DEVRIM Y. Hydrogen generation from sodium borohydride hydrolysis by multi-walled carbon nanotube supported platinum catalyst：A kinetic study［J］. International Journal of Hydrogen Energy， 2019， 44（33）：17586-17594. doi: 10.1016/j.ijhydene.2019.04.188
2	AVCı HANSU T. A novel and active ruthenium based supported multiwalled carbon nanotube tungsten nanoalloy catalyst for sodium borohydride hydrolysis［J］. International Journal of Hydrogen Energy， 2023， 48（18）：6788-6797. doi: 10.1016/j.ijhydene.2022.04.269
3	SINGH S K， IIZUKA Y， XU Qiang. Nickel-palladium nanoparticle catalyzed hydrogen generation from hydrous hydrazine for chemical hydrogen storage［J］. International Journal of Hydrogen Energy， 2011， 36（18）：11794-11801. doi: 10.1016/j.ijhydene.2011.06.069
4	SCHLESINGER H I， BROWN H C， FINHOLT A E， et al. Sodium borohydride，its hydrolysis and its use as a reducing agent and in the generation of Hydrogen¹ ［J］. Journal of the American Chemical Society， 1953， 75（1）：215-219. doi: 10.1021/ja01097a057
5	SHEN Jiale， XU Danyun， JI Jian， et al. In situ evolved defective TiO₂ as robust support for CoB-catalyzed hydrolysis of NaBH₄ ［J］. International Journal of Hydrogen Energy， 2023， 48（3）：1001-1010. doi: 10.1016/j.ijhydene.2022.09.257
6	LARICHEV Y V， NETSKINA O V， KOMOVA O V， et al. Comparative XPS study of Rh/Al₂O₃ and Rh/TiO₂ as catalysts for NaBH₄ hydrolysis［J］. International Journal of Hydrogen Energy， 2010， 35（13）：6501-6507. doi: 10.1016/j.ijhydene.2010.04.048
7	YANG Feiyan， RUAN Junfeng， LI Tianshuo， et al. Hydrolysis of sodium borohydride using a highly stable catalyst of ruthenium nanoparticles supported by cobalt-nickel hydroxide-coated nickel foam［J］. Journal of Alloys and Compounds， 2022， 926：166902. doi: 10.1016/j.jallcom.2022.166902
8	HUANG Yueqiang， WANG Yi， ZHAO Ruixiong， et al. Accurately measuring the hydrogen generation rate for hydrolysis of sodium borohydride on multiwalled carbon nanotubes/Co-B catalysts［J］. International Journal of Hydrogen Energy， 2008， 33（23）：7110-7115. doi: 10.1016/j.ijhydene.2008.09.046
9	LEI Wang， JIN Huiming， GAO Jichen， et al. Efficient hydrogen generation from the NaBH₄ hydrolysis by amorphous Co-Mo-B alloy supported on reduced graphene oxide［J］. Journal of Materials Research， 2021， 36（20）：4154-4168. doi: 10.1557/s43578-021-00374-4
10	SHI Limin， XIE Wei， JIAN Zengyun， et al. Graphene modified Co-B catalysts for rapid hydrogen production from NaBH₄ hydrolysis［J］. International Journal of Hydrogen Energy， 2019， 44（33）：17954-17962. doi: 10.1016/j.ijhydene.2019.05.104
11	HOLBROOK K A， TWIST P J. Hydrolysis of the borohydride ion catalysed by metal-boron alloys［J］. Journal of the Chemical Society A：Inorganic，Physical，Theoretical， 1971. Doi：10.1039/j19710000890 .
12	MUIR S S， YAO Xiangdong. Progress in sodium borohydride as a hydrogen storage material：Development of hydrolysis catalysts and reaction systems［J］. International Journal of Hydrogen Energy， 2011， 36（10）：5983-5997. doi: 10.1016/j.ijhydene.2011.02.032
13	陈悦蓉，靳惠明，俞亮，等. Cr掺杂的Co-B非晶态合金的制备及催化硼氢化钠水解制氢［J］. 无机盐工业， 2020， 52（2）：91-96.
	CHEN Yuerong， JIN Huiming， YU Liang， et al. Preparation of amorphous Co-Cr-B and catalytic sodium borohydride hydrolysis for hydrogen generation［J］. Inorganic Chemicals Industry， 2020， 52（2）：91-96.
14	NIU Weiling， REN Dengbo， HAN Yuanyuan， et al. Optimizing preparation of carbon supported cobalt catalyst for hydrogen generation from NaBH₄ hydrolysis［J］. Journal of Alloys and Compounds， 2012， 543：159-166. doi: 10.1016/j.jallcom.2012.07.099
15	JIA Xinlei， SANG Zhen， SUN Lixian， et al. Graphene-modified Co-B-P catalysts for hydrogen generation from sodium borohydride hydrolysis［J］. Nanomaterials， 2022， 12（16）：2732. doi: 10.3390/nano12162732
16	ZHU Jie， LI Rong， NIU Weiling， et al. Fast hydrogen generation from NaBH₄ hydrolysis catalyzed by carbon aerogels supported cobalt nanoparticles［J］. International Journal of Hydrogen Energy， 2013， 38（25）：10864-10870. doi: 10.1016/j.ijhydene.2013.01.150
17	WANG Weili， ZHAO Yanchun， CHEN Duhong， et al. Promoted Mo incorporated Co-Ru-B catalyst for fast hydrolysis of NaBH₄ in alkaline solutions［J］. International Journal of Hydrogen Energy， 2014， 39（28）：16202-16211. doi: 10.1016/j.ijhydene.2013.12.093
18	RAKAP M， KALU E E， ÖZKAR S. Cobalt-nickel-phosphorus supported on Pd-activated TiO₂（Co-Ni-P/Pd-TiO₂） as cost-effective and reusable catalyst for hydrogen generation from hydrolysis of alkaline sodium borohydride solution［J］. Journal of Alloys and Compounds， 2011， 509（25）：7016-7021. doi: 10.1016/j.jallcom.2011.04.023
19	WEI Yongsheng， WANG Ru， MENG Liyuan， et al. Hydrogen generation from alkaline NaBH₄ solution using a dandelion-like Co-Mo-B catalyst supported on carbon cloth［J］. International Journal of Hydrogen Energy， 2017， 42（15）：9945-9951. doi: 10.1016/j.ijhydene.2016.12.130
20	KıPÇAK İ， KALPAZAN E. Preparation of CoB catalysts supported on raw and Na-exchanged bentonite clays and their application in hydrogen generation from the hydrolysis of NaBH₄ ［J］. International Journal of Hydrogen Energy， 2020， 45（50）：26434-26444. doi: 10.1016/j.ijhydene.2020.03.230
21	LI Mingbin， GUAN Shuyan， AN Lulu， et al. Protection and confinement effect of carbon on Co/Co _x O _y nano-catalyst for efficient NaBH₄ hydrolysis［J］. International Journal of Hydrogen Energy， 2022， 47（46）：20185-20193. doi: 10.1016/j.ijhydene.2022.04.139
22	CHEN Yuerong， JIN Huiming. Fabrication of amorphous Co-Cr-B and catalytic sodium borohydride hydrolysis for hydrogen generation［J］. Journal of Materials Research， 2020， 35（3）：281-288. doi: 10.1557/jmr.2019.411

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