Citation: LI Zhong, WANG Li-na, WANG Gui-xue, XIE Guang-wen. Hydrogen generation from the hydrolysis of sodium borohydride solution over the supported Ni-Co-P/CNFs catalysts[J]. Journal of Fuel Chemistry and Technology, ;2015, 43(3): 372-378. shu

Hydrogen generation from the hydrolysis of sodium borohydride solution over the supported Ni-Co-P/CNFs catalysts

1.
College of Material Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Corresponding author: XIE Guang-wen,
Received Date: 13 August 2014

Fund Project: 山东省自然科学基金(ZR2011EMM005)。 (ZR2011EMM005)

The Ni-Co-P catalysts supported on carbon nanofibers (CNFs) were prepared via electroless deposition; the mass fractions of nickel, cobalt and phosphorus in Ni-Co-P layer are 13.30%, 82.25% and 4.45%, respectively, as determined by ICP-AES. The effects of catalyst amount, sodium borohydride and sodium hydroxide concentrations and reaction temperature on the rate of hydrogen generation in the hydrolysis of alkaline NaBH₄ solution were investigated. The results indicated that the rate of hydrogen generation is proportional to the used catalyst amount; a maximum hydrogen generation rate of 18.044 L/(g·min) is achieved at 45 ℃ by hydrolysis of 2.5% NaBH₄ solution containing 5% NaOH and 7.5 g/L Ni-Co-P/CNFs catalyst with a Ni-Co-P loading of 18.127%. Moreover, a kinetic study shows that the activation energy for the hydrolysis of alkaline NaBH₄ solution under those conditions is 51.57 kJ/mol.
- electroless deposition,
- nickel-cobalt-phosphorus,
- carbon nanofibers,
- sodium borohydride,
- hydrogen generation
1. [1]
  [1] HOFFERT M. Governments must pay for clean-energy innovation[J]. Nature, 2011, 472: 137-137.
2. [2]
  [2] SCHLAPBACH L, ZVTTEL A. Hydrogen-storage materials for mobile applications[J]. Nature, 2001, 414: 353-358.
3. [3]
  [3] 王威燕, 杨运泉, 罗和安, 彭会左, 张小哲, 胡韬. Ni-Co-W-B非晶态催化剂的制备及其加氢脱氧性能[J]. 催化学报, 2011, 32(10): 1645-1650.(WANG Wei-yan, YANG Yun-quan, LUO He-an, PENG Hui-zuo, ZHANG Xiao-zhe, HU Tao. Preparation and hydrodexy genation properities of Ni-Co-W-B amorphous catalyst[J]. Chin J Catal, 2011, 32(10): 1645-1650.)
4. [4]
  [4] SANTOS D M F, SEQUEIRA C A C. Sodium borohydride as a fuel for the future[J]. Renew Sust Energy Rev, 2011, 15(8): 3980-4001.
5. [5]
  [5] 王晓磊, 邓文义, 于伟超, 苏亚欣. 污泥微波高温热解条件下富氢气体生成特征研究[J]. 燃料化学学报, 2013, 41(2): 243-250.(WANG Xiao-lei, DENG Wen-yi, YU Wei-chao, SU Ya-xin. Hydrogen-rich gas formation characteristics during microwave-induced high temperature pyrolysis of sewage sludge[J]. J Fuel Chem Technol, 2013, 41(2): 243-250.)
6. [6]
  [6] HUANG Z M, SU A, LIU Y C. Hydrogen generator system using Ru catalyst for PEMFC (proton exchange membrane fuel cell) applications[J]. Energy, 2013, 51: 230-236.
7. [7]
  [7] YU L, MATTHEWS M A. A reactor model for hydrogen generation from sodium borohydride and water vapor[J]. Int J Hydrogen Energy, 2014, 39(8): 3830-3836.
8. [8]
  [8] JENA P. Materials for hydrogen storage: Past, present, and future[J]. J Phys Chen Lett, 2011, 2(3): 206-211.
9. [9]
  [9] KWON H J, KIM J, CHO S W, YOO J H, ROH K M, KIM W. The effect of Sc addition on the hydrogen storage capacity of Ti_0.32Cr_0.43V_0.25 alloy[J]. Int J Hydrogen Energy, 2014, 39(20): 10600-10605.
10. [10]
  [10] ZHAO Y P, DING L Z, ZHONG T S, YUAN H T, JIAO L F. Hydrogen storage behavior of 2LiBH₄/MgH₂ composites improved by the catalysis of CoNiB nanoparticles[J]. Int J Hydrogen Energy, 2014, 39(21): 11055-11060.
11. [11]
  [11] ZHU X L, PEI L C, ZHAO Z Y, LIU B Z, HAN S M, WANG R B. The catalysis mechanism of La hydrides on hydrogen storage properties of MgH₂ in MgH₂ + x wt.% LaH₃(x= 0, 10, 20, and 30) composites[J]. J Alloy Compd, 2013, 577: 64-69.
12. [12]
  [12] LEE J K, ANN H H, YI Y, LEE K W, UHM S, LEE J. A stable Ni-B catalyst in hydrogen generation via NaBH₄ hydrolysis[J]. Catal Commun, 2011, 16(1): 120-123.
13. [13]
  [13] ZHENG X P, ZHENG J J, MA Q H, LIU S L, XIN F, LIN X B, XIAO G. Study on dehydrogenation properties of the LiAlH₄-NH₄Cl system[J]. J Alloy Compd, 2013, 551: 508-511.
14. [14]
  [14] VARIN R A, ZBRONIEC L. Decomposition behavior of unmilled and ball milled lithium alanate (LiAlH₄) including long-term storage and moisture effects[J]. J Alloy Compd, 2010, 504(1): 89-101.
15. [15]
  [15] EASTON D S, SCHNEIBEL J H, SPEAKMAN S A. Factors affecting hydrogen release from lithium alanate (LiAlH₄)[J]. J Alloy Compd, 2005, 398(1/2): 245-248.
16. [16]
  [16] MOHAJERI N, TRAISSI A, ADEBIYI O. Hydrolytic cleavage of ammonia-boranecomplex for hydrogen production[J]. J Power Sources, 2007, 167(2): 482-485.
17. [17]
  [17] KUMAR R H, KE X Z, ZHANG J Z, LIN Z J, VOGEL S C, HARTL M, SINOGEIKIN S, DAEMEN L, CORNELIUS A L, CHEN C F, ZHAO Y S. Pressure induced structural changes in the potential hydrogen storage compound ammonia borane: A combined X-ray, neutron and theoretical investigation[J]. Chem phys lett, 2010, 495(4/6): 203-207.
18. [18]
  [18] FIGEN A K, PISKIN M B, COSKUNER B, IMAMOGLU V. Synthesis, structural characterization, and hydrolysis of Ammonia Borane (NH₃BH₃) as a hydrogen storage carrier[J]. Int J Hydrogen Energy, 2013, 38(36): 16215-16228.
19. [19]
  [19] WU C, BAI Y, LIU D X, WU F, PANG M L, YI B L. Ni-Co-B catalyst-promoted hydrogen generation by hydrolyzing NaBH₄ solution for in situ hydrogen supply of portable fuel cells[J]. Catal Today, 2011, 170(1): 33-39.
20. [20]
  [20] WU C, BAI Y, WU F, YI B L, ZHANG H M. Highly active cobalt-based catalysts in situ prepared from CoX₂ (X = Cl^-, NO₃^-) and used for promoting hydrogen generation from NaBH₄ solution[J]. Int J Hydrogen Energy, 2010, 35(7): 2675-2679.
21. [21]
  [21] XU D Y, ZHANG H M, YE W. Hydrogen generation from hydrolysis of alkaline sodium borohydride solution using Pt/C catalyst[J]. Catal Commun, 2007, 8(11): 1767-1771.
22. [22]
  [22] DCMIRCI U B, GARN F. Ru-based bimetallic alloys for hydrogen generation by hydrolysis of sodium tetrahydroborate[J]. J Alloy Compd, 2008, 463(1/2): 107-111.
23. [23]
  [23] ALONSO R P, SICURELLI A, CALLONE E, GARTURAN G, RAJ R. A picoscale catalyst for hydrogen generation from NaBH₄ for fuel cells[J]. J Power Sources, 2007, 165(1): 315-323.
24. [24]
  [24] BAYDAROGLU F, ÖZDEMIR E, HASIMOGLU A. An effective synthesis route for improving the catalytic activity of carbon-supported Co-B catalyst for hydrogen generation through hydrolysis of NaBH₄[J]. Int J Hydrogen Energy, 2014, 39(3): 1516-1522.
25. [25]
  [25] OCON J D, TUAN T N, YI Y, LEON R L, LEE J K, LEE J. Ultrafast and stable hydrogen generation from sodium borohydride in methanol and water over Fe-B nanoparticles[J]. J Power Sources, 2013, 243: 444-450.
26. [26]
  [26] ZHANG X W, ZHAO J Z, CHENG F Y, LIANG J, TAO Z L, CHEN J. Electroless-deposited Co-P catalysts for hydrogen generation from alkaline NaBH₄ solution[J]. Int J Hydrogen Energy, 2010, 35(15): 8363-8369.
27. [27]
  [27] DAI H B, LIANG Y, WANG P, YAO X D, RUFFORD T, LU M, CHENG H M. High-performance cobalt-tungsten-boron catalyst supported on Ni foam for hydrogen generation from alkaline sodium borohydride sodium[J]. Int J Hydrogen Energy, 2008, 33(16): 4405-4412.
28. [28]
  [28] ZHU J, LI R, NIU W L, WU Y J, GOU X L. Facile hydrogen generation using colloidal carbon supported cobalt to catalyze hydrolysis of sodium borohydride[J]. J Power Sources, 2012, 211(1): 33-39.
29. [29]
  [29] LI Z, LI H L, WANG L N, LIU T Y, ZHANG T, WANG G X, XIE G W. Hydrogen generation from catalytic hydrolysis of sodium borohydride solution using supported amorphous alloy catalysts (Ni-Co-P/ γ-Al₂O₃)[J]. Int J Hydrogen Energy, 2014, 39(27): 14935-14941.
30. [30]
  [30] KREEVOY M M, JACOBSON R W. The rate of decomposition of NaBH₄ in basic aqueous solution[J]. Ventron Alembic, 1979, 15: 2-3.
31. [31]
  [31] ZHAO J Z, MA H, CHEN J. Improved hydrogen generation from alkaline NaBH₄ solution using cabon-supported Co-B as catalysts[J]. Int J Hydrogen Energy, 2007, 32(18): 4711-4716.
32. [32]
  [32] LIU Z L, GUO B, CHAN S H, TANG E H, HONG L. Pt and Ru dispersed on LiCoO₂ for hydrogen generation from sodium borohydridesolutions[J]. J Power Sources, 2008, 176(1): 306-311.
33. [33]
  [33] LIU C H, CHEN B H, HSUEH C L, KU J R, JENG M S, TASU F. Hydrogen generation from hydrolysis of sodium borohydride using Ni-Runanocomposite as catalysts[J]. Int J Hydrogen Energy, 2009, 34(5): 2153-2163.
34. [34]
  [34] VERNEKAR A A, BUGDE S T, TILVE S. Sustainable hydrogen production by catalytic hydrolysis of alkaline sodium borohydriable Co-Co₂B and Ni-Ni₃B nanocomposites[J]. Int J Hydrogen Energy, 2012, 37(1): 327-334.
35. [35]
  [35] GUO Y P, FENG Q H, MA J T. The hydrogen generation from alkaline NaBH4 solution by using electroplated amorphous Co-Ni-P film catalysts[J]. Appl Surf Sci, 2013, 273: 253-256.
36. [36]
  [36] NIE M, ZOU Y C, HUANG Y M, WANG J Q. Ni-Fe-B catalysts for NaBH₄ hydrolysis[J]. Int J Hydrogen Energy, 2012, 37(2): 1568-1576.
37. [37]
  [37] PATEL N, FERNANDES R, BAZZANELLA N, MIOTELLO A. Enhanced hydrogen production by hydrolysis of NaBH₄ using "Co-B nanoparticles supported on carbon film" catalyst synthesized by pulsed laser deposition[J]. Catal Today, 2011, 170(1): 20-26.
38. [38]
  [38] ZHU J, LI R, NIU W L, WU Y J, GOU X L. Fast hydrogen generation from NaBH₄ hydrolysis catalyzed by carbon aerogels supported cobalt nanoparticles[J]. Int J Hydrogen Energy, 2013, 38(25): 10864-10870.
39. [39]
  [39] 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 borohydridesolution[J]. J Alloy Compd, 2011, 509(25): 7010-7021.
40. [40]
  [40] BILEN M, GVRVM, AKANYIRIM. Role of NaCl in NaBH₄ production and its hydrolysis[J]. Energy Convers Manage, 2013, 72: 134-140.
1. [1]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
2. [2]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
3. [3]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Corrosion inhibition of nickel-cobalt-phosphide in water by coating TiO₂ layer. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 365-384. doi: 10.11862/CJIC.20240063
4. [4]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
5. [5]
  Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce₄^ⅢCe₆^Ⅳ(μ₃-O)₄(μ₄-O)₄(acac)₁₄(CH₃O)₆]·2CH₃OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342
6. [6]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
7. [7]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
8. [8]
  Zhicheng JU , Wenxuan FU , Baoyan WANG , Ao LUO , Jiangmin JIANG , Yueli SHI , Yongli CUI . MOF-derived nickel-cobalt bimetallic sulfide microspheres coated by carbon: Preparation and long cycling performance for sodium storage. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 661-674. doi: 10.11862/CJIC.20240363
9. [9]
  Wuxin Bai , Qianqian Zhou , Zhenjie Lu , Ye Song , Yongsheng Fu . Co-Ni Bimetallic Zeolitic Imidazolate Frameworks Supported on Carbon Cloth as Free-Standing Electrode for Highly Efficient Oxygen Evolution. Acta Physico-Chimica Sinica, 2024, 40(3): 2305041-0. doi: 10.3866/PKU.WHXB202305041
10. [10]
  Juan WANG , Zhongqiu WANG , Qin SHANG , Guohong WANG , Jinmao LI . NiS and Pt as dual co-catalysts for the enhanced photocatalytic H₂ production activity of BaTiO₃ nanofibers. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1719-1730. doi: 10.11862/CJIC.20240102
11. [11]
  Xiaojing Tian , Zhichun Huang , Qingsong Zhang , Xu Wang , Ning Yang , Nanping Deng . PNIPAm Thermo-Responsive Nanofibers Mats: Morphological Stability and Response Behavior under Cross-Linking. Acta Physico-Chimica Sinica, 2024, 40(4): 2304037-0. doi: 10.3866/PKU.WHXB202304037
12. [12]
  Jun Huang , Pengfei Nie , Yongchao Lu , Jiayang Li , Yiwen Wang , Jianyun Liu . 丝光沸石负载自支撑氮掺杂多孔碳纳米纤维电容器及高效选择性去除硬度离子. Acta Physico-Chimica Sinica, 2025, 41(7): 100066-0. doi: 10.1016/j.actphy.2025.100066
13. [13]
  Ying Li , Yushen Zhao , Kai Chen , Xu Liu , Tingfeng Yi , Li-Feng Chen . Rational Design of Cross-Linked N-Doped C-Sn Nanofibers as Free-Standing Electrodes towards High-Performance Li-Ion Battery Anodes. Acta Physico-Chimica Sinica, 2024, 40(3): 2305007-0. doi: 10.3866/PKU.WHXB202305007
14. [14]
  Bizhu Shao , Huijun Dong , Yunnan Gong , Jianhua Mei , Fengshi Cai , Jinbiao Liu , Dichang Zhong , Tongbu Lu . Metal-Organic Framework-Derived Nickel Nanoparticles for Efficient CO₂ Electroreduction in Wide Potential Windows. Acta Physico-Chimica Sinica, 2024, 40(4): 2305026-0. doi: 10.3866/PKU.WHXB202305026
15. [15]
  Linfeng Zhou , Yulin Zhang , Suhao Lin , Longguan Zhu . 2023年北京大学金秋营及第37届中国化学奥林匹克决赛磷团簇相关试题解析与拓展. University Chemistry, 2025, 40(8): 376-387. doi: 10.12461/PKU.DXHX202411030
16. [16]
  Jiahong ZHENG , Jiajun SHEN , Xin BAI . Preparation and electrochemical properties of nickel foam loaded NiMoO₄/NiMoS₄ composites. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 581-590. doi: 10.11862/CJIC.20230253
17. [17]
  Yuting ZHANG , Zunyi LIU , Ning LI , Dongqiang ZHANG , Shiling ZHAO , Yu ZHAO . Nickel vanadate anode material with high specific surface area through improved co-precipitation method: Preparation and electrochemical properties. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2163-2174. doi: 10.11862/CJIC.20240204
18. [18]
  Zhengli Hu , Jia Wang , Yi-Lun Ying , Shaochuang Liu , Hui Ma , Wenwei Zhang , Jianrong Zhang , Yi-Tao Long . Exploration of Ideological and Political Elements in the Development History of Nanopore Electrochemistry. University Chemistry, 2024, 39(8): 344-350. doi: 10.3866/PKU.DXHX202401072
19. [19]
  Jing Wang , Pingping Li , Yuehui Wang , Yifan Xiu , Bingqian Zhang , Shuwen Wang , Hongtao Gao . Treatment and Discharge Evaluation of Phosphorus-Containing Wastewater. University Chemistry, 2024, 39(5): 52-62. doi: 10.3866/PKU.DXHX202309097
20. [20]
  Yang Li , Jiachen Li , Daidi Fan . 二硫化钼纳米片的制备及其纳米酶性能探究——介绍一个大学化学综合实验. University Chemistry, 2025, 40(8): 233-240. doi: 10.12461/PKU.DXHX202410016

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(394)
HTML views(39)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142