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

doi:10.11962/1006-4990.2019-0135

摘要/Abstract

摘要：

采用化学还原法制备了三元非晶态Co-Cr-B纳米催化剂。采用透射电镜（TEM）、扫描电镜（SEM）、X射线衍射仪（XRD）等测试方法对催化剂的形貌、结构、成分做了表征。通过排水法进行NaBH₄溶液水解产氢反应,测量了催化剂的催化性能。结果表明,当掺杂少量的Cr时,催化剂的粒径明显减小,比表面积明显增大,催化剂的性能提高。过量的Cr会导致出现过多的氧化物和Cr ³⁺,覆盖了催化剂表面活性位点,降低催化剂的性能。当Cr与Co物质的量比为0.005时,催化剂性能最佳。与纯Co-B相比,其对硼氢化钠水解产氢速率提高了2倍。此外,研究了催化剂用量、NaBH₄浓度、反应温度、NaOH浓度等因素对NaBH₄溶液水解产氢反应的影响。

关键词: 非晶态催化剂, Co-Cr-B, 硼氢化钠水解

Abstract:

Co-Cr-B amorphous catalysts were synthesized by chemical reduction method.The morphology,structure and composition of the catalyst were characterized by scanning electron microscopy,transmission electron microscopy and X-ray diffraction.The catalytic performance of the catalyst was measured by hydrogen generation from NaBH₄ solution hydrolysis. The results showed that the particle size of the catalyst was reduced with the addition of a small amount of Cr.The specific surface area increased significantly,and the performance of the catalyst was improved.However,excessive addition of Cr caused excessive oxides and Cr ³⁺,covering the surface active sites of the catalyst,which degraded the performance of the catalyst.When the amount-of-substance ratio of Cr to Co was 0.005,the catalyst property was optimal.It showed nearly 2 times higher H₂ generation rate than that of pure Co-B catalyst.In addition,the effect of catalyst quantities,NaBH₄ concentration,reaction temperature and NaOH concentration on the hydrogen generation from NaBH₄ solution hydrolysis were also studied.

Key words: amorphous catalyst, Co-Cr-B, sodium borohydride hydrolysis

中图分类号:

TQ136.1

陈悦蓉,靳惠明,俞亮,邵阳阳. 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,Shao Yangyang. Preparation of amorphous Co-Cr-B and catalytic sodium borohydride hydrolysis for hydrogen generation[J]. Inorganic Chemicals Industry, 2020, 52(2): 91-96.

图/表 9

图1

图 2

图3

图 4

图5

图6

图7

图8

图9

参考文献 25

[1]	Sandy T C E, Lloyd A C . Stopping climate change:The case for coal and hydroge[J]. International Journal of Hydrogen Energy, 2017,42(12):8406-8407.
[2]	Demirci U B, Miele P . Sodium borohydride versus ammonia borane,in hydrogen storage and direct fuel cell applications[J]. Energy & Environmental Science, 2009,2(6):627-637.
[3]	Liu B H, Li Z P . A review:Hydrogen generation from borohydride hydrolysis reaction[J]. Journal of Power Sources, 2009,187(2):527-534.
[4]	Amendola S C, Sharp-Goldman S L, Janjua M S , et al. An ultrasafe hydrogen generator:Aqueous,alkaline borohydride solutions and Rucatalyst[J]. Journal of Power Sources, 2000,85:186-189.
[5]	Kim K, Kim T, Lee K , et al. Fuel cell system with sodium borohydri-de as hydrogen source for unmanned aerial vehicles[J]. Journal of Power Sources, 2011,196:9069-9075.
[6]	Ke D, Tao Y, Li Y , et al. Kinetics study on hydrolytic dehydrogena-tion of alkaline sodium borohydride catalyzed by Mo-modified Co-Bnanoparticles[J]. International Journal of Hydrogen Energy, 2015,40:7308-7317.
[7]	Edla R, Gupta S, Patel N , et al. Enhanced H₂ production from hydro-lysis of sodium borohydride using Co₃O₄ nanoparticles assembled coatings prepared by pulsed laser deposition[J]. Applied Catalysis, 2016,515:1-9.
[8]	Liu C H, Kuo Y C, Chen B H , et al. Synjournal of solid-state NaBH₄/Co-based catalystcomposite for hydrogen storage through a high-energy ball-milling process[J]. International Journal of Hydrogen Energy, 2010,35(9):4027-4040.
[9]	Kim H J, Shin K, Kim H , et al. Hydrogen generation from aqueous acid-catalyzed hydrolysis of sodium borohydride[J]. International Journal of Hydrogen Energy, 2010,35(22):12239-12245.
[10]	Gencç A E, Kutl B . The catalytic effect of the Au(Ⅲ) and Pt(Ⅲ)surfaces to the sodium borohydride hydrolysis reaction mechanism:A DFT study[J]. International Journal of Hydrogen Energy, 2018,42(31):14347-14359.
[11]	Ezgi Keceli, Saim Ozkar . Ruthenium(Ⅲ) acetylacetonate:A homo-geneous catalyst in the hydrolysis of sodium borohydride[J]. Jo-urnal of Molecular Catalysis A:Chemical, 2008,286:87-91.
[12]	Dandan K, Yang T, Yuan L . Kinetics study on hydrolytic dehydro-genation of alkalinesodium borohydride catalyzed by Mo-modified Co-B nanoparticles[J]. International Journal of Hydrogen Energy, 2015,40:7308-7317.
[13]	Ömer Sahin, Dilek Kılınç, Cafer Saka . Bimetallic Co-Ni based co-mplex catalyst for hydrogen production by catalytic hydrolysis of sodium borohydride with an alternative approach[J]. Journal of the Energy Institute, 2016,89(4):617-626.
[14]	Fernandes R, Patel N, Miotello A . Hydrogen generation by hydroly-sis of alkaline NaBH₄ solution with Cr-promoted Co-B amorphous catalyst[J]. Applied Catalysis B:Environmental, 2009,92:68-74.
[15]	Patel N, Fernandes R, Miotello A . Promoting effect of transition metal-doped Co-B alloy catalysts for hydrogen production by hy-drolysis of alkaline NaBH₄ solution[J]. Journal of Catalysis, 2010,271:315-324.
[16]	Ding X L, Yuan X X, Jia C , et al. Hydrogen generation from cataly-tic hydrolysis of sodium borohydride solution using cobalt-copper-boride(Co-Cu-B) catalysts[J]. International Journal of Hydrogen Energy, 2010,35(20):11077-11084.
[17]	Fang J, Chen X, Liu B , et al. Liquid-phase chemoselective hydro-genation of 2-ethylanthraquinone over chromium-modified nano-sized amorphous Ni-B catalysts[J]. Journal of Catalysis, 2005,229:97-104.
[18]	Fernandes R, Patel N, Miotello A , et al. Studies on catalytic beha-vior of Co-Ni-B in hydrogen production by hydrolysis of NaBH₄[J]. Journal of Molecular Catalysis A:Chemical, 2009,298:1-6.
[19]	Liang Y, Wang P, Dai H B . Hydrogen bubbles dynamic template preparation of a porous Fe-Co-B/Ni foam catalyst for hydrogen generation from hydrolysis of alkaline sodium borohydride solu-tion[J]. Journal of Alloys and Compounds, 2010,491:359-365.
[20]	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.
[21]	Sibel Duman, Saim Ozkar . Ceria supported manganese(0) nanopa-rticle catalysts for hydrogen generation from the hydrolysis of sodi-um borohydride[J]. International Journal of Hydrogen Energy, 2018,43:15262-15274.
[22]	Vinokurov V, Stavitskaya A, Glotov A , et al. Halloysite nanotube-based cobalt mesocatalysts for hydrogen production from sodium borohydride[J]. Journal of Solid State Chemistry, 2018,268:182-189.
[23]	Chou C C, Hsieh C H, Chen B H . Hydrogen generation from cataly-tic hydrolysis of sodium borohydride using bimetallic Ni-Co nano-particles on reduced graphene oxide as catalysts[J]. Energy, 2015,90:1973-1982.
[24]	孙海杰, 陈凌霞, 张玉凤 , 等. 钴-硼/二氧化锆催化剂催化硼氢化钠水解制氢研究[J]. 无机盐工业, 2019,51(8):72-75.
[25]	Li Z, Li H L, Wang L N , et al. Hydrogen generation from catalytic hydrolysis of sodium borohydride solution using supported amorph-ous alloy catalysts(Ni-Co-P/γ-Al₂O₃)[J]. International Journal of Hydrogen Energy, 2014,39:14935-14941.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会