Hydrogen generation from the hydrolysis of sodium borohydride solution over the supported Ni-Co-P/CNFs catalysts
-
摘要: 以纳米碳纤维(CNFs)为基体材料,采用化学镀法在CNFs表面沉积了Ni-Co-P催化剂。研究了催化剂用量,硼氢化钠、氢氧化钠浓度,温度等对碱性硼氢化钠溶液水解释氢的影响。电感耦合等离子体原子发射光谱法(ICP-AES)测试得出负载型Ni-Co-P催化剂含镍13.30%(质量分数,下同)、钴82.25%、磷4.45%。硼氢化钠水解释氢实验结果表明,产氢速率与催化剂用量呈线性关系。当温度为45 ℃、催化剂浓度为7.5 g/L、氢氧化钠浓度为5%、硼氢化钠浓度为2.5%时,氢气释放速率达到最大值18.044 L/(g·min)。通过对负载型催化剂Ni-Co-P/CNFs催化碱性硼氢化钠溶液释放氢气动力学研究表明,该催化剂的活化能Ea为51.57 kJ/mol。Abstract: 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.
-
HOFFERT M. Governments must pay for clean-energy innovation[J]. Nature, 2011, 472: 137-137. SCHLAPBACH L, ZVTTEL A. Hydrogen-storage materials for mobile applications[J]. Nature, 2001, 414: 353-358. 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.) 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. 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.) 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. 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. JENA P. Materials for hydrogen storage: Past, present, and future[J]. J Phys Chen Lett, 2011, 2(3): 206-211. 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 Ti0.32Cr0.43V0.25 alloy[J]. Int J Hydrogen Energy, 2014, 39(20): 10600-10605. 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. 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. 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. 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. 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. 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. MOHAJERI N, TRAISSI A, ADEBIYI O. Hydrolytic cleavage of ammonia-boranecomplex for hydrogen production[J]. J Power Sources, 2007, 167(2): 482-485. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. KREEVOY M M, JACOBSON R W. The rate of decomposition of NaBH4 in basic aqueous solution[J]. Ventron Alembic, 1979, 15: 2-3. 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. 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. 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. 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. 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. 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. 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. 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. 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. BILEN M, GVRVM, AKANYIRIM. Role of NaCl in NaBH4 production and its hydrolysis[J]. Energy Convers Manage, 2013, 72: 134-140.
点击查看大图
计量
- 文章访问数: 408
- HTML全文浏览量: 13
- PDF下载量: 484
- 被引次数: 0