This paper reports kinetic investigation on dehydrogenation kinetics of magnesium hydride (MgH2) in aqueous solutions of cobalt chloride (CoCl2) under various conditions. For this aim, various CoCl2 solutions (2.5–10 wt%) as activator and hydrolysis temperatures (293–363 K) were tested for achieving active hydrogen production by breaking out passive surface. nucleation-growth and surface area approaches were used for investigation of dehydrogenation mechanism and samples characteristic features were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The optimum activator concentration was determined as 6.25 wt% CoCl2 with fastest hydrogen production rate 18.55 mL min−1 g−1 with complete conversion of MgH2 to Mg(OH)2 at room temperature. The kinetic and thermodynamic assessments of dehydrogenation were deduced basing on power law kinetic models with Arrhenius and Eyring approaches. Experimental results dedicated that this approach provided practical and basic application for hydrogen generation by using macroscale MgH2 particles in presence of CoCl2 solution via inhibiting formation of passivation layer with 20 kJmol−1 apparent activation energy.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Wang M, Chen L, Sun L (2012) Recent progress in electrochemical hydrogen production with earth-abundant metal complexes as catalysts. Energy Environ Sci 5:6763–6778. https://doi.org/10.1039/c2ee03309g
Huang Z, Autrey T (2012) Boron–nitrogen–hydrogen (BNH) compounds: recent developments in hydrogen storage, applications in hydrogenation and catalysis, and new syntheses. Energy Environ Sci 5:9257. https://doi.org/10.1039/c2ee23039a
Sun Q, Zou M, Guo X et al (2015) A study of hydrogen generation by reaction of an activated Mg-CoCl2 (magnesium-cobalt chloride) composite with pure water for portable applications. Energy 79:310–314. https://doi.org/10.1016/j.energy.2014.11.016
Umegaki T, Xu Q, Kojima Y (2015) Porous materials for hydrolytic dehydrogenation of ammonia borane. Materials (Basel) 8:4512–4534. https://doi.org/10.3390/ma8074512
Liu Y, Wang X, Dong Z et al (2013) Hydrogen generation from the hydrolysis of Mg powder ball-milled with AlCl3. Energy 53:147–152. https://doi.org/10.1016/j.energy.2013.01.073
Fan MQ, Sun LX, Xu F (2010) Experiment assessment of hydrogen production from activated aluminum alloys in portable generator for fuel cell applications. Energy 35:2922–2926. https://doi.org/10.1016/j.energy.2010.03.023
Qiang FM, Xian SL, Xu F (2010) Feasibility study of hydrogen production for micro fuel cell from activated Al-In mixture in water. Energy 35:1333–1337. https://doi.org/10.1016/j.energy.2009.11.016
Öz Ç, Coşkuner Filiz B, Kantürk Figen A (2018) Talaş Magnezyum Atığından Hidrojen Gazı Üretimi ve Hız Profillerinin İncelenmesi. J Polytech 0900:681–684. https://doi.org/10.2339/politeknik.403972
Öz Ç, Coşkuner Filiz B, Kantürk Figen A (2017) The effect of vinegar–acetic acid solution on the hydrogen generation performance of mechanochemically modified Magnesium (Mg) granules. Energy 127:328–334. https://doi.org/10.1016/j.energy.2017.03.106
Kantürk Figen A, Coşkuner Filiz B (2015) Hydrogen production by the hydrolysis of milled waste magnesium scraps in nickel chloride solutions and nickel chloride added in Marmara Sea and Aegean Sea Water. Int J Hydrogen Energy 40:16169–16177. https://doi.org/10.1016/j.ijhydene.2015.07.170
Kantürk Figen A, Coşkuner B, Pişkin S (2015) Hydrogen generation from waste Mg based material in various saline solutions (NiCl2, CoCl2, CuCl2, FeCl3, MnCl2). Int J Hydrogen Energy 40:7483–7489. https://doi.org/10.1016/j.ijhydene.2015.01.022
Tegel M, Schöne S, Kieback B, Röntzsch L (2017) An efficient hydrolysis of MgH2-based materials. Int J Hydrogen Energy 42:2167–2176. https://doi.org/10.1016/j.ijhydene.2016.09.084
Chen J, Fu H, Xiong Y et al (2014) MgCl2 promoted hydrolysis of MgH2 nanoparticles for highly efficient H2 generation. Nano Energy 10:337–343. https://doi.org/10.1016/j.nanoen.2014.10.002
Ouyang LZ, Cao ZJ, Wang H et al (2014) Enhanced dehydriding thermodynamics and kinetics in Mg(In)-MgF2 composite directly synthesized by plasma milling. J Alloys Compd 586:113–117. https://doi.org/10.1016/j.jallcom.2013.10.029
Kadri A, Jia Y, Chen Z, Yao X (2015) Catalytically enhanced hydrogen sorption in Mg-MgH2 by coupling vanadium-based catalyst and carbon nanotubes. Materials (Basel) 8:3491–3507. https://doi.org/10.3390/ma8063491
Kantürk Figen A, Pişkin S (2014) Characterization and modification of waste magnesium chip utilized as an Mg-rich intermetallic composite. Particuology 17:158–164. https://doi.org/10.1016/j.partic.2014.01.005
Cho CY, Wang KH, Uan JY (2005) Evaluation of a new hydrogen generating system: Ni-rich magnesium alloy catalyzed by platinum wire in sodium chloride solutio. Mater Trans 46:2704–2708. https://doi.org/10.2320/matertrans.46.2704
Huang M, Ouyang L, Wang H et al (2015) Hydrogen generation by hydrolysis of MgH2 and enhanced kinetics performance of ammonium chloride introducing. Int J Hydrogen Energy 40:6145–6150. https://doi.org/10.1016/j.ijhydene.2015.03.058
Li B, Hao Y, Zhang B et al (2017) A multifunctional noble-metal-free catalyst of CuO/TiO2 hybrid nanofibers. Appl Catal A Gen 531:1–12. https://doi.org/10.1016/j.apcata.2016.12.002
Demirci UB, Akdim O, Hannauer J et al (2010) Cobalt, a reactive metal in releasing hydrogen from sodium borohydride by hydrolysis: A short review and a research perspective. Sci China Chem 53:1870–1879. https://doi.org/10.1007/s11426-010-4081-1
Chen K, Ouyang L, Wang H et al (2020) A high-performance hydrogen generation system: Hydrolysis of LiBH4-based materials catalyzed by transition metal chlorides. Renew Energy 156:655–664. https://doi.org/10.1016/j.renene.2020.04.030
Coşkuner Filiz B, Kantürk Figen A, Pişkin S (2018) Dual combining transition metal hybrid nanoparticles for ammonia borane hydrolytic dehydrogenation. Appl Catal A Gen 550:320–330. https://doi.org/10.1016/j.apcata.2017.11.022
Akdim O, Demirci UB, Miele P (2009) More reactive cobalt chloride in the hydrolysis of sodium borohydride. Int J Hydrogen Energy 34:9444–9449. https://doi.org/10.1016/j.ijhydene.2009.09.085
Lente G (2015) Deterministic Kinetics in Chemistry and Systems Biology: The Dynamics of Complex Reaction Networks. Springer, New York
Lente G (2018) Facts and alternative facts in chemical kinetics: remarks about the kinetic use of activities, termolecular processes, and linearization techniques. Curr Opin Chem Eng 21:76–83. https://doi.org/10.1016/j.coche.2018.03.007
Uribe E, Vega-Gálvez A, Di Scala K et al (2011) Characteristics of Convective Drying of Pepino Fruit (Solanum muricatum Ait.): Application of Weibull Distribution. Food Bioprocess Technol 4:1349–1356. https://doi.org/10.1007/s11947-009-0230-y
Hiraki T, Hiroi S, Akashi T et al (2012) Chemical equilibrium analysis for hydrolysis of magnesium hydride to generate hydrogen. Int J Hydrogen Energy 37:12114–12119. https://doi.org/10.1016/j.ijhydene.2012.06.012
Grosjean MH, Zidoune M, Roué L, Huot JY (2006) Hydrogen production via hydrolysis reaction from ball-milled Mg-based materials. Int J Hydrogen Energy 31:109–119. https://doi.org/10.1016/j.ijhydene.2005.01.001
Ouyang LZ, Huang JM, Wang H et al (2013) Excellent hydrolysis performances of Mg3RE hydrides. Int J Hydrogen Energy 38:2973–2978. https://doi.org/10.1016/j.ijhydene.2012.12.092
Gan D, Liu Y, Zhang J et al (2018) Kinetic performance of hydrogen generation enhanced by AlCl3 via hydrolysis of MgH2 prepared by hydriding combustion synthesis. Int J Hydrogen Energy 43:10232–10239. https://doi.org/10.1016/j.ijhydene.2018.04.119
Coşkuner Filiz B, Kantürk Figen A, Pişkin S (2018) The remarkable role of metal promoters on the catalytic activity of Co-Cu based nanoparticles for boosting hydrogen evolution: Ammonia borane hydrolysis. Appl Catal B Environ 238:365–380. https://doi.org/10.1016/j.apcatb.2018.07.031
Muñoz M, Moreno S, Molina R (2012) Synthesis of Ce and Pr-promoted Ni and Co catalysts from hydrotalcite type precursors by reconstruction method. Int J Hydrogen Energy 37:18827–18842. https://doi.org/10.1016/j.ijhydene.2012.09.132
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Below is the link to the electronic supplementary material.
About this article
Cite this article
Coşkuner Filiz, B. Investigation of the reaction mechanism of the hydrolysis of MgH2 in CoCl2 solutions under various kinetic conditions. Reac Kinet Mech Cat 132, 93–109 (2021). https://doi.org/10.1007/s11144-020-01923-4
- Magnesium hydride
- Cobalt chloride