Abstract
Hydrolysis of sodium borohydride (NaBH4) offers substantial applications in the production of hydrogen but requires an inexpensive catalyst. Herein, silica (SP) and phosphorylated silica (SP-PA) are used as a catalyst for the generation of hydrogen from NaBH4 hydrolysis. The catalyst is prepared by sol–gel route synthesis by taking tetraethyl orthosilicate as the precursor of silica whereas phosphoric acid served as the gelation and phosphorylating agent. The prepared catalyst is characterized by FT-IR spectroscopy, XRD, SEM, and EDAX. The hydrogen generation rate at SP-PA particles (762.4 mL min−1 g−1) is higher than that of silica particles (133 mL min−1 g−1 of catalyst). The higher catalytic activity of SP-PA particles might be due to the acidic functionalities that enhance the hydrogen production rate. The kinetic parameters (activation energy and pre-exponential factor) are calculated from the Arrhenius plot and the thermodynamic parameters (enthalpy, entropy, and free energy change) are evaluated using the Erying plot. The calculated activation energy for NaBH4 hydrolysis at SP-PA catalyst is 29.92 kJ.mol−1 suggesting the high catalytic activity of SP-PA particles. The obtained entropy of activation (ΔS‡ = − 97.75 JK−1) suggested the Langmuir–Hinshelwood type associative mechanism for the hydrolysis of NaBH4 at SP-PA particles.
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References
Abdalla AM, Hossain S, Nisfindy QB, Azad AT, Dawood M, Azad AK (2018) Hydrogen production, storage, transportation and key challenges with applications: a review. Energy Convers Manage 165:602–627. https://doi.org/10.1016/j.enconman.2018.03.088
Abdelhamid HN (2020) Hierarchical porous ZIF-8 for hydrogen production via the hydrolysis of sodium borohydride. Dalton Trans 49:4416–4424. https://doi.org/10.1039/D0DT00145G
Abdelhamid HN (2021) Dehydrogenation of sodium borohydride using cobalt embedded zeolitic imidazolate frameworks. J Solid State Chem 297:122034. https://doi.org/10.1016/j.jssc.2021.122034
Akti F (2021) Hydrogen generation from hydrolysis of sodium borohydride by silica xerogel supported cobalt catalysts: positive roles of amine modification and calcination treatment. Fuel 303:121326. https://doi.org/10.1016/j.fuel.2021.121326
Alamgholiloo H, Rostamnia S, Hassankhani A, Liu X, Eftekhari A, Hasanzadeh A, Zhang K, Karimi-Maleh H, Khaksar S, Varma RS, Shokouhimehr M (2020) Formation and stabilization of colloidal ultra-small palladium nanoparticles on diamine-modified Cr-MIL-101: synergic boost to hydrogen production from formic acid. J Colloid Interface Sci 567(1):126–135. https://doi.org/10.1016/j.jcis.2020.01.087
Al-Thabaiti SA, Khan Z, Malik MA (2019) Bimetallic Ag-Ni nanoparticles as an effective catalyst for hydrogen generation from hydrolysis of sodium borohydride. Int J Hydrogen Energy 44(31):16452–16466. https://doi.org/10.1016/j.ijhydene.2019.04.240
Bozkurt G, Özer A, Yurtcan AB (2018) Hydrogen generation from sodium borohydride with Ni and Co based catalysts supported on Co3O4. Int J Hydrogen Energy 43(49):22205–22214. https://doi.org/10.1016/j.ijhydene.2018.10.106
Chou CC, Hsieh CH, Chen BH (2015) Hydrogen generation from catalytic hydrolysis of sodium borohydride using bimetallic Ni–Co nanoparticles on reduced graphene oxide as catalysts. Energy 90(2):1973–1982. https://doi.org/10.1016/j.energy.2015.07.023
Dawood F, Anda M, Shafiullah GM (2020) Hydrogen production for energy: an overview. Int J Hydrogen Energy 45(7):3847–3869. https://doi.org/10.1016/j.ijhydene.2019.12.059
Demirci S, Yildiz M, Inger E, Sahiner N (2020) Porous carbon particles as metal-free superior catalyst for hydrogen release from methanolysis of sodium borohydride. Renew Energy 147(1):69–76. https://doi.org/10.1016/j.renene.2019.08.131
Demirci UB (2015) The hydrogen cycle with the hydrolysis of sodium borohydride: a statistical approach for highlighting the scientific/technical issues to prioritize in the field. Int J Hydrogen Energy 40(6):2673–2691. https://doi.org/10.1016/j.ijhydene.2014.12.067
Deng J, Sun B, Xu J, Shi Y, Xie L, Zheng J, Li X (2021) A monolithic sponge catalyst for hydrogen generation from sodium borohydride solution for portable fuel cells. Inorg Chem Front 8:35–40. https://doi.org/10.1039/D0QI00911C
Didehban A, Zabihi M, Shahrouzi JR (2018) Experimental studies on the catalytic behavior of alloy and core-shell supported Co-Ni bimetallic nano-catalysts for hydrogen generation by hydrolysis of sodium borohydride. Int J Hydrogen Energy 43(45):20645–20660. https://doi.org/10.1016/j.ijhydene.2018.09.127
Didehban A, Zabihi M, Babajani N (2020) Preparation of the efficient nano-bimetallic cobalt-nickel catalysts supported on the various magnetic substrates for hydrogen generation from hydrolysis of sodium borohydride in alkaline solutions. Polyhedron 180(1–12):114405. https://doi.org/10.1016/j.poly.2020.114405
Doustkhah E, Mohtasham H, Farajzadeh M, Rostamnia S, Wang Y, Arandiyan H, Assadi MHN (2020) Organosiloxane tunability in mesoporous organosilica and punctuated Pd nanoparticles growth; theory and experiment. Microporous Mesoporous Mater 293:109832. https://doi.org/10.1016/j.micromeso.2019.109832
Doustkhah E, Rostamnia S, Tsunoji N, Henzie J, Takei T, Yamauchi Y, Ide Y (2018) Templated synthesis of atomically-thin Ag nanocrystal catalysts in the interstitial space of a layered silicate. Chem Commun 54:4402–4405. https://doi.org/10.1039/C8CC00275D
Durano MM, Tamboli AH, Kim H (2017) Cobalt oxide synthesized using urea precipitation method as catalyst for the hydrolysis of sodium borohydride. Colloids Surf A 520:355–360. https://doi.org/10.1016/j.colsurfa.2017.02.005
Elghniji K, Virlan C, Elaloui E, Pui A (2018) Synthesis, characterization of SiO2 supported-industrial phosphoric acid catalyst for hydrolysis of NaBH4 solution. Phosphorus Sulfur Silicon Relat Elem 193(12):806–821. https://doi.org/10.1080/10426507.2018.1515946
Fangaj E, Ceyhan AA (2020) Apricot Kernel shell waste treated with phosphoric acid used as a green, metal-free catalyst for hydrogen generation from hydrolysis of sodium borohydride. Int J Hydrogen Energy 45(35):17104–17117. https://doi.org/10.1016/j.ijhydene.2020.04.133
Farajzadeh M, Alamgholiloo H, Nasibipour F, Banaei R, Rostamnia S (2020) Anchoring Pd-nanoparticles on dithiocarbamate- functionalized SBA-15 for hydrogen generation from formic acid. Sci Rep 10:18188. https://doi.org/10.1038/s41598-020-75369-y
Ghodke NP, Rayaprol S, Bhoraskar SV, Mathe VL (2020) Catalytic hydrolysis of sodium borohydride solution for hydrogen production using thermal plasma synthesized nickel nanoparticles. Int J Hydrogen Energy 45(33):16591–16605. https://doi.org/10.1016/j.ijhydene.2020.04.143
Gholipour B, Zonouzi A, Shokouhimehr M, Rostamnia S (2022) Integration of plasmonic AgPd alloy nanoparticles with single-layer graphitic carbon nitride as Mott-Schottky junction toward photo-promoted H2 evolution. Sci Rep 12:13583. https://doi.org/10.1038/s41598-022-17238-4
Gulbinski J, Ren L, Vattipalli V, Chen H, Delaney J, Bai P, Dauenhauer P, Tsapatsis M, Abdelrahman OA, Fan W (2020) Role of silica support in phosphoric acid catalyzed production of p-Xylene from 2,5-dimethylfuran and ethylene. Ind Eng Chem Res 59(51):22049–22056. https://doi.org/10.1021/acs.iecr.0c04493
Hasani A, Le QV, Tekalgne M, Choi MJ, Choi S, Lee TH, Kim H, Ahn SH, Jang HW, Kim SY (2019) Fabrication of a WS2/p-Si heterostructure photocathode using direct hybrid thermolysis. ACS Appl Mater Interfaces 11(33):29910–29916. https://doi.org/10.1021/acsami.9b08654
Hayagreevan C, Siva B, Rahul R, Denisdon S, John Jeevagan A, Adinaveen T, Amalraj M (2021) Sulphonated silica and sulphonated silica / carbon particles as efficient catalysts for hydrogen generation from sodium borohydride hydrolysis. Int J Hydrogen Energy 46(68):33849–33863. https://doi.org/10.1016/j.ijhydene.2021.07.195
Huff C, Dushatinski T, Abdel-Fattah TM (2017) Gold nanoparticle/multi-walled carbon nanotube composite as novel catalyst for hydrogen evolution reactions. Int J Hydrogen Energy 42(30):18985–18990. https://doi.org/10.1016/j.ijhydene.2017.05.226
Jin YG, Qiao SZ, Xu ZP, Yan ZM, Huang YN, da Costa JCD, Lu GQ (2009) Phosphonic acid functionalized silicas for intermediate temperature proton conduction. J Mater Chem 19:2363–2372. https://doi.org/10.1039/b819379g
Kaya M (2020) Evaluating organic waste sources (spent coffee ground) as metal-free catalyst for hydrogen generation by the methanolysis of sodium borohydride. Int J Hydrogen Energy 45(23):12743–12754. https://doi.org/10.1016/j.ijhydene.2019.10.180
Kim KC (2018) A review on design strategies for metal hydrides with enhanced reaction thermodynamics for hydrogen storage applications. Int J Energy Res 42(4):1455–1468. https://doi.org/10.1002/er.3919
Kıpçak İ, Kalpazan E (2020) Preparation of CoB catalysts supported on raw and Na-exchanged bentonite clays and their application in hydrogen generation from the hydrolysis of NaBH4. Int J Hydrogen Energy 45(50):26434–26444. https://doi.org/10.1016/j.ijhydene.2020.03.230
Kojima Y (2019) Hydrogen storage materials for hydrogen and energy carriers. Int J Hydrogen Energy 44(33):18179–18192. https://doi.org/10.1016/j.ijhydene.2019.05.119
Lee H, Lee JW, Kim DY, Park J, Seo YT, Zeng H, Moudrakovski IL, Ratcliffe CI, Ripmeester JA (2005) Tuning clathrate hydrates for hydrogen storage. Nature 434:743–746. https://doi.org/10.1038/nature03457
Li F, Li J, Chen L, Dong Y, Xie P, Li Q (2020) Hydrogen production through hydrolysis of sodium borohydride: highly dispersed CoB particles immobilized in carbon nanofibers as a novel catalyst. Int J Hydrogen Energy 45(56):32145–32156. https://doi.org/10.1016/j.ijhydene.2020.08.137
Liu BH, Li ZP (2009) A review: hydrogen generation from borohydride hydrolysis reaction. J Power Sources 187(2):527–534. https://doi.org/10.1016/j.jpowsour.2008.11.032
Matsuda A, Kanzaki T, Kotani Y, Tatsumisago M, Minami T (2001) Proton conductivity and structure of phosphosilicate gels derived from tetraethoxysilane and phosphoric acid or triethylphosphate. Solid State Ionics 139(1–2):113–119. https://doi.org/10.1016/S0167-2738(00)00819-5
Nandan D, Sreenivasulu P, Saxena SK, Viswanadham N (2011) Facile synthesis of a sulfonated carbon−silica-meso composite and mesoporous silica. Chem Commun 47:11537–11539. https://doi.org/10.1039/c1cc14673d
Nouruzi N, Dinari M, Gholipour B, Mokhtari N, Farajzadeh M, Rostamnia S, Shokouhimehr M (2022a) Photocatalytic hydrogen generation using colloidal covalent organic polymers decorated bimetallic Au-Pd nanoalloy (COPs/Pd-Au). Mol Catal 518:112058. https://doi.org/10.1016/j.mcat.2021.112058
Nouruzi N, Dinari M, Gholipour B, Afshari M, Rostamnia S (2022b) In situ organized Pd and Au nanoparticles in a naphthalene-based imine-linked covalent triazine framework for catalytic Suzuki reactions and H2 generation from formic acid. ACS Appl Nano Mater 5(5):6241–6248. https://doi.org/10.1021/acsanm.2c00285
Patel N, Patton B, Zanchetta C, Ferandes R, Guella G, Kale A, Miotello A (2008) Pd-C powder and thin film catalysts for hydrogen production by hydrolysis of sodium borohydride. Int J Hydrogen Energy 33(1):287–292. https://doi.org/10.1016/j.ijhydene.2007.07.018
Patil KN, Prasad D, Bhanushali JT, Kim H, Atar AB, Nagaraja BM, Jadhav AH (2020) Sustainable hydrogen generation by catalytic hydrolysis of NaBH4 using tailored nanostructured urchin-like CuCo2O4 spinel catalyst. Catal Lett 150(2):586–604. https://doi.org/10.1007/s10562-019-03025-w
Qin H, Wang F, Wang P, Zhao L, Zhu J, Yang Q, Wu R, Yea M, Zou H (2012) Phosphoric acid functionalized mesoporous organo-silica (EPO) as the adsorbent for in situ enrichment and isotope labeling of endogenous phosphopeptides. Chem Commun 48:961–963. https://doi.org/10.1039/C1CC15222J
Rambabu K, Hai A, Bharath G, Banat F, Lokeshow P (2019) Molybdenum disulfide decorated palm oil waste activated carbon as an efficient catalyst for hydrogen generation by sodium borohydride hydrolysis. Int J Hydrogen Energy 44(28):14406–14415. https://doi.org/10.1016/j.ijhydene.2019.03.085
Şahin Ö, İzgi MS, Tayboğa S, Kazıcı HC (2021) Effect of plasma pretreatment of Co–Cu–B catalyst on hydrogen generation from sodium borohydride methanolysis. Reac Kinet Mech Cat 133(2):851–861. https://doi.org/10.1007/s11144-021-02004-w
Sahiner N, Sengel SB (2017) Various amine functionalized halloysite nanotube as efficient metal free catalysts for H2 generation from sodium borohydride methanolysis. Appl Clay Sci 146:517–525. https://doi.org/10.1016/j.clay.2017.07.008
Sahiner N, Sengel SB (2016) Quaternized polymeric microgels as metal free catalyst for H2 production from the methanolysis of sodium borohydride. J Power Sources 336:27–34. https://doi.org/10.1016/j.jpowsour.2016.10.054
Saka C (2021) Metal-free catalysts with phosphorus and oxygen doped on carbon-based on Chlorella Vulgaris microalgae for hydrogen generation via sodium borohydride methanolysis reaction. Int J Hydrogen Energy 46(7):5150–5157. https://doi.org/10.1016/j.ijhydene.2020.09.220
Saka C, Eygi MS, Balbay A (2020a) CoB doped acid modified zeolite catalyst for enhanced hydrogen release from sodium borohydride hydrolysis. Int J Hydrogen Energy 45(30):15086–15099. https://doi.org/10.1016/j.ijhydene.2020.03.238
Saka C, Kaya M, Bekiroğullari M (2020b) Spirulina microalgal strain as efficient a metal-free catalyst to generate hydrogen via methanolysis of sodium borohydride. Int J Energy Res 44(1):402–410. https://doi.org/10.1002/er.4936
Santander JA, Alvarez M, Gutierrez V, Volpe MA (2019) Solid phosphoric acid catalysts based on mesoporous silica for levoglucosenone production via cellulose fast pyrolysis. J Chem Technol Biotechnol 94(2):484–493. https://doi.org/10.1002/jctb.5795
Seven F, Sahiner N (2014) Enhanced catalytic performance in hydrogen generation from NaBH4 hydrolysis by super porous cryogel supported Co and Ni catalysts. J Power Sources 272:128–136. https://doi.org/10.1016/j.jpowsour.2014.08.047
Tang M, Xia F, Gao C, Qiu H (2016) Preparation of magnetically recyclable CuFe2O4/RGO for catalytic hydrolysis of sodium borohydride. Int J Hydrogen Energy 41(30):13058–13068. https://doi.org/10.1016/j.ijhydene.2016.05.034
Wei L, Ma M, Lu Y, Zhang S, Gao J, Dong X (2017) Electrodeposited Co–Zn on Ni foam as efficient catalysts for hydrogen generation from hydrolysis of sodium borohydride. Funct. Mater. Lett. 10 (5):1750065 (1–5). https://doi.org/10.1142/S1793604717500655
Wei L, Dong X, Ma M, Lu Y, Wang D, Zhang S, Zhao D, Wang Q (2018) Co3O4 hollow fiber: an efficient catalyst precursor for hydrolysis of sodium borohydride to generate hydrogen. Int J Hydrogen Energy 43(3):1529–1533. https://doi.org/10.1016/j.ijhydene.2017.11.113
Xu D, Zhang X, Zhao X, Dai P, Wang C, Gao J, Liu X (2019) Stability and kinetic studies of MOF-derived carbon-confined ultrafine Co catalyst for sodium borohydride hydrolysis. Int J Energy Res 43(8):3702–3710. https://doi.org/10.1002/er.4524
Yang L, Huang X, Zhang J, Dong H (2020) Protonated poly(ethylene imine)-coated silica nanoparticles for promoting hydrogen generation by hydrolysis of sodium borohydride. ChemPlusChem 85(3):390–390. https://doi.org/10.1002/cplu.202000020
Zeng J, He B, Lamb K, Marco RD, Shen PK, Jiang SP (2013) Anhydrous phosphoric acid functionalized sintered mesoporous silica nanocomposite proton exchange membranes for fuel cells. ACS Appl Mater Interfaces 5(21):11240–11248. https://doi.org/10.1021/am403479t
Zhang F, Li R, Zhang J, Dong H (2021) KCC-1 Supported CuCo bimetal catalysts for promoting hydrogen production from ammonia borane hydrolysis. Catal Lett 152:2832–2839. https://doi.org/10.1007/s10562-021-03859-3
Zhou G, He Z, Dong X (2021) Role of metal oxides in Cu-based catalysts with NaBH4 reduction for the synthesis of methanol from CO2/H2. Catal Lett 151(4):1091–1101. https://doi.org/10.1007/s10562-020-03379-6
Zhou J, Yan J, Meng X, Chen X, Guo J, Liu X (2022) Co0.45W0.55 nanocomposite from ZIF-67: an efficient and heterogeneous catalyst for H2 generation upon NaBH4 hydrolysis. Catal Lett 152(2):610–618. https://doi.org/10.1007/s10562-021-03661-1
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The authors thank DST-FIST lab, Arul Anandar College for the instrumentation facilities.
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The authors thank Arul Anandar College (Autonomous), Karumathur for providing seed money research grant 2020–21 and 2021–22.
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The authors confirm contribution to the paper as follows:
Study conception and design: K. Ganesan, D.S. Bhuvaneshwari, P. Muthukumar, M. Amalraj.
Synthesis of catalyst and experimental data collection: C. Hayagreevan and R. Rahul.
Interpretation of results: K. Ganesan, A. John Jeevagan, T. Adinaveen and M. Amalraj.
Draft manuscript preparation: D.S. Bhuvaneshwari, P. Muthukumar and M. Amalraj.
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Ganesan, K., Hayagreevan, C., Rahul, R. et al. Catalytic hydrolysis of sodium borohydride for hydrogen production using phosphorylated silica particles. Environ Sci Pollut Res 30, 21199–21212 (2023). https://doi.org/10.1007/s11356-022-23672-8
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DOI: https://doi.org/10.1007/s11356-022-23672-8