Boric acid versus boron trioxide as catalysts for green energy source H2 production from sodium borohydride methanolysis

Abstract

Here, boric acid (H3BO3) and its dewatered form, boron trioxide (B2O3) were tested as catalysts for hydrogen (H2) evolution in the methanolysis of sodium borohydride (NaBH4) in methanol. Parameters such as catalyst types and their amounts, NaBH4 concentration, and the reaction temperature affecting the hydrogen generation rate (HGR) were studied. It has been found that H3BO3 and B2O3 catalyzed methanolysis reaction of NaBH4 follow up first-order kinetics relative to the concentration of NaBH4. Furthermore, the conversion and activity of these catalysts were examined to determine their performance in ten consecutive use. Interestingly, H3BO3 and B2O3 have demonstrated superior catalytic performances in methanolysis of NaBH4 comparing to the studies published in literature with the activation energy of respectively 22.08 kJ.mol^-1, and 23.30 kJ.mol^-1 in H2 production. The HGR was calculated as 6481 mL.min^-1.g^-1 and 5163 mL.min^-1.g^-1 for H3BO3 and B2O3 catalyst, respectively for 50 mg catalyst at 298 K. These results are comparably better than most metal nanoparticle catalysts used for H2 production in addition to the naturally occurring boron-based environmentally friendliness of these materials.

Keywords

• boric acid
• boron oxide
• catalyst
• hydrogen production
• NaBH4 methanolysis
• natural catalyst

References

1. Stern A.G., “A new sustainable hydrogen clean energy paradigm”, International Journal of Hydrogen Energy, 43, (2018), 4244 – 4255.
2. Gustafsson Ö., Kruså M., Zencak Z., Sheesley R.J., Granat L., Engström E., Praveen P.S., Rao P.S.P., Leck C., Rodhe H., “Brown clouds over South Asia: biomass or fossil fuel combustion?”, Science, 323, (2009), 495 – 498.
3. Baykara S.Z., “Hydrogen: A brief overview on its sources, production and environmental impact”, International Journal of Hydrogen Energy 43, (2018), 10605 – 10614.
4. Cui L., Cao X., Sun X., Yang W., Liu J., “A bunch-like copper oxide nanowire array as an efficient, durable, and economical catalyst for the methanolysis of ammonia borane”, ChemCatChem, 10, (2018), 710 – 715.
5. Arzac G.M., Fernández A., “Hydrogen production through sodium borohydride ethanolysis”, International Journal of Hydrogen Energy, 40, (2015), 5326 – 5332.
6. Kalidindi S.B., Nethaji M., Jagirdar B.R., “Dehydrogenation of ammonia borane in fluoro alcohols”, International Journal of Hydrogen Energy, 35, (2010), 10819 – 10825.
7. Kojima Y., Kawai Y., Nakanishi H., Matsumoto S., “Compressed hydrogen generation using chemical hydride”, Journal of Power Sources, 135, (2004), 36 – 41.
8. Hannauer J., Demirci U.B., Pastor G., Geantet C., Herrmann J.M., Mielea P., “Hydrogen release through catalyzed methanolysis of solid sodium borohydride”, Energy & Environmental Science, 3, (2010), 1796 – 1803.

9. Lin K.A., Chang H., “Efficient hydrogen production from NaBH4 hydrolysis catalyzed by a magnetic cobalt/carbon composite derived from a zeolitic imidazolate framework”, Chemical Engineering Journal, 296, (2016), 243 – 251.
10. Lo C.F., Karan K., Davis B.R., “Kinetic studies of reaction between sodium borohydride and methanol, water, and their mixtures” Industrial & Engineering Chemistry Research, 46, (2007), 5478 – 5484.
11. Inger E., Sunol A.K., Sahiner N., “Catalytic activity of metal‐free amine‐modified dextran microgels in hydrogen release through methanolysis of NaBH4”, International Journal of Energy Research, 7, (2020), 5990 – 6001.
12. Saka C., Balbay A., “Fast and effective hydrogen production from ethanolysis and hydrolysis reactions of potassium borohydride using phosphoric acid”, International Journal of Hydrogen Energy, 43, (2018), 19976 – 19983.
13. Chozhavendhan S., Singh M.V.P., Fransila B., Kumar R.P., Devi G.K., “A review on influencing parameters of biodiesel production and purification processes”, Current Research in Green and Sustainable Chemistry, 1-2, (2020), 1 – 6.
14. Saka C., Şahin Ö., Demir H., Karabulut A., Sarikaya A., “Hydrogen generation from sodium borohydride hydrolysis with a Cu-Co-based catalyst: A kinetic study”, Energy Source, 37, (2015), 956 – 964.
15. Yan K., Li Y., Zhang X., Yang X., Zhang N., Zheng J., Chen B., Smith K.J., “Effect of preparation method on Ni2P/SiO2 catalytic activity for NaBH4 methanolysis and phenol hydrodeoxygenation”, International Journal of Hydrogen Energy, 40, (2015), 16137 – 16146.
16. Lo C.F., Karan K., Davis B.R., “Kinetic assessment of catalysts for the methanolysis of sodium borohydride for hydrogen generation”, Industrial & Engineering Chemistry Research, 48, (2009), 5177 – 5184.
17. Su C., Lu M., Wang S., Huang Y., “Ruthenium immobilized on Al2O3 pellets as a catalyst for hydrogen generation from hydrolysis and methanolysis of sodium borohydride”, RSC Advances, 2, (2012), 2073 – 2079.
18. Wang F., Wang Y., Zhang Y., Luo Y., Zhu H., “Highly dispersed RuCo bimetallic nanoparticles supported on carbon black: enhanced catalytic activity for hydrogen generation from NaBH4 methanolysis”, Journal of Materials Science, 53, (2018), 6831 – 6841.
19. Wang F., Zhang Y., Wang Y., Luo Y., Chen Y., Zhu H., “Co-P nanoparticles supported on dandelion-like CNTs-Ni foam composite carrier as a novel catalyst for hydrogen generation from NaBH4 methanolysis” International Journal of Hydrogen Energy, 43, (2018), 8805 – 8814.
20. 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”, Journal of Power Sources, 243, (2013), 444 – 450.
21. Sahiner N., Demirci S., “Natural microgranular cellulose as alternative catalyst to metal nanoparticles for H2 production from NaBH4 methanolysis”, Applied Catalysis B: Environmental, 202, (2017), 199 – 206.
22. Pham D.D., Cho J., “Low-energy catalytic methanolysis of poly(ethyleneterephthalate)”, Green Chemistry, 23, (2021), 511 – 525.
23. Ozturk O.F., Demirci S., Sengel S.B., Sahiner N., “Highly regenerable ionic liquid microgels as inherently metal-free green catalyst for H2 generation”. Polymers for Advanced Technologies, 29, (2017), 1426 – 1434.
24. Chinnappan A., Puguan J.M.C., Chung W.J., Kim H. “Hydrogen generation from the hydrolysis of sodium borohydride using chemically modified multiwalled carbon nanotubes with pyridinium based ionic liquid and decorated with highly dispersed Mn nanoparticles”. Journal of Power Sources, 293, (2015), 429 – 436.
25. Tamboli A.H., Chaugule A.A., Kim H., “Highly selective and multifunctional chitosan/ionic liquids for conversion of CO2 and methanol to dimethyl carbonates at mild reaction conditions”, Fuel, 166 (2016), 495 – 501.
26. Wei L., Dong X.L., Yang Y.M., Shi Q.Y., Lu Y.H., Liu H.Y., Yu Y.N., Zhang M.H., Qi M., Wang Q.,” Co−O−P composite nanocatalysts for hydrogen generation from the hydrolysis of alkaline sodium borohydride solution”, International Journal of Hydrogen Energy, 45, (2020), 10745 – 10753.
27. Gnanakumar E.S., Chandran N., Kozhevnikov I.V., Atienza A., Fernandez E.V.R., Escibano A., Shiju N.R., “Highly efficient nickel-niobia composite catalysts for hydrogenation of CO2 to methane”, Chemical Engineering Science, 194, (2019), 2 – 9.
28. Khan S.B., “Metal nanoparticles containing chitosan wrapped cellulose nanocomposites for catalytic hydrogen production and reduction of environmental pollutants”, Carbohydrate Polymers, 242, (2020), 116286.
29. Manna J., Roy B., Sharma P., “Efficient hydrogen generation from sodium borohydride hydrolysis using silica sulfuric acid catalyst”, Journal of Power Sources, 275, (2015), 727 – 733.
30. Balbay A., Şahin Ö., Saka C., “Effect of acid addition on hydrogen production from potassium borohydride hydrolysis”, Energy Sources Part A, 39, (2017), 1383 – 1389.
31. Balbay A., Saka C., “The effect of the concentration of hydrochloric acid and acetic acid aqueous solution for fast hydrogen production from methanol solution of NaBH4”, International Journal of Hydrogen Energy, 43, (2018), 14265 – 14272.
32. Brack P., Dann S.E., Wijayantha K.G.U., “Heterogenous and homogenous catalysts for hydrogen generation by hydrolysis of aqueous sodium borohydride (NaBH4)”, Energy Science& Engineering, 3, (2015), 174 – 188.
33. Wang N., Zhao L., Zhang C., Li L., “Water states and thermal processability of boric acid modified poly(vinyl alcohol)”, Journal of Applied Polymer Science, 133, (2016), 43246.
34. Balcı S., Sezgi N.A., Eren E., “Boron oxide production kinetics using boric acid as raw material”, Industrial & Engineering Chemistry Research, 51, (2012), 11091 – 11096.
35. Nath J., Chaudhuri M.K., “Boric acid catalyzed bromination of a variety of organic substrates: an eco-friendly and practical protocol”, Green Chemistry Letters and Reviews, 1, (2008), 223 – 230.
36. Saka C., Balbay A., “Influence of process parameters on enhanced hydrogen evolution from alcoholysis of sodium borohydride with a boric acid catalyst”, International Journal of Hydrogen Energy, 45, (2020), 16193 – 16200.
37. Xu D., Zhao L., Dai P., Ji S., “Hydrogen generation from methanolysis of sodium borohydride over Co/Al2O3 catalyst”, Journal of Natural Gas Chemistry, 21, (2012), 488 – 494.