An alternative to metal catalysts: Poly(4-vinyl pyridine)-based polymeric ionic liquid catalyst for H2 generation from hydrolysis and methanolysis of NaBH4. (7th December 2016)

• Record Type: Journal Article
• Authors: Sahiner, Nurettin; Yasar, Alper O.; Aktas, Nahit
• Is Part Of: International journal of hydrogen energy. Volume 41:Number 45(2016)
• Page Start: 20562
• Page End: 20572
• Publication Date: 2016-12-07
• Subjects: Microgel/nanogel ionic liquids -- Polymeric ionic liquid (PIL) catalyst -- PIL composites -- Metal free catalyst -- H2 production -- Hydrolysis/methanolysis of NaBH4; Hydrogen as fuel -- Periodicals; Hydrogène (Combustible) -- Périodiques; Hydrogen as fuel; Periodicals; 665.81
• DOI: 10.1016/j.ijhydene.2016.08.182
• Languages: English
• ISSNs: 0360-3199

Abstract

Abstract: Monodispersed p(4-VP) (poly(4-vinyl pyridine)) polymeric particles were synthesized via self-emulsion polymerization and modified with 1, 2-dibromobutane 1, 4-dibromobutane and 1, 6-dibromobutane, to obtain polymeric ionic liquid (PIL) particles of poly(4-vinyl pyridine)-dibromoethane (p(4-VP) ++ C2 ), poly(4-vinyl pyridine)-dibromobuthane (p(4-VP) ++ C4 ), and poly(4-vinyl pyridine)-dibromohexane (p(4-VP) ++ C6 ) particles. Highly monodispersed p(4-VP), p(4-VP) ++ C2, p(4-VP) ++ C4 and p(4-VP) ++ C6 particles were obtained with the sizes of 335 ± 10, 451 ± 17, 432 ± 13 and 443 ± 24 nm, and the zeta potential values of 6.3 ± 0.6, 31.2 ± 2.1, 33.3 ± 1.0 and 35.5 ± 1.1 mV. PIL-metal composites of p(4-VP) ++ C6 -Co p(4-VP) ++ C6 -Ni and p(4-VP) ++ C6 -Fe particles were prepared by reducing CoCl2, NiCl2 and FeCl3 metal salts loaded into p(4-VP) ++ C6 microgels and then reducing with NaBH4 . The prepared PIL-metal composites and PIL particles were used as catalysts in H2 generation from the hydrolysis and methanolysis of NaBH4 . It was found that the prepared PIL-metal composites (e.g., p(4-VP) ++ C6 -Co) showed better catalytic performances than PIL particles (e.g., p(4-VP) ++ C6 ) for the hydrolysis reaction of NaBH4 whereas, PIL catalytic performances were much better than PIL-metal composites for the methanolysis of NaBH4 . Various parameters affecting the hydrolysis and methanolysis reactions of NaBH4 such as the types of PIL/PIL-metal particle, the amount of PIL particles, the amount of NaBH4 and temperature were investigated. A very high hydrogen generation rate (HGR) value for the methanolysis reaction of 500 mM NaBH4 catalyzed by 50 mg p(4-VP) ++ C6 at 25 °C was calculated as 9125 ± 177 mL H2 (g of catalyst min) −1 . Furthermore, very low activation energy (Ea), 13.78 ± 0.23 kJ mol −1 was calculated for the methanolysis of NaBH4 catalyzed by p(4-VP) ++ C6 at temperatures in the range of 0–40 °C. Graphical abstract: Highlights: Metal free catalyst for fast H2 production from methanolysis of NaBH4. Monodisperse poylmeric ionic liquid (PIL) catalyst for fast H2 production. PILs as green catalyst for environmentally benign energy carrier of H2 production. Very low Ea (13.78 ± 0.23 kJ mol −1 ) from PILs catalyst NaBH4 methanolysis is obtained. 9125 ± 177 mL H2 (g of catalyst min) −1 HGR from 500 mM NaBH4 catalyzed by 50 mg PILs.