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Mesoporous silica beads encapsulated with functionalized palladium nanocrystallites: Novel catalyst for selective hydrogen evolution

  • Prem Chandra Pandey (a1), Shubhangi Shukla (a1) and Yashashwa Pandey (a1)

2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane (EETMS)/3-glycidoxypropyltrimethoxysilane (GPTMS) mediated, in situ synthesis of functional palladium (Pd) nanocomposites over the graphene oxide (GO) surface is reported. The prepared nanocomposites viz, Pd/EETMS, Pd/GPTMS, Pd/GO/EETMS, and Pd/GO/GPTMS, are encapsulated into mesoporous (2–10 nm) silica-alginate beads to primarily serve the development of cost-effective catalyst for on-board generation of hydrogen. Major findings involve: (i) the synthesis of porous silica alginate beads, with the controlled pore sizes (2–10 nm) as a function of concentration of alkoxysilanes, (ii) onboard release of hydrogen from the decomposition of hydrazine, which is evaluated as: (1) time-dependent disappearance of the N–N bond stretching band at 1069 cm−1 based on the FTIR spectroscopy, (2) volumetric estimation of the equimolar hydrogen using methylene blue (MB); (3) catalytic reduction of p-nitroaniline (PNA). The decomposition of high concentration of hydrazine is made possible using very low concentration of palladium. On calcination the efficiency of catalysts found to enhance further. The noteworthy finding is probing the hydrogen evolution using FTIR spectroscopy. Hydrogen selectivity of ∼100% is obtained from the most efficient catalyst (Pd/GO/EETMS-623 K).

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1. Li X., Yu J., Low J., Fang Y., Xiaoc J., and Chen X.: Engineering heterogeneous semiconductors for solar water splitting. J. Mater. Chem. A 3, 24852534 (2015).
2. Chen X., Shen S., Guo L., and Mao S.S.: Semiconductor-based photocatalytic hydrogen generation. Chem. Rev. 110, 65036570 (2010).
3. Chen X., Li C., Grätzel M., Kosteckid R., and Mao S.S.: Nanomaterials for renewable energy production and storage. Chem. Soc. Rev. 41, 79097937 (2012).
4. Singh S.K. and Xu Q.: Nanocatalysts for hydrogen generation from hydrazine. Catal. Sci. Technol. 3, 18891900 (2013).
5. Orimo S.I., Nakamori Y., Jennifer R.E., Zuttel A., and Jensen C.M.: Complex hydrides for hydrogen storage. Chem. Rev. 107, 41114132 (2007).
6. Yadav M. and Xu Q.: Liquid-phase chemical hydrogen storage materials. Energy Environ. Sci. 5, 96989725 (2012).
7. Zheng M., Cheng R., Chen X., Li N., Li L., Wang X., and Zhang T.: A novel approach for CO-free H2 production via catalytic decomposition of hydrazine. Int. J. Hydrogen Energy 30, 10811089 (2005).
8. Singh S.K., Singh A.K., Aranishi K., and Xu Q.: Noble-metal-free bimetallic nanoparticle-catalyzed selective hydrogen generation from hydrous hydrazine for chemical hydrogen storage. J. Am. Chem. Soc. 133, 1963819641 (2011).
9. Singh S.K., Zhang X.B., and Xu Q.: Room-temperature hydrogen generation from hydrous hydrazine for chemical hydrogen storage. J. Am. Chem. Soc. 131, 98949895 (2009).
10. Liu L.J., Burghaus U., Besenbacher F., and Wang Z.L.: Preparation and characterization of nanomaterials for sustainable energy production. ACS Nano 4, 55175526 (2010).
11. Bunker C.E. and Smith M.J.: Nanoparticles for hydrogen generation. J. Mater. Chem. 21, 1217312180 (2011).
12. Manukyan K.V., Cros A., Rouvimov S., Miller J., Mukasyan A.S., and Wolf E.E.: Low temperature decomposition of hydrous hydrazine over FeNi/Cu nanoparticles. Appl. Catal., A 476, 4753 (2014).
13. Oliaee S.N., Zhang C., Hwang S.Y., Cheung H.M., and Peng Z.: Hydrogen production via hydrazine decomposition on model platinum–nickel nanocatalyst with a single (111) facet. J. Phys. Chem. C 120, 97649772 (2016).
14. Singh S.K. and Xu Q.: Complete conversion of hydrous hydrazine to hydrogen at room temperature for chemical hydrogen storage. J. Am. Chem. Soc. 131, 1803218033 (2009).
15. Wang J., Zhang X-B., Wang Z-L., Wang L-M., and Zhang Y.: Rhodium–nickel nanoparticles grown on graphene as highly efficient catalyst for complete decomposition of hydrous hydrazine at room temperature for chemical hydrogen storage. Energy Environ. Sci. 5, 68856888 (2012).
16. Yang X., Zhang X., Ma Y., Huang Y., Wang Y., and Chen Y.: Superparamagnetic graphene oxide–Fe3O4 nanoparticles hybrid for controlled targeted drug carriers. J. Mater. Chem. 19, 27102714 (2009).
17. Choi Y., Bae H.S., Seo E., Jang S., Park K.H., and Kim B.S.: Hybrid gold nanoparticle-reduced graphene oxide nanosheets as active catalysts for highly efficient reduction of nitroarenes. J. Mater. Chem. 21, 1543115436 (2011).
18. Kim Y.K., Han S.W., and Min D.H.: Graphene oxide sheath on Ag nanoparticle/graphene hybrid films as an antioxidative coating and enhancer of surface-enhanced Raman scattering. ACS Appl. Mater. Interfaces 4, 65456551 (2012).
19. Bezbaruah A.N., Krajangpan S., Chisholm B.J., Khan E., and Elorza Bermudez J.J.: Entrapment of iron nanoparticles in calcium alginate beads for groundwater remediation applications. J. Hazard. Mater. 166, 13391343 (2009).
20. Kim H., Hong H.J., Jung J., Kim S.H., and Yang J.W.: Degradation of trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) immobilized in alginate bead. J. Hazard. Mater. 176, 10381043 (2010).
21. Pankongadisak P., Ruktanonchai U.R., Supaphol P., and Suwantong O.: Preparation and characterization of silver nanoparticles-loaded calcium alginate beads embedded in gelatin scaffolds. AAPS PharmSciTech 15, 11051115 (2014).
22. Kuang Y., Jianhua D., Zhou R., Chen Z., Megharaj M., and Naidu R.: Calcium alginate encapsulated Ni/Fe nanoparticles beads for simultaneous removal of Cu (II) and monochlorobenzene. J. Colloid Interface Sci. 447, 8591 (2015).
23. Klein J., Stock J., and Vorlop K.D.: Pore size and properties of spherical Ca-alginate biocatalysts. Eur. J. Appl. Microbiol. Biotechnol. 18, 8691 (1983).
24. Brunel D., Cauvel A., Renzo F.D., Fajula F., Fubini B., Onida B., and Garrone E.: Preferential grafting of alkoxysilane coupling agents on the hydrophobic portion of the surface of micelle-templated silica. New J. Chem. 24, 807813 (2000).
25. Pandey P.C. and Singh R.: Tetrahydrofuran hydroperoxide and 3-aminopropyl trimethoxysilane mediated controlled synthesis of Pd, Pd–Au, Au–Pd nanoparticles: Role of palladium nanoparticles on the redox electrochemistry of ferrocene monocarboxylic acid. Electrochim. Acta 138, 163173 (2014).
26. Pandey P.C. and Pandey G.: One-pot two-step rapid synthesis of 3-aminopropyltrimethoxysilane-mediated highly catalytic Ag@(PdAu) trimetallic nanoparticles. Catal. Sci. Technol. 6, 39113917 (2016).
27. Pandey P.C., Shukla S., and Pandey Y.: 3-aminopropyltrimethoxysilane and grapheneoxide/reduced graphene oxide-induced generation of gold nanoparticles and their nanocomposites: Electrocatalytic and kinetic activity. RSC Adv. 6, 8054980556 (2016).
28. Pandey P.C. and Pandey G.: Synthesis of gold nanoparticles resistant to pH and salt for biomedical applications; functional activity of organic amine. J. Mater. Res. 31, 33133323 (2016).
29. Tafreshi S., Roldanab A., and Nora de Leeuw H.: Density functional theory calculations of the hydrazine decomposition mechanism on the planar and stepped Cu (111) surfaces. Phys. Chem. Chem. Phys. 17, 2153321546 (2015).
30. Seo T., Kurokawa R., and Sato B.: A convenient method for determining the concentration of hydrogen in water: Use of methylene blue with colloidal platinum. Med. Gas Res. 2, 1 (2012). doi: 10.1186/2045-9912-2-1.
31. Pozun Z.D., Rodenbusch S.E., Keller E., Tran K., Tang W., Stevenson K.J., and Henkelman G.: A systematic investigation of p-nitrophenol reduction by bimetallic dendrimer encapsulated nanoparticles. J. Phys. Chem. C 117, 75987604 (2013).
32. Gu S., Wunder S., Lu Y., and Ballauff M.: Kinetic analysis of the catalytic reduction of 4-nitrophenol by metallic nanoparticles. J. Phys. Chem. C 118, 1861818625 (2014).
33. Zhang R., Liu Lu., Li Y., Wang W., Li R.: Electroxidation Kinetics of Hydrazine on Y-type Zeolite encapsulated Ni(II)(salen) Complex Supported on Graphite Modified Electrode. Int. J. Electrochem. Sci., 10, 23552369 (2015).
34. Darensbourg D.J., Rodgers J.L., and Fang C.C.: The copolymerization of carbon dioxide and [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane catalyzed by (salen)CrCl. Formation of a CO2 soluble polycarbonate. Inorg. Chem. 42, 44984500 (2003).
35. Paredes J.I., Villar-Rodil S., Martínez-Alonso A., and Tascón J.M.D.: Graphene oxide dispersions in organic solvents. Langmuir 24, 1056010564 (2008).
36. Konios D., Stylianakis M.M., Stratakis E., and Kymakis E.: Dispersion behaviour of graphene oxide and reduced graphene oxide. J. Colloid Interface Sci. 430, 108112 (2014).
37. Pérez-Lorenzo M.: Palladium nanoparticles as efficient catalysts for Suzuki cross-coupling reactions. J. Phys. Chem. Lett. 3, 167174 (2012).
38. Krittayavathananon A., Srimuk P., Luanwuthi S., and Sawangphruk M.: Palladium nanoparticles decorated on reduced graphene oxide rotating disk electrodes toward ultrasensitive hydrazine detection: Effects of particle size and hydrodynamic diffusion. Anal. Chem. 86, 1227212278 (2014).
39. Zhang X., Zhu J., Tiwary C.S., Ma Z., Huang H., Zhang J., Lu Z., Huang W., and Wu Y.: Palladium nanoparticles supported on nitrogen and sulfur dual-doped graphene as highly active electrocatalysts for formic acid and methanol oxidation. ACS Appl. Mater. Interfaces 8, 1085810865 (2016).
40. Huang Y.X., Xie J.F., Zhang X., Xiong L., and Yu H.Q.: Reduced graphene oxide supported palladium nanoparticles via photoassisted citrate reduction for enhanced electrocatalytic activities. ACS Appl. Mater. Interfaces 6, 1579515801S (2014).
41. Kocak C.C., Altın A., Aslisen B., and Kocak S.: Electrochemical preparation and characterization of gold and platinum nanoparticles modified poly(taurine) film electrode and its application to hydrazine determination. Int. J. Electrochem. Sci. 11, 233249 (2016).
42. Park K., Yu H.J., Chung W.K., Kim B.J., and Kim S.H.: Effect of heat-treatment on CdS and CdS/ZnS nanoparticles. J. Mater. Sci. 44, 43154320 (2009).
43. Kuroda K., Ishida T., and Haruta M.: Reduction of 4-nitrophenol to 4-aminophenol over Au nanoparticles deposited on PMMA. J. Mol. Catal. 298, 711 (2009).
44. Wunder S., Polzer F., Lu Y., Mei Y., and Ballauff M.: Kinetic analysis of catalytic reduction of 4-nitrophenol by metallic nanoparticles immobilized in spherical polyelectrolyte brushes. J. Phys. Chem. C 114, 88148820 (2010).
45. Kastner C. and Thunemann A.F.: Catalytic reduction of 4-nitrophenol using silver nanoparticles with adjustable activity. Langmuir 32, 73837391 (2016).
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