Supported palladium nanoclusters: morphological modification towards enhancement of catalytic performance using surfactant-assisted metal deposition

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In the present study, alumina-supported palladium catalysts were prepared by modified electroless deposition (ED) method in presence of surfactants and their performance was significantly improved compared to that prepared in absence of surfactants. Depending on the type and concentration of surfactant, loading and morphology of deposited palladium varied. Both anionic (sodium dodecyl sulphate) and non-ionic (Tween 20) surfactants were observed to be the most effective in dispersing the metals in the precursor solution. Average metal cluster sizes obtained for catalysts prepared by wetness impregnation, modified electroless deposition and surfactant-assisted deposition method were 11.89, 4.6 and 1.18 nm, respectively. The conversion of butane and selectivity to butene was observed to be function of size of deposited Pd cluster. The conversion and selectivity towards butenes increased with the decreasing particle size. The SDS surfactant-assisted prepared catalyst, having the lowest metal cluster size (1.18 nm), showed the highest activity (33% conversion at 600 °C) and over 99% selectivity for butenes.

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  1. Afroukhteh S, Dehghanian C, Emamy M (2012) Preparation of electroless Ni–P composite coatings containing nano-scattered alumina in presence of polymeric surfactant. Prog Nat Sci Mater Int 22:318–325.

  2. Agarwal A, Pujari M, Uppaluri R, Verma A (2016) Efficacy of palladium solution concentration on electroless fabrication of dense metal ceramic composite membranes coupled with surfactant and sonication. Mater Manuf Process 31:18–23.

  3. Ariyarathna IR, Rajakaruna RMPI, Karunaratne DN (2017) The rise of inorganic nanomaterial implementation in food applications. Food Control 77:251–259.

  4. Ataci N, Sarac A (2014) Determination of critical micel concentration of PEG-10 tallow propane amine: effects of salt and pH. Am J Anal Chem 05:22–27.

  5. Bakshi MS (2016) How surfactants control crystal growth of nanomaterials. Cryst Growth Des 16:1104–1133.

  6. Baldan A (2002) Review progress in ostwald ripening theories and their applications to nickel-base superalloys—part I: Ostwald ripening theories. J Mater Sci 37:2171–2202.

  7. Ballarini A, Bocanegra S, de Miguel S, Zgolicz P (2018) Synthesis of spherical structured catalysts by dip-coating: application to n-butane dehydrogenation. Can J Chem Eng 96:696–703.

  8. Beard KD, Schaal MT, Van Zee JW, Monnier JR (2007) Preparation of highly dispersed PEM fuel cell catalysts using electroless deposition methods. Appl Catal B Environ 72:262–271.

  9. Beard KD, Van Zee JW, Monnier JR (2009) Preparation of carbon-supported Pt–Pd electrocatalysts with improved physical properties using electroless deposition methods. Appl Catal B Environ 88:185–193.

  10. Bowker M, Nuhu A, Soares J (2007) High activity supported gold catalysts by incipient wetness impregnation. Catal Today 122:245–247.

  11. Chang FW, Kuo MS, Tsay MT, Hsieh MC (2003) Hydrogenation of CO2 over nickel catalysts on rice husk ash-alumina prepared by incipient wetness impregnation. Appl Catal A Gen 247:309–320.

  12. Delannoy L, El Hassan N, Musi A, Le To NN, Krafft J-M, Louis C (2006) Preparation of supported gold nanoparticles by a modified incipient wetness impregnation method. J Phys Chem B 110:22471–22478.

  13. Eom KS, Cho KW, Kwon HS (2008) Effects of electroless deposition conditions on microstructures of cobalt–phosphorous catalysts and their hydrogen generation properties in alkaline sodium borohydride solution. J Power Source 180:484–490.

  14. Gu B, He S, Rong X, Shi Y, Sun C (2016) Dehydrogenation of i-butane over tunable mesoporous alumina supported Pt–Sn catalyst. Catal Lett 146:1415–1422.

  15. Hamid ZA (2003) Mechanism of electroless deposition of Ni–W–P alloys by adding surfactants. Surf Interface Anal 35:496–501.

  16. Jackson SD, Rugmini S (2007) Dehydrogenation of n-butane over vanadia catalysts supported on θ-alumina. J Catal 251:59–68.

  17. Jana NR, Gearheart L, Murphy CJ (2001) Seed-mediated growth approach for shape-controlled synthesis of spheroidal and rod-like gold nanoparticles using a surfactant template. Adv Mater 13:1389–1393.;2-F

  18. Johnson CJ, Dujardin E, Davis SA, Murphy CJ, Mann S (2002) Growth and form of gold nanorods prepared by seed-mediated, surfactant-directed synthesis. J Mater Chem 12:1765–1770.

  19. Kang SW, Kim K, Chun DH, Yang J-II, Lee H-T, Jung H, Lim JT, Jang S, Kim CS, Lee C-W, Joo SH, Han JW, Park JC (2017) High-performance Fe5C2@CMK-3 nanocatalyst for selective and high-yield production of gasoline-range hydrocarbons. J Catal 349:66–74.

  20. Lee MH, Nagaraja BM, Lee KY, Jung KD (2014) Dehydrogenation of alkane to light olefin over PtSn/θ-Al2O3 catalyst: effects of Sn loading. Catal Today 232:53–62.

  21. Li X, Magnuson CW, Venugopal A, Tromp RM, Hannon JB, Vogel EM, Colombo L, Ruoff RS (2011) Large-area graphene single crystals grown by low-pressure chemical vapor deposition of methane on copper. J Am Chem Soc 133:2816–2819.

  22. Li H, Gao M, Gao Q, Wang H, Han B, Xia K, Zhou C (2019) Palladium nanoparticles uniformly and firmly supported on hierarchical flower-like TiO2 nanospheres as a highly active and reusable catalyst for detoxification of Cr(VI)-contaminated water. Appl Nanosci.

  23. Liu D, Yan Y, Lee K, Yu J (2009) Effect of surfactant on the alumina dispersion and corrosion behavior of electroless Ni–P–Al2O3 composite coatings. Mater Corros 60:690–694.

  24. Metzler M, Thorwart A, Zeller S, Diemant T, Behm RJ, Jacob T (2015) Electroless deposition of Au/Pt/Pd nanoparticles on p-Si(1 1 1) for the light-induced hydrogen evolution reaction. Catal Today 244:3–9.

  25. Nagaraja BM, Shin CH, Jung KD (2013) Selective and stable bimetallic PtSn/θ-Al2O3 catalyst for dehydrogenation of n-butane to n-butenes. Appl Catal A Gen 467:211–223.

  26. Nagaraja BM, Jung H, Yang DR, Jung KD (2014) Effect of potassium addition on bimetallic PtSn supported θ-Al2O3 catalyst for n-butane dehydrogenation to olefins. Catal Today 232:40–52.

  27. Nawaz Z, Baksh F, Zhu J, Wei F (2013) Dehydrogenation of C3–C4 paraffin’s to corresponding olefins over slit-SAPO-34 supported Pt-Sn-based novel catalyst. J Ind Eng Chem 19:540–546

  28. Neal LM, Jones SD, Everett ML, Hoflund GB, Hagelin-Weaver HE (2010) Characterization of alumina-supported palladium oxide catalysts used in the oxidative coupling of 4-methylpyridine. J Mol Catal A Chem 325:25–35.

  29. Park H-Y, Jang I, Jung N, Chung Y-H, Ryu J, Cha IY, Kim H-J, Jang JH, Yoo SJ (2015) Green synthesis of carbon-supported nanoparticle catalysts by physical vapor deposition on soluble powder substrates. Sci Rep 5:1–8.

  30. Patel CK, Sarma PJ, De M (2015) Comparative parametric study on development of porous structure of aluminium oxide in presence of anionic and cationic surfactants. Ceram Int 41:3578–3588.

  31. Plieth WJ (1982) Electrochemical properties of small clusters of metal atoms and their role in surface enhanced Raman scattering. J Phys Chem 86:3166–3170.

  32. Pujari M, Agarwal A, Uppaluri R, Verma A (2014) Effect of surfactant concentration and loading ratio on the electroless plating characteristics of dense Pd composite membranes. Ind Eng Chem Res 53:3105–3115.

  33. Qu L, Dai L (2005) Substrate-enhanced electroless deposition of metal nanoparticles on carbon nanotubes. J AM CHEM SOC 127:10806–10807.

  34. Rodríguez L, Romero D, Rodríguez D, Sanchez J, Dominguez F, Arteaga G (2010) Dehydrogenation of n-butane over Pd-Ga/Al2O3 catalysts. Appl Catal A Gen 373:66–70.

  35. Rosen M (1974) Relationship of structure properties in surfactants: II. Efficiency in surfaces or interfacial tension reduction. J Am Oil Chem Soc 51:461–465

  36. Sato H (2017) Extremely low catalyst loading for electroless deposition on a non-conductive surface by a treatment for reduced graphene oxide. Chem Commun 53:9198–9201.

  37. Schaal MT, Metcalf AY, Montoya JH, Wilkinson JP, Stork CC, Williams CT, Monnier JR (2007) Hydrogenation of 3,4-epoxy-1-butene over Cu-Pd/SiO2 catalysts prepared by electroless deposition. Catal Today 123:142–150.

  38. Schaal MT, Pickerell AC, Williams CT, Monnier JR (2008) Characterization and evaluation of Ag-Pt/SiO2 catalysts prepared by electroless deposition. J Catal 254:131–143.

  39. Seo H, Lee JK, Hong UG, Park G, Yoo Y, Lee J, Chang H, Song IK (2014) Direct dehydrogenation of n-butane over Pt/Sn/M/γ-Al2O3 catalysts: effect of third metal (M) addition. Catal Commun 47:22–27.

  40. Serp P, Kalck P (2002) Chemical vapor deposition methods for the controlled preparation of supported catalytic materials. Chem Rev 102:3085–3128.

  41. Shervani Z, Ikushima Y, Sato M, Kawanami H, Hakuta Y, Yokoyama T, Nagase T, Kuneida H, Aramaki K (2008) Morphology and size-controlled synthesis of silver nanoparticles in aqueous surfactant polymer solutions. Colloid Polym Sci 286:403–410.

  42. Soni KC, Krishna R, Chandra Shekar S, Singh B (2016) Catalytic oxidation of carbon monoxide over supported palladium nanoparticles. Appl Nanosci 6:7–17.

  43. Sriring N, Tantavichet N, Pruksathorn K (2010) Preparation of Pt/C catalysts by electroless deposition for proton exchange membrane fuel cells. Korean J Chem Eng 27:439–445.

  44. Stark WJ, Stoessel PR, Wohlleben W, Hafner A (2015) Industrial applications of nanoparticles. Chem Soc Rev 44:5793–5805.

  45. Starov VM (2004) Surfactant solutions and porous substrates: spreading and imbibition. Adv Colloid Interface Sci 111:3–27.

  46. Tung Y-L, Tseng W-C, Lee C-Y, Hsu P-F, Chi Y, Peng S-M, Lee G-H (1999) Synthesis and characterization of Allyl(β-ketoiminato)palladium(II) complexes: new precursors for chemical vapor deposition of palladium thin films. Organometallics 18:864–869.

  47. Wang Q, Robert F, Xu H, Li X (2005) On the critical radius in generalized Ostwald ripening. J Zhejiang Univ Sci 6B:705–707.

  48. Wang L, Li Z, Zhang Y, Zhang T, Xie G (2017) Hydrogen generation from alkaline NaBH4 solution using electroless-deposited Co–Ni–W–P/γ-Al2O3 as catalysts. J Alloys Compd 702:649–658.

  49. Wu W, Jiang C, Roy VAL (2015) Recent progress in magnetic iron oxide-semiconductor composite nanomaterials as promising photocatalysts. Nanoscale 7:38–58.

  50. Yang D, Kim D, Ko SH, Pisano AP, Li Z, Park I (2015) Focused energy field method for the localized synthesis and direct integration of 1D nanomaterials on microelectronic devices. Adv Mater 27:1207–1215.

  51. Yi H, Huang D, Qin L, Zeng G, Lai C, Cheng M, Ye S, Song B, Ren X, Guo X (2018) Selective prepared carbon nanomaterials for advanced photocatalytic application in environmental pollutant treatment and hydrogen production. Appl Catal B Environ 239:408–424.

  52. Zecevic J, Vanbutsele G, De Jong KP, Martens JA (2015) Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons. Nature 528:245–254.

  53. Zhang Z, Song Y, Xu C, Guo D (2012) A novel model for undeformed nanometer chips of soft-brittle HgCdTe films induced by ultrafine diamond grits. Scr Mater 67:197–200.

  54. Zhang D, Okajima T, Lu D, Ohsaka T (2013) Electroless deposition of platinum nanoparticles in room-temperature ionic liquids. Langmuir 29:11931–11940.

  55. Zhang Z, Guo D, Wang B, Kang R, Zhang B (2015a) A novel approach of high speed scratching on silicon wafers at nanoscale depths of cut. Sci Rep 5:1–9.

  56. Zhang Z, Wang Z, He S, Wang C, Jin M, Yin Y (2015b) Redox reaction induced Ostwald ripening for size- and shape-focusing of palladium nanocrystals. Chem Sci 6:5197–5203.

  57. Zhang Z, Wang B, Zhou P, Guo D, Kang R, Zhang B (2016) A novel approach of chemical mechanical polishing using environment-friendly slurry for mercury cadmium telluride semiconductors. Sci Rep 6:1–9.

  58. Zhang Z, Shi Z, Du Y, Yu Z, Guo L, Guo D (2018) A novel approach of chemical mechanical polishing for a titanium alloy using an environment-friendly slurry. Appl Surf Sci 427:409–415.

  59. Zhang Z, Cui J, Zhang J, Liu D, Yu Z, Guo D (2019) Environment friendly chemical mechanical polishing of copper. Appl Surf Sci 467–468:5–11.

  60. Zhao Y, Burda C (2012) Development of plasmonic semiconductor nanomaterials with copper chalcogenides for a future with sustainable energy materials. Energy Environ Sci 5:5564–5576.

  61. Zielińska K, Stankiewicz A, Szczygieł I (2012) Electroless deposition of Ni–P-nano-ZrO2 composite coatings in the presence of various types of surfactants. J Colloid Interface Sci 377:362–367.

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The authors acknowledge the financial support provided by DST-SERB India (SB/S3/CE/080/2013), and instrumental facilities provided by CIF, IIT Guwahati, India.

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Correspondence to Mahuya De.

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Saxena, R., Ukkandath Aravindakshan, S., Uppaluri, R. et al. Supported palladium nanoclusters: morphological modification towards enhancement of catalytic performance using surfactant-assisted metal deposition. Appl Nanosci (2020).

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  • Surfactant-assisted deposition
  • Palladium
  • Enhanced dispersion
  • Butane dehydrogenation