Selective Aerobic Oxidation of Benzyl Alcohols with Palladium(0) Nanoparticles Suspension in Water

Abstract

This study concerns one of the rare applications of a suspension of palladium nanoparticles in water for oxidation reactions. The aqueous suspension containing well dispersed nanoparticles of 3.85 nm was obtained following a straightforward procedure involving the reduction of Na2PdCl4 with NaBH4 in the presence of PVP as stabilizing agent. In the way of oxidative catalytic valorisation of lignin, the aqueous suspension was directly applied as catalytic medium for the selective oxidation of vanillic alcohol into vanillin (80 °C, O2, 1 h) with more than 90% yield. Reusability of the catalytic medium has been demonstrated, acting as “quasi-homogeneous catalyst”. More sophisticated lignin-derived substrates like veratryl alcohol and hydrobenzoin gave yields of 50–80% to the respective aldehyde and ketone. In parallel, this as-synthesized suspension was directly used to prepare a Pd/TiO2 catalyst, the latter showing less efficiency for the catalytic transformations.

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References

  1. 1.

    Parmeggiani C, Cardona F (2012) Transition metal based catalysts in the aerobic oxidation of alcohols. Green Chem 14:547–564

    CAS  Article  Google Scholar 

  2. 2.

    Davis SE, Ide MS, Davis RJ (2013) Selective oxidation of alcohols and aldehydes over supported metal nanoparticles. Green Chem 15:17–45

    CAS  Article  Google Scholar 

  3. 3.

    Chan-Thaw CE, Savara A, Villa A (2018) Selective benzyl alcohol oxidation over Pd catalysts. Catalysts 8:431/431-431/421

    Article  CAS  Google Scholar 

  4. 4.

    Durndell LJ, Lee AF, Bailie DS, Muldoon MJ (2015) Selective palladium-catalysed aerobic oxidation of alcohols. RSC Green Chem Ser 28:92–132

    CAS  Google Scholar 

  5. 5.

    Muzart J (2003) Palladium-catalysed oxidation of primary and secondary alcohols. Tetrahedron 59:5789–5816

    CAS  Article  Google Scholar 

  6. 6.

    Bourbiaux D, Pu J, Rataboul F, Djakovitch L, Geantet C, Laurenti D (2021) Reductive or oxidative catalytic lignin depolymerization: an overview of recent advances. Catal Today (Under revision)

  7. 7.

    Sun Z, Fridrich B, de Santi A, Elangovan S, Barta K (2018) Bright side of lignin depolymerization: toward new platform chemicals. Chem Rev 118:614–678

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  8. 8.

    Zakzeski J, Bruijnincx PCA, Jongerius AL, Weckhuysen BM (2010) The catalytic valorization of lignin for the production of renewable chemicals. Chem Rev 110:3552–3599

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  9. 9.

    Ma R, Guo M, Zhang X (2018) Recent advances in oxidative valorization of lignin. Catal Today 302:50–60

    CAS  Article  Google Scholar 

  10. 10.

    Vangeel T, Schutyser W, Renders T, Sels BF (2018) Perspective on lignin oxidation: advances, challenges, and future directions. Top Curr Chem 376:30

    Article  CAS  Google Scholar 

  11. 11.

    Dell’Anna MM, Mali M, Mastrorilli P, Cotugno P, Monopoli A (2014) Oxidation of benzyl alcohols to aldehydes and ketones under air in water using a polymer supported palladium catalyst. J Mol Catal A 386:114–119

    Article  CAS  Google Scholar 

  12. 12.

    Zhang W, Xiao Z, Wang J, Fu W, Tan R, Yin D (2019) Selective aerobic oxidation of alcohols over gold-palladium alloy catalysts using air at atmospheric pressure in water. ChemCatChem 11:1779–1788

    Article  CAS  Google Scholar 

  13. 13.

    Ganji N, Karimi B, Najafvand-Derikvandi S, Vali H (2020) Palladium supported on a novel ordered mesoporous polypyrrole/carbon nanocomposite as a powerful heterogeneous catalyst for the aerobic oxidation of alcohols to carboxylic acids and ketones on water. RSC Adv 10:13616–13631

    CAS  Article  Google Scholar 

  14. 14.

    Favier I, Pla D, Gómez M (2020) Palladium nanoparticles in polyols: synthesis, catalytic couplings, and hydrogenations. Chem Rev 120:1146–1183

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  15. 15.

    Axet MR, Philippot K (2020) Catalysis with colloidal ruthenium nanoparticles. Chem Rev 120:1085–1145

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  16. 16.

    Astruc D, Lu F, Aranzaes JR (2005) Nanoparticles as recyclable catalysts: the frontier between homogeneous and heterogeneous catalysis. Angew Chem Int Ed 44:7852–7872

    CAS  Article  Google Scholar 

  17. 17.

    Prati L, Villa A (2014) Gold colloids: from quasi-homogeneous to heterogeneous catalytic systems. Acc Chem Res 47:855–863

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  18. 18.

    Denicourt-Nowicki A, Roucoux A (2016) Odyssey in polyphasic catalysis by metal nanoparticles. Chem Rec 16:2127–2141

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  19. 19.

    Wang X, Huang C, Li X, Xie C, Yu S (2019) PVA-encapsulated palladium nanoparticles: eco-friendly and highly selective catalyst for hydrogenation of nitrobenzene in aqueous medium. Chem Asian J 14:2266–2272

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  20. 20.

    Llevot A, Monney B, Sehlinger A, Behrens S, Meier M (2017) Highly efficient Tsuji–Trost allylation in water catalyzed by Pd-nanoparticles. Chem Commun 53:5175–5178

    CAS  Article  Google Scholar 

  21. 21.

    Levi N, Neumann R (2013) Diastereoselective and enantiospecific direct reductive amination in water catalyzed by palladium nanoparticles stabilized by polyethyleneimine derivatives. ACS Catal 3:1915–1918

    CAS  Article  Google Scholar 

  22. 22.

    Ohtaka A, Teratani T, Fujii R, Ikeshita K, Kawashima T, Tatsumi K, Shimomura O, Nomura R (2011) Linear polystyrene-stabilized palladium nanoparticles-catalyzed C–C coupling reaction in water. J Org Chem 76:4052–4060

    CAS  PubMed  Article  Google Scholar 

  23. 23.

    Sawoo S, Srimani D, Dutta P, Lahiri R, Sarkar A (2009) Size controlled synthesis of Pd nanoparticles in water and their catalytic application in C–C coupling reactions. Tetrahedron 65:4367–4374

    CAS  Article  Google Scholar 

  24. 24.

    La Sorella G, Sperni L, Canton P, Coletti L, Fabris F, Strukul G, Scarso A (2018) Selective hydrogenations and dechlorinations in water mediated by anionic surfactant-stabilized Pd nanoparticles. J Org Chem 83:7438–7446

    PubMed  Article  CAS  Google Scholar 

  25. 25.

    Zhang Y, Zhu J, Xia Y-T, Sun X-T, Wu L (2016) Efficient hydrogenation of nitrogen heterocycles catalyzed by carbon-metal covalent bonds-stabilized palladium nanoparticles: synergistic effects of particle size and water. Adv Synth Catal 358:3039–3045

    CAS  Article  Google Scholar 

  26. 26.

    Noel S, Leger B, Ponchel A, Philippot K, Denicourt-Nowicki A, Roucoux A, Monflier E (2014) Cyclodextrin-based systems for the stabilization of metallic(0) nanoparticles and their versatile applications in catalysis. Catal Today 235:20–32

    CAS  Article  Google Scholar 

  27. 27.

    Mehta V, Panchal M, Kongor A, Panchal U, Jain VK (2016) Synthesis of water-dispersible Pd nanoparticles using a novel oxacalixarene derivative and their catalytic application in C–C coupling reactions. Catal Lett 146:1581–1590

    CAS  Article  Google Scholar 

  28. 28.

    Dhara K, Parasar B, Patil AJ, Dash J (2019) Microwave assisted cross-coupling reactions using palladium nanoparticles in aqueous media. Synth Commun 49:859–868

    CAS  Article  Google Scholar 

  29. 29.

    Dewan A, Bharali P, Bora U, Thakur AJ (2016) Starch assisted palladium(0) nanoparticles as in situ generated catalysts for room temperature Suzuki–Miyaura reactions in water. RSC Adv 6:11758–11762

    CAS  Article  Google Scholar 

  30. 30.

    Prastaro A, Ceci P, Chiancone E, Boffi A, Cirilli R, Colone M, Fabrizi G, Stringaro A, Cacchi S (2009) Suzuki–Miyaura cross-coupling catalyzed by protein-stabilized palladium nanoparticles under aerobic conditions in water: application to a one-pot chemoenzymatic enantioselective synthesis of chiral biaryl alcohols. Green Chem 11:1929–1932

    CAS  Article  Google Scholar 

  31. 31.

    Iben Ayad A, Belda Marin C, Colaco E, Lefevre C, Methivier C, Ould Driss A, Landoulsi J, Guenin E (2019) “Water soluble” palladium nanoparticle engineering for C–C coupling, reduction and cyclization catalysis. Green Chem 21:6646–6657

    CAS  Article  Google Scholar 

  32. 32.

    Ge J, Jiang J, Yuan C, Zhang C, Liu M (2017) Palladium nanoparticles stabilized by phosphine ligand for aqueous phase room temperature Suzuki–Miyaura coupling. Tetrahedron Lett 58:1142–1145

    CAS  Article  Google Scholar 

  33. 33.

    Asensio JM, Tricard S, Coppel Y, Andres R, Chaudret B, de Jesus E (2017) Synthesis of water-soluble palladium nanoparticles stabilized by sulfonated N-heterocyclic carbenes. Chem Eur J 23:13435–13444

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  34. 34.

    Hou W, Dehm NA, Scott RWJ (2008) Alcohol oxidations in aqueous solutions using Au, Pd, and bimetallic AuPd nanoparticle catalysts. J Catal 253:22–27

    CAS  Article  Google Scholar 

  35. 35.

    Balcha T, Strobl JR, Fowler C, Dash P, Scott RWJ (2011) Selective aerobic oxidation of crotyl alcohol using AuPd core-shell nanoparticles. ACS Catal 1:425–436

    CAS  Article  Google Scholar 

  36. 36.

    Giachi G, Oberhauser W, Frediani M, Passaglia E, Capozzoli L, Rosi L (2013) Pd-nanoparticles stabilized by pyridine-functionalized poly(ethylene glycol) as catalyst for the aerobic oxidation of α, β-unsaturated alcohols in water. J Polym Sci A 51:2518–2526

    CAS  Article  Google Scholar 

  37. 37.

    Matsura VA, Potekhin VV, Ukraintsev VB (2002) Kinetics of hydrogenation and oxidation of benzyl alcohol in the presence of colloid palladium in situ. Russ J Gen Chem 72:105–109

    CAS  Article  Google Scholar 

  38. 38.

    Behling R, Valange S, Chatel G (2016) Heterogeneous catalytic oxidation for lignin valorization into valuable chemicals: what results? What limitations? What trends? Green Chem 18:1839–1854

    CAS  Article  Google Scholar 

  39. 39.

    Hanson SK, Baker RT (2015) Knocking on wood: base metal complexes as catalysts for selective oxidation of lignin models and extracts. Acc Chem Res 48:2037–2048

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  40. 40.

    Dong Y, Jin Y, Wang J, Shu J, Zhang M (2017) Pd nanoparticles stabilized by a simple pH-sensitive p(acrylamide-co-acrylic acid) copolymer: a recyclable and highly active catalyst system in aqueous medium. Chem Eng J 324:303–312

    CAS  Article  Google Scholar 

  41. 41.

    Zhang J, Bai X (2017) Microwave-assisted synthesis of Pd nanoparticles and their catalysis application for Suzuki cross-coupling reactions. Inorg Nano-Met Chem 47:672–676

    CAS  Article  Google Scholar 

  42. 42.

    Zhao Y, Baeza JA, Koteswara Rao N, Calvo L, Gilarranz MA, Li YD, Lefferts L (2014) Unsupported PVA- and PVP-stabilized Pd nanoparticles as catalyst for nitrite hydrogenation in aqueous phase. J Catal 318:162–169

    CAS  Article  Google Scholar 

  43. 43.

    Zhu J-F, Tao G-H, Liu H-Y, He L, Sun Q-H, Liu H-C (2014) Aqueous-phase selective hydrogenation of phenol to cyclohexanone over soluble Pd nanoparticles. Green Chem 16:2664–2669

    CAS  Article  Google Scholar 

  44. 44.

    Narayanan R, El-Sayed MA (2003) Effect of catalysis on the stability of metallic nanoparticles: Suzuki reaction catalyzed by PVP-palladium nanoparticles. J Am Chem Soc 125:8340–8347

    CAS  PubMed  Article  PubMed Central  Google Scholar 

  45. 45.

    Tarnowicz S, Alsalahi W, Mieczyńska E, Trzeciak AM (2017) Heck arylation of allyl alcohol catalyzed by Pd(0) nanoparticles. Tetrahedron 73:5605–5612

    CAS  Article  Google Scholar 

  46. 46.

    Uberman PM, Pérez LA, Martín SE, Lacconi GI (2014) Electrochemical synthesis of palladium nanoparticles in PVP solutions and their catalytic activity in Suzuki and Heck reactions in aqueous medium. RSC Adv 4:12330–12341

    CAS  Article  Google Scholar 

  47. 47.

    Rautiainen S, Chen J, Vehkamäki M, Repo T (2016) Oxidation of vanillin with supported gold nanoparticles. Top Catal 59:1138–1142

    CAS  Article  Google Scholar 

  48. 48.

    Bayer T, Milker S, Wiesinger T, Winkler M, Mihovilovic MD, Rudroff F (2017) In vivo synthesis of polyhydroxylated compounds from a “hidden reservoir” of toxic aldehyde species. ChemCatChem 9:2919–2923

    CAS  Article  Google Scholar 

  49. 49.

    Zhu Y, Liu J, Liao Y, Lv W, Ma L, Wang C (2018) Degradation of vanillin during lignin valorization under alkaline oxidation. Top Curr Chem 376:29

    Article  CAS  Google Scholar 

  50. 50.

    Wu M, Pang J-H, Song P-P, Peng J-J, Xu F, Li Q, Zhang X-M (2019) Visible light-driven oxidation of vanillyl alcohol in air with Au–Pd bimetallic nanoparticles on phosphorylated hydrotalcite. New J Chem 43:1964–1971

    CAS  Article  Google Scholar 

  51. 51.

    Enache DI, Edwards JK, Landon P, Solsona-Espriu B, Carley AF, Herzing AA, Watanabe M, Kiely CJ, Knight DW, Hutchings GJ (2006) Solvent-free oxidation of primary alcohols to aldehydes using Au–Pd/TiO2 catalysts. Science 311:362–365

    CAS  PubMed  Article  Google Scholar 

  52. 52.

    Chen G, Wu S, Liu H, Jiang H, Li Y (2013) Palladium supported on an acidic metal–organic framework as an efficient catalyst in selective aerobic oxidation of alcohols. Green Chem 15:230–235

    CAS  Article  Google Scholar 

  53. 53.

    Layek K, Maheswaran H, Arundhathi R, Kantam ML, Bhargava SK (2011) Nanocrystalline magnesium oxide stabilized palladium(0): an efficient reusable catalyst for room temperature selective aerobic oxidation of alcohols. Adv Synth Catal 353:606–616

    CAS  Article  Google Scholar 

  54. 54.

    Anderson M, Afewerki S, Berglund P, Córdova A (2014) Total synthesis of capsaicin analogues from lignin-derived compounds by combined heterogeneous metal, organocatalytic and enzymatic cascades in one pot. Adv Synth Catal 356:2113–2118

    CAS  Article  Google Scholar 

  55. 55.

    Hinde CS, Ansovini D, Wells PP, Collins G, Aswegen SV, Holmes JD, Hor TSA, Raja R (2015) Elucidating structure–property relationships in the design of metal nanoparticle catalysts for the activation of molecular oxygen. ACS Catal 5:3807–3816

    CAS  Article  Google Scholar 

  56. 56.

    Fu W, Yue L, Duan X, Li J, Lu G (2016) Acceptor-free dehydrogenation of 4-hydroxy-3-methoxybenzyl alcohol to vanillin over a palladium complex. Green Chem 18:6136–6142

    CAS  Article  Google Scholar 

  57. 57.

    Zhang Z, Khrouz L, Yin G, Andrioletti B (2019) Efficient oxidation of benzylic and aliphatic alcohols using a bioinspired cross-bridged cyclam manganese complex with H2O2. Eur J Org Chem 2019:323–327

    CAS  Article  Google Scholar 

  58. 58.

    Dadras A, Naimi-Jamal MR, Moghaddam FM, Ayati SE (2018) Green and selective oxidation of alcohols by immobilized Pd onto triazole functionalized Fe3O4 magnetic nanoparticles. J Chem Sci 130:162

    Article  CAS  Google Scholar 

  59. 59.

    Lu Y-M, Zhu H-Z, Liu J-W, Yu S-H (2015) Palladium nanoparticles supported on titanate nanobelts for solvent-free aerobic oxidation of alcohols. ChemCatChem 7:4131–4136

    CAS  Article  Google Scholar 

  60. 60.

    Abad A, Almela C, Corma A, Garcia H (2006) Efficient chemoselective alcohol oxidation using oxygen as oxidant. Superior performance of gold over palladium catalysts. Tetrahedron 62:6666–6672

    CAS  Article  Google Scholar 

  61. 61.

    Buffin BP, Clarkson JP, Belitz NL, Kundu A (2005) Pd(II)-biquinoline catalyzed aerobic oxidation of alcohols in water. J Mol Catal A 225:111–116

    CAS  Article  Google Scholar 

  62. 62.

    Kim A, Bae HS, Park JC, Song H, Park KH (2015) Surfactant-free Pd@SiO2 yolk–shell nanocatalysts for selective oxidation of primary alcohols to aldehydes. New J Chem 39:8153–8157

    CAS  Article  Google Scholar 

  63. 63.

    Olmos CM, Chinchilla LE, Cappella AM, Villa A, Delgado JJ, Hungria AB, Blanco G, Calvino JJ, Prati L, Chen X (2018) Selective oxidation of veratryl alcohol over Au–Pd/Ce0.62Zr0.38O2 catalysts synthesized by sol-immobilization: effect of Au:Pd molar ratio. Nanomaterials 8:669/661-669/616

    Google Scholar 

  64. 64.

    Yang Z-W, Zhao X, Li T-J, Chen W-L, Kang Q-X, Xu X-Q, Liang X-X, Feng Y, Duan H-H, Lei Z-q (2015) Catalytic properties of palygorskite supported Ru and Pd for efficient oxidation of alcohols. Catal Commun 65:34–40

    CAS  Article  Google Scholar 

  65. 65.

    Zhang L, Li P, Yang J, Wang M, Wang L (2014) Palladium supported on magnetic core-shell nanoparticles: an efficient and reusable catalyst for the oxidation of alcohols into aldehydes and ketones by molecular oxygen. ChemPlusChem 79:217–222

    CAS  PubMed  Article  Google Scholar 

  66. 66.

    Mecozzi F, Dong JJ, Saisaha P, Browne WR (2017) Oxidation of vicinal diols to α-hydroxy ketones with H2O2 and a simple manganese catalyst. Eur J Org Chem 2017:6919–6925

    CAS  Article  Google Scholar 

  67. 67.

    De Crisci AG, Chung K, Oliver AG, Solis-Ibarra D, Waymouth RM (2013) Chemoselective oxidation of polyols with chiral palladium catalysts. Organometallics 32:2257–2266

    Article  CAS  Google Scholar 

  68. 68.

    Steele AM, Zhu J, Tsang SC (2001) Noble metal catalyzed aerobic oxidation of alcohols to aldehydes in supercritical carbon dioxide. Catal Lett 73:9–13

    CAS  Article  Google Scholar 

  69. 69.

    Iwahama T, Yoshino Y, Keitoku T, Sakaguchi S, Ishii Y (2000) Efficient oxidation of alcohols to carbonyl compounds with molecular oxygen catalyzed by N-hydroxyphthalimide combined with a Co species. J Org Chem 65:6502–6507

    CAS  PubMed  Article  Google Scholar 

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Acknowledgements

The authors thank the French National Research Agency for funding through NANOTRAP Project (ANR-17-CE07-0027). The authors thanks L. Burel (IRCELYON) for precious discussion concerning TEM analysis.

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Correspondence to Franck Rataboul.

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Bourbiaux, D., Mangematin, S., Djakovitch, L. et al. Selective Aerobic Oxidation of Benzyl Alcohols with Palladium(0) Nanoparticles Suspension in Water. Catal Lett (2021). https://doi.org/10.1007/s10562-021-03581-0

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Keywords

  • Metallic nanoparticles
  • Catalysis
  • Alcohols oxidation
  • Aqueous suspension