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Preparation of the Pd/C catalysts: A molecular-level study of active site formation

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Abstract

This review summarizes the results of molecular-level studies on the mechanism of Pd/C catalyst formation from the PdCl2 precursor. Two processes occur in acidic media during the contact of H2PdCl4 with carbon: (a) adsorption of palladium chloride to form surface complexes and (b) redox interaction between PdCl2 and carbon with the formation of palladium metal particles. The ratio between these adsorbed palladium species depends on the conditions of adsorption and especially on the size of carbon support grains and the oxidative atmosphere. The observations are explained by the fact that carbon support exhibits electrochemical and ligand properties. X-ray diffraction, X-ray scattering, XPS, and high-resolution electron microscopy revealed that the nanostructure of carbon materials, in particular the extent of their three-dimensional ordering, is crucial for the ligand properties. The presence of two forms, metallic and ionic, of sorbed palladium determines the bimodal size distribution of the metal. After the reduction of ionic species, metal particles are “blocked” with support. The nature of the ionic forms of palladium (mostly (PdCl2)n) clusters chemically and epitaxially bound to the carbon surface suggests the mechanisms of the bimodal distribution of the supported metal particles on the surface and the methods for the control of the ratio between “blocked,” low-dispersed, and highly-dispersed particles in the catalyst. One of these methods is the use of palladium polynuclear hydroxo complexes (PHCs) with low oxidation potentials as starting compounds for catalysts preparation. The data on the PHC structure in a solution and its change upon the adsorption of PHC on the surface of the carbon material obtained by the17O,23Na,133Cs, and35Cl NMR techniques are discussed. PHCs are shown to be a clew of the [Pd(OH)2]n polymeric filament, whose fractions are bound with alkali metal ions. When PHC is adsorbed on the surface of the carbon support and then dried, palladium oxide is formed from which highly dispersed metal particles are formed during reduction. The nature of alkali metal ions in PHC affects the activity of the Pd/C catalyst. An important role of the ligand, electrochemical, and lyophilic properties of carbon material during the formation of the species of the active catalyst component is discussed.

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References

  1. Takidzawa, Kh.,Kagaku to Kogyo, 1978, no. 4, p. 128.

  2. Semikolenov, V.A.,Usp. Khim., 1992, vol. 61, no. 2, p. 320.

    CAS  Google Scholar 

  3. Simonov, P.A., Romanenko, A.V., and Prosvirin, I.P.,Carbon, 1997, vol. 35, p. 73.

    Article  CAS  Google Scholar 

  4. Simonov, P.A., Semikolenov, V.A., Likholobov, V.A.,et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1988, no. 12, p. 2719.

  5. Kublanovskii, V.S., Tarasenko, Yu.A., Danilov, M.A., and Antonov, S.P.,Ukr. Khim. Zh., 1985, vol. 51, no. 9, p. 948.

    CAS  Google Scholar 

  6. Simonov, P.A., Moroz, E.M., Chuvilin, A.L.,et al., 6th Int. Symp. “Scietific Bases for the Preparation of Heterogeneous Catalysts,” Louvain-La-Neuve, 1994, vol. 3, p. 201.

    Google Scholar 

  7. Frumkin, A.,Zh. Fiz, Khim., 1934, vol. 5, no. 2/3, p. 240.

    Google Scholar 

  8. Kuchinskii, E., Burshtein, R., and Frumkin, A.,Zh. Fiz. Khim., 1940, vol. 14, no. 4, p. 441.

    CAS  Google Scholar 

  9. Frumkin, A.N.,Usp. Khim., 1949, vol. 18, no. 1, p. 9.

    CAS  Google Scholar 

  10. Frumkin, A.N., Ponomarenko, E.A., and Burshtein, R.Kh.,Dokl. Akad. Nauk SSSR, 1963, vol. 149, no. 5, p. 1123.

    CAS  Google Scholar 

  11. Frumkin, A.N.,Potentsialy nulevogo zaryada (Zero-Charge Potentials), Moscow: Nauka, 1982.

    Google Scholar 

  12. Strazhesko, D.N. and Tartakovskaya, B.E.,Dokl. Akad. Nauk SSSR, 1954, vol. 98, no. 1, p. 107.

    CAS  Google Scholar 

  13. Strazhesko, D.N.,Dokl. Akad. Nauk SSSR, 1955, vol. 102, no. 4, p. 775.

    CAS  Google Scholar 

  14. Matskevich, E.S., Strazhesko, D.N., and Goba, V.E.,Adsorbtsiya i adsorbenty (Adsorption and Adsorbents), Kiev: Naukova Dumka, 1974, no. 2, p. 36.

    Google Scholar 

  15. Tarasenko, Yu.A., Bagreev, A.A., Dudarenko, V.V.,et al., Ukr. Khim. Zh., 1989, vol. 55, no. 3, p. 233.

    CAS  Google Scholar 

  16. Strelko, V.V., Tarasenko, Yu.A., Bagreev, A.A., and Lavrinenko-Ometsinskaya, E.D.,Ukr. Khim. Zh., 1991, vol. 57, no. 9, p. 920.

    CAS  Google Scholar 

  17. Simonov, P.A., Romanenko, A.V., Prosvirin, I.P.,et al., Stud. Surf. Sci. Catal, 1998, vol. 118, p. 15.

    CAS  Google Scholar 

  18. Tarasenko, Yu.A., Bagreev, A.A., Gorban’, S.A.,et al., Ukr. Khim. Zh., 1989, vol. 55, no. 12, p. 1269.

    CAS  Google Scholar 

  19. Simonov, P.A., Moroz, E.M., Likholobov, V.A., and Plaksin, G.V.,Materialy II Vsesoyuznogo seminara po adsorbtsii i zhidkostnoi khromatografii elastomerov (Proc. of II All-Union Seminar on Adsorption and Liquid Chromatography of Elastoplastics), Moscow: TsNIITEneftekhim, 1989, vol. l,p. 115.

    Google Scholar 

  20. Simonov, P.A., Chuvilin, A.L., and Likholobov, V.A.,Izv. Akad. Nauk SSSR, Ser. Khim., 1989, no. 9, p. 1952.

  21. Simonov, P.A., Moroz, E.M., Likholobov, V.A., and Plaksin, G.V.,Izv. Akad. Nauk SSSR, Ser. Khim., 1990, no. 7, p. 1478.

  22. Kuznetsov, V.L., Chuvilin, A.L., Butenko, Yu.V.,et al., Chem. Phys. Lett., 1994, vol. 222, p. 343.

    Article  CAS  Google Scholar 

  23. Simonov, P.A., Filimonova, S.V., Kryukova, G.N.,et al., Carbon (in press).

  24. Moroz, E.M., Bogdanov, S.V., and Simonov, P.A.,Proc. of 6th Eur. Powder Diffraction Conf. (EPDIC-6), Budarest, 1998, p. 281.

  25. Lisitsyn, A.S., Simonov, P.A., Ketterling, A.A., and Likholobov, V.A.,Stud. Surf. Sci. Catal, 1991, vol. 63, p. 449.

    CAS  Google Scholar 

  26. Lamber, R., Jaeger, N., and Schulz-Ekloff, G.,Surf. Sci., 1990, vol. 227, no. 1/2, p. 15.

    Article  CAS  Google Scholar 

  27. Krishnankutty, N. and Vannice, M.A.,J. Catal., 1995, vol. 155, no. 1,p. 316.

    Google Scholar 

  28. Dacey, J.R.,The Solid-Gas Interface, Flood, E.A., Ed., New York: Marcel Dekker, 1967, vol. 2, p. 1019.

    Google Scholar 

  29. Ivanova, T.N., Vartapenyan, R.Sh., and Voloshchuk, A.M.,Uglerodnye adsorbenty i ikh primenenie v promyshlennosti: Tezisy dokladov V Vsesoyuznogo soveshchaniya (Carbon Adsorbents and Their Application in Industry: Abstracts of papers of the V All-Union Workshop), Perm: Vsesoyuznyi Nauchno-Issledovatel’skii Tekhnologicheskii Institut Uglerodnykh Adsorbentov, 1991, p. 71.

    Google Scholar 

  30. Kaneko, K., Ishii, C., Ruike, M., and Kuwabara, H.,Carbon, 1992, vol. 30, no. 7, p. 1075.

    Article  CAS  Google Scholar 

  31. Kinoshita, K.,Carbon, Electrochemical, and Physico-chemical Properties, New York: Willey, 1988.

    Google Scholar 

  32. Tardy, B., Nuopa, C., Leclerco, C.,et al., J. Catal., 1991, vol. 129, no. 1, p. 1.

    Article  CAS  Google Scholar 

  33. Wu, N.L. and Phillips, J.,Surf. Sci., 1987, vol. 184, no. 3, p. 463.

    Article  CAS  Google Scholar 

  34. Morikawa, K., Shirasaki, T., and Okada, M.,Adv. Catal., 1969, vol. 20, p. 97.

    Article  CAS  Google Scholar 

  35. Heal, G.R. and Mkayula, L.L.,Carbon, 1988, vol. 26, no. 3, p. 803.

    Article  CAS  Google Scholar 

  36. Suh, D.J., Park, T.-J., and Ihm, S.-K.,Carbon, 1993, vol. 31, no. 3, p. 427.

    Article  CAS  Google Scholar 

  37. Kuretzky, T.,Ph.D. Thesis, Munich: Inst. of Inorg. Chem., Munich Univ., 1993.

    Google Scholar 

  38. Herberhold, M.,Metal π-Complexes: Complexes with Mono-Olefinic Ligands, Amsterdam: Elsevier, 1974, vol. 2(2).

    Google Scholar 

  39. Fenelonov, V.B., Avdeeva, L.B., Goncharova, O.V.,et al., 6th Int. Symp. “Scientific Bases for the Preparation of Heterogeneous Catalysts,” Louvain-La-Neuve, 1994, vol. 3, p. 43.

    Google Scholar 

  40. US Patent 3 138 560.

  41. Chang, K.R., Chen, H.W., and Wan, Ch.C.,J. Chem. Technol. Biotechnol. A, 1984, vol. 34, no. 5, p. 237.

    Article  CAS  Google Scholar 

  42. Yang, Y., Zhou, Y., Cha, C.,et al., Electrochim. Acta, 1993, vol. 38, p. 2333.

    Article  CAS  Google Scholar 

  43. Alberts, P., Burmeister, R., Seibold, K.,et al., J. Catal., 1999, vol. 181, no. 1, p. 145.

    Article  Google Scholar 

  44. Beck, M. and Nagypal, I.,Chemistry of Complex Equilibria, Budapest: Akademiai Kiado, 1989.

    Google Scholar 

  45. Milic, N.B. and Bugarcic, J.D.,Transition Metal Chemistry, 1984, vol. 9, no. 5, p. 173.

    Article  CAS  Google Scholar 

  46. Izatt, R.M., Eatough, D., and Christensen, J.,J. Chem. Soc.A, 1967, no. 8, p. 1301.

  47. Nabivanets, V.I. and Kalibina, A.V.,Zh. Neorg. Khim., 1970, vol. 10, no. 6, p. 1595.

    Google Scholar 

  48. US Patent 3 736 265.

  49. Wyatt, Ir.R.,Chem. Weekbland, 1966, no. 62, p. 310.

  50. Pshenitsyn, N.K. and Ginzburg, S.I.,Izv. Sektora Platiny Inst. Org. Khim., 1954, no. 28, p. 213.

  51. Ivanov-Emin, B.N., Petrishcheva, L.P., and Zaitsev, B.E.,Koord. Khim., 1986, vol. 12, no. 4, p. 537.

    CAS  Google Scholar 

  52. Kravchuk, L.S., Stremok, I.P., and Markevich, S.V.,Zh. Neorg. Khim., 1976, vol. 21, no. 3, p. 728.

    CAS  Google Scholar 

  53. Kaszonyi, A., Voitko, J., and Hrusovsky, M.,Collect. Czech. Chem. Commun., 1978, vol. 43, no. 11, p. 3002.

    CAS  Google Scholar 

  54. McCaffery, A.J., Schatz, P.N., and Stephens, P.J.,J. Phys. Chem., 1978, vol. 82, no. 1, p. 69.

    Article  Google Scholar 

  55. Pechenyuk, S.I.,Sorbtsionno-gidroliticheskoe osazhdenie platinovykh metallov na poverkhnosti neorganicheskikh sorbentov (Sorption-Hydrolytic Deposition of Metals on Surfaces of Inorganic Sorbents), Leningrad: Nauka, 1991.

    Google Scholar 

  56. Troitskii, S.Yu., Chuvilin, A.V., Fedotov, M.A.,et al., Tezisy dokladov V mezhdunarodnogo simpoziuma po svyazi mezhdu gomogennym i geterogennym katalizom (Proc. of V Int. Symp. on the Relations between Homogeneous and Heterogeneous Catalysis), Novosibirsk, 1986, p. 247.

  57. Troitskii, S.Yu., Fedotov, M.A., and Likholobov, V.A.,Izv. Akad. Nauk, Ser. Khim., 1993, no. 4, p. 679.

  58. Fedotov, M.A., Troitskii, S.Yu., and Likholobov, V.A.,Koord. Khim., vol. 16, no. 12, p. 1675.

  59. Troitskii, S.Yu., Chuvilin, A.L., Kochubei, D.I.,et al., Izv. Akad. Nauk, Ser. Khim., 1995, no. 10, p. 1901.

  60. Troitskii, S.Yu., Chuvilin, A.L., Bogdanov, S.V.,et al., Izv. Akad. Nauk, Ser. Khim., 1996, no. 6, p. 1366.

  61. Fedotov, M.A., Krivoruchko, O.P., and Buyanov, R.A.,Izv. Akad. Nauk SSSR, Ser. Khim., 1977, no. 12, p. 2647.

  62. Ormont, B.F.,Struktury neorganicheskikh veshchestv (Structures of Inorganic Substances), Moscow: Gos. Izd. Tekh. Teor. Lit., 1950.

    Google Scholar 

  63. Didilon, B., Merlen, E., Pages, T., and Uzio, D.,Preparation of Catalysts, Amsterdam: Elsevier, 1998, vol. 7, p. 41.

    Google Scholar 

  64. Aica, K.I., Kawahara, T., Murata, S., and Onishi, T.,Bull. Chem. Soc. Jpn., 1990, vol. 63, no. 4, p. 1221.

    Article  Google Scholar 

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  1. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, 630090, Novosibirsk, Russia

    P. A. Simonov, S. Yu. Troitskii & V. A. Likholobov

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Simonov, P.A., Troitskii, S.Y. & Likholobov, V.A. Preparation of the Pd/C catalysts: A molecular-level study of active site formation. Kinet Catal 41, 255–269 (2000). https://doi.org/10.1007/BF02771428

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