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Hydrogenation of diacetyl over composite-supported egg-shell noble metal catalysts

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Abstract

Two composite supports with a mixed inorganic–organic structure were synthesized: BTAl and UTAl. Hydrophilic–hydrophobic dual properties of the supports were suitable for preparing egg-shell-supported metal catalysts for selective hydrogenation reactions. The catalysts were characterized by ICP, XRD, OM, TEM, EPMA, XPS and TGA. Their mechanical resistance was assessed. Activity and selectivity were tested with the hydrogenation of 2,3-butanedione (diacetyl) to 3-hydroxy-2-butanoneacetoin (acetoin). The same order of increasing metal particle size was found for the two tested supports: Pt < Ru < Pd. The XPS analysis showed that the metal/composite catalysts reduced in H2 at 503 K had two kinds of active sites: reduced (Me°) and electron-deficient (Me+). It was rationalized that the hydrogen bond cleavage was performed on the Me° active sites, while reactant adsorption occurred on the Me+ sites. The differences in activity and selectivity between the composite catalysts were attributed to electronic effects on the different metals and to different adsorptive properties of the different polymers. The high selectivity to acetoin was attributed to the preferential adsorption of diacetyl as compared to the adsorption of acetoin. The BTAl catalysts were slightly more active and selective than the UTAl ones. This was attributed to electronic effects caused by remnant organic groups on the composite supports (urethane or biphenyl on UTAl or BTAl, respectively). Pd-BTAl was the most active and selective catalyst, a fact related to electronic effects of both palladium and the support.

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References

  • Andrzejewska E, Kusch P, Andrzejewski M (1993) Thermal decomposition of crosslinked polymers of some dimethacrylate esters. Polym Degrad Stab 40:27–30

    Article  CAS  Google Scholar 

  • Augustine RL (1997) Selective heterogeneously catalyzed hydrogenations. Catal Today 37:419–440

    Article  CAS  Google Scholar 

  • Badano JM, Betti C, Rintoul I, Vich-Berlanga J, Cagnola E, Torres G, Vera C, Yori J, Quiroga M (2010a) New composite materials as support for selective hydrogenation; egg-shell catalysts. Appl Catal A 390:166–174. doi:10.1016/j.apcata.2010.10.008

    Article  CAS  Google Scholar 

  • Badano JM, Quiroga M, Betti C, Vera C, Canavese S, Coloma-Pascual F (2010b) Resistance to sulfur and oxygenated compounds of supported Pd, Pt, Rh, Ru catalysts. Catal Lett 137:35–44. doi:10.1007/s10562-010-0336-x

    Article  CAS  Google Scholar 

  • Cagnola E, Liprandi D, Paredes J, Badano JM, Quiroga M (2012) A high (Z)/(E) ratio obtained during the 3-hexyne hydrogenation with a catalyst based on a Rh(I) complex anchored on a carbonaceous support. Catal Lett 142:231–237

    Article  Google Scholar 

  • Carrara N, Badano JM, Torres G, Bertero N, Betti C, Martinez-Bovier L, Quiroga M, Vera C (2014) Kinetics of the liquid phase selective hydrogenation of 2,3-butanedione over new composite supported Pd catalysts. J Chem Technol Biotechnol 89(2):265–275. doi:10.1002/jctb.4113

    Article  CAS  Google Scholar 

  • Carrara N, Badano JM, Betti C, Lederhos C, Rintoul I, Coloma-Pascual F, Vera C, Quiroga M (2015) Selective hydrogenation by novel composite supported Pd egg-shell catalysts. Catal Commun 61:72–77. doi:10.1016/j.catcom.2014.12.012

    Article  CAS  Google Scholar 

  • Di Vona ML, Floris B, Luchetti L, Rosnati V (1990) Single electron transfers in zinc-promoted reactions. The mechanisms of the clemmensen reduction and related reactions. Tetrahedron Lett 31:6081–6084

    Article  Google Scholar 

  • Gertosio V, Santini CC, Basset JM, Buendia J, Vivat M (1999) Heterogeneous chemo-, regio- and diastereoselective hydrogenation of steroidic alpha-diketone. J Mol Catal A Chem 142:141–145

    Article  CAS  Google Scholar 

  • Grafje H, Kornig W, Weitz H, Reib W, Steffan G, Diehl H, Bosche H, Schneider K, Kieczka H (2012) Butanediols, butenediol, and butynediol. In: Wiley-VCH Verlag GmbH & Co. KGaA W (ed) Ullman’s encyclopedia of industrial chemistry, vol 6, pp 407–415

  • Greenwood NN, Earnshaw A (1997) Chemistry of the elements, 2nd edn. Butterwoth-Heinemann, Leeds

    Google Scholar 

  • Hayakawa R, Sahara T, Shimizu M (2000) Reduction of 1,2-diketones with titanium tetraiodide: a simple approach to a -hydroxy ketones. Tetrahedron Lett 41:7939–7942

    Article  CAS  Google Scholar 

  • Huang SY, Chang SM, Yeh CT (2006) Characterization of surface composition of platinum and ruthenium nanoalloys dispersed on active carbon. J Phys Chem B 110:234–239. doi:10.1021/jp054870k

    Article  CAS  Google Scholar 

  • Huang S, Zhang C, He H (2008) Complete oxidation of o-xylene over Pd/Al2O3 catalyst at low temperatura. Catal Today 139:15–23

    Article  CAS  Google Scholar 

  • Iglesia E, Soled S, Baumgartner JE, Reyes S (1995) Synthesis and catalytic properties of eggshell cobalt catalysts for the Fisher–Tropsch synthesis. J Catal 153:108–122

    Article  CAS  Google Scholar 

  • La surface (2016) In: La Surf. Database. XPS X-Ray photoelectron spectroscopy. Roland Benoit CNRS Orléans. http://www.lasurface.com

  • Lin T, Chou T (1994) Selective hydrogenation of isoprene on eggshell and uniform palladium profile catalysts. Appl Catal A 108:7–19

    Article  CAS  Google Scholar 

  • Marshall R, Webb G, Jackson SD, Lennon D (2005) Propyne hydrogenation: characteristics of a carbon-supported palladium catalyst that exhibits a kinetic discontinuity effect. J Mol Catal A Chem 226:227–230

    Article  CAS  Google Scholar 

  • Nakamura K, Kondo S, Kawai Y, Hida K, Kitano K, Ohno A (1996) Enantio- and regioselective reduction of alfa-diketones by Baker’s yeast. Tetrahedron Asymmetry 7:409–412

    Article  Google Scholar 

  • Ngamsom B, Bogdanchikova N, Borja MA, Praserthdam P (2004) Characterisations of Pd-Ag/Al2O3 catalysts for selective acetylene hydrogenation: effect of pretreatment with NO and N2O. Catal Commun 5:243–248

    Article  CAS  Google Scholar 

  • NIST National Institute of Standarts and Technology (2016) In: X-ray photoelectron spectroscopy. Database NIST Stand. Ref. Database 20, Version 3.5. National Institute of Standards and Technology (NIST), USA. https://srdata.nist.gov/xps

  • Onoe T, Iwamoto S, Inoue M (2007) Synthesis and activity of the Pt catalyst supported on CNT. Catal Commun 8:701–706

    Article  CAS  Google Scholar 

  • Osawa T, Harada T, Takayasu O (2000) Progress of enantio-differentiating hydrogenation of prochiral ketones over asymmetrically modified nickel catalysts and a newly proposed enantio-differentiation model. Top Catal 13:155–168

    Article  CAS  Google Scholar 

  • Parent YO, Magrini K, Landin SM, Ritland MA (2011) Attrition resistant fluidizable reforming catalyst. United States Patent US 7,915,196 B2

  • Rylander PN (1985) Hydrogenation methods. Academic Press, London

    Google Scholar 

  • Scherzer J (1991) Attrition resistant cracking catalyst. United States Patent US 4,987,110

  • Serrano-Ruiz JC, Huber GW, Sánchez-Castillo MA, Dumesic JA, Rodríguez-Reinoso F, Sepúlveda-Escribano A (2006) Effect of Sn addition to Pt/CeO2–Al2O3 and Pt/Al2O3 catalysts: an XPS, 119Sn Mössbauer and microcalorimetry study. J Catal 241(2):378–388

    Article  CAS  Google Scholar 

  • Shriver DF, Atkins PW, Langford CH (1994) Inorganic chemistry, 3rd edn. WH Freeman and Co., New York

    Google Scholar 

  • Shul YG, Sugiura T, Tatsumi T, Tominaga H (1986) Durability of zeolite supported RusinglebondPt bimetallic catalysts for isoalkane synthesis from synthesis gas. Appl Catal 24:131–143

    Article  CAS  Google Scholar 

  • Toukoniitty E, Kuusisto J, Nieminen V, Hotokka M, Salmi T (2003) Solvent effects in enantioselective hydrogenation of 1-phenyl-1,2-propanedione. J Mol Catal A Chem 192:135–151

    Article  CAS  Google Scholar 

  • Zuo X, Li Y, Liu H (2001) Modification effect of metal cations on the stereoselective hydrogenation of 2, 3-butanedione. Catal Lett 71:177–180

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank CONICET, ANPCyT and UNL for the financial assistance of this work (Grants PIP 112-201101-00410 and 112-201301-00457, PICT and CAI + D).

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Authors and Affiliations

  1. INCAPE-CONICET, Instituto de Investigaciones en Catálisis y Petroquímica, Ruta 168 Km 0, S3000AOJ, Santa Fe, Argentina

    N. Carrara, J. M. Badano, C. Vera & M. Quiroga

  2. Universidad Tecnológica Nacional, Facultad Regional Santa Fe, Lavaise 610, S3004EWB, Santa Fe, Argentina

    N. Carrara

  3. Facultad de IngenieríaQuímica (UNL), Santiago del Estero 2829, S3000AOJ, Santa Fe, Argentina

    J. M. Badano, C. Vera & M. Quiroga

  4. Servicios Técnicos de Investigación, Facultad de Ciencias, Universidad de Alicante, Apartado 99, 03080, Alicante, Spain

    F. Coloma-Pascual

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  1. N. Carrara
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  2. J. M. Badano
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  3. F. Coloma-Pascual
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  4. C. Vera
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  5. M. Quiroga
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Correspondence to J. M. Badano.

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Carrara, N., Badano, J.M., Coloma-Pascual, F. et al. Hydrogenation of diacetyl over composite-supported egg-shell noble metal catalysts. Chem. Pap. 71, 1669–1683 (2017). https://doi.org/10.1007/s11696-017-0161-4

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  • DOI: https://doi.org/10.1007/s11696-017-0161-4

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