Skip to main content
Log in

On the Use of Calcined Agro-Industrial Waste as Palladium Supports in the Production of Eco-Friendly Catalysts: Rice Husks and Banana Peels Tested in the Suzuki–Miyaura Reaction

  • Original Paper
  • Published:
Waste and Biomass Valorization Aims and scope Submit manuscript

Abstract

Two calcined agro-industrial wastes [rice husk ash (RHA) and banana peel ash (BPA)] with immobilized PdCl2 (Pd/RHA and Pd/BPA, respectively) that were produced at an extremely low cost were found to be efficient catalysts for Suzuki–Miyaura cross-coupling reactions. Iodo- and bromoarenes coupled with aryllboronic acid under eco-friendly conditions (i.e., phosphine-free and with ethanol as the solvent) to give very good product yields. The study of Pd/RHA in the Suzuki–Miyaura reaction showed that the catalyst only promoted the cross-coupling of bromoarenes after no iodoarenes in the reaction medium remained (competition study). Also, the Pd/RHA showed catalytic activity up to the fifth recycling, as evidenced by active soluble Pd found with a new proposed method based on the use of hollow fiber. An Hg(0) poisoning test did not find the presence of unprotected Pd(0) in the system. Thus, it is believed that there is a synergistic catalytic action between Pd supported in Pd/RHA and leached Pd(II).

Graphical Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Scheme 1
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. de Oliveira, J.P., Bruni, G.P., Lima, K.O., El Halal, S.L.M., da Rosa, G.S., Dias, A.R.G., Zavareze, E.R.: Cellulose fibers extracted from rice and oat husks and their application in hydrogel. Food Chem. 221, 153–160 (2017)

    Article  Google Scholar 

  2. Frías, O.R.M., Rojas, M.I.S., Villar-Cociña, E., Rodrigues, M.S., Savastano-Junior, H.: Advances on the development of ternary cements elaborated with biomass ashes coming from different activation process. Constr. Build. Mater. 136, 73–80 (2017)

    Article  Google Scholar 

  3. Salim, A.A., Grbavčić, S., Šekuljica, N., Stefanović, A., Tanasković, S.J., Luković, N., Knežević-Jugović, Z.: Production of enzymes by a newly isolated Bacillus sp. TMF-1 in solid state fermentation on agricultural by-products: the evaluation of substrate pretreatment methods. Bioresource Technol. 228, 193–200 (2017)

    Article  Google Scholar 

  4. Selvaraju, G., Bakar, N.K.A.: Production of a new industrially viable green-activated carbon from Artocarpus integer fruit processing waste and evaluation of its chemical, morphological and adsorption properties. J. Clean. Prod. 141, 989–999 (2017)

    Article  Google Scholar 

  5. Costa, M.S.S.M., Bernardi, F.H., Costa, L.A.M., Pereira, D.C., Lorin, H.E.F., Rozatti, M.A.T., Carneiro, L.J.: Composting as a cleaner strategy to broiler agro-industrial wastes: selecting carbon source to optimize the process and improve the quality of the final compost. J. Clean. Prod. 142, 2084–2092 (2017)

    Article  Google Scholar 

  6. Holanda, L.R., Ramos, F.S.: Reuse of waste sugarcane agribusiness and green power generation. J. Clean Energy Technol. 4, 341–345 (2016)

    Article  Google Scholar 

  7. Brazilian Institute of Geography and Statistics: http://agenciadenoticias.ibge.gov.br/agencia-sala-de-imprensa/2013-agencia-de-noticias/releases/10168-em-maio-ibge-preve-safra-de-graos-29-2-maior-que-em-2016.html (2017). Accessed 08 June 2017

  8. Foletto, E.L., Hoffmann, R., Hoffmann, R.S., Portugal, U.L. Jr., Jahn, S.L.: Applicability of rice husk ash. Quim. Nova 28, 1055–1060 (2005)

    Article  Google Scholar 

  9. Negishi, E.: Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley, New York (2002)

    Book  Google Scholar 

  10. Diederich, F., Meijere, A.: Metal-Catalyzed Cross-Coupling Reactions. Wiley, Weinheim (2004)

    Google Scholar 

  11. Miyaura, N., Suzuki, A.: Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev. 7, 2457–2483 (1995)

    Article  Google Scholar 

  12. Yılmaz, Ü, Küçükbay, H., Deniz, S., Şireci, N.: Synthesis, characterization and microwave-promoted catalytic activity of novel N-phenylbenzimidazolium salts in Heck-Mizoroki and Suzuki-Miyaura cross-coupling reactions under mild conditions. Molecules 18, 2501–2517 (2013)

    Article  Google Scholar 

  13. Azua, A., Mata, J.A., Heymes, P., Peris, E., Lamaty, F., Martinez, J., Colacino, E.: Palladium N-heterocyclic carbene catalysts for the ultrasound-promoted Suzuki-Miyaura reaction in glycerol. Adv. Synth. Catal. 355, 1107–1116 (2013)

    Article  Google Scholar 

  14. Faria, V.W., Oliveira, D.G.M., Kurz, M.H.S., Gonçalves, F.F., Scheeren, C.W., Rosa, G.R.: Palladium nanoparticles supported in a polymeric membrane: an efficient phosphine-free “green” catalyst for Suzuki-Miyaura reactions in water. RSC Adv. 4, 13446–13452 (2014)

    Article  Google Scholar 

  15. Lebaschi, S., Hekmati, M., Veisi, H.: Green synthesis of palladium nanoparticles mediated by black tea leaves (Camellia sinensis) extract: catalytic activity in the reduction of 4-nitrophenol and Suzuki-Miyaura coupling reaction under ligand-free conditions. J. Colloid Interface Sci. 485, 223–231 (2017)

    Article  Google Scholar 

  16. Khan, M., Albalawi, G.H., Shaik, M.R., Khan, M., Adil, S.F., Kuniyil, M., Alkhathlan, H.Z., Al-Warthan, A., Siddiqui, M.R.H.: Miswak mediated green synthesized palladium nanoparticles as effective catalysts for the Suzuki coupling reactions in aqueous media. J. Saudi Chem. Soc. 21, 450–457 (2017)

    Article  Google Scholar 

  17. Veisi, H., Rashtiani, A., Barjasteh, V.: Biosynthesis of palladium nanoparticles using Rosa canina fruit extract and their use as a heterogeneous and recyclable catalyst for Suzuki–Miyaura coupling reactions in water. Appl. Organometal. Chem. 30, 231–235 (2016)

    Article  Google Scholar 

  18. Veisi, H., Nasrabadi, N.H., Mohammadi, P.: Biosynthesis of palladium nanoparticles as a heterogeneous and reusable nanocatalyst for reduction of nitroarenes and Suzuki coupling reactions. Appl. Organometal. Chem. 30, 890–896 (2016)

    Article  Google Scholar 

  19. Veisi, H., Ghorbani-Vaghei, R., Hemmati, S., Aliani, M.H., Ozturk, T.: Green and effective route for the synthesis of monodispersed palladium nanoparticles using herbal tea extract (Stachys lavandulifolia) as reductant, stabilizer and capping agent, and their application as homogeneous and reusable catalyst in Suzuki coupling reactions in water. Appl. Organometal. Chem. 29, 26–32 (2015)

    Article  Google Scholar 

  20. Veisi, H., Faraji, A.R., Hemmati, S., Gil, A.: Green synthesis of palladium nanoparticles using Pistacia atlantica kurdica gum and their catalytic performance in Mizoroki–Heck and Suzuki–Miyaura coupling reactions in aqueous solutions. Appl. Organometal. Chem. 29, 517–523 (2015)

    Article  Google Scholar 

  21. Baran, T., Açiksöz, E., Menteş, A.: Carboxymethyl chitosan Schiff base supported heterogeneous palladium(II) catalysts for Suzuki cross-coupling reaction. J. Mol. Catal. A 407, 47–52 (2015)

    Article  Google Scholar 

  22. Baran, T., Sargin, I., Kaya, M., Menteş, A.: Green heterogeneous Pd(II) catalyst produced from chitosan-cellulose micro beads for green synthesis of biaryls. Carbohydr. Polym. 152, 181–188 (2016)

    Article  Google Scholar 

  23. Baran, T.: Practical, economical, and eco-friendly starch-supported palladium catalyst for Suzuki coupling reactions. J. Colloid Interface Sci. 496, 446–455 (2017)

    Article  Google Scholar 

  24. Soares, B.M., Vieira, A.A., Lemões, J.S., Santos, C.M.M., Mesko, M.F., Primel, E.G., D’Oca, M.G.M., Duarte, F.A.: Investigation of major and trace element distribution in the extraction-transesterification process of fatty acid methyl esters from microalgae Chlorella sp. Bioresour. Technol. 110, 730–734 (2012)

    Article  Google Scholar 

  25. Alvarenga, G., Ruas, C.P., Vicenti, J.R.M., Duarte, F.A., Gelesky, M.A., Rosa, G.R.: PdCl2 immobilized in polyacrylamide: a low cost and eco-friendly catalyst for Suzuki-Miyaura reactions. J. Braz. Chem. Soc. 27, 787–793 (2016)

    Google Scholar 

  26. Chahdoura, F., Pradel, C., Gomez, M.: Palladium nanoparticles in glycerol: a versatile catalytic system for C-X bond formation and hydrogenation processes. Adv. Synth. Catal. 355, 3648–3660 (2013)

    Article  Google Scholar 

  27. Civicos, J.F., Gholinejad, M., Alonso, D.A., Najera, C.: Phosphane-free Suzuki-Miyaura coupling of aryl imidazolesulfonates with arylboronic acids and potassium aryltrifluoroborates under aqueous conditions. Chem. Lett. 40, 907–909 (2011)

    Article  Google Scholar 

  28. Hashmi, A.S.K., Lothschütz, C., Döpp, R., Rudolph, M., Ramamurthi, T.D., Rominger, F.: Gold and palladium combined for cross-coupling. Angew. Chem. Int. Ed. 48, 8243 – 8246 (2009)

    Article  Google Scholar 

  29. Oliveira, D.G.M., Alvarenga, G., Scheeren, C.W., Rosa, G.R.: Development of reactor-type “dip catalyst” for transition metal nanoparticle-embedded polymer thin films. Quim. Nova 37, 1401–1403 (2014)

    Google Scholar 

  30. Busca, G., Lorenzelli, V.: Infrared spectroscopic identification of species arising from reactive adsorption of carbon oxides on metal-oxide surfaces. Mater. Chem. 2, 89–126 (1982)

    Article  Google Scholar 

  31. Tarley, C.R.T., Arruda, M.A.Z.: Biosorption of heavy metals using rice milling by-products. Characterisation and application for removal of metals from aqueous effluents. Chemosphere 54, 987–995 (2004)

    Article  Google Scholar 

  32. Baran, N.Y., Baran, T., Menteş, A.: Fabrication and application of cellulose Schiff base supported Pd(II) catalyst for fast and simple synthesis of biaryls via Suzuki coupling reaction. Appl. Catal. A 531, 36–44 (2017)

    Article  Google Scholar 

  33. Baran, T., Menteş, A.: Construction of new biopolymer (chitosan)-based pincer-type Pd(II) complex and its catalytic application in Suzuki cross coupling reactions. J. Mol. Struct. 1134, 591–598 (2017)

    Article  Google Scholar 

  34. Baran, T., Sargin, I., Kaya, M., Menteş, A., Ceter, T.: Design and application of sporopollenin microcapsule supported palladium catalyst: remarkably high turnover frequency and reusability in catalysis of biaryls. J. Colloid Interface Sci. 486, 194–203 (2017)

    Article  Google Scholar 

  35. Rosa, G.R., Rosa, C.H., Rominger, F., Dupont, J., Monteiro, A.L.: A mixed NCP pincer palladacycle as catalyst precursor for the coupling of aryl halides with aryl boronic acids. Inorg. Chim. Acta 359, 1947–1954 (2006)

    Article  Google Scholar 

  36. Phan, N.T.S., Van Der Sluys, M., Jones, C.W.: On the nature of the active species in palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura couplings – homogeneous or heterogeneous catalysis, a critical review. Adv. Synth. Catal. 348, 609–679 (2006)

    Article  Google Scholar 

  37. Xu, H., Mi, H.Y., Guan, M.M., Shan, H.Y., Fei, Q., Huan, Y.F., Zhang, Z.Q., Feng, G.D.: Residue analysis of tetracyclines in milk by HPLC coupled with hollow fiber membranes-based dynamic liquid-liquid micro-extraction. Food Chem. 232, 198–202 (2017)

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by Grants from CNPq, and FAPERGS (edital FAPERGS/CNPq 12/2014 – PRONEX, protocol 18795.341.30460.15012015), Brazil. The authors would like to thank CEME-SUL FURG for the SEM microscopy analyses.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Gilber R. Rosa.

Electronic Supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 4537 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Rosa, D.S., Vargas, B.P., Silveira, M.V. et al. On the Use of Calcined Agro-Industrial Waste as Palladium Supports in the Production of Eco-Friendly Catalysts: Rice Husks and Banana Peels Tested in the Suzuki–Miyaura Reaction. Waste Biomass Valor 10, 2285–2296 (2019). https://doi.org/10.1007/s12649-018-0252-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12649-018-0252-7

Keywords

Navigation