Cross-linked chitosan aerogel modified with Pd(II)/phthalocyanine: Synthesis, characterization, and catalytic application

Scientific Reports - Tập 9 Số 1
Amal Al‐Azmi1, Sajjad Keshipour2
1Chemistry Department, Kuwait University, P.O. Box 5969, Safat 13060, Kuwait
2Department of Nanochemistry, Nanotechnology Research Center, Urmia University, Urmia, Iran

Tóm tắt

AbstractPalladium(II) phthalocyanine (PdPc) tetrasulfonate was chemically bonded to an amine moiety of chitosan aerogel. The reaction was promoted by the transformation of sulfonic acid groups of PdPc to sulfonyl chloride, which is highly active for amination. The porous composite showed good catalytic activity in the oxidation reaction of some alkylarenes, aliphatic and benzylic alcohols, and cyclohexanol. High conversions and excellent selectivities were obtained for the solvent-free reactions under aerobic conditions at 80 °C during 24 h. While many oxidation reactions have been reported catalysed with palladium phthalocyanine, this is the first reported oxidation of alkylarenes via this catalyst. The organometallic compound is applicable as a heterogeneous catalyst having high chemical stability with recyclability up to six times.

Từ khóa


Tài liệu tham khảo

Schaefer, B. Natural Products in the Chemical Industry, Springer, New York (2014).

Mondal, M. I. H. Cellulose-Based Superabsorbent Hydrogels. Keshipour, S. & Maleki, A. Modification of Cellulose. Springer, Cham (2018).

Ali, A. & Ahmed, S. A review on chitosan and its nanocomposites in drug delivery. Int. J. Biol. Macromol. 109, 273–286 (2018).

Maleki, A., Ghamari, N. & Kamalzare, M. Chitosan-supported Fe3O4 nanoparticles, a magnetically recyclable heterogeneous nanocatalyst for the syntheses of multifunctional benzimidazoles and benzodiazepines. RSC Adv. 4, 9416–9423 (2014).

Maleki, A. & Paydar, R. Graphene oxide–chitosan bionanocomposite, a highly efficient nanocatalyst for the one-pot three-component synthesis of trisubstituted imidazoles under solvent-free conditions. RSC Adv. 5, 33177–33184 (2015).

Zargar, V., Asghari, M. & Dashti, A. A review on chitin and chitosan polymers: Structure, chemistry, solubility, derivatives, and applications. ChemBioEng Rev. 2, 204–226 (2015).

Chauhan, S. Modification of chitosan for sorption of metal ions. J. Chem. Pharm. Res. 7, 49–55 (2015).

Szőllősi, G. & Kolcsár, V. J. Highly enantioselective transfer hydrogenation of prochiral ketones using Ru(II) chitosan catalyst in aqueous media. ChemCatChem 11, 820–830 (2019).

El Kadib, A. Chitosan as a sustainable organocatalyst, a concise Overview. ChemSusChem 8, 217–244 (2015).

El Kadib, A. & Bousmina, M. Chitosan bio based organic–inorganic hybrid aerogel microspheres. Chem. A Eur. J. 18, 8264–8277 (2012).

Guibal, E. Heterogeneous catalysis on chitosan-based materials, A review. Prog. Polym. Sci. 30, 71–109 (2005).

Li, A. et al. An environment-friendly and multi-functional absorbent from chitosan for organic pollutants and heavy metal ion. Carbohydr. Polym. 148, 272–280 (2016).

Varma, A. J., Deshpande, S. V. & Kennedy, J. F. Metal complexation by chitosan and its derivatives a review. Carbohydr. Polym. 55, 77–93 (2004).

Rinki, K., Dutta, P. K., Hunt, A., Macquarrie, D. J. & Clark, J. H. Nanocomposites based on chitosan-graft-poly(N-vinyl-2-pyrrolidone), synthesis, characterization, and bological activity. Int. J. Polym. Mater. 60, 988–999 (2011).

Santos-López, G. et al. Aerogels from chitosan solutions in ionic liquids. Polymers 9, 722–735 (2017).

Takeshita, S. & Yoda, S. Upscaled preparation of trimethylsilylated chitosan aerogel. Ind. Eng. Chem. Res. 57, 10421–10430 (2018).

Pestov, A. & Bratskaya, S. Chitosan and its derivatives as highly efficient polymer ligands. Molecules 21, 330–365 (2016).

Kyzas, G. Z. & Bikiaris, D. N. Recent modifications of chitosan for adsorption applications, a critical and systematic review. Mar. Drugs 13, 312–337 (2015).

Barskiy, D. A. et al. Selective hydrogenation of 1,3 butadiene and 1 butyne over a Rh/chitosan catalyst investigated by using parahydrogen induced polarization. ChemCatChem 4, 2031–2035 (2012).

Frindy, S., El Kadib, A., Lahcini, M., Primo, A. & García, H. Copper nanoparticles stabilized in a porous chitosan aerogel as a heterogeneous catalyst for C−S cross-coupling. ChemCatChem 7, 3307–3315 (2015).

Katritzky, R., Meth-Cohn, O., Rees, C. W. & Pattenden, G. Comprehensive Organic Functional Group Transformations. Elsevier Science, Oxford (1995).

Larock, R. C. In Comprehensive Organic Transformations, A Guide to Functional Group Preparations. 2nd ed. Wiley-VCH, New York (1999).

Ferraudi, G. & Lappin, A. G. Properties and chemical reactivity of metallo phthalocyanine and tetramethylbenzoannulene complexes grafted into a polymer backbone. J. Coord. Chem. 67, 3822–3839 (2014).

Verma, P. K. et al. Iron and palladium(II) phthalocyanines as recyclable catalysts for reduction of nitroarenes. Catal. Lett. 144, 1258–1267 (2014).

Xiong, Z., Xu, Y., Zhu, L. & Zhao, J. Enhanced photodegradation of 2,4,6-trichlorophenol over palladium phthalocyaninesulfonate modified organobentonite. Langmuir 21, 10602–10607 (2005).

Ikeue, T. et al. Annulated dinuclear palladium(II) phthalocyanine complex as an effective photo-oxidation catalyst for near-infrared region light. Inorg. Chem. Commun. 13, 1170–1172 (2010).

Ogunbayo, T. B., Antunes, E. & Nyokong, T. Investigation of homogeneous photosensitized oxidation activities of palladium and platinum octasubstituted phthalocyanines: Oxidation of 4-nitrophenol. J. Mol. Catal. A Chem. 334, 123–129 (2011).

Hu, M., Xu, Y. & Xiong, Z. A novel photosensitizer of palladium(II) phthalocyanine tetrasulfonate for chlorophenol oxidation under visible light irradiation. Chem. Lett. 33, 1092–1093 (2004).

Keshipour, S., Ahmadi, F. & Seyyedi, B. Chitosan modified Pd(II)-D-penicillamine; Preparation, characterization., and catalyst application. Cellulose 24, 1455–1462 (2017).

Keshipour, S. & Mirmasoudi, S. S. Cross-linked chitosan aerogel modified with Au: Synthesis, characterization and catalytic application. Carbohydr. Polym. 196, 494–500 (2018).

Tanaka, Y. Infrared absorption spectra of organic sulfur compounds. II. Studies on S-N stretching bands of methanesulfonamide derivatives. Chem. Pharm. Bull. (Tokyo) 13, 858–861 (1965).

Shaabani, A., Keshipour, S., Hamidzad, M. & Shaabani, S. Cobalt(II) phthalocyanine covalently anchored to cellulose as arecoverable and efficient catalyst for the aerobic oxidation of alkylarenes and alcohols. J. Mol. Catal. A 395, 494–499 (2014).

Schick, G. A. & Sun, Z. Q. Spectroscopic characterization of sulfonyl chloride immobilization on silica. Langmuir 10, 3105–3110 (1994).

Watkins, J. D. et al. Carbon nanoparticle surface functionalization, converting negatively charged sulfonate to positively charged sulphonamide. Phys. Chem. Chem. Phys. 12, 4872–4878 (2010).

Liu, Y. et al. Direct aerobic oxidative homocoupling of benzene to biphenyl over functional porous organic polymer supported atomically dispersed palladium catalyst. Appl. Catal. B Environ. 209, 679–688 (2017).

Li, Y. et al. Cooperative catalysis by acid–base bifunctional grapheme. RSC Adv. 33, 13655–13658 (2013).

Lim, B. Y., Poh, C. S., Voon, C. H. & Salmah, H. Rheological and thermal study of chitosan filled thermoplastic elastomer composites. Appl. Mech. Mater. 754-755, 34–38 (2015).

Kamiloglu, A. A., Acar, İ., Saka, E. T. & Bıyıklıoğlu, Z. Synthesis of polyfluoro substituted Co(II), Fe(II) phthalocyanines and their usage as catalysts for aerobic oxidation of benzyl alcohol. J. Organomet. Chem. 815-816, 1–7 (2016).

Hamza, A. & Srinivas, D. Selective oxidation of benzyl alcohol over copper phthalocyanine immobilized on MCM-41. Catal. Lett. 128, 434–442 (2009).

Chang, X., Chen, D. & Jiao, X. Chitosan-based aerogels with high adsorption performance. J. Phys. Chem. B 112, 7721–7725 (2008).