Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Palladium Nanoparticles on Silica Nanospheres for Switchable Reductive Coupling of Nitroarenes

  • 6 Accesses

Abstract

In this study, we synthesized a robust and sustainable Pd/SiO2 nanospheres catalyst. Further, its catalytic activity was demonstrated for the direct reductive coupling of nitroarenes under mild conditions. While the reaction with Pd nanoparticles on other supporting materials such as modified carbon materials and TiO2, under similar conditions, resulted formation of amines exclusively. Therefore, it was confirmed that the SiO2 was found to be the best supporting material towards the selective reductive coupling of nitroarenes. Also, the catalyst could be recycled up to five cycles with a marginal loss of product yield (< 2% yield).

Graphic Abstract

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

References

  1. 1.

    Ferlin F, Cappelletti M, Vivani R, Pica M, Piermatti O, Vaccaro L (2019) Au@zirconium-phosphonate nanoparticles as an effective catalytic system for the chemoselective and switchable reduction of nitroarenes. Green Chem 21:614

  2. 2.

    Hu L, Cao X, Shi L, Qi F, Guo Z, Lu J, Gu H (2011) A highly active nano-palladium catalyst for the preparation of aromatic azos under mild conditions. Org Lett 13:5640

  3. 3.

    Dai Y, Li C, Shen Y, Lim T, Xu J, Li Y, Hans N, Flemming B, Lock N, Su R (2018) Light-tuned selective photosynthesis of azo-and azoxy-aromatics using graphitic C3N4. Nat Commun 9:60

  4. 4.

    Dabbagh HA, Teimouri A, Chermahini AN (2007) Green and efficient diazotization and diazo coupling reactions on clays. Dyes Pigments 73:239

  5. 5.

    Grirrane A, Corma A, García H (2008) Gold-catalyzed synthesis of aromatic azo compounds from anilines and nitroaromatics. Science 322:1661

  6. 6.

    Acharyya SS, Ghosh S, Bal R (2014) Catalytic oxidation of aniline to azoxybenzene over CuCr2O4 spinel nanoparticle catalyst. ACS Sustain Chem Eng 2:584

  7. 7.

    Lakshminarayana B, Mahendar L, Ghosal P, Satyanarayana G, Subrahmanyam Ch (2017) Nano-sized recyclable PdO supported carbon nanostructures for Heck reaction: influence of carbon materials. ChemistrySelect 2:2700

  8. 8.

    Lakshminarayana B, Mahendar L, Chakraborty J, Satyanarayana G, Subrahmanyam Ch (2018) Organic transformations catalyzed by palladium nanoparticles on carbon nanomaterials. J Chem Sci 130:47

  9. 9.

    Lakshminarayana B, Mahendar L, Ghosal P, Sreedhar B, Satyanarayana G, Subrahmanyam Ch (2018) Fabrication of Pd/CuFe2O4 hybrid nanowires: a heterogeneous catalyst for Heck couplings. N J Chem 42:1646

  10. 10.

    Lakshminarayana B, Chakraborty J, Satyanarayana G, Subrahmanyam Ch (2018) Recyclable Pd/CuFe2O4 nanowires: a highly active catalyst for C-C couplings and synthesis of benzofuran derivatives. RSC Adv 8:21030

  11. 11.

    Srinivasa Rao A, Ashok Kumar KV, Lakshminarayana B, Satyanarayana G, Subrahmanyam Ch (2019) Photocatalytic hydrogenation of nitroarenes: supporting effect of CoOx on TiO2 nanoparticles. N J Chem 43:748

  12. 12.

    Lakshminarayana B, Satyanarayana G, Subrahmanyam Ch (2018) Bimetallic Pd–Au/TiO2 nanoparticles: an efficient and sustainable heterogeneous catalyst for rapid catalytic hydrogen transfer reduction of nitroarenes. ACS Omega 3:13065

  13. 13.

    Narayana BL, Mukri BD, Subrahmanyam Ch (2016) Mn ion substituted CeO2 nano spheres for low temperature CO oxidation: the promoting effect of Mn ions. ChemistrySelect 1:3150

  14. 14.

    Lakshminarayana B, Sarker S, Subrahmanyam Ch (2018) Improved performance of Mn ion substituted ceria nanospheres for water gas shift reaction: influence of preparation conditions. Mater Res Bull 103:309

  15. 15.

    Ray S, Das P, Bhaumik A, Dutta A, Mukhopadhyay C (2013) Covalently anchored organic carboxylic acid on porous silica nano particle: a novel organometallic catalyst (PSNP-CA) for the chromatography-free highly product selective synthesis of tetra substituted imidazoles. Appl Catal A 458:183

  16. 16.

    Ray S, Brown M, Bhaumik A, Dutta A, Mukhopadhyay C (2013) A new MCM-41 supported HPF6 catalyst for the library synthesis of highly substituted 1,4-dihydropyridines and oxidation to pyridines: report of one-dimensional packing towards LMSOMs and studies on their photophysical properties. Green Chem 15:1910

  17. 17.

    Kundu PK, Dhiman M, Modak A, Chowdhury A, Polshettiwar V, Maiti D (2016) Palladium nanoparticles supported on fibrous silica (KCC-1-PEI/Pd): a sustainable nanocatalyst for decarbonylation reactions. ChemPlusChem 81:1142

  18. 18.

    Gautam P, Dhiman M, Polshettiwar V, Bhanage BM (2016) KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling. Green Chem 18:5890

  19. 19.

    Dhiman M, Chalke B, Polshettiwar V (2015) Efficient synthesis of monodisperse metal (Rh, Ru, Pd) nanoparticles supported on fibrous nanosilica (KCC-1) for catalysis. ACS Sustain Chem Eng 3:3224

  20. 20.

    Shokouhimehr M, Hong K, Lee TH, Moon CW, Hong SP, Zhang K, Jang HW (2018) Magnetically retrievable nanocomposite adorned with Pd nanocatalysts: efficient reduction of nitroaromatics in aqueous media. Green Chem 20:3809

  21. 21.

    Byun S, Song Y, Kim BM (2016) Heterogenized bimetallic Pd–Pt–Fe3O4 nanoflakes as extremely robust, magnetically recyclable catalysts for chemoselective nitroarene reduction. ACS Appl Mater Interfaces 8:14637

  22. 22.

    Zhou J, Li Y, Sun HB, Tang Z, Qi L, Liu L, Ai Y, Li S, Shao Z, Liang Q (2017) Porous silica-encapsulated and magnetically recoverable Rh NPs: a highly efficient, stable and green catalyst for catalytic transfer hydrogenation with “slow-release” of stoichiometric hydrazine in water. Green Chem 19:3400

  23. 23.

    Xu X, Luo J, Li L, Zhang D, Wang Y, Li G (2018) Unprecedented catalytic performance in amine syntheses via Pd/g-C3N4 catalyst-assisted transfer hydrogenation. Green Chem 20:2038

  24. 24.

    Liu X, Li HQ, Ye S, Liu YM, He HY, Cao Y (2014) Gold-catalyzed direct hydrogenative coupling of nitroarenes to synthesize aromatic azo compounds. Angew Chem Int Ed 53:7624

  25. 25.

    Li HQ, Liu X, Zhang Q, Li SS, Liu YM, He HY, Cao Y (2015) Deoxygenative coupling of nitroarenes for the synthesis of aromatic azo compounds with CO using supported gold catalysts. Chem Commun 51:11217

  26. 26.

    Li J, Song S, Long Y, Wu L, Wang X, Xing Y, Zhang H (2018) Investigating the hybrid-structure-effect of CeO2-encapsulated Au nanostructures on the transfer coupling of nitrobenzene. Adv Mater 30:1704416

  27. 27.

    Liu X, Ye S, Li HQ, Liu YM, Cao Y, Fan KN (2013) Mild, selective and switchable transfer reduction of nitroarenes catalyzed by supported gold nanoparticles. Catal Sci Technol 3:3200

  28. 28.

    Grirrane A, Corma A, Garcia H (2010) Preparation of symmetric and asymmetric aromatic azo compounds from aromatic amines or nitro compounds using supported gold catalysts. Nat Protoc 5:429

  29. 29.

    Zhu H, Ke X, Yang X, Sarina S, Liu H (2010) Reduction of nitroaromatic compounds on supported gold nanoparticles by visible and ultraviolet light. Angew Chem Int Ed 122:9851

  30. 30.

    Combita D, Concepción P, Corma A (2014) Gold catalysts for the synthesis of aromatic azo compounds from nitroaromatics in one-step. J Catal 311:339

  31. 31.

    Liu W, Zhang L, Yan W, Liu X, Yang X, Miao S, Wang W, Wang A, Zhang T (2016) Single-atom dispersed Co–N–C catalyst: structure identification and performance for hydrogenative coupling of nitroarenes. Chem Sci 7:5758

  32. 32.

    Hu L, Cao X, Chen L, Zheng J, Lu J, Sun X, Gu H (2012) Highly efficient synthesis of aromatic azos catalyzed by unsupported ultra-thin Pt nanowires. Chem Commun 48:3445

  33. 33.

    Mondal B, Mukherjee PS (2018) Cage encapsulated gold nanoparticles as heterogeneous photocatalyst for facile and selective reduction of nitroarenes to azo compounds. J Am Chem Soc 140:12592

  34. 34.

    Wang J, Yu X, Shi C, Lin D, Li J, Jin H, Chen X, Wang S (2019) Iron and nitrogen co-doped mesoporous carbon-based heterogeneous catalysts for selective reduction of nitroarenes. Adv Synth Catal 361:1

  35. 35.

    Wang Y, Peng X, Shi J, Tang X, Jiang J, Liu W (2012) Highly selective fluorescent chemosensor for Zn2+ derived from inorganic–organic hybrid magnetic core/shell Fe3O4@SiO2 nanoparticles. Nanoscale Res Lett 7:86

  36. 36.

    Eisenberg D, Kauzman W (1969) The structure and properties of water. Science 166:861

  37. 37.

    Kronenberg AK, Wolf GH (1990) Fourier transform infrared spectroscopy determinations of intragranular water content in quartz-bearing rocks: implications for hydrolytic weakening in the laboratory and within the earth. Tectonophysics 172:255

  38. 38.

    Fukuda JI (2012) Water in rocks and minerals—species, distributions, and temperature dependences. IntechOpen. https://doi.org/10.5772/35668

  39. 39.

    Wu Y, Zhang L, Li G, Liang C, Huang X, Zhang Y, Song G, Jia J, Zhixiang C (2001) Synthesis and characterization of nanocomposites with palladium embedded in mesoporous silica. Mater Res Bull 36:253

  40. 40.

    Lin J, Chen H, Fei T, Zhang J (2013) Highly transparent superhydrophobic organic–inorganic nanocoating from the aggregation of silica nanoparticles. Colloids Surf A 421:51

  41. 41.

    Manatunga DC, de Silva RM, de Silva KN (2016) Double layer approach to create durable superhydrophobicity on cotton fabric using nano silica and auxiliary non fluorinated materials. Appl Surf Sci 360:777

  42. 42.

    Rahul R, Singh RK, Bera B, Devivaraprasad R, Neergat M (2015) The role of surface oxygenated-species and adsorbed hydrogen in the oxygen reduction reaction (ORR) mechanism and product selectivity on Pd-based catalysts in acid media. Phys Chem Chem Phys 17:15146

  43. 43.

    Al-Hinai MN, Hassanien R, Wright NG, Horsfall AB, Houlton A, Horrocks BR (2013) Networks of DNA-templated palladium nanowires: structural and electrical characterisation and their use as hydrogen gas sensors. Faraday Discuss 164:71

  44. 44.

    Zhou X, Shi T (2012) One-pot hydrothermal synthesis of a mesoporous SiO2–graphene hybrid with tunable surface area and pore size. Appl Surf Sci 259:566

  45. 45.

    Cincotto FH, Canevari TC, Campos AM, Landers R, Machado SA (2014) Simultaneous determination of epinephrine and dopamine by electrochemical reduction on the hybrid material SiO2/graphene oxide decorated with Ag nanoparticles. Analyst 139:4634

  46. 46.

    Ulgut B, Suzer S (2003) XPS studies of SiO2/Si system under external bias. J Phys Chem B 107:2939

Download references

Acknowledgements

BL thanks to the University Grant Commission (UGC), New Delhi, India for the award of the fellowship.

Author information

Correspondence to G. Satyanarayana or Ch. Subrahmanyam.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 3465 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Lakshminarayana, B., Manna, A.K., Satyanarayana, G. et al. Palladium Nanoparticles on Silica Nanospheres for Switchable Reductive Coupling of Nitroarenes. Catal Lett (2020). https://doi.org/10.1007/s10562-020-03127-w

Download citation

Keywords

  • Heterogeneous catalysis
  • Hydrogenation of nitroarenes
  • Nanocatalysis