Polymer Based Palladium Nanocatalyst for the Degradation of Nitrate and Congo Red

  • Irshad Ul Haq BhatEmail author
  • Mohamad Nur Khairul Anwar
  • Jimmy Nelson Appaturi
Original paper


In this study, the Pd catalyst based on chitosan-tannin (CT) framework as support was prepared and characterized. The CT support and Pd catalyst were characterized by attenuated total reflection (ATR) spectroscopy and Raman spectroscopy, Scanning electron microscopy-energy dispersive X-ray analyzer (SEM–EDX) and transmission electron microscopy (TEM) and X-ray diffractometry (XRD). Attenuated total reflection (ATR) spectra revealed the coordination of Pd via hydroxyl and amino functional groups. Raman spectral analysis was carried out to give information about the structural defect of the catalyst compared to CT support. The SEM–EDX results revealed regular surface morphology and presence of Pd in the catalyst as compared to CT support. TEM analysis revealed that the deposition of Pd on organic support with a spherical shape possessing size in the range of 6.01 nm–20.7 nm (average particle size = 12.65 ± 3.14 nm). The XRD results revealed the amorphous nature of the catalyst compared to CT support. TGA analysis revealed that the catalyst is highly thermally-stable compared to CT support. The catalytic activity of Pd catalyst was investigated for the reduction of nitrate and Congo red in the presence and absence of H2. The catalytic activities exhibited 71.11% and 23% removal of nitrate and Congo red in 20 and 60 min, respectively. Thus, results suggested that Pd catalyst has a potential of catalytic activity toward reduction of nitrate and Congo red in presence H2.


Chitosan Tannic acid Glutaraldehyde Catalytic reduction Oxyanion Dye 



The authors highly acknowledge the Minsistry of Education, Malaysia, for providing the financial assistance through Fundamental Research Grant Scheme (FRGS) (R/FRGS/A08.00/00769A/001/2015/00296).


  1. 1.
    Krantzberg G, Tanik A, do Carmo JSA, Indarto A, Ekdal A, Gurel M, Machiwal D (2010) Advances in water quality control. Scientific Research Publishing, Inc, IrvineGoogle Scholar
  2. 2.
    Teng Y, Yang J, Zuo R, Wang J (2011) Impact of urbanization and industrialization upon surface water quality: a pilot study of Panzhihua mining town. J Earth Science 22(5):658–668CrossRefGoogle Scholar
  3. 3.
    Davis ML (2010) Water and wastewater engineering: design principles and practice. McGraw-Hill, New York, pp 2–21Google Scholar
  4. 4.
    Sano D, Amarasiri M, Hata A, Watanabe T, Katayama H (2016) Risk management of viral infectious diseases in wastewater reclamation and reuse: review. Environ Int 91:220–229CrossRefGoogle Scholar
  5. 5.
    Ajmal M, Demirci S, Siddiq M, Aktas N, Sahiner N (2015) Amidoximated poly(acrylonitrile) particles for environmental applications: removal of heavy metal ions, dyes, and herbicides from water with different sources. J Appl Polym Sci 133(7):1–11Google Scholar
  6. 6.
    Chaplin BP, Reinhard M, Schneider WF, Schuth C, Shapley JR, Strathmann TJ, Werth CJ (2012) Critical review of Pd-based catalytic treatment of priority contaminants in water. Environ Sci Technol 46:3655–3670CrossRefGoogle Scholar
  7. 7.
    Slack RJ (2014) Water and health. In: Holden J (ed) Water resources: an integrated approach. Routledge, Abingdon, pp 223–263Google Scholar
  8. 8.
    Trang DT, van Der Hoek W, Tuan ND, Cam PD, Viet VH, Luu DD, Konradsen F, Dalsgaard A (2007) Skin disease among farmers using wastewater in rice cultivation in Nam Dinh, Vietnam. Trop Med Int Health 12(2):51–58CrossRefGoogle Scholar
  9. 9.
    Pérez RA, Sánchez-Brunete C, Albero B, Miguel E, Tadeo JL, Alonso J, Lobo MC (2016) Quality assessment of three industry-derived organic amendments for agricultural use. Compos Sci Util 24(3):190–202CrossRefGoogle Scholar
  10. 10.
    Durkin DP, Ye T, Choi J, Livi KJ, Hugh C, Trulove PC, Fairbrother DH, Haverhals LM, Shuai D (2018) Sustainable and scalable natural fiber welded palladium-indium catalysts for nitrate reduction. Appl Catal B 221:290–301CrossRefGoogle Scholar
  11. 11.
    Naseem K, Farooqi ZH, Begum R, Irfan A (2018) Removal of Congo red dye from aqueous medium by its catalytic reduction using sodium borohydride in the presence of various inorganic nano-catalysts: a review. J Clean Prod 187:296–307CrossRefGoogle Scholar
  12. 12.
    Azizul-Rahman MFH, Mohd-Suhaimi AA, Othman N (2014) Biosorption of Pb(II) and Zn (II) in synthetic waste water by watermelon rind (Citrullus lanatus). Appl Mech Mater 465:906–910Google Scholar
  13. 13.
    Chao HP, Chang CC, Nieva A (2014) Biosorption of heavy metals on Citrus maxima peel, passion fruit shell, and sugarcane bagasse in a fixed-bed column. J Ind Eng Chem 20(5):3408–3414CrossRefGoogle Scholar
  14. 14.
    Kushwah RK, Bajpai A, Malik S (2011) Characteristics of waste water in sewage treatment plant of Bhopal (India). J Chem Pharm Res 3(6):766–771Google Scholar
  15. 15.
    Śrębowata A, Tarach K, Girman V, Góra-Marek K (2016) Catalytic removal of trichloroethylene from water over palladium loaded microporous and hierarchical zeolites. Appl Catal B 181:550–560CrossRefGoogle Scholar
  16. 16.
    Shiraz HG, Shiraz MG (2017) Palladium nanoparticle and decorated carbon nanotube for electrochemical hydrogen storage. Int J Hydrogen Energy 42(16):11528–11533CrossRefGoogle Scholar
  17. 17.
    Begum R, Naseem K, Ejaz Ahmed, Sharif A, Farooqi ZH (2016) Simultaneous catalytic reduction of nitroarenes using silvernanoparticles fabricated in poly(N-isopropylacrylamide acrylicacid-acrylamide) microgels. Colloids Surf A 511:17–26CrossRefGoogle Scholar
  18. 18.
    Naseem K, Begum R, Wu W, Irfan A, Al-Sehemi AG, Farooqi ZH (2019) Catalytic reduction of toxic dyes in the presence of silver nanoparticles impregnated core-shell composite microgels. J Clean Prod 211:855–864CrossRefGoogle Scholar
  19. 19.
    Begum R, Farooqi ZH, Ahmed E, Naseem K, Ashraf S, Sharif A, Rehan R (2017) Catalytic reduction of 4-nitrophenol using silver nanoparticles-engineered poly (N-isopropylacrylamide-co-acrylamide) hybrid microgels. Appl Organomet Chem 31(2):e3563CrossRefGoogle Scholar
  20. 20.
    Farooqi ZH, Khalid R, Begum R, Umar U, Wu Q, Ajmal M, Irfan A, Naseem K (2018) Facile synthesis of silver nanoparticles in a crosslinked polymeric system by in situ reduction method for catalytic reduction of 4-nitroaniline. Environ Technol. Google Scholar
  21. 21.
    Chang W, Kim H, Oh J, Ahn BJ (2018) Hydrodechlorination of chlorophenols over Pd catalysts supported on zeolite Y, MCM-41 and graphene. Res Chem Intermed 44(6):3835–3847CrossRefGoogle Scholar
  22. 22.
    Dhanavel S, Manivannan N, Mathivanan N, Gupta VK, Narayanan V, Stephen A (2018) Preparation and characterization of cross-linked chitosan/palladium nanocomposites for catalytic and antibacterial activity. J Mol Liq 257:32–41CrossRefGoogle Scholar
  23. 23.
    Palomares AE, Franch C, Yuranova T, Kiwi-Minsker L, García-Bordeje E, Derrouiche S (2014) The use of Pd catalysts on carbon-based structured materials for the catalytic hydrogenation of bromates in different types of water. Appl Catal B 146:186–191CrossRefGoogle Scholar
  24. 24.
    Jia Z, Sun H, Du Z, Lei Z (2014) Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium nanoparticles. J Environ Sci 26(2):478–482CrossRefGoogle Scholar
  25. 25.
    Naseem K, Farooqi ZH, Begum R, Wu W, Irfan A, Al-Sehemi AG (2018) Silver nanoparticles engineered polystyrene-poly(nisopropylmethacrylamide- acrylic acid) core shell hybrid polymer microgels for catalytic reduction of Congo red. Macromol Chem Phys 219:1800211CrossRefGoogle Scholar
  26. 26.
    Islam MT, Saenz-Arana R, Wang H, Bernal R, Noveron JC (2018) Green synthesis of gold, silver, platinum, and palladium nanoparticles reduced and stabilized by sodium rhodizonate and their catalytic reduction of 4-nitrophenol and methyl orange. New J Chem 42(8):6472–6478CrossRefGoogle Scholar
  27. 27.
    Umamaheswari C, Lakshmanan A, Nagarajan NS (2018) Green synthesis, characterization and catalytic degradation studies of gold nanoparticles against Congo red and methyl orange. J Photochem Photobiol B 178:33–39CrossRefGoogle Scholar
  28. 28.
    Huang X, Niu T, Shi Y, Jiang Y (2018) Synthesis of Au-modified Reduced Graphene Oxide Supported Pd-Ni nanocomposites and electrocatalytic activity for propane-1, 3-diol oxidation. Int J Electrochem Sci 13(3):2299–2309CrossRefGoogle Scholar
  29. 29.
    Badawi MA, Negm NA, Kana MA, Hefni HH, Moneem MA (2017) Adsorption of aluminum and lead from wastewater by chitosan-tannic acid modified biopolymers: isotherms, kinetics, thermodynamics and process mechanism. Int J Biol Macromol 99:465–476CrossRefGoogle Scholar
  30. 30.
    Zhou Z, Liu F, Huang Y, Wang Z, Li G (2015) Biosorption of palladium (II) from aqueous solution by grafting chitosan on persimmon tannin extract. Int J Biol Macromol 77:336–343CrossRefGoogle Scholar
  31. 31.
    Omran AR, Baiee MA, Juda SA, Salman JM, AlKaim AF (2016) Removal of Congo red dye from aqueous solution using a new adsorbent surface developed from aquatic plant (Phragmites australis). Int J ChemTech Res 9(4):334–342Google Scholar
  32. 32.
    Shi J, Long C, Li A (2016) Selective reduction of nitrate into nitrogen using Fe–Pd bimetallic nanoparticle supported on chelating resin at near-neutral pH. Chem Eng J 286:408–415CrossRefGoogle Scholar
  33. 33.
    Cano OA, González CR, Paz JH, Madrid PA, Casillas PG, Hernández AM, Pérez CM (2017) Catalytic activity of palladium nanocubes/multiwalled carbon nanotubes structures for methyl orange dye removal. Catal Today 282:168–173CrossRefGoogle Scholar
  34. 34.
    Gao H, Zhou W, Jang JH, Goodenough JB (2016) Cross-linked chitosan as a polymer network binder for an antimony anode in sodium-ion batteries. Adv Energy Mater 6(6):1502130CrossRefGoogle Scholar
  35. 35.
    Tripathi RP, Verma SS, Pandey J, Tiwari VK (2008) Recent development on catalytic reductive amination and applications. Curr Org Chem 12(13):1093–1115CrossRefGoogle Scholar
  36. 36.
    McDonald M, Mila I, Scalbert A (1996) Precipitation of metal ions by plant polyphenols: optimal conditions and origin of precipitation. J Agric Food Chem 44(2):599–606CrossRefGoogle Scholar
  37. 37.
    Abdulsahib HT, Taobi AH, Hashim SS (2015) Removal of Bentonite from Raw water by Novel Coagulant Based on Chitosan and Tannin. Asian J Res Chem 8(4):241CrossRefGoogle Scholar
  38. 38.
    Sharma C, Dinda AK, Mishra NC (2013) Fabrication and characterization of natural origin chitosan-gelatin-alginate composite scaffold by foaming method without using surfactant. J Appl Polym Sci 127(4):3228–3241CrossRefGoogle Scholar
  39. 39.
    Li X, Wang Z, Liang H, Ning J, Li G, Zhou Z (2019) Chitosan modification persimmon tannin bioadsorbent for highly efficient removal of Pb(II) from aqueous environment: the adsorption equilibrium, kinetics and thermodynamics. Environ Technol 40:112–124CrossRefGoogle Scholar
  40. 40.
    Baran T, Sargin I, Menteş A, Kaya M (2016) Exceptionally high turnover frequencies recorded for a new chitosan-based palladium (II) catalyst. Appl Catal A 523:12–20CrossRefGoogle Scholar
  41. 41.
    Ćirić-Marjanović G, Pašti I, Gavrilov N, Janošević A, Mentus S (2013) Carbonised polyaniline and polypyrrole: towards advanced nitrogen-containing carbon materials. Chem Pap 67(8):781–813Google Scholar
  42. 42.
    Fu L, Yu S, Thompson L, Yu A (2012) Development of a novel nitrite electrochemical sensor by stepwise in situ formation of palladium and reduced graphene oxide nanocomposites. RSC Adv 5(50):40111–40116CrossRefGoogle Scholar
  43. 43.
    Ferrari AC, Robertson J (2001) Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon. Phys Rev B 64(7):075414CrossRefGoogle Scholar
  44. 44.
    Zhou M, Han D, Liu X, Ma C, Wang H, Tang Y, Yonsengand Yang J (2015) Enhanced visible light photocatalytic activity of alkaline earth metal ions-doped CdSe/rGO photocatalysts synthesized by hydrothermal method. Appl Catal B 172:174–184CrossRefGoogle Scholar
  45. 45.
    Baran T, Menteş A (2017) Construction of new biopolymer (chitosan)-based pincer-type Pd (II) complex and its catalytic application in Suzuki cross coupling reactions. J Mol Struct 1134:591–598CrossRefGoogle Scholar
  46. 46.
    Duan L, Li M, Liu H (2015) Biosynthesised palladium nanoparticles using Eucommia ulmoides bark aqueous extract and their catalytic activity. IET Nanobiotechnol 9(6):349–354CrossRefGoogle Scholar
  47. 47.
    Kannan R, Kim AR, Lee HK, Yoo DJ (2015) Coordinated fast synthesis of electrocatalytic palladium nanoparticles decorated graphene oxide nanocomposite for fuel cell applications. J Nanosci Nanotechnol 15(8):5711–5717CrossRefGoogle Scholar
  48. 48.
    Demetgül C (2012) Synthesis of the ketimine of chitosan and 4, 6-diacetylresorcinol, and study of the catalase-like activity of its copper chelate. Carbohydr Polym 89(2):354–361CrossRefGoogle Scholar
  49. 49.
    Antony R, David ST, Saravanan K, Karuppasamy K, Balakumar S (2013) Synthesis, spectrochemical characterisation and catalytic activity of transition metal complexes derived from Schiff base modified chitosan. Spectrochim Acta Part A 103:423–430CrossRefGoogle Scholar
  50. 50.
    Han B, Liu W, Li J, Wang J, Zhao D, Xu R, Lin Z (2017) Catalytic hydrodechlorination of triclosan using a new class of anion-exchange-resin supported palladium catalysts. Water Res 120:199–210CrossRefGoogle Scholar
  51. 51.
    Naghipour A, Fakhri A (2016) Heterogeneous Fe3O4@ chitosan-Schiff base Pd nanocatalyst: fabrication, characterization and application as highly efficient and magnetically-recoverable catalyst for Suzuki-Miyaura and Heck-Mizoroki C-C coupling reactions. Catal Commun 73:39–45CrossRefGoogle Scholar
  52. 52.
    Baran T, Menteş A, Arslan H (2015) Synthesis and characterization of water soluble O-carboxymethyl chitosan Schiff bases and Cu (II) complexes. Int J Biol Macromol 72:94–103CrossRefGoogle Scholar
  53. 53.
    Li B, Shan CL, Zhou Q, Fang Y, Wang YL, Xu F, Han LR, Ibrahim M, Guo LB, Xie GL, Sun GC (2013) Synthesis, characterization, and antibacterial activity of cross-linked chitosan-glutaraldehyde. Mar Drugs 11(5):1534–1552CrossRefGoogle Scholar
  54. 54.
    Mohammadkhanni A, Bazgir A (2018) Palladium supported SBA-functionalizd 1, 2-dicarboxylic acid: the first Pd-based heterogeneous synthesis of fluorenones. Mol Catal 447:28–36CrossRefGoogle Scholar
  55. 55.
    Baran NY, Baran T, Menteş A (2018) Production of novel palladium nanocatalyst stabilized with sustainable chitosan/cellulose composite and its catalytic performance in Suzuki-Miyaura coupling reactions. Carbohydr Polym 181:596–604CrossRefGoogle Scholar
  56. 56.
    Baran T, Yılmaz Baran N, Menteş A (2018) A new air and moisture stable robust bio-polymer based palladium catalyst for highly efficient synthesis of biaryl compounds. Appl Organomet Chem 32(2):e4076CrossRefGoogle Scholar
  57. 57.
    Gao S, Zhao N, Shu M, Che S (2010) Palladium nanoparticles supported on MOF-5: a highly active catalyst for a ligand-and copper-free Sonogashira coupling reaction. Appl Catal A 388(1–2):196–201CrossRefGoogle Scholar
  58. 58.
    Hamid S, Kumar MA, Lee W (2016) Highly reactive and selective Sn-Pd bimetallic catalyst supported by nanocrystalline ZSM-5 for aqueous nitrate reduction. Appl Catal B 187:37–46CrossRefGoogle Scholar
  59. 59.
    Chen X, Huo X, Liu J, Wang Y, Werth CJ, Strathmann TJ (2016) Exploring beyond palladium: catalytic reduction of aqueous oxyanion pollutants with alternative platinum group metals and new mechanistic implications. Chem Eng J 313:745–752CrossRefGoogle Scholar
  60. 60.
    Ganapuram BR, Alle M, Dadigala R, Dasari A, Maragoni V, Guttena V (2015) Catalytic reduction of methylene blue and Congo red dyes using green synthesized gold nanoparticles capped by salmalia malabarica gum. Int Nano Lett 5(4):215–222CrossRefGoogle Scholar
  61. 61.
    Pizarro AH, Molina CB, Rodriguez JJ (2016) Decoloration of azo and triarylmethane dyes in the aqueous phase by catalytic hydrotreatment with Pd supported on pillared clays. RSC Adv 6(115):113820–113825CrossRefGoogle Scholar
  62. 62.
    Pizarro AH (2017) Decoloration of organic dyes in aqueous phase by catalytic hydrotreatment. Catal Commun 90:100–105CrossRefGoogle Scholar
  63. 63.
    Bhankhar A, Giri M, Yadav K, Jaggi N (2014) Study on degradation of methyl orange-an azo dye by silver nanoparticles using UV–Visible spectroscopy. Indian J Phys 88(11):1191–1196CrossRefGoogle Scholar
  64. 64.
    Rajesh R, Kumar SS, Venkatesan R (2014) Efficient degradation of azo dyes using Ag and Au nanoparticles stabilized on graphene oxide functionalized with PAMAM dendrimers. New J Chem 38(4):1551–1558CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Irshad Ul Haq Bhat
    • 1
    • 2
    Email author
  • Mohamad Nur Khairul Anwar
    • 1
  • Jimmy Nelson Appaturi
    • 3
  1. 1.Faculty of Earth ScienceUniversiti Malaysia KelantanJeliMalaysia
  2. 2.School of Fundamental ScienceUniversiti Malaysia TerengganuKuala TerengganuMalaysia
  3. 3.Nanotechnology and Catalysis Research Centre, Institute of Advanced StudiesUniversiti MalayaKuala LumpurMalaysia

Personalised recommendations