Immobilisation of palladium nanostructures in polyethersulfone beads: recyclable catalyst for chromium(VI) remediation
Uddhav S. Markad A B , Devidas B. Naik B , Krishan Kant Singh B , Manmohan Kumar B and Geeta K. Sharma A CA Department of Chemistry, Savitribai Phule Pune University, Pune 411007, Maharashtra, India.
B Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, Maharashtra, India.
C Corresponding author. Email: geetas@chem.unipune.ac.in
Environmental Chemistry 16(8) 622-629 https://doi.org/10.1071/EN19035
Submitted: 2 February 2019 Accepted: 25 July 2019 Published: 20 September 2019
Environmental context. Chromium, a carcinogenic metal present in the wastewater of several industries, is currently removed by treatment with large amounts of chemicals and expensive nano-catalysts. We have immobilised a nano-catalyst in tiny polymeric balls that are highly efficient at capturing chromium, and are easy to isolate for multiple reuse. Using our methodology, consumption of chemicals for removing chromium from wastewater is reduced by 97 %.
Abstract. We have synthesised and immobilised palladium nanostructures in porous polyethersulfone beads for the first time and demonstrated their catalytic application for the reductive transformation of toxic CrVI to nontoxic CrIII by formic acid at 25 °C. The reduction of CrVI using palladium-polyethersulfone composite beads (Pd-PES), with a minimal Pd loading of 0.4 wt%, is found to be 98 % with excellent operational stability retained up to 100 consecutive reaction cycles. Pseudo-first-order rate constant kapp for the 1st and 100th catalytic cycles is 0.167 and 0.158 min−1 respectively. Pd-PES beads having a diameter of 2 mm are easy to isolate post reduction by simple mesh filtration and can be re-used consecutively without any treatment. Owing to the high catalytic stability of the Pd nanostructures inside the beads, and the good mechanical and thermal stability of polyethersulfone, these beads can withstand rigorous treatment like mechanical stirring and elevated temperature, which renders them as highly reusable and as promising metal-polymer composite for practical application in CrVI remediation. For large scale application of this catalyst, we have demonstrated a methodology which reduces the consumption of formic acid by 98 % in chromium remediation technology.
Additional keywords: nanocatalyst, Pd-polymer composite, room temperature CrVI reduction.
References
Bhowmik K, Mukherjee A, Mishra MK, De G (2014). Stable Ni Nanoparticle–Reduced Graphene Oxide Composites for the Reduction of Highly Toxic Aqueous Cr(VI) at Room Temperature. Langmuir 30, 3209–3216.| Stable Ni Nanoparticle–Reduced Graphene Oxide Composites for the Reduction of Highly Toxic Aqueous Cr(VI) at Room TemperatureCrossref | GoogleScholarGoogle Scholar | 24588068PubMed |
Celebi M, Yurderi M, Bulut A, Kaya M, Zahmakiran M (2016). Palladium nanoparticles supported on amine-functionalized SiO2 for the catalytic hexavalent chromium reduction. Applied Catalysis B: Environmental 180, 53–64.
| Palladium nanoparticles supported on amine-functionalized SiO2 for the catalytic hexavalent chromium reductionCrossref | GoogleScholarGoogle Scholar |
Celebi M, Karakas K, Ertas IE, Kaya M, Zahmakiran M (2017). Palladium Nanoparticles Decorated Graphene Oxide: Active and Reusable Nanocatalyst for the Catalytic Reduction of Hexavalent Chromium(VI). ChemistrySelect 2, 8312–8319.
| Palladium Nanoparticles Decorated Graphene Oxide: Active and Reusable Nanocatalyst for the Catalytic Reduction of Hexavalent Chromium(VI)Crossref | GoogleScholarGoogle Scholar |
Dandapat A, Jana D, De G (2011). Pd nanoparticles supported mesoporous γ-Al2O3 film as a reusable catalyst for reduction of toxic CrVI to CrIII in aqueous solution. Applied Catalysis A, General 396, 34–39.
| Pd nanoparticles supported mesoporous γ-Al2O3 film as a reusable catalyst for reduction of toxic CrVI to CrIII in aqueous solutionCrossref | GoogleScholarGoogle Scholar |
El-Hout SI, El-Sheikh SM, Hassan HMA, Harraz FA, Ibrahim IA, El-Sharkawy EA (2015). A Green Chemical Route for Synthesis of Graphene Supported Palladium Nanoparticles: A Highly Active and Recyclable Catalyst for Reduction of Nitrobenzene. Applied Catalysis A: General 503, 176–185.
| A Green Chemical Route for Synthesis of Graphene Supported Palladium Nanoparticles: A Highly Active and Recyclable Catalyst for Reduction of NitrobenzeneCrossref | GoogleScholarGoogle Scholar |
Ghiaci M, Aghaei H, Oroojeni M, Aghabarari B, Rives V, Vicente MA, Sobrados I, Sanz J (2009). Synthesis of paracetamol by liquid phase Beckmann rearrangement of 4-hydroxyacetophenone oxime over H3PO4/Al-MCM-41. Catalysis Communications 10, 1486–1492.
| Synthesis of paracetamol by liquid phase Beckmann rearrangement of 4-hydroxyacetophenone oxime over H3PO4/Al-MCM-41Crossref | GoogleScholarGoogle Scholar |
Han S-H, Bai J, Liu H-M, Zeng J-H, Jiang J-X, Chen Y, Lee J-M (2016). One-Pot Fabrication of Hollow and Porous Pd–Cu Alloy Nanospheres and Their Remarkably Improved Catalytic Performance for Hexavalent Chromium Reduction. ACS Applied Materials & Interfaces 8, 30948–30955.
| One-Pot Fabrication of Hollow and Porous Pd–Cu Alloy Nanospheres and Their Remarkably Improved Catalytic Performance for Hexavalent Chromium ReductionCrossref | GoogleScholarGoogle Scholar |
Hassan HMA, Abdelsayed V, Khder AERS, AbouZeid KM, Terner J, El-Shall MS, Al-Resayes SI, El-Azhary AA (2009). Microwave synthesis of graphene sheets supporting metal nanocrystals in aqueous and organic media. Journal of Materials Chemistry 19, 3832–3837.
| Microwave synthesis of graphene sheets supporting metal nanocrystals in aqueous and organic mediaCrossref | GoogleScholarGoogle Scholar |
Hu M, Liu Y, Yao Z, Ma L, Wang X (2018). Catalytic reduction for water treatment. Frontiers of Environmental Science & Engineering 12, 3
| Catalytic reduction for water treatmentCrossref | GoogleScholarGoogle Scholar |
Huang Y, Ma H, Wang S, Shen M, Guo R, Cao X, Zhu M, Shi X (2012). Efficient Catalytic Reduction of Hexavalent Chromium Using Palladium Nanoparticle-Immobilized Electrospun Polymer Nanofibers. ACS Applied Materials & Interfaces 4, 3054–3061.
| Efficient Catalytic Reduction of Hexavalent Chromium Using Palladium Nanoparticle-Immobilized Electrospun Polymer NanofibersCrossref | GoogleScholarGoogle Scholar |
Kalekar AM, Sharma KKK, Luwang MN, Sharma GK (2016). Catalytic activity of bare and porous palladium nanostructures in the reduction of 4-nitrophenol. RSC Advances 6, 11911–11920.
| Catalytic activity of bare and porous palladium nanostructures in the reduction of 4-nitrophenolCrossref | GoogleScholarGoogle Scholar |
Kang S, Wang G, Zhao H, Cai W (2017). Highly efficient removal of hexavalent chromium in aqueous solutions via chemical reduction of plate-like micro/nanostructured zero valent iron. RSC Advances 7, 55905–55911.
| Highly efficient removal of hexavalent chromium in aqueous solutions via chemical reduction of plate-like micro/nanostructured zero valent ironCrossref | GoogleScholarGoogle Scholar |
Kim JD, Choi HC (2016). Efficient Catalytic Reduction of Hexavalent Chromium With Pd-decorated Carbon Nanotubes. Bulletin of the Korean Chemical Society 37, 744–747.
| Efficient Catalytic Reduction of Hexavalent Chromium With Pd-decorated Carbon NanotubesCrossref | GoogleScholarGoogle Scholar |
Leong KH, Chu HY, Ibrahim S, Saravanan P (2015). Palladium nanoparticles anchored to anatase TiO2 for enhanced surface plasmon resonance-stimulated, visible-light-driven photocatalytic activity. Beilstein Journal of Nanotechnology 6, 428–437.
| Palladium nanoparticles anchored to anatase TiO2 for enhanced surface plasmon resonance-stimulated, visible-light-driven photocatalytic activityCrossref | GoogleScholarGoogle Scholar | 25821683PubMed |
Li H-C, Liu W-J, Han H-X, Yu H-Q (2016). Hydrophilic swellable metal–organic framework encapsulated Pd nanoparticles as an efficient catalyst for Cr(VI) reduction. Journal of Materials Chemistry A 4, 11680–11687.
| Hydrophilic swellable metal–organic framework encapsulated Pd nanoparticles as an efficient catalyst for Cr(VI) reductionCrossref | GoogleScholarGoogle Scholar |
Liang M, Su R, Qi W, Zhang Y, Huang R, Yu Y, Wang L, He Z (2014). Reduction of Hexavalent Chromium Using Recyclable Pt/Pd Nanoparticles Immobilized on Procyanidin-Grafted Eggshell Membrane. Industrial & Engineering Chemistry Research 53, 13635–13643.
| Reduction of Hexavalent Chromium Using Recyclable Pt/Pd Nanoparticles Immobilized on Procyanidin-Grafted Eggshell MembraneCrossref | GoogleScholarGoogle Scholar |
Liu K, Shi Z, Zhou S (2016). Reduction of hexavalent chromium using epigallocatechin gallate in aqueous solutions: kinetics and mechanism. RSC Advances 6, 67196–67203.
| Reduction of hexavalent chromium using epigallocatechin gallate in aqueous solutions: kinetics and mechanismCrossref | GoogleScholarGoogle Scholar |
Lv W, Liu Z, Lan J, Liu Z, Mi W, Lei J, Wang L, Liu Y, Zhang J (2017). Visible-light-induced reduction of hexavalent chromium utilizing cobalt phosphate (Co-Pi) sensitized inverse opal TiO2 as a photocatalyst. Catalysis Science & Technology 7, 5687–5693.
| Visible-light-induced reduction of hexavalent chromium utilizing cobalt phosphate (Co-Pi) sensitized inverse opal TiO2 as a photocatalystCrossref | GoogleScholarGoogle Scholar |
Markad US, Kalekar AM, Naik DB, Sharma KKK, Kshirasagar KJ, Sharma GK (2017). Photo enhanced detoxification of chromium (VI) by formic acid using 3D palladium nanocatalyst. Journal of Photochemistry and Photobiology A: Chemistry 338, 115–122.
| Photo enhanced detoxification of chromium (VI) by formic acid using 3D palladium nanocatalystCrossref | GoogleScholarGoogle Scholar |
Tu W, Li K, Shu X, Yu WW (2013). Reduction of hexavalent chromium with colloidal and supported palladium nanocatalysts. Journal of Nanoparticle Research 15, 1593
| Reduction of hexavalent chromium with colloidal and supported palladium nanocatalystsCrossref | GoogleScholarGoogle Scholar |
Veerakumar P, Panneer Muthuselvam I, Hung C-T, Lin K-C, Chou F, Liu S (2016). Biomass-Derived Activated Carbon Supported Fe3O4 Nanoparticles as Recyclable Catalysts for Reduction of Nitroarenes. ACS Sustainable Chemistry & Engineering 4, 6772–6782.
| Biomass-Derived Activated Carbon Supported Fe3O4 Nanoparticles as Recyclable Catalysts for Reduction of NitroarenesCrossref | GoogleScholarGoogle Scholar |
Veerakumar P, Thanasekaran P, Lin K-C, Liu S-B (2017). Biomass Derived Sheet-like Carbon/Palladium Nanocomposite: An Excellent Opportunity for Reduction of Toxic Hexavalent Chromium. ACS Sustainable Chemistry & Engineering 5, 5302–5312.
| Biomass Derived Sheet-like Carbon/Palladium Nanocomposite: An Excellent Opportunity for Reduction of Toxic Hexavalent ChromiumCrossref | GoogleScholarGoogle Scholar |
Vellaichamy B, Periakaruppan P (2016). A facile, one-pot and eco-friendly synthesis of gold/silver nanobimetallics smartened rGO for enhanced catalytic reduction of hexavalent chromium. RSC Advances 6, 57380–57388.
| A facile, one-pot and eco-friendly synthesis of gold/silver nanobimetallics smartened rGO for enhanced catalytic reduction of hexavalent chromiumCrossref | GoogleScholarGoogle Scholar |
Yadav M, Xu Q (2013). Catalytic chromium reduction using formic acid and metal nanoparticles immobilized in a metal–organic framework. Chemical Communications 49, 3327–3329.
| Catalytic chromium reduction using formic acid and metal nanoparticles immobilized in a metal–organic frameworkCrossref | GoogleScholarGoogle Scholar | 23505626PubMed |
Yao Y, Wang Z, Zhao S, Wang D, Wu Z, Zhang M (2014). A stable and effective Ru/polyethersulfone catalyst for levulinic acid hydrogenation to γ-valerolactone in aqueous solution. Catalysis Today 234, 245–250.
| A stable and effective Ru/polyethersulfone catalyst for levulinic acid hydrogenation to γ-valerolactone in aqueous solutionCrossref | GoogleScholarGoogle Scholar |
Zhitkovich A (2011). Chromium in Drinking Water: Sources, Metabolism, and Cancer Risks. Chemical Research in Toxicology 24, 1617–1629.
| Chromium in Drinking Water: Sources, Metabolism, and Cancer RisksCrossref | GoogleScholarGoogle Scholar | 21766833PubMed |