3D-macroporous chitosan-based scaffolds with in situ formed Pd and Pt nanoparticles for nitrophenol reduction

Dmitriy Berillo, Andrew Cundy

Research output: Contribution to journalArticle

  • 2 Citations

Abstract

3D-macroporous chitosan-based scaffolds (cryogels) were produced via growth of metal-polymer coordinated complexes and electrostatic interactions between oppositely charged groups of chitosan and metal ions under subzero temperatures. A mechanism of reduction of noble metal complexes inside the cryogel walls by glutaraldehyde is proposed, which produces discrete and dispersed noble metal nanoparticles. 3D-macroporous scaffolds prepared under different conditions were characterised using TGA, FTIR, nitrogen adsorption, SEM, EDX and TEM, and the distribution of platinum nanoparticles (PtNPs) and palladium nanoparticles (PdNPs) in the material assessed. The catalytic activity of the in situ synthesised PdNPs, at 2.6, 12.5 and 21.0 μg total mass, respectively, was studied utilising a model system of 4-nitrophenol reduction. The kinetics of the reaction under different conditions (temperature, concentration of catalyst) were examined, and a decrease of catalytic activity was not observed over 17 treatment cycles. Increasing the temperature of the catalytic reaction from 10 to 22 and 35 °C by PdNPs supported within the cryogel increased the kinetic rate by 44 and 126%, respectively. Turnover number and turnover frequency of the PdNPs catalysts at room temperature were in the range 0.20–0.53 h−1. The conversion degree of 4-nitrophenol at room temperature reached 98.9% (21.0 μg PdNPs). Significantly less mass of palladium nanoparticles (by 30–40 times) was needed compared to published data to obtain comparable rates of reduction of 4-nitrophenol.

LanguageEnglish
Pages166-175
Number of pages10
JournalCarbohydrate Polymers
Volume192
DOIs
Publication statusPublished - Jul 15 2018

Fingerprint

Nitrophenols
Chitosan
Scaffolds
Palladium
Cryogels
Nanoparticles
Precious metals
Catalyst activity
Temperature
Catalysts
Kinetics
Metal nanoparticles
Coordination Complexes
Glutaral
Metal complexes
Coulomb interactions
Platinum
Metal ions
Energy dispersive spectroscopy
Polymers

Keywords

  • Catalysis
  • Chitosan
  • Macroporous cryogels
  • Nitrophenol
  • Palladium nanoparticles
  • Platinum nanoparticles

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Cite this

3D-macroporous chitosan-based scaffolds with in situ formed Pd and Pt nanoparticles for nitrophenol reduction. / Berillo, Dmitriy; Cundy, Andrew.

In: Carbohydrate Polymers, Vol. 192, 15.07.2018, p. 166-175.

Research output: Contribution to journalArticle

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AB - 3D-macroporous chitosan-based scaffolds (cryogels) were produced via growth of metal-polymer coordinated complexes and electrostatic interactions between oppositely charged groups of chitosan and metal ions under subzero temperatures. A mechanism of reduction of noble metal complexes inside the cryogel walls by glutaraldehyde is proposed, which produces discrete and dispersed noble metal nanoparticles. 3D-macroporous scaffolds prepared under different conditions were characterised using TGA, FTIR, nitrogen adsorption, SEM, EDX and TEM, and the distribution of platinum nanoparticles (PtNPs) and palladium nanoparticles (PdNPs) in the material assessed. The catalytic activity of the in situ synthesised PdNPs, at 2.6, 12.5 and 21.0 μg total mass, respectively, was studied utilising a model system of 4-nitrophenol reduction. The kinetics of the reaction under different conditions (temperature, concentration of catalyst) were examined, and a decrease of catalytic activity was not observed over 17 treatment cycles. Increasing the temperature of the catalytic reaction from 10 to 22 and 35 °C by PdNPs supported within the cryogel increased the kinetic rate by 44 and 126%, respectively. Turnover number and turnover frequency of the PdNPs catalysts at room temperature were in the range 0.20–0.53 h−1. The conversion degree of 4-nitrophenol at room temperature reached 98.9% (21.0 μg PdNPs). Significantly less mass of palladium nanoparticles (by 30–40 times) was needed compared to published data to obtain comparable rates of reduction of 4-nitrophenol.

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