title: Understanding the degradation pathway of the pesticide, chlorpyrifos by noble metal nanoparticles.
abstract: Application of nanoparticles (NPs) in environmental remediation such as water purification requires a detailed understanding of the mechanistic aspects of the interaction between the species involved. Here, an attempt was made to understand the chemistry of noble metal nanoparticle-pesticide interaction, as these nanosystems are being used extensively for water purification. Our model pesticide, chlorpyrifos (CP), belonging to the organophosphorothioate group, is shown to decompose to 3,5,6-trichloro-2-pyridinol (TCP) and diethyl thiophosphate at room temperature over Ag and Au NPs, in supported and unsupported forms. The degradation products were characterized by absorption spectroscopy and electrospray ionization mass spectrometry (ESI MS). These were further confirmed by ESI tandem mass spectrometry. The interaction of CP with NP surfaces was investigated using transmission electron microscopy, energy dispersive analysis of X-rays, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS reveals no change in the oxidation state of silver after the degradation of CP. It is proposed that the degradation of CP proceeds through the formation of AgNP-S surface complex, which is confirmed by Raman spectroscopy. In this complex, the P-O bond cleaves to yield a stable aromatic species, TCP. The rate of degradation of CP increases with increase of temperature and pH. Complete degradation of 10 mL of 2 ppm CP solution is achieved in 3 h using 100 mg of supported Ag@citrate NPs on neutral alumina at room temperature at a loading of ∼0.5 wt %. The effect of alumina and monolayer protection of NPs on the degradation of CP is also investigated. The rate of degradation of CP by Ag NPs is greater than that of Au NPs. The results have implications to the application of noble metal NPs for drinking water purification, as pesticide contamination is prevalent in many parts of the world. Study shows that supported Ag and Au NPs may be employed in sustainable environmental remediation, as they can be used at room temperature in aqueous solutions without the use of additional stimulus such as UV light.
authors.affiliation: DST Unit of Nanoscience, Department of Chemistry, Indian Institute of Technology Madras, Chennai-600 036, India.
authors.forename: M S
authors.initials: MS
authors.lastname: Bootharaju
authors.forename: T
authors.initials: T
authors.lastname: Pradeep
mesh_terms: D000537:Aluminum Oxide / Q000737:chemistry; D004390:Chlorpyrifos / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D015394:Molecular Structure; D010316:Particle Size; D012834:Silver / Q000737:chemistry*; D012996:Solutions; D013499:Surface Properties; D014867:Water / Q000737:chemistry
chemical_list: D012996:Solutions; D014867:Water; D012834:Silver; D006046:Gold; D004390:Chlorpyrifos; D000537:Aluminum Oxide