title: Inhibiting plasmon catalyzed conversion of para-nitrothiophenol on monolayer film of Au nanoparticles probed by surface enhanced Raman spectroscopy.
abstract: The plasmon catalyzed surface reaction has been attracted considerable attention due to its promising application in heterogeneous catalysis. This kind of plasmon catalysis played bilateral roles in driving the unconventional reactions or destructing the surface molecule layer. The acceleration or inhibition on this catalysis is still remained significant challenge. In this paper, monolayer film of Au nanoparticles was fabricated at air/water interface as substrates both for surface enhanced Raman spectroscopy (SERS) and plasmon catalyzed surface reaction. The influence from several issues, involving surfactants, coadsorption species, the solvent and water, were systemically investigated to probe the acceleration and inhibition on the plasmon catalysis reaction. The concentration and molecular weight of surfactant polyvinylpyrrolidone (PVP) exhibited significant influence in the reactive activity for the plasmon catalyzed dimerization of para-nitrothiophenol (PNTP) to p,p'-dimercaptoazobenzene (DMAB). A suitable molecular weight of 10,000 and concentration of 10mg/mL were beneficial for improving the conversion efficiency of PNTP to DMAB. The higher molar ratio of coadsorbed 1-octanethiol and the aprotic solvents resulted in the inhibition of dimerization because 1-octanethiol occupied the surface sites to isolate the adsorbed PNTP molecules with a larger distance and lack of proton source. The plasmon catalysis occurred in ionic liquids suggested that water was essential for the dimerization of PNTP, in which it was used to accelerate the reaction rate and severed as the hydrogen source.
authors.affiliation: College of Chemistry, Chemical Engineering & Materials Science, Soochow University, Suzhou 215123, China.
authors.forename: Hua-Yi
authors.initials: HY
authors.lastname: Weng
authors.affiliation: College of Chemistry, Chemical Engineering & Materials Science, Soochow University, Suzhou 215123, China.
authors.forename: Qing-Hua
authors.initials: QH
authors.lastname: Guo
authors.affiliation: College of Chemistry, Chemical Engineering & Materials Science, Soochow University, Suzhou 215123, China.
authors.forename: Xing-Rong
authors.initials: XR
authors.lastname: Wang
authors.affiliation: College of Chemistry, Chemical Engineering & Materials Science, Soochow University, Suzhou 215123, China. Electronic address: xumm@suda.edu.cn.
authors.forename: Min-Min
authors.initials: MM
authors.lastname: Xu
authors.affiliation: College of Chemistry, Chemical Engineering & Materials Science, Soochow University, Suzhou 215123, China.
authors.forename: Ya-Xian
authors.initials: YX
authors.lastname: Yuan
authors.affiliation: College of Chemistry, Chemical Engineering & Materials Science, Soochow University, Suzhou 215123, China.
authors.forename: Ren-Ao
authors.initials: RA
authors.lastname: Gu
authors.affiliation: College of Chemistry, Chemical Engineering & Materials Science, Soochow University, Suzhou 215123, China. Electronic address: jlyao@suda.edu.cn.
authors.forename: Jian-Lin
authors.initials: JL
authors.lastname: Yao
keywords: Coadsorption; Inhibition; Para-nitrothiophenol; Surface enhanced Raman spectroscopy; Surface plasmon catalysis