title: Mechanistic understanding of surface plasmon assisted catalysis on a single particle: cyclic redox of 4-aminothiophenol.
abstract: Surface plasmon assisted catalysis (SPAC) reactions of 4-aminothiophenol (4ATP) to and back from 4,4'-dimercaptoazobenzene (DMAB) have been investigated by single particle surface enhanced Raman spectroscopy, using a self-designed gas flow cell to control the reductive/oxidative environment over the reactions. Conversion of 4ATP into DMAB is induced by energy transfer (plasmonic heating) from surface plasmon resonance to 4ATP, where O₂ (as an electron acceptor) is essential and H₂O (as a base) can accelerate the reaction. In contrast, hot electron (from surface plasmon decay) induction drives the reverse reaction of DMAB to 4ATP, where H₂O (or H₂) acts as the hydrogen source. More interestingly, the cyclic redox between 4ATP and DMAB by SPAC approach has been demonstrated. This SPAC methodology presents a unique platform for studying chemical reactions that are not possible under standard synthetic conditions.
authors.affiliation: 1] Department of Chemistry, Harbin Institute of Technology, Harbin 150001, People's Republic of China [2] Chemistry Division, Physical Chemistry and Applied Spectroscopy, Los Alamos National Laboratory, Los Alamos, NM 87545, United States of America.
authors.forename: Ping
authors.initials: P
authors.lastname: Xu
authors.forename: Leilei
authors.initials: L
authors.lastname: Kang
authors.forename: Nathan H
authors.initials: NH
authors.lastname: Mack
authors.forename: Kirk S
authors.initials: KS
authors.lastname: Schanze
authors.forename: Xijiang
authors.initials: X
authors.lastname: Han
authors.forename: Hsing-Lin
authors.initials: HL
authors.lastname: Wang
mesh_terms: D000255:Adenosine Triphosphate / Q000737:chemistry; D000814:Aniline Compounds / Q000737:chemistry*; D002384:Catalysis; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D020349:Surface Plasmon Resonance
chemical_list: D000814:Aniline Compounds; D013438:Sulfhydryl Compounds; D000255:Adenosine Triphosphate; C064316:4-aminothiophenol; D010100:Oxygen