Operando electrochemical SERS monitors nanoparticle reactions by capping agent fingerprints  

作　　者：Kevin Wonner Steffen Murke Serena RAlfarano Pouya Hosseini Martina Havenith Kristina Tschulik 

机构地区：[1]Chair of Analytical Chemistry Ⅱ,Faculty of Chemistry and Biochemistry,Ruhr University Bochum,Bochum 44801,Germany [2]Chair of Physical Chemistry Ⅱ,Faculty of Chemistry and Biochemistry,Ruhr University Bochum,Bochum 44801,Germany

出　　处：《Nano Research》2022年第5期4517-4524,共8页纳米研究（英文版）

基　　金：K.W.acknowledges the German Chemical Industry Fund(FCI Kekule Stipendium).This work was supported by the Research Training group“Confinement-controlled Chemistry”funded by the Deutsche Forschungsgemeinschaft(DFG)(No.GRK2376/331085229);K.T.thanks the Ministry of Innovation,Science and Research of North Rhine-Westphalia for funds(NRW Ruckkehrerprogramm);This work was funded by the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)under Germany’s Excellence Strategy-EXC 2033-90677874-RESOLV and the European Research Council(ERC)under the European Union’s Horizon 2020 research and innovation programme(MITICAT;grant agreement No.949724).

摘　　要：Nanomaterials are frequently employed in daily life goods,including health,textile,and food industry.A comprehensive picture is lacking on the role of the capping agents,added ligand molecules,in case of nanoparticle reactions and degradation in aqueous solutions,like surface waters or biofluids.Here,we aim to elucidate the capping agent influence on nanoparticle reactivity probing two commonly employed capping agents citrate and polyvinylpyrrolidone(PVP).Their influence on silver nanoparticle(AgNP)transformation is studied,which is particularly important due to its application as an antimicrobial agent.We induce oxidation and reduction processes of AgNPs in halide solutions and we monitor the associated transformations of particles and capping agents by spectro-electrochemical surface-enhanced Raman spectroscopy(SERS).Raman bands of the capping agents are used here to track chemical changes of the nanoparticles under operando conditions.The sparingly soluble and non-plasmon active silver salts(AgBr and AgCl)are formed under potential bias.In addition,we spectroscopically observe plasmon-mediated structural changes of citrate to cis-or trans-aconitate,while PVP is unaltered.The different behavior of the capping agents implies a change in the physical properties on the surface of AgNPs,in particular with respect to the surface accessibility.Moreover,we showcase that reactions of the capping agents induced by different external stimuli,such as applied bias or laser irradiation,can be assessed.Our results demonstrate how SERS of capping agents can be exploited to operando track nanoparticle conversions in liquid media.This approach is envisaged to provide a more comprehensive understanding of nanoparticle fates in complex liquid environments and varied redox conditions.

关 键 词：capping agent electrochemical surface-enhanced Raman spectroscopy silver nanoparticle nanoparticle reaction 

分 类 号：O64[理学—物理化学]