Surface enhanced Raman spectroscopy measurement of surface pH at the electrode during Ni electrodeposition reaction
In this work, we developed a precise approach to analyze local proton concentration at the solid/liquid interface of electrodes, i.e. “surface pH”, during electrochemical reactions. For this, surface enhanced Raman spectroscopy (SERS) was applied to analyze pH-dependent structural changes of the –COOH group of p-mercaptobenzoic acid (p-MBA) modified onto Au nanoparticles (NPs) on the substrate close to a working electrode. Measurements using this system identified deprotonation of –COOH of p-MBA. Since preliminary experiments and density functional theory calculations suggest that the pKa of p-MBA attached to Au NPs is close to that in bulk solution, the SERS results indicate pH increase due to proton consumption by the cathodic overpotential of the working electrode. As an example, we applied this system to surface pH monitoring in electrodeposition process of Ni in an acidic bath, which indicated the validity of our method for precise detection of pH changes at electrode interfaces in situ.
KeywordsSurface pH Electrodeposition Surface enhanced Raman spectroscopy Au nano particles
This research was financially supported in part by “Development of Systems and Technology for Advanced Measurement and Analysis” program from JST, a “Grant-in-Aid for challenging Exploratory Research (26600065)” of the MEXT, Japan, and Waseda University Grant for Special Research Project number 2017B-189.
- 5.Romankiw LT (1970) Specific ion activity measurement at an electrode during electrolysis. IBM Tech Discl Bull 13:69Google Scholar
- 19.Frisch MJ et al (2009) Gaussian 09, revision A.01, Gaussian, Inc., WallingfordGoogle Scholar
- 23.Hehre WJ, Radom L, Schleyer PvR, Pople JA (1986) Ab initio molecular orbital theory. Wiley, New YorkGoogle Scholar
- 31.Zhao L, Jensen L, Schatz GC (2006) Pyridine-Ag20 cluster: a model system for studying surface-enhanced raman scattering. J Am Chem Soc 128:2911–2919Google Scholar
- 34.Atkins PW (1998) Physical chemistry, 6th edn. W. H. Freeman, New YorkGoogle Scholar