In situ SERS and SHINERS study of electrochemical hydrogenation of p-ethynylaniline in nonaqueous solvents |
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| Institution: | 1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China;2. MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P.R. China;1. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, Liaoning, China;2. School of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China;3. College of Chemistry, Chongqing Normal University, Chongqing 401331, China;1. Department of Organic Chemistry, Center for Physical Sciences and Technology (FTMC), Saulėtekio Ave. 3, LT-10257 Vilnius, Lithuania;2. Nature Research Centre, Akademijos 2, LT-08412 Vilnius, Lithuania;3. Department of Bioelectrochemistry and Biospectroscopy, Institute of Biochemistry, Life Sciences Center, Vilnius University, Saulėtekio av. 7, LT-10257 Vilnius, Lithuania |
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| Abstract: | Surface-enhanced Raman spectroscopy (SERS) studies of electrode/solution interfaces are important for understanding electrochemical processes. However, revealing the nature of reactions at well-defined single crystal electrode surfaces, which are SERS-inactive, remains challenging. In this work, shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) was used for the first time to study electrochemical adsorption and hydrogenation reactions at single crystal surfaces in nonaqueous solvents. A roughened Au surface was also studied for comparison. The experimental results show that the hydrogenation of adsorbed p-ethynylaniline (PEAN) on roughened Au electrode surfaces occurred at very negative potentials in methanol because of the catalytic effect of surface plasmon resonance (SPR). However, because “hot electrons” were blocked by the silica shell of Au@SiO2 nanoparticles and aprotic acetonitrile was an ineffective hydrogen source, surface reactions at Au(111) were inhibited in the systems studied. Density functional theory (DFT) calculations revealed that the PEAN triple bond opened, allowing adsorption in a flat configuration on the Au(111) surface via two carbon atoms. This work provides an advanced understanding of electrochemical interfacial processes at single crystal surfaces in nonaqueous systems. |
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