Shell‐isolated nanoparticle enhanced Raman spectroscopy (SHINERS) investigation of benzotriazole film formation on Cu(100), Cu(111), and Cu(poly)

Abstract

Benzotriazole (BTAH) is well known as an effective corrosion inhibitor for Cu because of its ability to make a coordination polymer film on the surface that provides a barrier to Cu oxidation. BTA − film formation was investigated on single-crystal and polycrystalline Cu surfaces with shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) using silica-encapsulated Au nanoparticles. Potential-dependent spectra display reversible film formation on polycrystalline Cu and irreversible film formation on single-crystal Cu. Grain boundaries leading to smaller BTA − -Cu oligomers are proposed to be the reason for cathodic degradation of the BTA − polymeric films on polycrystalline Cu.

Advances in surface-enhanced vibrational spectroscopy at electrochemical interfaces

“…Procedures to synthesise SHINs are now well-documented [85], typical particles comprising a 55-120 nm spherical gold or silver core [82,86,87] [92], graphene [93,94] and other carbon materials [95,96]. Example core-shell particles are depicted in Figure 5 The substrate generality of SHINERS has greatly benefitted electrochemical Raman spectroscopy and an impressive range of native electrode substrates have been investigated including Ag [97,98], Au [99][100][101][102][103][104], Pt [99,102], Pd [102], Rh [105], Ni alloys [106,107], Cu [108] and glassy carbon (GC) [102]. Moreover, SHINERS enables the detailed investigation of single crystal electrodes, which are of tremendous interest as model systems from a surface science perspective, allowing the effect of surface atomic structure on behaviour and reactivity to be systematically investigated [109].…”

“…In the latter case, the dominant surface adsorbate was demonstrated to be highly sensitive to atomic structure of the Pt surface, and in particular, the presence of surface defects. Corrosion inhibitors have also been studied using this approach, which highlighted differences in protective film formation at various metal surfaces under potential control [107,108].…”

Shell‐Isolated Nanoparticle‐Enhanced Raman Spectroscopy (SHINERS)

“…We call this new technique "shell-isolated nanoparticle-enhanced Raman spectroscopy" (SHINERS) [45][46][47], which very recently has been applied successfully to several systems. [45][46][47][52][53][54][55][56][57][58][59][60][61][62][63].…”

Large scale synthesis of pinhole‐free shell‐isolated nanoparticles (SHINs) using improved atomic layer deposition (ALD) method for practical applications

“…The rapid development of SHINERS technique offsets the longstanding limitations of SERS such as substrate and morphology generality to a certain extent. Therefore, SHINERS has been widely accepted by different fields such as surface science, [14,15] analytical science, [16] electrochemistry, [17][18][19][20][21][22] material science, [23][24][25] life science [26,27] and other fields. [28][29][30][31] Chemical method is the conventional protocol to prepare metal nanoparticles with thin layer of inert dielectric shell; the shell thickness can be adjusted between 1 and 5 nm with controlled reaction time.…”