Laser Raman Spectroscopy in Studies of Corrosion and Electrocatalysis

Melendres, C. A.

doi:10.1007/978-94-011-3782-9_6

Cited by 9 publications
(4 citation statements)

~~References 86 publications~~

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“…However, researchers have never given up their efforts to extend SERS to the study of other metallic and nonmetallic surfaces. − In the 1980s, a strategy based on “borrowing SERS” was proposed, either by depositing SERS-active metals onto non-SERS-active substrates, including semiconductors, or by depositing non-SERS-active materials over SERS-active substrates. , For example, SERS-active Ag or Au electrodes were coated with ultrathin films of other metals such as Ni, Co and Fe, Pt, Pd, Rh, and Ru by electrochemical deposition. With the aid of the long-range effect of the electromagnetic (EM) enhancement created by the SERS-active substrate underneath, weak SERS spectra of adsorbates on the transition metal overlayer can be obtained. , It should be noted that the strong electromagnetic field generated on the SERS-active substrate is damped significantly by the coated film so that the film has to be ultrathin, normally 3−10 atomic layers.…”

Section: Introductionmentioning
confidence: 99%

See 1 more Smart Citation
Surface-Enhanced Raman Scattering: From Noble to Transition Metals and from Rough Surfaces to Ordered Nanostructures
Zhang
¹
,
Ren
²
,
Wu
³

2002
J. Phys. Chem. B
1,326
19
1,064
1
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In the mid-1970s, surface-enhanced Raman scattering (SERS) was discovered which impacted on surface science and spectroscopy because of its extremely high surface sensitivity. However, SERS had not developed as many people had hoped to be a powerful surface diagnostic technique that can be widely used because of some obstacles. For example, only three noble metals Au, Ag, and Cu could provide large enhancement, severely limiting the widespread applications involving other metallic materials of both fundamental and practical importance. In this article, emphasis is put on the recent work of our group to directly generate SERS on net transition metals (e.g., Pt, Ru, Rh, Pd, Fe, Co, Ni, and their alloys) by developing various roughening procedures and optimizing the performance of the confocal Raman microscope. An approach of replacing the randomly roughened surface with ordered nanorod arrays of transition metals is introduced as a promising class of highly SERS-active substrates. The surface enhancement factor for transition metals was calculated, which ranged from 1 to 4 orders of magnitude. The applications of SERS in surface adsorption, electro-catalysis, and corrosion of transition-metal-based systems demonstrated several advantages of in situ surface Raman spectroscopy. A preliminary theoretical approach, considering the electromagnetic and chemical contributions, is presented to explain the SERS behavior of transition metal electrodes and nanorod arrays. It has been shown that SERS together with other surface-enhanced optical phenomena could be one of important issues not only in surface science but also in nanoscale science. Prospects and further developments in this exciting field are discussed with emphasis on the emerging experimental methodology.
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Section: Introductionmentioning
confidence: 99%

“…Its advantage of high sensitivity enables one to probe ultrathin film with a few atomic monolayers. Without the aid of SERS, Raman spectroscopy is rather possible using rather thick films with thickness ranging from submicron to minimeters. 1b,c, …”

Section: Introductionmentioning
confidence: 99%

Surface-Enhanced Raman Scattering: From Noble to Transition Metals and from Rough Surfaces to Ordered Nanostructures
Zhang
¹
,
Ren
²
,
Wu
³

2002
J. Phys. Chem. B
1,326
19
1,064
1
View full text Add to dashboard Cite

In the mid-1970s, surface-enhanced Raman scattering (SERS) was discovered which impacted on surface science and spectroscopy because of its extremely high surface sensitivity. However, SERS had not developed as many people had hoped to be a powerful surface diagnostic technique that can be widely used because of some obstacles. For example, only three noble metals Au, Ag, and Cu could provide large enhancement, severely limiting the widespread applications involving other metallic materials of both fundamental and practical importance. In this article, emphasis is put on the recent work of our group to directly generate SERS on net transition metals (e.g., Pt, Ru, Rh, Pd, Fe, Co, Ni, and their alloys) by developing various roughening procedures and optimizing the performance of the confocal Raman microscope. An approach of replacing the randomly roughened surface with ordered nanorod arrays of transition metals is introduced as a promising class of highly SERS-active substrates. The surface enhancement factor for transition metals was calculated, which ranged from 1 to 4 orders of magnitude. The applications of SERS in surface adsorption, electro-catalysis, and corrosion of transition-metal-based systems demonstrated several advantages of in situ surface Raman spectroscopy. A preliminary theoretical approach, considering the electromagnetic and chemical contributions, is presented to explain the SERS behavior of transition metal electrodes and nanorod arrays. It has been shown that SERS together with other surface-enhanced optical phenomena could be one of important issues not only in surface science but also in nanoscale science. Prospects and further developments in this exciting field are discussed with emphasis on the emerging experimental methodology.

~~show abstract~~

“…In corrosion science, surface-enhanced Raman scattering (SERS) and resonance Raman scattering (RRS) techniques have been used individually or together to enhance the scattering signal from the electrochemical interface. − Of these studies, copper and silver are the substrates investigated extensively due to their giant enhancing effect. Kester and co-workers 5 first utilized SERS to study the structure of benzotriazole (BTAH) adsorbed on a copper surface.…”

Section: Introductionmentioning
confidence: 99%

Comparative Study of Inhibition Effects of Benzotriazole for Metals in Neutral Solutions As Observed with Surface-Enhanced Raman Spectroscopy
Cao
¹
,
Yao
²
,
Zheng
³

et al. 2001
Langmuir
194
6
124
1
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Surface-enhanced Raman spectroscopy has been successfully extended to the study of corrosion inhibition of bare iron and nickel metals. The inhibition effects of benzotriazole (BTAH) for copper, iron, and nickel electrodes in 0.1 M KCl solution were investigated by using both polarization curves and in situ Raman techniques. The protective films formed on copper and iron surfaces, in the presence of BTAH, are characterized as [Cu I BTA]n and [Fe II (BTA)2]n, respectively. The formation of Fe-N coordinated bonds and the deprotonation of the triazole ring may occur while BTAH interacts with the iron surface. On the contrary, BTAH may interact with the nickel surface as neutral molecules in the whole potential range investigated resulting in a poor inhibition effect. The surface complex is characterized as [Ni-BTAH]. The potential dependence of the Raman spectra on copper and iron shows that the BTAion in the surface complex may rebind with H + at more negative potentials and accordingly the inhibition efficiency of benzotriazole decreases.

~~show abstract~~

“…To get detailed and direct vibrational information reflecting the surface bond, adsorption type, and their changes with outer factors, in situ techniques including spectroelectrochemical measurements are favorable. Unfortunately, up to now there have been few techniques which have the required sensitivity to directly investigate the interaction of inhibitors with a metal surface …”

Section: Introductionmentioning
confidence: 99%

Electrochemical and Surface-Enhanced Raman Spectroscopy Studies on Inhibition of Iron Corrosion by Benzotriazole
Cao
¹
,
Gu
²
,
Zhang
³

2002
Langmuir
102
2
56
0
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The different initial interactions of benzotriazole (BTAH) with iron in both 0.5 M H2SO4 and simulated saline water (3.4% NaCl) have been investigated systematically by using a confocal microprobe Raman system, surface-enhanced Raman spectroscopy (SERS), and electrochemical potentiodynamic polarization curves. The SERS spectra of BTAH at the bare iron electrodes in both 0.5 M H2SO4 and simulated saline water have been obtained successfully for the first time. Electrochemical measurements show that the inhibition efficiency of BTAH is higher in saline water than that in acid solution, which is in accordance with the identification of the surface interaction on the basis of the SERS data. BTAH may be physisorbed onto the iron surface through its neutral molecule form or protonated BTAH2 + ions. While in saline water, the formation of the surface coordination compound characterized as Fe(II)-BTA may contribute to the outstanding spectral features. A cleavage of the NH bond is believed to occur while adsorption of BTAH onto iron proceeds. This more compact surface film results in a higher inhibition efficiency in comparison with that in an acid solution.

~~show abstract~~

Laser Raman Spectroscopy in Studies of Corrosion and Electrocatalysis

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Cited by 9 publications

References 86 publications

Surface-Enhanced Raman Scattering: From Noble to Transition Metals and from Rough Surfaces to Ordered Nanostructures

Surface-Enhanced Raman Scattering: From Noble to Transition Metals and from Rough Surfaces to Ordered Nanostructures

Comparative Study of Inhibition Effects of Benzotriazole for Metals in Neutral Solutions As Observed with Surface-Enhanced Raman Spectroscopy

Electrochemical and Surface-Enhanced Raman Spectroscopy Studies on Inhibition of Iron Corrosion by Benzotriazole

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