260:
189:
311:. It records the scattered radiation and provides the Raman spectra of the molecules. In Raman-SEC, spectrometers are usually combined with confocal microscopes (micro-Raman) to remove the information out of the focus, obtaining an excellent spectral resolution. However, it is possible to work with low resolution Raman spectrometers obtaining very good results.
99:
Surface-Enhanced Raman
Scattering (SERS) is a technique capable of increasing Raman signal intensity up to 10 times. This phenomenon is based on the interaction of monochromatic light with materials that exhibit plasmonic properties. The most common metals used in SERS are nanostructured metals with
88:
The Raman resonance effect produces an increase in Raman intensity up to 10 times. In this phenomenon, the monochromatic light interaction with the sample produces the transition of the molecules from the fundamental state to an excited electronic state, instead of a virtual state as in normal Raman
69:
The main advantage of Raman spectroelectrochemistry is that it is not limited to the selected solvent, and aqueous and organic solutions can be used. However, the main disadvantage is the intrinsic low Raman signal intensity. Different methods as well as new substrates were developed to improve the
127:
Surface-oxidation enhanced Raman scattering (SOERS) is a process similar to SERS, which allows the Raman signal to be enhanced when a silver electrode is oxidized in a particular electrolyte composition. This process is carried out at sufficiently positive potentials to ensure the oxidation of the
181:
Tip-enhanced Raman scattering (TERS) is a technique that provides molecular information at nanoscale. In these experiments, metal nanostructures are replaced by a sharp metal tip of nanometric size, concentrating the roughness directly on a small region that improves the spatial resolution of
222:, since it is possible to focus and collect the scattered photons in a highly efficient way. Low resolution Raman spectrometers can be also used, providing suitable results. Using this setup, the sampling area is larger and average information about the electrode surface is obtained.
300:
that interacts with the sample during the electrochemical process. In Raman-SEC, the light source is usually a laser corresponding to the VIS or NIR regions, which commonly emits at 532, 633, 785 or 1064 nm, although there is the possibility of using many other lasers, including
283:, a spectroelectrochemical cell, a three-electrode system, radiation beam conducting devices, data collection and analysis devices. Nowadays, there are commercial instruments that integrate all these elements in a single instrument, significantly simplifying the performance of
116:
electrode surfaces can be generated by depositing metallic nanostructures of these materials. A disadvantage of this phenomenon is, sometimes, the lack of reproducibility of the spectra due to the difficulty of obtaining identical nanostructured surfaces in each experiment.
842:
Królikowska, Agata (2013-07-26), Wieckowski, Andrzej; Korzeniewski, Carol; Braunschweig, Björn (eds.), "Surface-Enhanced
Resonance Raman Scattering (SERRS) Studies of Electron-Transfer Redox-Active Protein Attached to Thiol-Modified Metal: Case of Cytochrome c",
385:
over long distances with hardly any losses. In addition, they simplify the optical configurations since they allow working with a small amount of solution; in this way, it is easier to conduct and collect the light in the nearness of the
369:. It is the device that includes the three-electrode system and allows the simultaneous recording of the Raman spectra of the species and the electrochemical signal. It is the link between optical and electrochemical techniques.
30:
of monochromatic light related to chemical compounds involved in an electrode process. This technique provides information about vibrational energy transitions of molecules, using a monochromatic light source, usually from a
263:
Raman-SEC configurations. The first picture shows the normal arrangement, the second the inverted microscope configuration and the last the angle arrangement. All of them are shown on screen-printed electrodes.
162:
signals by preventing the molecules from being directly adsorbed onto them. Silica and alumina coating can improve the chemical and thermal stability of nanoparticles. This fact has great importance in the
205:
provides spectra with very weak Raman bands, therefore, a very well aligned optical configuration is required. Laser has to be focused on the electrode surface and an efficient collection of the scattered
158:. The metallic nucleus (Au or Ag) is responsible of the enhancement of the Raman signals of the nearby molecules, while the coating layers eliminate the influence of the metallic nucleus on the Raman and
73:
For researchers, a few experimental considerations related to Raman spectroelectrochemistry include electrode preparation, cell design, laser parameters, electrochemical sequence and data process.
738:
Perales-Rondon, Juan V.; Hernandez, Sheila; Martin-Yerga, Daniel; Fanjul-Bolado, Pablo; Heras, Aranzazu; Colina, Alvaro (2018). "Electrochemical surface oxidation enhanced Raman scattering".
470:
Transfer processes at the liquid/liquid interfaces: Raman-SEC is used to monitor ion or electron transfer processes at polarizable interfaces between immiscible electrolyte solutions.
35:
that belongs to the UV, Vis or NIR region. Raman spectroelectrochemistry provides specific information about structural changes, composition and orientation of the molecules on the
167:
study of catalytic reactions. The high sensitivity of the SHINERS surfaces makes these nanostructures a promising tool for the study of liquid-solid interfaces, especially in
1201:
Zhang, Hua; Duan, Sai; Radjenovic, Petar M.; Tian, Zhong-Qun; Li, Jian-Feng (2020-04-21). "CoreâShell
Nanostructure-Enhanced Raman Spectroscopy for Surface Catalysis".
1108:
Li, Jian-Feng; Zhang, Yue-Jiao; Ding, Song-Yuan; Panneerselvam, Rajapandiyan; Tian, Zhong-Qun (2017-04-12). "CoreâShell
Nanoparticle-Enhanced Raman Spectroscopy".
408:
In recent years Raman-SEC has become an important tool in the study of electrochemical processes and in the characterization of many molecules, providing specific
50:
are scattered elastically, with the same energy than the incident light. However, a small fraction is scattered inelastically, being the energy of the laser
232:. The laser beam samples the electrode/solution interface in a normal way respect to the electrode surface. The scattered radiation is collected, and the
978:"In situ Raman and surface-enhanced Raman spectroscopy on working electrodes: spectroelectrochemical characterization of water oxidation electrocatalysts"
606:
GarozâRuiz, Jesus; PeralesâRondon, Juan Victor; Heras, Aranzazu; Colina, Alvaro (2019). "Spectroelectrochemical
Sensing: Current Trends and Challenges".
66:
techniques, makes Raman spectroelectrochemistry a powerful technique in the identification, characterization and quantification of molecules.
860:
128:
electrode surface. There are significant differences with the SERS effect, but it is a phenomenon that also enhances the Raman signal.
499:"Spectroelectrochemistry, the future of visualizing electrode processes by hyphenating electrochemistry with spectroscopic techniques"
244:. In this configuration the electrode/solution is sampled from behind the electrode, using optically transparent electrodes (OTE).
358:
678:
GarozâRuiz, Jesus; PeralesâRondon, Juan V.; Heras, Aranzazu; Colina, Alvaro (2019). "Spectroelectrochemistry of
Quantum Dots".
259:
1081:
LĂłpez-Lorente, Ăngela I.; Kranz, Christine (2017). "Recent advances in biomolecular vibrational spectroelectrochemistry".
1463:
391:
Data collection and analysis devices. It consists of a computer to collect simultaneously the signals provided by the
1154:
Ding, Song-Yuan; Yi, Jun; Li, Jian-Feng; Ren, Bin; Wu, De-Yin; Panneerselvam, Rajapandiyan; Tian, Zhong-Qun (2016).
441:
Qualitative and quantitative analysis: Raman-SEC can be applied to highly complex samples, such as the detection of
1468:
382:
297:
89:
spectroscopy. This phenomenon of increased intensity could be observed in materials such as carbon nanotubes.
284:
168:
18:
556:"Raman Microspectroscopic Imaging of Binder Remnants in Historical Mortars Reveals Processing Conditions"
1308:
1167:
989:
937:
803:
510:
23:
1299:
Rasmussen, A.; Deckert, V. (2006). "Surface- and tip-enhanced Raman scattering of DNA components".
924:
Jorio, A; Pimenta, M A; Filho, A G Souza; Saito, R; Dresselhaus, G; Dresselhaus, M S (2003-10-16).
787:
354:
350:
334:
330:
219:
55:
1409:
1234:
906:
765:
713:
641:
252:. This configuration is usually selected when electrochemical techniques are combined with TERS.
465:
Energy. Raman-SEC were used in the study of solar cells, batteries and catalysts for fuel cells.
416:
Materials: Raman-SEC is widely used in the study and characterization of new materials, such as
1401:
1324:
1281:
1273:
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1218:
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633:
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346:
326:
275:
The experimental setup to perform Raman spectroelectrochemistry consists of a light source, a
1439:
1391:
1358:
1316:
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518:
433:
202:
188:
159:
63:
59:
40:
27:
1156:"Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials"
210:
is mandatory. Many of the instruments used for Raman-SEC are based on the combination of a
421:
236:
allows passing only the light beam with wavelengths different from that of the laser used.
151:
1312:
1171:
993:
941:
807:
514:
192:
Diagram of the different energy levels showing the states involved in the Raman signal
1347:"Electrochemical tip-enhanced Raman spectroscopy imaging with 8 nm lateral resolution"
46:
When a monochromatic light beam samples the electrode/solution interface, most of the
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1413:
1238:
910:
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717:
645:
378:
233:
113:
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816:
791:
751:
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43:
reaction, being the Raman spectra registered a real fingerprint of the compounds.
1155:
1430:
LeĂłn, L.; Mozo, J.D. (2018). "Designing spectroelectrochemical cells: A review".
1363:
1346:
1345:
Touzalin, Thomas; Joiret, Suzanne; Lucas, Ivan T.; Maisonhaute, Emmanuel (2019).
1214:
1094:
54:
shifted up or down. When the scattering is elastic, the phenomenon is denoted as
1121:
321:
1443:
1179:
1034:
Zhai, Yanling; Zhu, Zhijun; Zhou, Susan; Zhu, Chengzhou; Dong, Shaojun (2018).
497:
Lozeman, Jasper J. A.; FĂŒhrer, Pascal; Olthuis, Wouter; Odijk, Mathieu (2020).
399:, the generated signals can be acquired, transformed, analyzed and interpreted.
1380:"Beginner's Guide to Raman Spectroelectrochemistry for Electrocatalysis Study"
877:"Beginner's Guide to Raman Spectroelectrochemistry for Electrocatalysis Study"
852:
147:
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709:
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capable of forming monolayers on the electrode, and in the study of proteins.
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555:
453:
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36:
1396:
1379:
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1067:
1017:
893:
876:
691:
619:
540:
325:. It is the electronic device that allows controlling the potential of the
442:
417:
396:
926:"Characterizing carbon nanotube samples with resonance Raman scattering"
792:"Characterizing carbon nanotube samples with resonance Raman scattering"
1051:
1035:
1001:
977:
523:
498:
425:
201:
Different configurations can be used to perform Raman-SEC experiments.
143:
760:
700:
628:
1320:
1269:
1253:
460:, among others. In addition, very low concentrations can be detected.
207:
109:
105:
51:
47:
786:
Jorio, A; Pimenta, M A; Filho, A G Souza; Saito, R; Dresselhaus, G;
847:, Hoboken, NJ, USA: John Wiley & Sons, Inc., pp. 151â219,
457:
291:
258:
187:
32:
133:
SHINERS (Shell-Isolated
Nanoparticle-Enhanced Raman Spectroscopy)
101:
70:
sensitivity and selectivity of this multirresponse technique.
446:
429:
445:
in milk, the identification of bacteria, the detection of
395:
and the electrochemical instrument. Using an appropriate
333:, or controlling the current that passes respect to the
361:
that include all three electrodes in a single holder.
428:, among others. It is also applied in the study of
122:
SOERS (Surface-Oxidation-Enhanced Raman
Scattering)
845:Vibrational Spectroscopy at Electrified Interfaces
146:properties are coated with ultra-thin homogeneous
412:information about them. Some applications are:
8:
1036:"Recent advances in spectroelectrochemistry"
182:scanning techniques in Raman spectroscopy.
22:(Raman-SEC) is a technique that studies the
554:Schmid, Thomas; Dariz, Petra (2019-06-14).
58:, while when it is inelastic it is called
1395:
1362:
949:
892:
815:
759:
699:
627:
571:
522:
375:Devices for conducting the radiation beam
357:. This system can be simplified by using
94:SERS (Surface-Enhanced Raman Scattering)
976:Joya, Khurram S.; Sala, Xavier (2015).
480:
83:RRS effect (Resonance Raman Scaterring)
1425:
1423:
1252:Bailo, Elena; Deckert, Volker (2008).
367:Spectroelectrochemical cell (SEC cell)
1340:
1338:
1149:
1147:
1029:
1027:
971:
969:
225:Typical configurations in Raman-SEC:
7:
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176:TERS (Tip-Enhanced Raman Scattering)
1432:TrAC Trends in Analytical Chemistry
1083:Current Opinion in Electrochemistry
982:Physical Chemistry Chemical Physics
62:. Raman spectroscopy combined with
14:
296:. It provides the monochromatic
1351:Electrochemistry Communications
1254:"Tip-enhanced Raman scattering"
752:10.1016/j.electacta.2018.06.079
1:
1301:Journal of Raman Spectroscopy
1203:Accounts of Chemical Research
1378:Zheng, Weiran (2022-10-26).
1364:10.1016/j.elecom.2019.106557
1215:10.1021/acs.accounts.9b00545
1095:10.1016/j.coelec.2017.07.011
875:Zheng, Weiran (2022-10-26).
381:. The last ones conduct the
1122:10.1021/acs.chemrev.6b00596
680:Israel Journal of Chemistry
1485:
1444:10.1016/j.trac.2018.02.002
1180:10.1038/natrevmats.2016.21
951:10.1088/1367-2630/5/1/139
853:10.1002/9781118658871.ch5
817:10.1088/1367-2630/5/1/139
383:electromagnetic radiation
377:: lenses, mirrors and/or
359:screen-printed electrodes
298:electromagnetic radiation
154:layers, forming isolated
1258:Chemical Society Reviews
1160:Nature Reviews Materials
573:10.3390/heritage2020102
169:spectroelectrochemistry
39:surface involved in an
19:spectroelectrochemistry
1397:10.1002/cmtd.202200042
930:New Journal of Physics
894:10.1002/cmtd.202200042
796:New Journal of Physics
692:10.1002/ijch.201900028
620:10.1002/elan.201900075
343:Three-electrode system
285:spectroelectrochemical
264:
193:
262:
250:Angular configuration
191:
138:In SHINERS, metallic
230:Normal configuration
24:inelastic scattering
1313:2006JRSp...37..311R
1172:2016NatRM...116021D
994:2015PCCP...1721094J
988:(33): 21094â21103.
942:2003NJPh....5..139J
808:2003NJPh....5..139J
740:Electrochimica Acta
515:2020Ana...145.2482L
355:auxiliary electrode
351:reference electrode
335:auxiliary electrode
331:reference electrode
242:Inverted microscope
220:confocal microscope
56:Rayleigh scattering
1464:Raman spectroscopy
1384:Chemistry: Methods
1052:10.1039/C7NR07803J
1002:10.1039/C4CP05053C
881:Chemistry: Methods
524:10.1039/C9AN02105A
265:
194:
862:978-1-118-65887-1
434:organic molecules
347:working electrode
327:working electrode
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1469:Electrochemistry
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1307:(1â3): 311â317.
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1116:(7): 5002â5069.
1110:Chemical Reviews
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1046:(7): 3089â3111.
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788:Dresselhaus, M S
783:
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551:
545:
544:
526:
509:(7): 2482â2509.
494:
422:carbon nanotubes
345:. It contains a
203:Raman scattering
100:plasmonic band (
60:Raman scattering
28:Raman scattering
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329:respect to the
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64:electrochemical
41:electrochemical
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1166:(6): 16021.
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880:
870:
844:
799:
795:
743:
739:
683:
679:
611:
607:
563:
559:
549:
506:
502:
409:
407:
404:Applications
393:spectrometer
374:
366:
342:
318:Potentiostat
316:
308:Spectrometer
306:
293:Light source
292:
281:potentiostat
277:spectrometer
274:
266:
255:
249:
241:
229:
224:
216:potentiostat
212:spectrometer
200:
184:
180:
175:
164:
137:
132:
126:
121:
98:
93:
87:
82:
72:
68:
45:
16:
15:
1438:: 147â169.
746:: 377â383.
503:The Analyst
322:Galvanostat
1458:Categories
1357:: 106557.
936:(1): 139.
802:(1): 139.
761:10259/4832
701:10259/6123
629:10259/6122
475:References
450:biomarkers
386:electrode.
301:UV-lasers.
1414:253166002
1406:2628-9725
1329:0377-0486
1278:0306-0012
1239:211046645
1223:0001-4842
1188:2058-8437
1130:0009-2665
1060:2040-3364
1040:Nanoscale
1010:1463-9076
960:1367-2630
911:253166002
903:2628-9725
826:1367-2630
770:103005252
718:155767924
710:0021-2148
646:133304199
638:1040-0397
582:2571-9408
533:0003-2654
454:uric acid
144:plasmonic
37:electrode
1286:18443677
1231:32031367
1138:28271881
1068:29379916
1018:25698502
560:Heritage
541:31998878
443:melamine
426:polymers
418:graphene
397:software
1309:Bibcode
1168:Bibcode
990:Bibcode
938:Bibcode
804:Bibcode
511:Bibcode
452:and/or
410:in situ
353:and an
208:photons
165:in-situ
152:alumina
77:Methods
52:photons
48:photons
1412:
1404:
1327:
1284:
1276:
1237:
1229:
1221:
1186:
1136:
1128:
1066:
1058:
1016:
1008:
958:
909:
901:
859:
824:
768:
716:
708:
644:
636:
580:
539:
531:
218:and a
148:silica
110:copper
106:silver
17:Raman
1410:S2CID
1390:(2).
1235:S2CID
907:S2CID
887:(2).
766:S2CID
714:S2CID
642:S2CID
458:urine
142:with
33:laser
1402:ISSN
1325:ISSN
1282:PMID
1274:ISSN
1227:PMID
1219:ISSN
1184:ISSN
1134:PMID
1126:ISSN
1064:PMID
1056:ISSN
1014:PMID
1006:ISSN
956:ISSN
899:ISSN
857:ISBN
822:ISSN
706:ISSN
634:ISSN
578:ISSN
537:PMID
529:ISSN
430:dyes
349:, a
279:, a
214:, a
102:gold
1440:doi
1436:102
1392:doi
1359:doi
1355:108
1317:doi
1266:doi
1211:doi
1176:doi
1118:doi
1114:117
1091:doi
1048:doi
998:doi
946:doi
889:doi
849:doi
812:doi
756:hdl
748:doi
744:282
696:hdl
688:doi
624:hdl
616:doi
568:doi
519:doi
507:145
456:in
447:DNA
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112:).
108:or
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