- Email: [email protected]
Recent progress in the studies of electrochemical interfaces by surface plasmon resonance spectroscopy and microscopy
Accepted Manuscript Recent progress in the studies of electrochemical interfaces by surface plasmon resonance spectroscopy and microscopy Andy Chieng, Michelle Chiang, Kraisarun Triloges, Megan Chang, Yixian Wang PII:
S2451-9103(18)30150-9
DOI:
https://doi.org/10.1016/j.coelec.2018.11.002
Reference:
COELEC 327
To appear in:
Current Opinion in Electrochemistry
Received Date: 21 August 2018 Revised Date:
29 October 2018
Accepted Date: 1 November 2018
Please cite this article as: Chieng A, Chiang M, Triloges K, Chang M, Wang Y, Recent progress in the studies of electrochemical interfaces by surface plasmon resonance spectroscopy and microscopy, Current Opinion in Electrochemistry, https://doi.org/10.1016/j.coelec.2018.11.002. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Recent progress in the studies of electrochemical interfaces by surface plasmon resonance spectroscopy and microscopy Andy Chieng, Michelle Chiang, Kraisarun Triloges, Megan Chang, Yixian Wang*
RI PT
Department of Chemistry and Biochemistry, California State University Los Angeles, 5151 State University Dr, Los Angeles, CA 90032
M AN U
SC
Abstract Surface plasmon resonance (SPR) is a label-free spectroscopic technique that is highly sensitive to various surface reactions. Incorporating SPR into electrochemical measurements has emerged as a powerful method to study both faradaic and nonfaradaic processes. SPR microscopy (SPRM) integrates an optical microscope into SPR detection, which further offers high throughput detection and spatially resolved information at an electrode surface and thus, has attracted attention especially in single entity electrochemical studies. In this review, the progress in the studies of electrochemical interfaces by SPR and SPRM during the past two years will be discussed.
AC C
EP
TE D
Introduction Surface plasmon resonance (SPR) is a label-free sensing technique that utilizes the collective excitation of electrons in a thin metal film (e.g. Au and Ag) to probe small changes occurring at the solid/solution interface.[1] Electrochemical SPR (EC-SPR) utilizes SPR to provide additional information for studying local electrochemical reactions on electrode surfaces (i.e. the bare or modified gold SPR sensing chips) and has been applied to studying various faradaic processes including redox reactions near the interface or at surface-bound molecules, electropolymerization, and redox-induced protein conformational changes.[2]–[11] SPR is also sensitive to non-faradaic processes and has been applied to measure surface charges and electric field.[12], [13] In general, the SPR signal is represented as a resonance angular shift, ∆θ, which is detected by the drift of the dark band in the detected spectrum, e.g. moving from 1 to 2 as shown in Figs. 1A and 1C. In any EC processes, ∆θ is predominantly governed by (i) redox reaction induced bulk refractive index changes near the metal film, (ii) dielectric property changes of the metal film, and (iii) redox molecular binding or EC-induced deposition of an extra layer onto the metal film.[5], [8] Theoretically, EC-SPR is capable of studying all types of EC processes that can cause changes near or at the liquid/solid interface.
RI PT
ACCEPTED MANUSCRIPT
SC
Figure 1. Overview of SPR and SPRM techniques for EC studies. (A) Schematic of a typical ECSPR setup. (B) Schematic of a typical EC-SPRM setup. (C) The relationship between the SPR angular shift and intensity shift.
AC C
EP
TE D
M AN U
Incorporating optical imaging capability into traditional EC-SPR provides spatial resolution over the electrode surface. The imaging setup could be either based on a prism, which is normally called SPR imaging (SPRi) [12] or a high N.A. microscope objective (Fig. 1B), which is generally referred as SPR microscopy (SPRM) [14]. For EC studies with SPRM, other terms such as plasmonic-based electrochemical current microscopy (PECM) and plasmonic-based electrochemical impedance microscopy (PEIM) were also used based on experimental protocols.[•15] In this review, we will use SPRM/EC-SPRM to refer to all types of imaging-based SPR approaches. In SPRM, instead of the resonance angular shift, the SPR intensity change at any region of interest (ROI), ∆I, at a certain incident angle is monitored (Fig. 1C). This value is proportional to ∆θ and can be converted to EC signal by calibration.[•15] This minireview will highlight the novel applications of SPR/SPRM in electrochemical studies during the last two years. Note that research related to another important field, localized SPR[16], [17], is not within the scope of this mini-review.
Figure 2. EC-SPR recordings of electropolymerization: (A) Representative CV curve (Blue) and simultaneous SPR response (Black). Sweep rate: 50 mV/s; (B) SPR corresponding to stepping potentials: (a) 0, (b) 0.03, (c) -0.06, (d) -0.10, and (e) -0.15 V. The electrolyte is CuBr2 (1.0 mg/mL), Bipy (1.4 mg/mL), GMA (1% v/v), and KCl (0.1 M) in methanol/H2O (6:1 v/v). Adapted with permission from ref. [21]. Copyright 2017 American Chemical Society
Quantitative analysis using EC-SPR EC-SPR has been continuously used to monitor electropolymerization processes and provide quantitative information on film thickness in real-time.[18]–[20] Hu et al. recently
ACCEPTED MANUSCRIPT
M AN U
SC
RI PT
reported the first in-situ investigation of electrochemically mediated atom transfer radical polymerization (eATRP) using EC-SPR.[•21] The polymerization process was controlled by electrochemically tuning the ratio between the activator Cu(I)(Bipy)2 and the deactivator Cu(II)(Bipy)2, and SPR was applied to observe the effects from the polymerization process (Fig. 2A). The novelty is that, when using a potential step method, the transient charging current decays rapidly to near zero and the disturbance from double layer charging and the electrochemical reaction could be efficiently suppressed. As a result, SPR signal variation is primarily determined by the polymer growth and can provide quantitative information about the growth speed, as shown in Fig. 2B. EC-SPR was also proven efficient in monitoring phenol electropolymerization at ultralow ionic strength, where the oxidation peak was virtually indistinguishable in the cyclic voltammogram (CV).[19] The SPR response is unrelated to the ionic strength, allowing it to reflect the reaction in ultrapure water more effectively than CV. The ultrahigh sensitivity of EC-SPR to film thickness was also applied to quantify redoxinduced film thickness changes in self-assembled monolayers (SAMs).[22] This work shows that SPR is highly sensitive to similar structures with a slight difference in dielectric constants on metal surfaces. EC-SPR was also used in monitoring protein immobilization process and quantitatively determining the surface coverage[23], observing the real-time stepwise reduction of graphene oxide (GO) in an effort to control the residual oxygen functionality and conductivity in GO sheets [24], [25], and loading the enzyme Myrothecium verrucaria bilirubin oxidase (Mv BOD) onto two oppositely charged SAMs.[26]
AC C
EP
TE D
Fast electron transfer studies with SPRM Measuring electron transfer (ET) in molecules is critical to the understanding of many basic chemical and biological phenomena. However, one limiting factor for fast ET measurements is the response time of an EC cell, which is determined by the capacitance and resistance of the system. Wang et al. reported using SPRM to study fast ET of a redox protein (cytochrome c) adsorbed on a 3-mercaptopropionic acid (3MPA) modified microelectrode and claimed a response time limit of a few ns.[•27] The system measured both the capacitive charging and ET currents, but the former was greatly suppressed in the imaging technique, allowing the direct study of ET kinetics with chronoamperometry over a broad time window (100 ns to 1 ms). Moreover, the signal of SPRM is not scaled with electrode size, which helps to maintain a good signalto-noise ratio. In a bio-compatible buffer, the system showed a sub-microsecond response time, which is one of the fastest measurements of ET in cytochrome c. The obtained kinetic constant was consistent with traditional EC methods. Moreover, the results revealed that the ET process occurs at multiple time scales indicating stepwise conformational changes. This work shows that SPRM could provide additional information to the study of fast ET processes and is worth further investigation. Single nanoparticle (NP) EC studies with SPRM Traditional EC approaches toward NP studies measure averaged quantities of a large ensemble of these individual entities. A real system is usually heterogeneous, e.g., containing nanoparticles with different sizes and shapes, therefore, much effort has been placed on developing methods for single entity electrochemical analysis.[28] As
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
one of the newly developed methods, SPRM is sensitive to all types of EC reactions, has imaging capability, can provide size information of the NPs and analyze multiple NPs simultaneously with high throughput and temporal resolution, and reveals heterogeneity among individual NPs.[12], [••29]–[34] Wang and co-workers studied surface oxidation and reduction at individual gold nanowires (AuNWs) (Figs. 3A-E).[•35] In this work, the large background signal from the gold film that interfered with the EC reaction signals, a previous limitation of this method, was removed through coating the gold film with a Cytop layer followed by a graphene layer to establish the electrical connections to the AuNWs. Through these methods, they were able to reveal the differences in EC activities between single AuNWs and bulk Au electrodes, large variability of different AuNWs, and location dependent reaction activity within a single AuNW. EC-SPRM was also applied to identify silver, gold, and copper NPs as reported by Nizamov et al.[••36] Identifying the chemical composition of the particles using plasmonic signal alone is difficult since the size, shape, and the refractive index of NPs are often very similar. However, when combined with electrochemistry, as the dissolution potentials of each NP studied were different, a CV scan was able to chemically identify NPs. Jiang et al. used SPRM to image the EC current formed from the phase transition and Li-ion diffusion kinetics of single LiCoO2 NPs.(Figs. 3F-G)[••37] They discovered that the crystallographic structures played essential roles in affecting the Li-ion diffusion kinetics, and the approach could be extended to a variety of anode and cathode materials. The same group reported on investigating the kinetics of the K+ ions into and out of single Prussian blue (PB) nanoparticles during EC cycling.[38]
Figure 3. Representative EC-SPRM based single entity studies. (A-E) Surface electrochemical reactions of single gold nanowires: (A-C) EC-SPRM images of multiple AuNWs at different potentials. Insets are the spatial fast Fourier transfer (FFT) of the P- ECM images; (D) overlaying the image in panel B with the corresponding transmitted image; (E) plasmonic CVs from multiple AuNWs as labeled in panel D. The electrolyte is 0.2 M NaOH and the potential cycling rate is 0.2 V/s. Adapted with permission from ref. [35]. Copyright 2017 American Chemical Society. (F,G) Phase transition and Li-ion diffusion kinetics of single LiCoO2 nanoparticles during electrochemical cycling: (F) SPR intensity curve of a single LiCoO2 nanoparticle with application of a cyclic voltammetry sweep between 0.3 and 0.8 V; (G) the first order derivative of the SPR intensity curve (red curve) represents the cyclic voltammogram of a single nanoparticle, which is in good agreement with the averaged electrochemical current
ACCEPTED MANUSCRIPT
contributed by all LiCoO2 nanoparticles on the gold film (blue curve). Adapted with permission from ref. [37]. Copyright 2017 American Chemical Society.
M AN U
SC
RI PT
Above works were for NPs pre-immobilized on the electrode surface. The collision of mobile NPs onto the electrode surface as well as the following EC processes can also be monitored in real-time. Sun et al. combined single nanoparticle collision (SNC) electrochemistry with SPRM to obtain information regarding the NP size, morphology, and location of LiCoO2 NP collision.[39] They also used this technique to simultaneously monitor the oxidation and dissolution reaction of silver NPs,[40] and recently observed that the AgNP oxidation peak consisted of multiple rapid and discrete spikes.[41] SPRM helps visualize the migration trajectory of single NPs after collisions and is fast enough (400 fps) to capture the multi-peak behavior that occurs at the sub-millisecond. One of the limitations in SPRM is the spatial resolution along the incident light propagation direction, which depends on the decaying length of plasmonic waves that is as large as tens of microns. Yu et al. proposed a digital method of improving the spatial resolution.[43] The images were reconstructed by first obtaining the scattered field and then reconstructing the object image by deconvolution of the scattered field by using a point spread function. Using this method, they were able to reconstruct a raw SPRM image of 100nm polystyrene NPs.
AC C
EP
TE D
Mapping of electric field, potential and surface charge The sensitivity of SPR to dielectric properties of the gold film makes it suitable for studying non-faradaic processes such as electrical double layer (EDL) charging and imaging local distribution of surface charges, electric field, and interfacial potential. See’s group recently presented on using SPR for voltage sensing applied to biological research questions.[44] Wang et al. demonstrated that SPRM can be used to study the local electric field generated by a micropipette probe.[45] An oscillating potential applied to the micropipette positioned near a substrate electrode induced a charge change on the electrode surface, which led to DC and AC plasmonic images. The former measures the scattering of the surface plasmonic waves by the micropipette, which provides the location and size information on the micropipette tip, while the later maps the surface charge density distribution and thus the electric field distribution. Luo et al. used SPRM to map the spatial distribution and temporal dynamics of the EDL change on a heterogeneous surface.[46] They considered the effect from both the electron density change and local re-arrangement of ions and concluded that they contributed comparably to the potential induced SPR response. SPRM was also used to visualize the potential distribution on bipolar electrodes.[•47], [48] Interfacial potential distribution was plotted by converting SPRM intensity signals to potentials using a calibration curve, based on the correlation between the interfacial potential and surface charge density. Other novel studies More EC systems have been explored by SPR and SPRM. Nishi et al. investigated the redox reaction occurring in ionic liquid and noticed that the SPR signal in ionic liquid systems was highly dependent on the diffusion coefficient ratio of reduced and oxidized species.[49] This work demonstrated that EC-SPR could be a useful tool for investigating complicated systems involving ionic liquids such as batteries. In another EC-SPR approach, Pradanawati et al. investigated the real-time formation of solid
ACCEPTED MANUSCRIPT
RI PT
electrolyte interphase (SEI), which is known to significantly affect the lifetime and performance of lithium ion batteries.[50] They demonstrated the dissociation reaction behaviors of an EC-Li+ ionic cluster in each potential region, which cannot be revealed using conventional tools such as CV. SPRM has been used to study the self-catalyzed formaldehyde (HCHO) burst in methanol oxidation reactions under open circuit conditions.[51] Utilizing the fact that the refractive index of HCHO (product) is much higher than that of CH3OH (reactant), a hidden pathway of HCHO accumulation was uncovered, which provided great advances in understanding the detailed reaction pathways in direct methanol fuel cells.
AC C
EP
TE D
M AN U
SC
Conclusion and prospective In this review, we highlighted the important progress in studying electrochemical interfaces using SPR spectroscopy and microscopy techniques. SPR has provided sensitive and real-time detection and offers complimentary information to traditional EC techniques, and in some cases provide better selectivity or quantitative control. Applying SPRM in EC studies offers both spatial and temporal resolution and has opened new avenues, especially for single entity studies. Another important feature of SPRM is that the signal is not scaled with electrode size and can be extracted from each pixel, which provides good signal-to-noise ratio for small features and makes it useful in studies involving nanoelectrodes. The major drawback of SPR/SPRM techniques is that both of them require thin metal films (Au or Ag) as electrodes. EC-SPR will continue its application in biosensor development and other systems in biological and materials sciences. One important task would be finding simpler protocols to isolate contribution to SPR signals from different sources, i.e. faradaic processes and non-faradaic processes. For expanding the applications, it is also important to develop solid theories for operating EC-SPR in protocols other than CV and chronoamperometry. In practical use, quantitative analysis with complex systems such as batteries, food, and environmental samples would be another field to explore. SPRM has been found powerful in studying single entity electrochemistry. Future direction would be expanding the technique to broader applications, further improving the spatial and temporal resolution, and developing hybrid imaging and sensing systems by combining SPRM with other techniques, such as bright field, dark field and fluorescence imaging, and scanning probe microscopy. For single nanoparticle studies, correlating the EC activities of each particle to their structures is important and requires combining including high-resolution structural imaging tools (e.g. transmission electron microscope and scanning electron microscope). Acknowledgments California State University Los Angeles (CSULA) new faculty start-up fund and California State University Program for Education & Research in Biotechnology (CSUPERB) new investigator grant is gratefully acknowledged. Reference [1] A. Fallis, Handbook of Surface Plasmon Resonance, The Royal Society of Chemistry, Cambridge, 2008. [2] Y. Iwasaki, T. Horiuchi, M. Morita, O. Niwa, Electrochemical reaction of Fe(CN) 63−/4− on gold electrodes analyzed by surface plasmon resonance, Surf. Sci. 427–428 (1999) 195–
ACCEPTED MANUSCRIPT
[16]
[17] [18] [19] [20]
AC C
EP
TE D
M AN U
SC
RI PT
198. [3] S. Wang, S. Boussaad, N.J. Tao, Surface plasmon resonance enhanced optical absorption spectroscopy for studying molecular adsorbates, Rev. Sci. Instrum. 72 (2001) 3055–3060. [4] S. Wang, E.S. Forzani, N. Tao, Detection of heavy metal ions in water by high-resolution surface plasmon resonance spectroscopy combined with anodic stripping voltammetry, Anal. Chem., 79 (2007) 4427-4432. [5] S. Wang, S. Boussaad, S. Wong, N.J. Tao, High-sensitivity stark spectroscopy obtained by surface plasmon resonance measurement, Anal. Chem. 72 (2000) 4003-4008. [6] X. Kang, G. Cheng, S. Dong, A novel electrochemical SPR biosensor, Electrochem. commun. 3 (2001) 489–493. [7] S. Boussaad, J. Pean, N.J. Tao, High-resolution multiwavelength surface plasmon resonance spectroscopy for probing conformational and electronic changes in redox proteins, Anal. Chem. 72 (2000) 222–226. [8] P. Zhai, J. Guo, J. Xiang, F. Zhou, Electrochemical surface plasmon resonance spectroscopy at bilayered silver/gold films, J. Phys. Chem. C. 111 (2007) 981–986. [9] R. Schweiss, J. F. Lübben, D. Johannsmann, W. Knoll, Electropolymerization of ethylene dioxythiophene (EDOT) in micellar aqueous solutions studied by electrochemical quartz crystal microbalance and surface plasmon resonance, Electrochim. Acta. 50 (2005) 2849–2856. [10] S. Kienle, S. Lingler, W. Kraas, A. Offenhäusser, W. Knol, G. Jung, Electropolymerization of a phenol-modified peptide for use in receptor–ligand interactions studied by surface plasmon resonance, Biosens. Bioelectron. 12 (1997) 779–786. [11] Y. Wang, W. Knoll, In situ electrochemical and surface plasmon resonance (SPR) studies of aniline-carboxylated aniline copolymers, Anal. Chim. Acta. 558 (2006) 150–157. [12] K.J. Foley, X. Shan, N.J. Tao, Surface impedance imaging technique, Anal. Chem. 80 (2008) 5146–5151. [13] D.G. Hanken, R.M. Corn, Electric fields and interference effects inside noncentrosymmetric multilayer films at electrode surfaces from electrochemically modulated surface plasmon resonance experiments, Anal. Chem. 69 (1997) 3665–3673. [14] B. Huang, F. Yu, R. N. Zare, Surface plasmon resonance imaging using a high numerical aperture microscope objective, Anal. Chem. 79 (2007) 2979–2983. • [15] X. Shan, Y. Wang, and N. Tao, Plasmonics-based electrochemical current and impedance imaging, in: R.C. Alkire, P.N. Bartlett, J. Lipkowski (Eds.), Advances in Electrochemical Science and Engineering: Nanopatterned and Nanoparticle‐Modified Electrodes, Volume 17, Wiley-VCH, Weinheim, 2017, pp. 373–401. This book chapter covered theory and applications of SPRM in electrochemcial studies. C.H. Choi, K. Chung, T.T.H. Nguyen, D.H. Kim, Plasmon-mediated electrocatalysis for sustainable energy: from electrochemical conversion of different feedstocks to fuel cell reactions, ACS Energy Lett. 3 (2018) 1415–1433. A. Agrawal, S.H. Cho, O. Zandi, S. Ghosh, R.W. Johns, D.J. Milliron, Localized surface plasmon resonance in semiconductor nanocrystals, Chem. Rev. 118 (2018) 3121–3207. S. Sriwichai, P. Netsuwan, S. Phanichphant, A. Baba, Electropolymerization and properties of poly (3-anilinethiophene) thin film, Chiang Mai J. Sci. 43 (2016) 863–869. C.C. Manole, C. Pirvu, I. Demetrescu, Surface plasmon resonance in the study of phenol electropolymerization at ultralow concentration, Rev. Chim. 67 (2016) 884–886. D. Chen, Y. Mei, W. Hu, C.M. Li, Electrochemically enhanced antibody immobilization on polydopamine thin film for sensitive surface plasmon resonance immunoassay, Talanta. 182 (2018) 470–475.
ACCEPTED MANUSCRIPT
• [21] D. Chen, W. Hu, In situ investigation of electrochemically mediated surface-initiated atom transfer radical polymerization by electrochemical surface plasmon resonance, Anal. Chem. 89 (2017) 4355–4358. This is the first in-situ investigation of electrochemically mediated atom transfer radical polymerization (eATRP) using EC-SPR. Y. Feng, E.R. Dionne, V. Toader, G. Beaudoin, A. Badia, Odd–even effects in electroactive self-assembled monolayers investigated by electrochemical surface plasmon resonance and impedance spectroscopy, J. Phys. Chem. C. 121 (2017) 2462624640. [23] B. Holzer, K. Manoli, N. Ditaranto, E. Macchia, A. Tiwari, C.D. Franco, G. Scamarcio, G. Palazzo, L. Torsi, Characterization of covalently bound anti-human immunoglobulins on self-assembled monolayer modified gold electrodes, Adv. Biosyst. 1 (2017) 1700055. [24] N.F. Chiu, C.D. Yang, Real-time and stepwise deoxidization processes to tune the photoluminescence properties of graphene oxide using EC-SPR spectroscopy, RSC Adv. 8 (2018) 11557–11565. [25] N.F. Chiu, C.D. Yang, C.C. Chen, C.T. Kuo, Stepwise control of reduction of graphene oxide and quantitative real-time evaluation of residual oxygen content using EC-SPR for a label-free electrochemical immunosensor, Sensors Actuators B Chem. 258 (2018) 981990. [26] C. Gutierrez-Sanchez, A. Ciaccafava, P.Y. Blanchard, K. Monsalve, M.T. Giudici-Orticoni, S. Lecomte, E. Lojou, Efficiency of enzymatic o2 reduction by myrothecium verrucaria bilirubin oxidase probed by surface plasmon resonance, pmirras, and electrochemistry, ACS Catal. 6 (2016) 5482–5492. • [27] Y. Wang, H. Wang, Y. Chen, Y. Wang, H. Chen, X. Shan, N. Tao, Fast electrochemical and plasmonic detection reveals multitime scale conformational gating of electron transfer in cytochrome c, J. Am. Chem. Soc. 139 (2017) 7244–7249. This work demonstrates that SPRM is powerful in measuring fast electron transfer processes. Y. Wang, X. Shan, N. Tao, Emerging tools for studying single entity electrochemistry, Faraday Discuss. 193 (2016) 9–39. • • [29] X. Shan, U. Patel, S. Wang, R. Iglesias, N. Tao, Imaging local electrochemical current via surface plasmon resonance, Science. 327 (2010) 1363-1366. This work is the first demonstration of an electrochemical microscopy technique using optical signals arising from surface plasmon resonance to detect variations in local electrochemical current.
EP
[28]
TE D
M AN U
SC
RI PT
[22]
AC C
[30] W. Wang, K. Foley, X. Shan, S. Wang, S. Eaton, V.J. Nagaraj, P. Wiktor, U. Patel, N. Tao, Single cells and intracellular processes studied by a plasmonic-based electrochemical impedance microscopy, Nat. Chem. 3 (2011) 249–255. [31] X. Shan, I. Diez-Perez, L. Wang, P. Wiktor, Y. Gu, L. Zhang, W. Wang, J. Lu, S. Wang, Q. Gong, J. Li, N. Tao, Imaging the electrocatalytic activity of single nanoparticles, Nat. Nanotechnol. 7 (2012) 668–672. [32] X. Shan, S. Chen, H. Wang, Z. Chen, Y. Guan, Y. Wang, S. Wang, H. Chen, N. Tao, Mapping local quantum capacitance and charged impurities in graphene via plasmonic impedance imaging, Adv. Mater. 27 (2015) 6213–6219. [33] Y. Fang, W. Wang, X. Wo, Y. Luo, S. Yin, Y. Wang, X. Shan, N. Tao, Plasmonic imaging of electrochemical oxidation of single nanoparticles, J. Am. Chem. Soc., 136 (2014) 12584–12587. [34] T. Yuan, W. Wang, Studying the electrochemistry of single nanoparticles with surface
ACCEPTED MANUSCRIPT
RI PT
plasmon resonance microscopy, Curr. Opin. Electrochem. 6 (2017) 17–22. • [35] Y. Wang, X. Shan, H. Wang, S. Wang, N. Tao, Plasmonic imaging of surface electrochemical reactions of single gold nanowires, J. Am. Chem. Soc. 139 (2017) 1376– 1379. This work shows that SPRM is capable of extracting CVs from individual NPs and at sub-NP level.
•• [36] S. Nizamov, O. Kasian, V.M. Mirsky, Individual detection and electrochemically assisted identification of adsorbed nanoparticles by using surface plasmon microscopy, Angew. Chemie - Int. Ed. 55 (2016) 7247–7251. This work shows that SPRM has chemical selectivity to various NPs.
•• [37] D. Jiang, Y. Jiang, Z. Li, T. Liu, X. Wo, Y. Fnag, N. Tao, W. Wang, H. Chen, Optical
M AN U
SC
imaging of phase transition and li-ion diffusion kinetics of single licoo2 nanoparticles during electrochemical cycling, J. Am. Chem. Soc. 139 (2017) 186–192. This work is the first demonstration of studying the phase transition and Li-ion diffusion kinetics at single nanoparticle level via SPRM. D. Jiang, L. Sun, T. Liu, W. Wang, Thin-film electrochemistry of single prussian blue nanoparticles revealed by surface plasmon resonance microscopy, Anal. Chem. 89 (2017) 11641–11647. [39] L. Sun, D. Jiang, M. Li, T. Liu, L. Yuan, W. Wang, H. Chen, Collision and oxidation of single licoo2 nanoparticles studied by correlated optical imaging and electrochemical recording, Anal. Chem. 89 (2017) 6050–6055. [40] L. Sun, Y. Fang, Z. Li, W. Wang, H. Chen, Simultaneous optical and electrochemical recording of single nanoparticle electrochemistry, Nano Res. 10 (2017) 1740–1748. [41] L. Sun, W. Wang, H.-Y. Chen, Dynamic nanoparticle-substrate contacts regulate multipeak behavior of single silver nanoparticle collisions, ChemElectroChem. 5 (2018) 1–6. [42] S.M. Oja, D.A. Robinson, N.J. Vitti, M.A. Edwards, Y. Liu, H.S. White, B. Zhang, Observation of multipeak collision behavior during the electro-oxidation of single ag nanoparticles, J. Am. Chem. Soc. 139 (2017) 708–718. [43] H. Yu, X. Shan, S. Wang, N. Tao, Achieving high spatial resolution surface plasmon resonance microscopy with image reconstruction, Anal. Chem. 89 (2017) 2704–2707. [44] S.A. Abayzeed, R.J. Smith, K. F. Webb, M.G. Somekh, C.W. See, Sensitive detection of voltage transients using differential intensity surface plasmon resonance system, Opt. Express. 25 (2017) 31552. [45] Y. Wang, X. Shan, S. Wang, N. Tao, Imaging local electric field distribution by plasmonic impedance microscopy, Anal. Chem. 88 (2016) 1547–1552. [46] X. Luo, S. Deng, P. Wang, Temporal–spatial-resolved mapping of the electrical double layer changes by surface plasmon resonance imaging, RSC Adv. 8 (2018) 28266–28274. • [47] M. Hasheminejad, Y. Fang, M. Li, Y. Jiang, W. Wang, H. Y. Chen, Plasmonic Imaging of the Interfacial Potential Distribution on Bipolar Electrodes, Angew. Chemie - Int. Ed. 56 (2017) 1629–1633. This is the first application of SPRM in mapping potential distributon on bipolar electrodes.
AC C
EP
TE D
[38]
[48] [49]
M. Li, S. Liu, Y. Jiang, W. Wang, Visualizing the zero-potential line of bipolar electrodes with arbitrary geometry, Anal. Chem. 90 (2018) 6390–6396. N. Nishi, Y. Ikeda, T. Sakka, Electrochemical surface plasmon resonance as a probe of redox reactions at the ionic liquid|gold interface, J. Electroanal. Chem. 817 (2018) 210– 216.
ACCEPTED MANUSCRIPT
RI PT SC M AN U TE D EP
[51]
S.A. Pradanawati, F.M. Wang, C.H. Su, Using electrochemical surface plasmon resonance for in-situ kinetic investigations of solid electrolyte interphase formation in lithium ion battery, J. Power Sources. 330 (2016) 127–131. L. Yuan, M. Li, T. Yuan, Y. Fang, W. Wang, In operando imaging of self-catalyzed formaldehyde burst in methanol oxidation reactions under open circuit conditions, Chem. Sci. 9 (2018) 3318–3323.
AC C
[50]
ACCEPTED MANUSCRIPT
Highlights:
RI PT SC M AN U TE D EP
•
Review the most recent progress in electrochemical surface plasmon resonance (EC-SPR) studies Perspectives on future directions of EC-SPR
AC C
•
S2451-9103(18)30150-9
DOI:
https://doi.org/10.1016/j.coelec.2018.11.002
Reference:
COELEC 327
To appear in:
Current Opinion in Electrochemistry
Received Date: 21 August 2018 Revised Date:
29 October 2018
Accepted Date: 1 November 2018
Please cite this article as: Chieng A, Chiang M, Triloges K, Chang M, Wang Y, Recent progress in the studies of electrochemical interfaces by surface plasmon resonance spectroscopy and microscopy, Current Opinion in Electrochemistry, https://doi.org/10.1016/j.coelec.2018.11.002. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Recent progress in the studies of electrochemical interfaces by surface plasmon resonance spectroscopy and microscopy Andy Chieng, Michelle Chiang, Kraisarun Triloges, Megan Chang, Yixian Wang*
RI PT
Department of Chemistry and Biochemistry, California State University Los Angeles, 5151 State University Dr, Los Angeles, CA 90032
M AN U
SC
Abstract Surface plasmon resonance (SPR) is a label-free spectroscopic technique that is highly sensitive to various surface reactions. Incorporating SPR into electrochemical measurements has emerged as a powerful method to study both faradaic and nonfaradaic processes. SPR microscopy (SPRM) integrates an optical microscope into SPR detection, which further offers high throughput detection and spatially resolved information at an electrode surface and thus, has attracted attention especially in single entity electrochemical studies. In this review, the progress in the studies of electrochemical interfaces by SPR and SPRM during the past two years will be discussed.
AC C
EP
TE D
Introduction Surface plasmon resonance (SPR) is a label-free sensing technique that utilizes the collective excitation of electrons in a thin metal film (e.g. Au and Ag) to probe small changes occurring at the solid/solution interface.[1] Electrochemical SPR (EC-SPR) utilizes SPR to provide additional information for studying local electrochemical reactions on electrode surfaces (i.e. the bare or modified gold SPR sensing chips) and has been applied to studying various faradaic processes including redox reactions near the interface or at surface-bound molecules, electropolymerization, and redox-induced protein conformational changes.[2]–[11] SPR is also sensitive to non-faradaic processes and has been applied to measure surface charges and electric field.[12], [13] In general, the SPR signal is represented as a resonance angular shift, ∆θ, which is detected by the drift of the dark band in the detected spectrum, e.g. moving from 1 to 2 as shown in Figs. 1A and 1C. In any EC processes, ∆θ is predominantly governed by (i) redox reaction induced bulk refractive index changes near the metal film, (ii) dielectric property changes of the metal film, and (iii) redox molecular binding or EC-induced deposition of an extra layer onto the metal film.[5], [8] Theoretically, EC-SPR is capable of studying all types of EC processes that can cause changes near or at the liquid/solid interface.
RI PT
ACCEPTED MANUSCRIPT
SC
Figure 1. Overview of SPR and SPRM techniques for EC studies. (A) Schematic of a typical ECSPR setup. (B) Schematic of a typical EC-SPRM setup. (C) The relationship between the SPR angular shift and intensity shift.
AC C
EP
TE D
M AN U
Incorporating optical imaging capability into traditional EC-SPR provides spatial resolution over the electrode surface. The imaging setup could be either based on a prism, which is normally called SPR imaging (SPRi) [12] or a high N.A. microscope objective (Fig. 1B), which is generally referred as SPR microscopy (SPRM) [14]. For EC studies with SPRM, other terms such as plasmonic-based electrochemical current microscopy (PECM) and plasmonic-based electrochemical impedance microscopy (PEIM) were also used based on experimental protocols.[•15] In this review, we will use SPRM/EC-SPRM to refer to all types of imaging-based SPR approaches. In SPRM, instead of the resonance angular shift, the SPR intensity change at any region of interest (ROI), ∆I, at a certain incident angle is monitored (Fig. 1C). This value is proportional to ∆θ and can be converted to EC signal by calibration.[•15] This minireview will highlight the novel applications of SPR/SPRM in electrochemical studies during the last two years. Note that research related to another important field, localized SPR[16], [17], is not within the scope of this mini-review.
Figure 2. EC-SPR recordings of electropolymerization: (A) Representative CV curve (Blue) and simultaneous SPR response (Black). Sweep rate: 50 mV/s; (B) SPR corresponding to stepping potentials: (a) 0, (b) 0.03, (c) -0.06, (d) -0.10, and (e) -0.15 V. The electrolyte is CuBr2 (1.0 mg/mL), Bipy (1.4 mg/mL), GMA (1% v/v), and KCl (0.1 M) in methanol/H2O (6:1 v/v). Adapted with permission from ref. [21]. Copyright 2017 American Chemical Society
Quantitative analysis using EC-SPR EC-SPR has been continuously used to monitor electropolymerization processes and provide quantitative information on film thickness in real-time.[18]–[20] Hu et al. recently
ACCEPTED MANUSCRIPT
M AN U
SC
RI PT
reported the first in-situ investigation of electrochemically mediated atom transfer radical polymerization (eATRP) using EC-SPR.[•21] The polymerization process was controlled by electrochemically tuning the ratio between the activator Cu(I)(Bipy)2 and the deactivator Cu(II)(Bipy)2, and SPR was applied to observe the effects from the polymerization process (Fig. 2A). The novelty is that, when using a potential step method, the transient charging current decays rapidly to near zero and the disturbance from double layer charging and the electrochemical reaction could be efficiently suppressed. As a result, SPR signal variation is primarily determined by the polymer growth and can provide quantitative information about the growth speed, as shown in Fig. 2B. EC-SPR was also proven efficient in monitoring phenol electropolymerization at ultralow ionic strength, where the oxidation peak was virtually indistinguishable in the cyclic voltammogram (CV).[19] The SPR response is unrelated to the ionic strength, allowing it to reflect the reaction in ultrapure water more effectively than CV. The ultrahigh sensitivity of EC-SPR to film thickness was also applied to quantify redoxinduced film thickness changes in self-assembled monolayers (SAMs).[22] This work shows that SPR is highly sensitive to similar structures with a slight difference in dielectric constants on metal surfaces. EC-SPR was also used in monitoring protein immobilization process and quantitatively determining the surface coverage[23], observing the real-time stepwise reduction of graphene oxide (GO) in an effort to control the residual oxygen functionality and conductivity in GO sheets [24], [25], and loading the enzyme Myrothecium verrucaria bilirubin oxidase (Mv BOD) onto two oppositely charged SAMs.[26]
AC C
EP
TE D
Fast electron transfer studies with SPRM Measuring electron transfer (ET) in molecules is critical to the understanding of many basic chemical and biological phenomena. However, one limiting factor for fast ET measurements is the response time of an EC cell, which is determined by the capacitance and resistance of the system. Wang et al. reported using SPRM to study fast ET of a redox protein (cytochrome c) adsorbed on a 3-mercaptopropionic acid (3MPA) modified microelectrode and claimed a response time limit of a few ns.[•27] The system measured both the capacitive charging and ET currents, but the former was greatly suppressed in the imaging technique, allowing the direct study of ET kinetics with chronoamperometry over a broad time window (100 ns to 1 ms). Moreover, the signal of SPRM is not scaled with electrode size, which helps to maintain a good signalto-noise ratio. In a bio-compatible buffer, the system showed a sub-microsecond response time, which is one of the fastest measurements of ET in cytochrome c. The obtained kinetic constant was consistent with traditional EC methods. Moreover, the results revealed that the ET process occurs at multiple time scales indicating stepwise conformational changes. This work shows that SPRM could provide additional information to the study of fast ET processes and is worth further investigation. Single nanoparticle (NP) EC studies with SPRM Traditional EC approaches toward NP studies measure averaged quantities of a large ensemble of these individual entities. A real system is usually heterogeneous, e.g., containing nanoparticles with different sizes and shapes, therefore, much effort has been placed on developing methods for single entity electrochemical analysis.[28] As
ACCEPTED MANUSCRIPT
AC C
EP
TE D
M AN U
SC
RI PT
one of the newly developed methods, SPRM is sensitive to all types of EC reactions, has imaging capability, can provide size information of the NPs and analyze multiple NPs simultaneously with high throughput and temporal resolution, and reveals heterogeneity among individual NPs.[12], [••29]–[34] Wang and co-workers studied surface oxidation and reduction at individual gold nanowires (AuNWs) (Figs. 3A-E).[•35] In this work, the large background signal from the gold film that interfered with the EC reaction signals, a previous limitation of this method, was removed through coating the gold film with a Cytop layer followed by a graphene layer to establish the electrical connections to the AuNWs. Through these methods, they were able to reveal the differences in EC activities between single AuNWs and bulk Au electrodes, large variability of different AuNWs, and location dependent reaction activity within a single AuNW. EC-SPRM was also applied to identify silver, gold, and copper NPs as reported by Nizamov et al.[••36] Identifying the chemical composition of the particles using plasmonic signal alone is difficult since the size, shape, and the refractive index of NPs are often very similar. However, when combined with electrochemistry, as the dissolution potentials of each NP studied were different, a CV scan was able to chemically identify NPs. Jiang et al. used SPRM to image the EC current formed from the phase transition and Li-ion diffusion kinetics of single LiCoO2 NPs.(Figs. 3F-G)[••37] They discovered that the crystallographic structures played essential roles in affecting the Li-ion diffusion kinetics, and the approach could be extended to a variety of anode and cathode materials. The same group reported on investigating the kinetics of the K+ ions into and out of single Prussian blue (PB) nanoparticles during EC cycling.[38]
Figure 3. Representative EC-SPRM based single entity studies. (A-E) Surface electrochemical reactions of single gold nanowires: (A-C) EC-SPRM images of multiple AuNWs at different potentials. Insets are the spatial fast Fourier transfer (FFT) of the P- ECM images; (D) overlaying the image in panel B with the corresponding transmitted image; (E) plasmonic CVs from multiple AuNWs as labeled in panel D. The electrolyte is 0.2 M NaOH and the potential cycling rate is 0.2 V/s. Adapted with permission from ref. [35]. Copyright 2017 American Chemical Society. (F,G) Phase transition and Li-ion diffusion kinetics of single LiCoO2 nanoparticles during electrochemical cycling: (F) SPR intensity curve of a single LiCoO2 nanoparticle with application of a cyclic voltammetry sweep between 0.3 and 0.8 V; (G) the first order derivative of the SPR intensity curve (red curve) represents the cyclic voltammogram of a single nanoparticle, which is in good agreement with the averaged electrochemical current
ACCEPTED MANUSCRIPT
contributed by all LiCoO2 nanoparticles on the gold film (blue curve). Adapted with permission from ref. [37]. Copyright 2017 American Chemical Society.
M AN U
SC
RI PT
Above works were for NPs pre-immobilized on the electrode surface. The collision of mobile NPs onto the electrode surface as well as the following EC processes can also be monitored in real-time. Sun et al. combined single nanoparticle collision (SNC) electrochemistry with SPRM to obtain information regarding the NP size, morphology, and location of LiCoO2 NP collision.[39] They also used this technique to simultaneously monitor the oxidation and dissolution reaction of silver NPs,[40] and recently observed that the AgNP oxidation peak consisted of multiple rapid and discrete spikes.[41] SPRM helps visualize the migration trajectory of single NPs after collisions and is fast enough (400 fps) to capture the multi-peak behavior that occurs at the sub-millisecond. One of the limitations in SPRM is the spatial resolution along the incident light propagation direction, which depends on the decaying length of plasmonic waves that is as large as tens of microns. Yu et al. proposed a digital method of improving the spatial resolution.[43] The images were reconstructed by first obtaining the scattered field and then reconstructing the object image by deconvolution of the scattered field by using a point spread function. Using this method, they were able to reconstruct a raw SPRM image of 100nm polystyrene NPs.
AC C
EP
TE D
Mapping of electric field, potential and surface charge The sensitivity of SPR to dielectric properties of the gold film makes it suitable for studying non-faradaic processes such as electrical double layer (EDL) charging and imaging local distribution of surface charges, electric field, and interfacial potential. See’s group recently presented on using SPR for voltage sensing applied to biological research questions.[44] Wang et al. demonstrated that SPRM can be used to study the local electric field generated by a micropipette probe.[45] An oscillating potential applied to the micropipette positioned near a substrate electrode induced a charge change on the electrode surface, which led to DC and AC plasmonic images. The former measures the scattering of the surface plasmonic waves by the micropipette, which provides the location and size information on the micropipette tip, while the later maps the surface charge density distribution and thus the electric field distribution. Luo et al. used SPRM to map the spatial distribution and temporal dynamics of the EDL change on a heterogeneous surface.[46] They considered the effect from both the electron density change and local re-arrangement of ions and concluded that they contributed comparably to the potential induced SPR response. SPRM was also used to visualize the potential distribution on bipolar electrodes.[•47], [48] Interfacial potential distribution was plotted by converting SPRM intensity signals to potentials using a calibration curve, based on the correlation between the interfacial potential and surface charge density. Other novel studies More EC systems have been explored by SPR and SPRM. Nishi et al. investigated the redox reaction occurring in ionic liquid and noticed that the SPR signal in ionic liquid systems was highly dependent on the diffusion coefficient ratio of reduced and oxidized species.[49] This work demonstrated that EC-SPR could be a useful tool for investigating complicated systems involving ionic liquids such as batteries. In another EC-SPR approach, Pradanawati et al. investigated the real-time formation of solid
ACCEPTED MANUSCRIPT
RI PT
electrolyte interphase (SEI), which is known to significantly affect the lifetime and performance of lithium ion batteries.[50] They demonstrated the dissociation reaction behaviors of an EC-Li+ ionic cluster in each potential region, which cannot be revealed using conventional tools such as CV. SPRM has been used to study the self-catalyzed formaldehyde (HCHO) burst in methanol oxidation reactions under open circuit conditions.[51] Utilizing the fact that the refractive index of HCHO (product) is much higher than that of CH3OH (reactant), a hidden pathway of HCHO accumulation was uncovered, which provided great advances in understanding the detailed reaction pathways in direct methanol fuel cells.
AC C
EP
TE D
M AN U
SC
Conclusion and prospective In this review, we highlighted the important progress in studying electrochemical interfaces using SPR spectroscopy and microscopy techniques. SPR has provided sensitive and real-time detection and offers complimentary information to traditional EC techniques, and in some cases provide better selectivity or quantitative control. Applying SPRM in EC studies offers both spatial and temporal resolution and has opened new avenues, especially for single entity studies. Another important feature of SPRM is that the signal is not scaled with electrode size and can be extracted from each pixel, which provides good signal-to-noise ratio for small features and makes it useful in studies involving nanoelectrodes. The major drawback of SPR/SPRM techniques is that both of them require thin metal films (Au or Ag) as electrodes. EC-SPR will continue its application in biosensor development and other systems in biological and materials sciences. One important task would be finding simpler protocols to isolate contribution to SPR signals from different sources, i.e. faradaic processes and non-faradaic processes. For expanding the applications, it is also important to develop solid theories for operating EC-SPR in protocols other than CV and chronoamperometry. In practical use, quantitative analysis with complex systems such as batteries, food, and environmental samples would be another field to explore. SPRM has been found powerful in studying single entity electrochemistry. Future direction would be expanding the technique to broader applications, further improving the spatial and temporal resolution, and developing hybrid imaging and sensing systems by combining SPRM with other techniques, such as bright field, dark field and fluorescence imaging, and scanning probe microscopy. For single nanoparticle studies, correlating the EC activities of each particle to their structures is important and requires combining including high-resolution structural imaging tools (e.g. transmission electron microscope and scanning electron microscope). Acknowledgments California State University Los Angeles (CSULA) new faculty start-up fund and California State University Program for Education & Research in Biotechnology (CSUPERB) new investigator grant is gratefully acknowledged. Reference [1] A. Fallis, Handbook of Surface Plasmon Resonance, The Royal Society of Chemistry, Cambridge, 2008. [2] Y. Iwasaki, T. Horiuchi, M. Morita, O. Niwa, Electrochemical reaction of Fe(CN) 63−/4− on gold electrodes analyzed by surface plasmon resonance, Surf. Sci. 427–428 (1999) 195–
ACCEPTED MANUSCRIPT
[16]
[17] [18] [19] [20]
AC C
EP
TE D
M AN U
SC
RI PT
198. [3] S. Wang, S. Boussaad, N.J. Tao, Surface plasmon resonance enhanced optical absorption spectroscopy for studying molecular adsorbates, Rev. Sci. Instrum. 72 (2001) 3055–3060. [4] S. Wang, E.S. Forzani, N. Tao, Detection of heavy metal ions in water by high-resolution surface plasmon resonance spectroscopy combined with anodic stripping voltammetry, Anal. Chem., 79 (2007) 4427-4432. [5] S. Wang, S. Boussaad, S. Wong, N.J. Tao, High-sensitivity stark spectroscopy obtained by surface plasmon resonance measurement, Anal. Chem. 72 (2000) 4003-4008. [6] X. Kang, G. Cheng, S. Dong, A novel electrochemical SPR biosensor, Electrochem. commun. 3 (2001) 489–493. [7] S. Boussaad, J. Pean, N.J. Tao, High-resolution multiwavelength surface plasmon resonance spectroscopy for probing conformational and electronic changes in redox proteins, Anal. Chem. 72 (2000) 222–226. [8] P. Zhai, J. Guo, J. Xiang, F. Zhou, Electrochemical surface plasmon resonance spectroscopy at bilayered silver/gold films, J. Phys. Chem. C. 111 (2007) 981–986. [9] R. Schweiss, J. F. Lübben, D. Johannsmann, W. Knoll, Electropolymerization of ethylene dioxythiophene (EDOT) in micellar aqueous solutions studied by electrochemical quartz crystal microbalance and surface plasmon resonance, Electrochim. Acta. 50 (2005) 2849–2856. [10] S. Kienle, S. Lingler, W. Kraas, A. Offenhäusser, W. Knol, G. Jung, Electropolymerization of a phenol-modified peptide for use in receptor–ligand interactions studied by surface plasmon resonance, Biosens. Bioelectron. 12 (1997) 779–786. [11] Y. Wang, W. Knoll, In situ electrochemical and surface plasmon resonance (SPR) studies of aniline-carboxylated aniline copolymers, Anal. Chim. Acta. 558 (2006) 150–157. [12] K.J. Foley, X. Shan, N.J. Tao, Surface impedance imaging technique, Anal. Chem. 80 (2008) 5146–5151. [13] D.G. Hanken, R.M. Corn, Electric fields and interference effects inside noncentrosymmetric multilayer films at electrode surfaces from electrochemically modulated surface plasmon resonance experiments, Anal. Chem. 69 (1997) 3665–3673. [14] B. Huang, F. Yu, R. N. Zare, Surface plasmon resonance imaging using a high numerical aperture microscope objective, Anal. Chem. 79 (2007) 2979–2983. • [15] X. Shan, Y. Wang, and N. Tao, Plasmonics-based electrochemical current and impedance imaging, in: R.C. Alkire, P.N. Bartlett, J. Lipkowski (Eds.), Advances in Electrochemical Science and Engineering: Nanopatterned and Nanoparticle‐Modified Electrodes, Volume 17, Wiley-VCH, Weinheim, 2017, pp. 373–401. This book chapter covered theory and applications of SPRM in electrochemcial studies. C.H. Choi, K. Chung, T.T.H. Nguyen, D.H. Kim, Plasmon-mediated electrocatalysis for sustainable energy: from electrochemical conversion of different feedstocks to fuel cell reactions, ACS Energy Lett. 3 (2018) 1415–1433. A. Agrawal, S.H. Cho, O. Zandi, S. Ghosh, R.W. Johns, D.J. Milliron, Localized surface plasmon resonance in semiconductor nanocrystals, Chem. Rev. 118 (2018) 3121–3207. S. Sriwichai, P. Netsuwan, S. Phanichphant, A. Baba, Electropolymerization and properties of poly (3-anilinethiophene) thin film, Chiang Mai J. Sci. 43 (2016) 863–869. C.C. Manole, C. Pirvu, I. Demetrescu, Surface plasmon resonance in the study of phenol electropolymerization at ultralow concentration, Rev. Chim. 67 (2016) 884–886. D. Chen, Y. Mei, W. Hu, C.M. Li, Electrochemically enhanced antibody immobilization on polydopamine thin film for sensitive surface plasmon resonance immunoassay, Talanta. 182 (2018) 470–475.
ACCEPTED MANUSCRIPT
• [21] D. Chen, W. Hu, In situ investigation of electrochemically mediated surface-initiated atom transfer radical polymerization by electrochemical surface plasmon resonance, Anal. Chem. 89 (2017) 4355–4358. This is the first in-situ investigation of electrochemically mediated atom transfer radical polymerization (eATRP) using EC-SPR. Y. Feng, E.R. Dionne, V. Toader, G. Beaudoin, A. Badia, Odd–even effects in electroactive self-assembled monolayers investigated by electrochemical surface plasmon resonance and impedance spectroscopy, J. Phys. Chem. C. 121 (2017) 2462624640. [23] B. Holzer, K. Manoli, N. Ditaranto, E. Macchia, A. Tiwari, C.D. Franco, G. Scamarcio, G. Palazzo, L. Torsi, Characterization of covalently bound anti-human immunoglobulins on self-assembled monolayer modified gold electrodes, Adv. Biosyst. 1 (2017) 1700055. [24] N.F. Chiu, C.D. Yang, Real-time and stepwise deoxidization processes to tune the photoluminescence properties of graphene oxide using EC-SPR spectroscopy, RSC Adv. 8 (2018) 11557–11565. [25] N.F. Chiu, C.D. Yang, C.C. Chen, C.T. Kuo, Stepwise control of reduction of graphene oxide and quantitative real-time evaluation of residual oxygen content using EC-SPR for a label-free electrochemical immunosensor, Sensors Actuators B Chem. 258 (2018) 981990. [26] C. Gutierrez-Sanchez, A. Ciaccafava, P.Y. Blanchard, K. Monsalve, M.T. Giudici-Orticoni, S. Lecomte, E. Lojou, Efficiency of enzymatic o2 reduction by myrothecium verrucaria bilirubin oxidase probed by surface plasmon resonance, pmirras, and electrochemistry, ACS Catal. 6 (2016) 5482–5492. • [27] Y. Wang, H. Wang, Y. Chen, Y. Wang, H. Chen, X. Shan, N. Tao, Fast electrochemical and plasmonic detection reveals multitime scale conformational gating of electron transfer in cytochrome c, J. Am. Chem. Soc. 139 (2017) 7244–7249. This work demonstrates that SPRM is powerful in measuring fast electron transfer processes. Y. Wang, X. Shan, N. Tao, Emerging tools for studying single entity electrochemistry, Faraday Discuss. 193 (2016) 9–39. • • [29] X. Shan, U. Patel, S. Wang, R. Iglesias, N. Tao, Imaging local electrochemical current via surface plasmon resonance, Science. 327 (2010) 1363-1366. This work is the first demonstration of an electrochemical microscopy technique using optical signals arising from surface plasmon resonance to detect variations in local electrochemical current.
EP
[28]
TE D
M AN U
SC
RI PT
[22]
AC C
[30] W. Wang, K. Foley, X. Shan, S. Wang, S. Eaton, V.J. Nagaraj, P. Wiktor, U. Patel, N. Tao, Single cells and intracellular processes studied by a plasmonic-based electrochemical impedance microscopy, Nat. Chem. 3 (2011) 249–255. [31] X. Shan, I. Diez-Perez, L. Wang, P. Wiktor, Y. Gu, L. Zhang, W. Wang, J. Lu, S. Wang, Q. Gong, J. Li, N. Tao, Imaging the electrocatalytic activity of single nanoparticles, Nat. Nanotechnol. 7 (2012) 668–672. [32] X. Shan, S. Chen, H. Wang, Z. Chen, Y. Guan, Y. Wang, S. Wang, H. Chen, N. Tao, Mapping local quantum capacitance and charged impurities in graphene via plasmonic impedance imaging, Adv. Mater. 27 (2015) 6213–6219. [33] Y. Fang, W. Wang, X. Wo, Y. Luo, S. Yin, Y. Wang, X. Shan, N. Tao, Plasmonic imaging of electrochemical oxidation of single nanoparticles, J. Am. Chem. Soc., 136 (2014) 12584–12587. [34] T. Yuan, W. Wang, Studying the electrochemistry of single nanoparticles with surface
ACCEPTED MANUSCRIPT
RI PT
plasmon resonance microscopy, Curr. Opin. Electrochem. 6 (2017) 17–22. • [35] Y. Wang, X. Shan, H. Wang, S. Wang, N. Tao, Plasmonic imaging of surface electrochemical reactions of single gold nanowires, J. Am. Chem. Soc. 139 (2017) 1376– 1379. This work shows that SPRM is capable of extracting CVs from individual NPs and at sub-NP level.
•• [36] S. Nizamov, O. Kasian, V.M. Mirsky, Individual detection and electrochemically assisted identification of adsorbed nanoparticles by using surface plasmon microscopy, Angew. Chemie - Int. Ed. 55 (2016) 7247–7251. This work shows that SPRM has chemical selectivity to various NPs.
•• [37] D. Jiang, Y. Jiang, Z. Li, T. Liu, X. Wo, Y. Fnag, N. Tao, W. Wang, H. Chen, Optical
M AN U
SC
imaging of phase transition and li-ion diffusion kinetics of single licoo2 nanoparticles during electrochemical cycling, J. Am. Chem. Soc. 139 (2017) 186–192. This work is the first demonstration of studying the phase transition and Li-ion diffusion kinetics at single nanoparticle level via SPRM. D. Jiang, L. Sun, T. Liu, W. Wang, Thin-film electrochemistry of single prussian blue nanoparticles revealed by surface plasmon resonance microscopy, Anal. Chem. 89 (2017) 11641–11647. [39] L. Sun, D. Jiang, M. Li, T. Liu, L. Yuan, W. Wang, H. Chen, Collision and oxidation of single licoo2 nanoparticles studied by correlated optical imaging and electrochemical recording, Anal. Chem. 89 (2017) 6050–6055. [40] L. Sun, Y. Fang, Z. Li, W. Wang, H. Chen, Simultaneous optical and electrochemical recording of single nanoparticle electrochemistry, Nano Res. 10 (2017) 1740–1748. [41] L. Sun, W. Wang, H.-Y. Chen, Dynamic nanoparticle-substrate contacts regulate multipeak behavior of single silver nanoparticle collisions, ChemElectroChem. 5 (2018) 1–6. [42] S.M. Oja, D.A. Robinson, N.J. Vitti, M.A. Edwards, Y. Liu, H.S. White, B. Zhang, Observation of multipeak collision behavior during the electro-oxidation of single ag nanoparticles, J. Am. Chem. Soc. 139 (2017) 708–718. [43] H. Yu, X. Shan, S. Wang, N. Tao, Achieving high spatial resolution surface plasmon resonance microscopy with image reconstruction, Anal. Chem. 89 (2017) 2704–2707. [44] S.A. Abayzeed, R.J. Smith, K. F. Webb, M.G. Somekh, C.W. See, Sensitive detection of voltage transients using differential intensity surface plasmon resonance system, Opt. Express. 25 (2017) 31552. [45] Y. Wang, X. Shan, S. Wang, N. Tao, Imaging local electric field distribution by plasmonic impedance microscopy, Anal. Chem. 88 (2016) 1547–1552. [46] X. Luo, S. Deng, P. Wang, Temporal–spatial-resolved mapping of the electrical double layer changes by surface plasmon resonance imaging, RSC Adv. 8 (2018) 28266–28274. • [47] M. Hasheminejad, Y. Fang, M. Li, Y. Jiang, W. Wang, H. Y. Chen, Plasmonic Imaging of the Interfacial Potential Distribution on Bipolar Electrodes, Angew. Chemie - Int. Ed. 56 (2017) 1629–1633. This is the first application of SPRM in mapping potential distributon on bipolar electrodes.
AC C
EP
TE D
[38]
[48] [49]
M. Li, S. Liu, Y. Jiang, W. Wang, Visualizing the zero-potential line of bipolar electrodes with arbitrary geometry, Anal. Chem. 90 (2018) 6390–6396. N. Nishi, Y. Ikeda, T. Sakka, Electrochemical surface plasmon resonance as a probe of redox reactions at the ionic liquid|gold interface, J. Electroanal. Chem. 817 (2018) 210– 216.
ACCEPTED MANUSCRIPT
RI PT SC M AN U TE D EP
[51]
S.A. Pradanawati, F.M. Wang, C.H. Su, Using electrochemical surface plasmon resonance for in-situ kinetic investigations of solid electrolyte interphase formation in lithium ion battery, J. Power Sources. 330 (2016) 127–131. L. Yuan, M. Li, T. Yuan, Y. Fang, W. Wang, In operando imaging of self-catalyzed formaldehyde burst in methanol oxidation reactions under open circuit conditions, Chem. Sci. 9 (2018) 3318–3323.
AC C
[50]
ACCEPTED MANUSCRIPT
Highlights:
RI PT SC M AN U TE D EP
•
Review the most recent progress in electrochemical surface plasmon resonance (EC-SPR) studies Perspectives on future directions of EC-SPR
AC C
•