Solid-liquid interface, scanning electrochemical

Barker A L, Gonsalves M, Maepherson J V, Slevin C J and Unwin P R 1999 Scanning electrochemical microscopy beyond the solid/liquid interface Anal. Chim. Acta 385 223... 

Scanning tunneling (STM) was invented a decade ago by Binnig and Rohrer [72], and was first applied to the solid-liquid interface by Sonnenfeld and Hansma in 1986 [73]. Since then, there have been numerous applications of STM to in situ electrochemical experiments [74-76]. Because the STM method is based on tunneling currents between the surface and an extremely small probe tip, the sample must be reasonably conductive. Hence, STM is particularly suited to investigations of redox and conducting polymer-modified electrodes [76,77],... 

Barker, A. L., Gonsalves, M., MacPherson, 1. V., Slevin, C. 1. and Unwin, P. R. (1999), Scanning electrochemical microscopy Beyond the solid/liquid interface. Anal. Chim. Acta, 385(1-3) 223-240. 

According to Sec. 3, the characterization of interface states at semiconductor electrodes is a key question since these states influence the behavior of the interface [76, 77]. The many different techniques of characterization have been reviewed [35, 76, 77] for the solid/liquid interface. True STS has not been applied until now. In first attempts to derive energy information the sample voltage was scanned to avoid problems with the electrochemical current at the tip extremity. The possibility of scanning the tip bias is discussed later. 

For the investigation of adsorption/desorption kinetics and surface diffusion rates, SECM is employed to locally perturb adsorption/desorption equilibria and measure the resulting flux of adsorbate from a surface. In this application, the technique is termed scanning electrochemical induced desorption (SECMID) (1), but historically this represents the first use of SECM in an equilibrium perturbation mode of operation. Later developments of this mode are highlighted towards the end of Sec. II.C. The principles of SECMID are illustrated schematically in Figure 2, with specific reference to proton adsorption/desorption at a metal oxide/aqueous interface, although the technique should be applicable to any solid/liquid interface, provided that the adsorbate of interest can be detected amperometrically. 

Gewirtli A A and Siegentlialer H (eds) 1995 Nanoscale Probes of the Solid/Liquid Interface (NATO ASI Series 288) (London Kluwer) A survey of applications of scanning probes to electrochemical problems. 

Nanocell is the smallest electrochemical cell developed by Sugimura and Nakagiri [11] and further developed and utilized for ENT by BloeB et al. [10]. The nanocell consists of two electrodes distance between electrodes is generally maintained in the order of less than 1 nm. In between two electrodes, absorbed water film acts as an electrolyte whose volume is maintained by vapor pressure and ranges from 10 to 10 cm. Double layer capacitance is not formed across the solid liquid interface in the nanocell due to the much smaller inter-electrode gap and hence, generated hydrogen ion and hydroxyl ion recombine immediately. Nanotip of microtool such as tip of scanning probe microscope (SPM) or AFM tip is most suitable for the formation of electrochemical nanoceU. 

Unwin PR, Bard AJ (1992) Scanning electrochemical microscopy. 14. Scanning electrochemical microscope induced desorption - a new technique for the measurement of adsorption desorption-kinetics and surface-diffusion rates at the solid liquid interface. J Phys Chem 96(12) 5035-5045... 

Electron Spectroscopy and Electrochemical Scanning Tunneling Microscopy of the Solid—Liquid Interface lodine-Catafyzed Dissolution of Pd(llO)... 

Wang, D. Wan, L.-J. 2007. Electrochemical scanning tunneling microscopy Adlayer structure and reaction at solid/liquid interface. J. Phys. Chem. C 111 16109-16130. 

This chapter is concerned with the study of interfacial processes and reactions that occur essentially at electrically insulating interfaces, where the role of the SECM tip is often to induce and monitor the reaction of interest. The work herein is an update of Chapter 12 Probing reactions at solid/liquid interfaces of the first edition of Scanning Electrochemical Microscopy [4] and highlights how the basic principles of the SECM-induced transfer (SECMIT) mode (or equilibrium perturbation mode) and related techniques— notably (multi-) potential step transient methods—can be applied to a wide variety of interfaces where flux measurements have traditionally been difficult. 

Macpherson, J. V., Unwin, P. R. Probing reactions at Solid/Liquid Interfaces, In Scanning Electrochemical Microscopy, Bard, A. J., Mirkin, M. V. (eds.). Marcel Dekker, New York, 2001, Chap. 12, pp. 521-592. 

Electrochemical scanning tunneling microscopy (ECSTM) is a very useful technique for investigating electrochemical processes at the solid-liquid interface at extremely high ( sub-A to nm level)... 

In scanning electrochemical microscopy (SECM) a microelectrode probe (tip) is used to examine solid-liquid and liquid-liquid interfaces. SECM can provide information about the chemical nature, reactivity, and topography of phase boundaries. The earlier SECM experiments employed microdisk metal electrodes as amperometric probes [29]. This limited the applicability of the SECM to studies of processes involving electroactive (i.e., either oxidizable or reducible) species. One can apply SECM to studies of processes involving electroinactive species by using potentiometric tips [36]. However, potentio-metric tips are suitable only for collection mode measurements, whereas the amperometric feedback mode has been used for most quantitative SECM applications. 

H Shiku, Y Hara, T Takeda, T Matsue, I Uchida. Microfabrication and characterization of solid surfaces patterned with enzymes or antigen-antibodies by scanning electrochemical microscopy. In G Jerkiewiecz, MP Soriaga, K Uosaki, A Wieckowski, eds. Solid-Liquid Electrochemical Interfaces. Washington, DC ACS, 1997, pp 202-209. 

Forrer P, Repphun G, Schmidt E, Siegenthaler H (1997) Electroactive polymers an electrochemical and in situ scanning probe microscopy study. In Jerkiewicz G, Soriaga MP, Uosaki K, Wieckowski A (eds) Solid-liquid electrochemical interfaces (ACS Symp Ser 656). American Chemical Society, Washington, DC, p210 Malhotra BD, Chaubey A, Singh SP (2006) Anal Chem Acta 578 59 Biallozor S, Kupniewska A (2005) Synth Met 155 443... 

Itaya, K., Batina, N., Kunitake, M. etal. (1997) In situ scanning tunneling microscopy of organic molecules adsorbed on iodine-modified Au( 111), Ag( 111), and Pt( 111) electrodes. Solid-Liquid Electrochemical Interfaces. ACS Symposium Series, 656, 171-188. 

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