Quartz crystal microbalances experiments

On a pc-Au electrode in 1 M NaF vertically oriented pyridine molecules have been observed at 0.7 V (versus Ag/AgCl), applying in situ IR. In contrast, they have not been detected at this potential in electrochemical method [240]. Considering the fact that adsorption of pyridine on gold electrodes is a replacement reaction and taking into account the results obtained from quartz crystal microbalance experiments, the conclusion has been made that adsorption of one pyridine molecule is accompanied by the removal of 10-12 water molecules [241]. 

Combined VIM and quartz crystal microbalance experiments allowed the determination of mass increases during electrochemical redox reactions, indicating ingress of ions or molecules from the electrolyte solution [4-7]. 

The measurement of mass using a quartz crystal microbalance is based on the piezoelectric effect.When a piezoelectric material, such as a quartz crystal, experiences a mechanical stress, it generates an electrical potential whose magnitude is proportional to the applied stress. Gonversely, when an alternating electrical field is... 

Studies have shown that the Pt oxides are not hydrated [Birss et al., 1993 Harrington, 1997 Jerkiewicz et al., 2004]. Electrochemical quartz crystal microbalance [Birss et al., 1993] and nanobalance [Jerkiewicz et al., 2004] experiments... 

We first experimented with the Quartz Crystal Microbalance (QCM) in order to measure the ablation rate in 1987 (12). The only technique used before was the stylus profilometer which revealed enough accuracy for etch rate of the order of 0.1 pm, but was unable to probe the region of the ablation threshold where the etch rate is expressed in a few A/pulse. Polymer surfaces are easily damaged by the probe tip and the meaning of these measurements are often questionable. Scanning electron microscopy (21) and more recently interferometry (22) were also used. The principle of the QCM was demonstrated in 1957 by Sauerbrey (22) and the technique was developed in thin film chemistiy. analytical and physical chemistry (24). The equipment used in this work is described in previous publications (25). When connected to an appropriate oscillating circuit, the basic vibration frequency (FQ) of the crystal is 5 MHz. When a film covers one of the electrodes, a negative shift <5F, proportional to its mass, is induced ... 

Fig. 14 Set-up of an electrogravimetric experiment with an electrochemical quartz crystal microbalance.

The monotonic increase of immobilized material vith the number of deposition cycles in the LbL technique is vhat allo vs control over film thickness on the nanometric scale. Eilm growth in LbL has been very well characterized by several complementary experimental techniques such as UV-visible spectroscopy [66, 67], quartz crystal microbalance (QCM) [68-70], X-ray [63] and neutron reflectometry [3], Fourier transform infrared spectroscopy (ETIR) [71], ellipsometry [68-70], cyclic voltammetry (CV) [67, 72], electrochemical impedance spectroscopy (EIS) [73], -potential [74] and so on. The complement of these techniques can be appreciated, for example, in the integrated charge in cyclic voltammetry experiments or the redox capacitance in EIS for redox PEMs The charge or redox capacitance is not necessarily that expected for the complete oxidation/reduction of all the redox-active groups that can be estimated by other techniques because of the experimental timescale and charge-transport limitations. 

A molecular beam of XeFj(gas) and a beam of argon ions were directed at the center of a silicon film which had been deposited on a quartz crystal microbalance. The sensitivity of the microbalance was such that the removal of one monolayer of silicon could be detected. In these experiments, the reaction products [e.g., SiF fgas)] were detected using mass spectrometry the surface concentrations were detected using Auger spectroscopy and the rate that material was being removed from the surface was measured with the microbalance. 

In addition to these, there were experiments exploiting quartz crystal microbalances (55), matrix isolation (86), differential scanning calorimetry (87), capillary electrophoresis (88), and inductively coupled plasma (1CP) spectrometers (89). 

Although less common, some third-order chemical sensors have found significant applications not only in sensing but also in research. One such example is Electrochemical Quartz Crystal Microbalance (EQCM). With EQCM, an electrochemical experiment can be performed in its inherently large experimental space, that is, various electrochemical waveforms, impedance analysis, gating, and different mass loading. As the dimensionality of the experiment is increased, so is its information content. 

The electrochemical quartz crystal microbalance (EQCM) has emerged as a very powerful in situ technique to complement electrochemical experiments [3-5]. Nomura and Okuhara [15] first used the quartz crystal microbalance (QCM) to detect mass changes at a metal coated quartz resonator immersed in electrolyte during electrochemical experiments. 

Since micro-gravimetry with the EQCM lacks specificity only the difference of cation and anion fluxes can be obtained by microgravimetry and therefore an independent measurement of specific ions is needed. Scanning electrochemical microscopy (SECM) coupled with a quartz crystal microbalance with independent potential control of the tip and substrate has been recently done by Cliffel and Bard [28]. In this experiment generation at the substrate (EQCM crystaj) working electrode and collection at the tip of an ultramicroelectrode (UNE) that was approached perpendicular to the EQCM crystal was employed with measurement of A/. Hillier and Ward [8] had previously used a scanning microelectrode to map the mass sensitivity across the surface of the QCM crystal. Reflection of longitudinal waves at the UME tip limits these experiments due to oscillations. 

Biosens Bioelectron 14 663 [v] HepelM (1999) Electrode-solution interface studied with electrochemical quartz crystal nanobalance. In Wieczkowski A (ed) Interfacial electrochemistry. Marcel Dekker, New York, pp 599-630 [vi] Hillman AR (2003) The Electrochemical quartz crystal microbalance. In Bard AJ, Stratmann M, Unwin PR (eds) Instrumentation and electroanalytical chemistry. Encyclopedia of electrochemistry, vol. 3. Wiley-VHC, Weinheim, pp 230-289 [vii] Tsionsky V, Daikhin L, Urbakh M, Gileadi E (2004) Looking at the metal/solution interface with electrochemical quartz-crystal microbalance Theory and experiment. In Bard AJ, Rubinstein I (eds) Electroanalytical chemistry, vol 22. Marcel Dekker, New York, pp 2-94 [viii] Vilas-Boas M, Henderson MJ, Freire C, Hillman AR, Vieil E (2000) Chem Eur / 6 1160 [ix] Inzelt G, Horanyi G (1989) / Electrochem Soc 136 1747 [x] Gollas B, Bartlett PN, Denuault (2000) Anal Chem 72 349 [xi] Gabrielli C, Ked-dam M, Perrot H, Torresi R (1994) ] Electroanal Chem 378 85... 

Through the combination of SPR with a - poten-tiostat, SPR can be measured in-situ during an electrochemical experiment (electrochemical surface plasmon resonace, ESPR). Respective setups are nowadays commercially available. Voltammetric methods, coupled to SPR, are advantageously utilized for investigations of - conducting polymers, thin film formation under influence of electric fields or potential variation, as well as - electropolymerization, or for development of -> biosensors and - modified electrodes. Further in-situ techniques, successfully used with SPR, include electrochemical - impedance measurements and -+ electrochemical quartz crystal microbalance. 

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