Electrochemical quartz crystal microbalance explained

Electrochemical quartz crystal microbalance (EQCM) is the combination of electrochemistry and quartz crystal microbalance, which was generated in the eighties.[1] [2] [3] Typically, an EQCM device contains an electrochemical cells part and a QCM part.[4] Two electrodes on both sides of the quartz crystal serve two purposes. Firstly, an alternating electric field is generated between the two electrodes for making up the oscillator. Secondly, the electrode contacting electrolyte is used as a working electrode (WE), together with a counter electrode (CE) and a reference electrode (RE), in the potentiostatic circuit constituting the electrochemistry cell. Thus, the working electrode of electrochemistry cell is the sensor of QCM.

As a high mass sensitive in-situ measurement, EQCM is suitable to monitor the dynamic response of reactions at the electrode–solution interface at the applied potential.[5] When the potential of a QCM metal electrode changes, a negative or positive mass change is monitored depending on the ratio of anions adoption on the electrode surface and the dissolution of metal ions into solution.

EQCM calibration

The EQCM sensitivity factor K can be calculated by combing the electrochemical cell measured charge density and QCM measured frequency shift.[6] The sensitivity factor is only valid when the mass change on the electrode is homogenous. Otherwise, K is taken as the average sensitivity factor of the EQCM.

\Deltaf=-\left(

2
2
f
o
S\sqrt{\mu\rho
}\right)\Delta m=-K\Delta m

where

\Deltaf

is the measured frequency shift (Hz), S is the quartz crystal active area (cm2), ρ is the density of quartz crystal,

\mu

is the quartz crystal shear modulus and

fo

is the fundamental quartz crystal frequency. K is the intrinsic sensitivity factor of the EQCM.

In a certain electrolyte solution, a metal film will deposited on the working electrode, which is the QCM sensor surface of QCM.

Mz++ze-\longrightarrowM

The charge density (

\DeltaQ
C

⋅ cm-2

) is involved in the electro-reduction of metal ions at a constant current

I

, in a period of time

\DeltaT

(

\DeltaQ=I\Deltat

).

The active areal mass density is calculated by

\Deltam=

Am
zF

\DeltaQ

where

Am

is the atomic weight of deposited metal, z is the electrovalency, and F is the Faraday constant.

The experimental sensitivity of the EQCM is calculated by combing

\Deltam

and

\Deltaf

.

K=-

zF
Am
\Deltaf
\DeltaQ

EQCM application

Application of EQCM in electrosynthesis

EQCM can be used to monitor the chemical reaction occurring on the electrode, which offers the optimized reaction condition by comparing the influence factors during the synthesis process.[7] Some previous work has already investigated the polymerization process and charge transport properties,[8] polymer film growth on gold electrode surface,[9] and polymerization process[10] of polypyrrole and its derivatives. EQCM was used to study electro-polymerization process and doping/de-doping properties of polyaniline film on gold electrode surface as well.[11] To investigate the electrosynthesis process, sometimes it is necessary to combine other characterization technologies, such as using FTIR and EQCM to study the effect of different conditions on the formation of poly(3,4-ethylenedioxythiophene) film structure,[12] and using EQCM, together with AFM, FTIR, EIS, to investigate the film formation process in the alkyl carbonate/lithium salt electrolyte solution on precious metal electrodes surfaces.[13]

Application of EQCM in electrodeposition and dissolution

EQCM is broadly used to study the deposition/dissolution process on electrode surface, such as the oscillation of electrode potential during Cu/CuO2 layered nanostructure electrodeposition,[14] deposition growth process of cobalt and nickel hexacyanoferrate in calcium nitrate and barium nitrate electrolyte solution,[15] and the Mg electrode electrochemical behaviour in various polar aprotic electrolyte solutions.[16] EQCM can be used as a powerful tool for corrosion and corrosion protection study, which is usually combined with other characterization technologies. A previous work used EQCM and XPS studied Fe-17Cr-33Mo/ Fe-25Cr alloy electrodes mass changes during the potential sweep and potential step experiments in the passive potential region in an acidic and a basic electrolyte.[17] Another previous work used EQCM and SEM to study the influence of purine (PU) on Cu electrode corrosion and spontaneous dissolution in NaCl electrolyte solution.[18]

Application of EQCM in adsorption and desorption

EQCM has been used to study the self-assembled monolayers of long chain alkyl mercaptan[19] and alkanethiol and mercaptoalkanoic[20] on gold electrode surface.

Application of EQCM in polymer modified electrode

EQCM can be used to ideally modify polymer membranes together with other electrochemical measurements or surface characterization methods. A team has used CV, UV-Vis, IR and EQCM studied irreversible changes of some polythiophenes in the electrochemical reduction process in acetonitrile.[21] Later on they used AFM and EQCM investigated growth of polypyrrole film in anionic surfactant micellar solution.[22] Then combing with CV, UV-Vis, FTIR, ESR, they used EQCM to study conductivity and magnetic properties of 3,4-dimethoxy and 3,4-ethylenedioxy-terminated polypyrrole and polythiophene.[23]

Application of EQCM in energy conversion and storage

EQCM can be used to study the process of adsorption and oxidation of fuel molecules on the electrode surface, and the effect of electrode catalyst or other additives on the electrode, such as assessment of polypyrrole internal Pt load in the polypyrrole/platinum composites fuel cell, methanol fuel cell anodizing process,[24] and electrodeposition of cerium oxide suspended nanoparticles doped with gadolinium oxide under the ultrasound for Co/CeO2 and Ni/CeO2 composite fuel cells.[25] EQCM can also be used to study the energy storage performance and influencing factors of supercapacitors[26] and electrochemical capacitors. For example, EQCM is used to study the ion movement gauge of conductive polymer of capacitor on cathode.[27] Some work studied the EQCM application in solar energy, which is mostly additive and thin film material related, for instance, using EQCM to study the electrochemical deposition process and stability of Co-Pi oxygen evolution catalyst for solar storage.[28]

Notes and References

  1. Schumacher. R.. Borges. G.. Kanazawa. K.K.. November 1985. The quartz microbalance: A sensitive tool to probe surface reconstructions on gold electrodes in liquid. Surface Science Letters. 163. 1. L621–L626. 10.1016/0167-2584(85)90839-4. 1985SurSL.163L.621S. 0167-2584.
  2. Bruckenstein. Stanley. Shay. Michael. June 1985. An in situ weighing study of the mechanism for the formation of the adsorbed oxygen monolayer at a gold electrode. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry. 188. 1–2. 131–136. 10.1016/s0022-0728(85)80057-7. 0022-0728.
  3. Kanazawa. K. Keiji.. Gordon. Joseph G.. July 1985. Frequency of a quartz microbalance in contact with liquid. Analytical Chemistry. 57. 8. 1770–1771. 10.1021/ac00285a062. 0003-2700.
  4. Streinz. Christopher C.. 1995. The Effect of Current and Nickel Nitrate Concentration on the Deposition of Nickel Hydroxide Films. Journal of the Electrochemical Society. 142. 4. 1084–1089. 10.1149/1.2044134. 1995JElS..142.1084S. 52106125 . 0013-4651.
  5. Schmutz. P.. Landolt. D.. December 1999. Electrochemical quartz crystal microbalance study of the transient response of passive Fe–25Cr alloy. Electrochimica Acta. 45. 6. 899–911. 10.1016/s0013-4686(99)00293-5. 0013-4686.
  6. Gabrielli. C.. 1991. Calibration of the Electrochemical Quartz Crystal Microbalance. Journal of the Electrochemical Society. 138. 9. 2657–2660. 10.1149/1.2086033. 1991JElS..138.2657G. 0013-4651.
  7. yan. xiao. Nov 2018. Application of Electrochemical Quartz Crystal Microbalance. Progress in Chemistry. 30. 11. 1701.
  8. Baker. Charles K.. Qiu. Yong Jian. Reynolds. John R.. May 1991. Electrochemically-induced charge and mass transport in polypyrrole/poly(styrene sulfonate) molecular composites. The Journal of Physical Chemistry. 95. 11. 4446–4452. 10.1021/j100164a053. 0022-3654.
  9. Chung. Sun-Mi. Paik. Woon-kie. Yeo. In-Hyeong. Jan 1997. A study on the initial growth of polypyrrole on a gold electrode by electrochemical quartz crystal microbalance. Synthetic Metals. 84. 1–3. 155–156. 10.1016/s0379-6779(97)80690-x. 0379-6779.
  10. Bose. C. S. C.. Basak. S.. Rajeshwar. K.. Nov 1992. Electrochemistry of poly(pyrrole chloride) films: a study of polymerization efficiency, ion transport during redox and doping level assay by electrochemical quartz crystal microgravimetry, pH and ion-selective electrode measurements. The Journal of Physical Chemistry. 96. 24. 9899–9906. 10.1021/j100203a059. 0022-3654.
  11. Baba. Akira. Tian. Shengjun. Stefani. Fernando. Xia. Chuanjun. Wang. Zhehui. Advincula. Rigoberto C. Johannsmann. Diethelm. Knoll. Wolfgang. Jan 2004. Electropolymerization and doping/dedoping properties of polyaniline thin films as studied by electrochemical-surface plasmon spectroscopy and by the quartz crystal microbalance. Journal of Electroanalytical Chemistry. 562. 1. 95–103. 10.1016/j.jelechem.2003.08.012. 1572-6657.
  12. Kvarnström. C.. Neugebauer. H.. Blomquist. S.. Ahonen. H.J.. Kankare. J.. Ivaska. A.. April 1999. In situ spectroelectrochemical characterization of poly(3,4-ethylenedioxythiophene). Electrochimica Acta. 44. 16. 2739–2750. 10.1016/s0013-4686(98)00405-8. 0013-4686.
  13. Aurbach. D.. Moshkovich. M.. Cohen. Y.. Schechter. A.. April 1999. The Study of Surface Film Formation on Noble-Metal Electrodes in Alkyl Carbonates/Li Salt Solutions, Using Simultaneous in Situ AFM, EQCM, FTIR, and EIS. Langmuir. 15. 8. 2947–2960. 10.1021/la981275j. 0743-7463.
  14. Bohannan. Eric W.. Huang. Ling-Yuang. Miller. F. Scott. Shumsky. Mark G.. Switzer. Jay A.. Feb 1999. In Situ Electrochemical Quartz Crystal Microbalance Study of Potential Oscillations during the Electrodeposition of Cu/Cu2O Layered Nanostructures. Langmuir. 15. 3. 813–818. 10.1021/la980825a. 0743-7463.
  15. Chen. S.-M.. March 2002. Preparation, characterization, and electrocatalytic oxidation properties of iron, cobalt, nickel, and indium hexacyanoferrate. Journal of Electroanalytical Chemistry. 521. 1–2. 29–52. 10.1016/s0022-0728(02)00677-0. 1572-6657.
  16. Lu. Z.. Schechter. A.. Moshkovich. M.. Aurbach. D.. May 1999. On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions. Journal of Electroanalytical Chemistry. 466. 2. 203–217. 10.1016/s0022-0728(99)00146-1. 1572-6657.
  17. Schmutz. P. Landolt. D. November 1999. In-situ microgravimetric studies of passive alloys: potential sweep and potential step experiments with Fe–25Cr and Fe–17Cr–33Mo in acid and alkaline solution. Corrosion Science. 41. 11. 2143–2163. 10.1016/s0010-938x(99)00038-4. 1999Corro..41.2143S. 0010-938X.
  18. Scendo. M.. Feb 2007. The effect of purine on the corrosion of copper in chloride solutions. Corrosion Science. 49. 2. 373–390. 10.1016/j.corsci.2006.06.022. 2007Corro..49..373S . 0010-938X.
  19. Schneider. Thomas W.. Buttry. Daniel A.. Dec 1993. Electrochemical quartz crystal microbalance studies of adsorption and desorption of self-assembled monolayers of alkyl thiols on gold. Journal of the American Chemical Society. 115. 26. 12391–12397. 10.1021/ja00079a021. 0002-7863.
  20. Kawaguchi. Toshikazu. Yasuda. Hiroaki. Shimazu. Katsuaki. Porter. Marc D.. Dec 2000. Electrochemical Quartz Crystal Microbalance Investigation of the Reductive Desorption of Self-Assembled Monolayers of Alkanethiols and Mercaptoalkanoic Acids on Au. Langmuir. 16. 25. 9830–9840. 10.1021/la000756b. 0743-7463.
  21. Zotti. G.. Schiavon. G.. Zecchin. S.. June 1995. Irreversible processes in the electrochemical reduction of polythiophenes. Chemical modifications of the polymer and charge-trapping phenomena. Synthetic Metals. 72. 3. 275–281. 10.1016/0379-6779(95)03280-0. 0379-6779.
  22. Naoi. Katsuhiko. 1995. Electrochemistry of Surfactant-Doped Polypyrrole Film(I): Formation of Columnar Structure by Electropolymerization. Journal of the Electrochemical Society. 142. 2. 417–422. 10.1149/1.2044042. 1995JElS..142..417N. 0013-4651.
  23. Zotti. Gianni. Zecchin. Sandro. Schiavon. Gilberto. Groenendaal. L. “Bert”. Oct 2000. Conductive and Magnetic Properties of 3,4-Dimethoxy- and 3,4-Ethylenedioxy-Capped Polypyrrole and Polythiophene. Chemistry of Materials. 12. 10. 2996–3005. 10.1021/cm000400l. 0897-4756.
  24. WU. Q. ZHEN. C. ZHOU. Z. SUN. S. Feb 2008. Electrochemical Behavior of Irreversibly Adsorbed Sb on Au Electrode. Acta Physico-Chimica Sinica. 24. 2. 201–204. 10.1016/s1872-1508(08)60010-8. 1872-1508.
  25. Argirusis. Chr.. Matić. S.. Schneider. O.. Oct 2008. An EQCM study of ultrasonically assisted electrodeposition of Co/CeO2and Ni/CeO2composites for fuel cell applications. Physica Status Solidi A. 205. 10. 2400–2404. 10.1002/pssa.200779409. 2008PSSAR.205.2400A. 123082512 . 1862-6300.
  26. Levi. Mikhael D.. Salitra. Grigory. Levy. Naomi. Aurbach. Doron. Maier. Joachim. 2009-10-18. Application of a quartz-crystal microbalance to measure ionic fluxes in microporous carbons for energy storage. Nature Materials. 8. 11. 872–875. 10.1038/nmat2559. 19838184. 2009NatMa...8..872L. 1476-1122.
  27. Farrington. G.C.. 1991-07-01. Polymeric electrolytes for ambient temperature lithium batteries. 10.2172/5176162. 94438069 .
  28. Irshad. Ahamed. Munichandraiah. Nookala. 2013-04-11. EQCM Investigation of Electrochemical Deposition and Stability of Co–Pi Oxygen Evolution Catalyst of Solar Energy Storage. The Journal of Physical Chemistry C. 117. 16. 8001–8008. 10.1021/jp312752q. 1932-7447.

This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Electrochemical quartz crystal microbalance".

Except where otherwise indicated, Everything.Explained.Today is © Copyright 2009-2024, A B Cryer, All Rights Reserved. Cookie policy.