Schematic Electrochemical Quartz Crystal Microbalance

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.[4] Firstly, an alternating electric field is generated between the two electrodes for making up the oscillator.[4] 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.[4] Thus, the working electrode of electrochemistry cell is the sensor of QCM.[2]

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.[5]

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.[6] Otherwise, K is taken as the average sensitivity factor of the EQCM.[6]

[6]

where is the measured frequency shift (Hz), S is the quartz crystal active area (cm2), ρ is the density of quartz crystal, is the quartz crystal shear modulus and is the fundamental quartz crystal frequency. K is the intrinsic sensitivity factor of the EQCM.[6]

In a certain electrolyte solution, a metal film will deposited on the working electrode, which is the QCM sensor surface of QCM.[6]

[6]

The charge density () is involved in the electro-reduction of metal ions at a constant current , in a period of time ().[6]

The active areal mass density is calculated by

[6]

where is the atomic weight of deposited metal, z is the electrovalency, and F is the Faraday constant.[6]

The experimental sensitivity of the EQCM is calculated by combing and .[6]

[6]

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.[5] 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.[7] 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,[24] methanol fuel cell anodizing process,[25] and electrodeposition of cerium oxide suspended nanoparticles doped with gadolinium oxide under the ultrasound for Co/CeO2 and Ni/CeO2 composite fuel cells.[26] EQCM can also be used to study the energy storage performance and influencing factors of supercapacitors[27] and electrochemical capacitors. For example, EQCM is used to study the ion movement gauge of conductive polymer of capacitor on cathode.[28] 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.[29]

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. Bibcode:1985SurSL.163L.621S. doi:10.1016/0167-2584(85)90839-4. ISSN 0167-2584.
  2. 1 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. doi:10.1016/s0022-0728(85)80057-7. ISSN 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. doi:10.1021/ac00285a062. ISSN 0003-2700.
  4. 1 2 3 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. Bibcode:1995JElS..142.1084S. doi:10.1149/1.2044134. ISSN 0013-4651.
  5. 1 2 3 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. doi:10.1016/s0013-4686(99)00293-5. ISSN 0013-4686.
  6. 1 2 3 4 5 6 7 8 9 10 11 12 Gabrielli, C. (1991). "Calibration of the Electrochemical Quartz Crystal Microbalance". Journal of the Electrochemical Society. 138 (9): 2657–2660. Bibcode:1991JElS..138.2657G. doi:10.1149/1.2086033. ISSN 0013-4651.
  7. 1 2 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. doi:10.1021/j100164a053. ISSN 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. doi:10.1016/s0379-6779(97)80690-x. ISSN 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. doi:10.1021/j100203a059. ISSN 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. doi:10.1016/j.jelechem.2003.08.012. ISSN 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. doi:10.1016/s0013-4686(98)00405-8. ISSN 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. doi:10.1021/la981275j. ISSN 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. doi:10.1021/la980825a. ISSN 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. doi:10.1016/s0022-0728(02)00677-0. ISSN 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. doi:10.1016/s0022-0728(99)00146-1. ISSN 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. doi:10.1016/s0010-938x(99)00038-4. ISSN 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. doi:10.1016/j.corsci.2006.06.022. ISSN 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. doi:10.1021/ja00079a021. ISSN 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. doi:10.1021/la000756b. ISSN 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. doi:10.1016/0379-6779(95)03280-0. ISSN 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. Bibcode:1995JElS..142..417N. doi:10.1149/1.2044042. ISSN 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. doi:10.1021/cm000400l. ISSN 0897-4756.
  24. ↑ Schmidt, V. M.; Stimming, U. (1996), "Fuel Cell Systems for Vehicle Applications", New Promising Electrochemical Systems for Rechargeable Batteries, Dordrecht: Springer Netherlands, pp. 233–246, doi:10.1007/978-94-009-1643-2_17, ISBN 978-94-010-7235-9
  25. ↑ 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. doi:10.1016/s1872-1508(08)60010-8. ISSN 1872-1508.
  26. ↑ 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. Bibcode:2008PSSAR.205.2400A. doi:10.1002/pssa.200779409. ISSN 1862-6300. S2CID 123082512.
  27. ↑ 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. Bibcode:2009NatMa...8..872L. doi:10.1038/nmat2559. ISSN 1476-1122. PMID 19838184.
  28. ↑ Farrington, G.C. (1991-07-01). "Polymeric electrolytes for ambient temperature lithium batteries". doi:10.2172/5176162. S2CID 94438069. {{cite journal}}: Cite journal requires |journal= (help)
  29. ↑ 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. doi:10.1021/jp312752q. ISSN 1932-7447.
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