High-Sensitivity Dual Electrochemical QCM for Reliable Three-Electrode Measurements

An electrochemical quartz crystal microbalance (EC-QCM) is a versatile gravimetric technique that allows for parallel characterization of mass deposition and electrochemical properties. Despite its broad applicability, simultaneous characterization of two electrodes remains challenging due to practical difficulties posed by the dampening from fixture parasitics and the dissipative medium. In this study, we present a dual electrochemical QCM (dual EC-QCM) that is employed in a three-electrode configuration to enable consequent monitoring of mass deposition and viscous loading on two crystals, the working electrode (WE) and the counter electrode (CE). A novel correction approach, along with a three standard complex impedance calibration, is employed to overcome the effect of dampening while keeping high spectral sensitivity. Separation of viscous loading and rigid mass deposition is achieved by robust characterization of the complex impedance at the resonance frequency. Validation of the presented system is done by cyclic voltammetry characterization of Ag underpotential deposition on gold. The results indicate mass deposition of 412.2 ng for the WE and 345.6 ng for the CE, reflecting a difference of the initially-present Ag adhered to the surface. We also performed higher harmonic measurements that further corroborate the sensitivity and reproducibility of the dual EC-QCM. The demonstrated approach is especially intriguing for electrochemical energy storage applications where mass detection with multiple electrodes is desired.

[1]  S. Nizkorodov,et al.  Photodegradation of Secondary Organic Aerosol Material Quantified with a Quartz Crystal Microbalance , 2018 .

[2]  Matthew C. Dixon,et al.  Quartz crystal microbalance with dissipation monitoring: enabling real-time characterization of biological materials and their interactions. , 2008, Journal of biomolecular techniques : JBT.

[3]  Chih‐shun Lu,et al.  Investigation of film‐thickness determination by oscillating quartz resonators with large mass load , 1972 .

[4]  Andreas Ebner,et al.  Broadband 120 MHz Impedance Quartz Crystal Microbalance (QCM) with Calibrated Resistance and Quantitative Dissipation for Biosensing Measurements at Higher Harmonic Frequencies , 2016, Biosensors.

[5]  D. Buttry,et al.  Electrochemical applications of the quartz crystal microbalance , 1989 .

[6]  Antonio Arnau,et al.  A Review of Interface Electronic Systems for AT-cut Quartz Crystal Microbalance Applications in Liquids , 2008, Sensors.

[7]  Stephen J. Martin,et al.  Characterization of a quartz crystal microbalance with simultaneous mass and liquid loading , 1991 .

[8]  S. Swathirajan,et al.  Potential dependence of lead and silver underpotential coverages in acetonitrile using a piezoelectric crystal oscillator method , 1985 .

[9]  P. Parren,et al.  Weak Fragment Crystallizable (Fc) Domain Interactions Drive the Dynamic Assembly of IgG Oligomers upon Antigen Recognition. , 2019, ACS nano.

[10]  D. Aurbach,et al.  In Situ Porous Structure Characterization of Electrodes for Energy Storage and Conversion by EQCM-D: a Review , 2017 .

[11]  E. Gileadi,et al.  Response of the Electrochemical Quartz Crystal Microbalance for Gold Electrodes in the Double‐Layer Region , 1996 .

[12]  K. Itaya,et al.  In situ scanning tunneling microscopy of underpotential and bulk deposition of silver on gold (111) , 1995 .

[13]  K. Itaya,et al.  In situ scanning tunneling microscopy of underpotential deposition in aqueous solution III. Silver adlayers on Au(111) , 1992 .

[14]  D. Aurbach,et al.  In situ real-time gravimetric and viscoelastic probing of surface films formation on lithium batteries electrodes , 2017, Nature Communications.

[15]  A. Arnau,et al.  Thickness-shear mode quartz crystal resonators in viscoelastic fluid media , 2000 .

[16]  J. Gordon,et al.  The oscillation frequency of a quartz resonator in contact with liquid , 1985 .

[17]  D. Akin,et al.  Real-time detection of airborne viruses on a mass-sensitive device. , 2008, Applied physics letters.

[18]  José Fariña,et al.  Resolution in QCM Sensors for the Viscosity and Density of Liquids: Application to Lead Acid Batteries , 2012, Sensors.