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Analyzing the Properties of IrOx Derived Electrochemical Sensors.
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Analyzing the Properties of IrOx Derived Electrochemical Sensors Brandon JohnsonUniversity Of California, IrvineDepartment of Electrical Engineering and Computer ScienceMentor: Dr. Marc MadouUniversity Of California, IrvineChancellor's Professor Department of Mechanical and Aerospace Engineering
Electrochemistry Background How does electrochemical sensing work? Snoswell, David Robert Evan. The Influence of Surface Heterogeneity and Solution Composition on the Colloid Stability of SiO2 and TiO2 Dispersions, Australian Digital Thesis Program, 2003.
Why Are We Even Interested? • Glass pH electrodes have their short commings • Extremely fragile • Relatively slow response times • Short lifetime • Cannot be used in certain media • Alkaline • HF • Organic Solutions
Science Looks Into Metal Oxides • Various Metal Oxides tested • Sb2O3 • Widely used for acid based titrations or solutions containing HF. However potential drift makes this unsuitable for pH measurements. • Bi2O3 • Used in pH measurements for KOH • PtO2, IrO2, RuO2, OsO2, TaO5, RhO2, TiO2, SnO2 • IrO2 held the most promise Sheng Yao, Min Wang, and Marc Madou. A pH Electrode Based on Melt-Oxidized Iridium Oxide, Journal of The Electrochemical Society, 148 (4) H29-H36 (2001)
Methods of Creating IrOx • Electrochemical growth • Electrodeposition • Sputtered Coating • Thermal method • Printing Method • Lithium Carbonate (Li2CO3) melt bath
Initial Claims Regarding these IrOx Sensors • Extremely consistent Eo regardless of storage medium
Initial Claims Regarding these IrOx Sensors • Super fast response times
Initial Claims Regarding these IrOx Sensors • Consistent and stable readings across a variety of pH’s
Initial Claims Regarding these IrOx Sensors • Additionally these sensors claimed to be stable in 4M HCL or a 5M H2SO4 solution • Claimed to have excellent mechanical stability
The Problem • These results were not corroborated in industry for some time.
Initial Results Results in a buffer of pH 8
Initial Results Results in a buffer of pH 3
Initial Results Analysis of Nernstian Slope
Initial Results Analysis of Nernstian Slope
Initial Results • So far the slopes look good but the Eo has an almost 200mV deviation between the probes • The response times are extremely slow
Significance of the BSE Results • The IrOx was not uniform • Was there a polymer coating? • Was there damage done to the probe? • Was there some sort of residue from being in the pH buffer solution?
The Answer • The required break-in period • Conversion of the Li8IrO6 to an unknown structure • Additionally hydration plays a major role in the ability of the IrOx sensors to respond rapidly and correctly Chrisanti, Santi. A pH Electrode Based on Melt-Oxidized Iridium Oxide, A Thesis Presented in Partial Fulfillment of the Requirement for the Degree Master of Science in the Graduate School of The Ohio State University, 2003.
Results Example response time of a non-hydrated probe after the initial break-in period
Results Example response time of a hydrated probe after the initial break-in period
Results Extrapolated slopes of 4 hydrated probes, post break-in
Results Probe stability and response results across a variety of pH buffers
Results Response time for a pH jump from pH 2 to pH 5.5
Results Response time for a pH jump from pH 2 to pH 3.5
Results Response time for a standard glass bulb working electrode
Results Results from a test in H2S04
Results An interesting result regarding mechanical stability
Significance • Consistencies with original publications • Response times consistent with original publications • Stability in a wide range of pH buffers also confirmed • Discrepancies with original publications • Break-in period • Necessity of hydration • Possibly the stability in a H2S04 solution • Consistency of the Eo
Acknowledgements • Mentor: Dr. Marc Madou • Lab Team: Kelvin Cheung, Jim Zoval, Horacio Kido, Chunlie (Peggy) Wang, Rabih Zaouk, Benjamin Park, Francesc Jornet, and Kuosheng Ma • IM-SURE: Said Shokair, Jerry McMillan, Goran Matijasevic • National Science Foundation (NSF)