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Title: Novel electrochemical methods for acidity monitoring : theory, design and application
Author: Gao, Xiangming
ISNI:       0000 0004 7661 2476
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2019
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This thesis reports the design and development of novel voltammetric pH sensors for buffered, low-buffered and unbuffered media. pH sensors in stagnant and hydrodynamic environments were designed and developed for performing measurements using square wave voltammetry. Chapter 1 introduces the motivation of this project, the current development of electrochemical sensors, and the basic theory and techniques of electrochemistry concerned within the thesis. The existing development of carbon-based electrochemical sensors and the application of screen-printing technology in sensor fabrication are highlighted. Chapter 2 introduces the screen-printing technology and the fundamental methods of numerical simulation. In addition, reagents, equipment and software packages used in the thesis are listed in this chapter. In Chapter 3, a novel design of quinone derivative-based pH probes is presented for the application in stagnant weakly buffered media (< 1mM), based on previous studies of quinone compounds in buffered media. The results from the weakly buffered system is consistent with the results in buffered systems. To further extend the application of this design in unbuffered media, a numerical model of a pH-sensitive redox particle immobilised on an electrode was developed, which predicted that the accumulation of hydrogen ions near the electrode is the possible limiting factor for the performance of this design in unbuffered media. To develop a pH-monitoring technology for unbuffered media, Chapter 4 reports on the design, fabrication and testing of different electropolymerised-phenol derivative modified electrodes, which overcome the limitation of hydrogen ions accumulation. The results revealed that 2-(methylthio)phenol graphite resin electrodes have high accuracy (ca. 1% error) in unbuffered media, benchmarked by a commercial glass pH meter. This is the first detailed study on the v application of the economical and scalable technology in pH sensing in unbuffered environment. Chapter 5 presents a unique design of electrochemical pH sensors, free from the need to use a glass reference electrode. This design integrates a pH indicator and an internal reference electrode. Different designs of ferrocene screen-printed electrodes were tested as the internal reference electrode. The nafion-coated ferrocene screen-printed electrode showed stable peak potential in a wide pH range (pH 1 - 12) with good durability (stable in 500+ cycles of test). It was then cross connected with an alizarin electrode, forming the pH sensor free from a glass reference electrode. Chapter 6 describes novel designs of hydrodynamic pH sensors. The design of a microfluidic pH sensor modified by poly-sodium salicylate was firstly demonstrated. The sensor showed a Nernstian response in a wide pH range and, in hydrodynamic conditions, provided improved accuracy in unbuffered media compared to the stagnant state. For more convenient measurements, a novel rocking disc electrode was studied for pH sensing, modified with alizarin and poly-salicylic acid as pH indicators. The electrodes modified by both chemicals showed a Nernstian response in buffered media and the highest accuracy in unbuffered media was reached at 50 rpm.
Supervisor: Fisher, Adrian Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
Keywords: pH ; Screen Printing ; Electrochemistry ; Microfabrication ; Rocking Disc