Elod Lajos Gyenge


Relevant Thesis-Based Degree Programs

Affiliations to Research Centres, Institutes & Clusters


Graduate Student Supervision

Doctoral Student Supervision

Dissertations completed in 2010 or later are listed below. Please note that there is a 6-12 month delay to add the latest dissertations.

Bifunctional manganese oxide electrodes for reversible oxygen reduction/evolution reactions (2024)

Efforts to develop cost-efficient, non-precious metal electrodes for reversible oxygen reduction and evolution reactions (ORR/OER) face challenges due to slow kinetics and rapid degradation. To accelerate the development of rechargeable metal-air batteries and regenerative fuel cells, this thesis systematically advances the understanding of nanostructure influence on MnOx electrochemical behaviours and develops innovative approaches for enhancing their stability and activity, positioning the MnOₓ electrodes as promising and sustainable alternatives to precious metal-based electrodes for ORR/OER catalysis.First, this work studies the electrochemical behavior and ORR/OER activity of core-porous shell Mn/Mn₃O₄ nanoparticles in comparison with MnO₂. The core-shell MnOₓ demonstrates higher ORR/OER activities during cycling in O₂-saturated KOH, outperforming exclusive ORR catalysis (influence of potential range) or OER catalysis in a N₂-purged environment (effect of O₂ presence). The unique behaviour of core-shell MnOₓ is attributed to the charge transfer between the low-valent Mn core and the high-valent Mn₃O₄ shell, thereby regenerating Mn(III) active sites through comproportionation.Next, the optimization of gas diffusion electrode (GDE) preparation and conditioning is explored. HNO₃-pretreatment on polytetrafluoroethylene (PTFE)-coated carbon papers was found to reduce overpotentials and eliminate the influence of PTFE loading on voltammograms. The Vulcan XC-72 and graphene mixture showed improved durability by stabilizing Mn sites and restraining Mn₂ oxidation. Lastly, a set of activation protocols was designed to generate and stabilize highly active MnOₓ phases. After cyclic voltammetry conditioning, the MnOₓ/Vulcan/graphene electrode demonstrated extended galvanostatic cyclic stability and a smaller potential gap between the anodic and cathodic reactions.Finally, in-situ electrochemical metallic cation-incorporation on MnOₓ GDE is investigated. In comparison to electrodes prepared through the chronopotentiometry and chronoamperometry approaches, the Co-MnOₓ electrodes prepared using the potentiodynamic method exhibited a significant increase in ORR catalytic current for up to 4.5 times higher and 2.1 times higher at 0.75 VRHE, respectively. Among the explored metal cations, the Ni²⁺ incorporation showed the most significant improvement in terms of activity and cyclic stability. The Ni-MnOₓ GDE demonstrated excellent stability for over 120 cycles in O₂-saturated KOH without losing OER activity, surpassing the Pt/C-IrO₂ benchmark.

View record

Impacts of electrolyzer design, operation, and measurement on ammonia electrosynthesis in aqueous and non-aqueous media (2024)

Ammonia (NH₃) is critical to sustaining agriculture for the rapid growth of global population. This thesis focuses on NH₃ electrosynthesis via the electrochemical nitrogen reduction reaction (ENRR) and develops customized flow electrolyzers for aqueous and non-aqueous ENRR conditions. The ENRR performance with commercial or research electrocatalysts was firstly evaluated in aqueous media, but the prevalence of false positives from contaminated cell components masked the genuine ENRR assessment. Contributing to the observed false positives, NH₃ or ammonium (NH₄⁺) crossover through the separator was then investigated. Despite frequent appearances in the literature, Nafion as a cation-exchange membrane is incapable of completely separating NH₃/NH₄⁺ and acts as a possible source or sink of contamination. The behaviors of NH₃/NH₄⁺ that include crossover, volatilization, and adsorption in Nafion were systematically evaluated under a variety of electrolyte compositions, operation conditions, concentration gradients, and feed locations. Additionally, an anion-exchange membrane and microporous polypropylene separators were evaluated as alternatives to the Nafion separator. However, only the hydrophobic Celgard separator demonstrates satisfactory NH₃/NH₄⁺ separation at open-circuit conditions. Lastly, a three-compartment cell was used to evaluate the non-aqueous lithium-mediated ENRR performance of gas-diffusion electrodes with a carbon-based reaction layer: carbon-supported Pt, carbon black, and graphite. The ENRR results achieved in tetrahydrofuran-based electrolyte can generally achieve one-order of magnitude higher NH₄⁺ concentration than in aqueous media, thus avoiding false positives. The current density (−5 mA cm⁻²) and the EtOH concentration (0.5 vol%) were optimized with a current-cycling operation strategy using the C45 carbon black cathode. Replacing the Nafion binder with polyvinylidene difluoride further improves the LNRR performance to 3.11 ± 0.41 μmol h⁻¹ cm⁻² in NH₃ production rate and 5.0 ± 0.65% in Faradaic efficiency that are comparable to or exceeding previous literature reported results. Since Li plating causes exfoliation of the electrode, poor LNRR durability was observed at −5 mA cm⁻². However, reducing the current density to −3 mA cm⁻² achieves a stable operation for over 8 h owing to the balanced Li plating and dissolution rates that mitigates the reaction layer delamination.

View record

Topological carbon defects based catalysts for the electrochemical reduction of carbon dioxide and oxygen (2022)

Defect engineering is a promising strategy for tailoring the electronic structure and charge distribution of catalysts, which could achieve unexpected physical and chemical properties to enhance the catalytic activity and durability. Recently, defect engineering is widely used in the design of carbon-based catalysts for electrochemical reactions. However, most of the research involving carbon defects relates to the heteroatom defects. The concept of topological carbon defects has been proposed and investigated in oxygen reduction reaction (ORR), but the exploration of topological carbon defects is still in its infancy. The design of carbon materials with high density homogeneous topological carbon defects and their extended application in other key electrochemical reactions are still big challenges. In this thesis, an efficient NH3 thermal treatment strategy is proposed for thoroughly removing pyrrolic N and pyridinic N dopants from N-enriched porous carbon particles, to create high-density topological carbon defects in carbon frameworks. The as-prepared 3-dimensional topological defected porous carbon (DPC) particles are investigated by near-edge X-ray absorption fine structure measurements and local density of states analysis, and the defect formation mechanism is revealed by reactive molecular dynamics simulations. The resultant DPC is used as an electrocatalyst in electrochemical carbon dioxide reduction (ECR), yielding a superficial current density of -2.8 mA cm⁻² (-28 A m⁻²) with Faradaic efficiency of 95% for CO generation at 25 °C and 101 kPa in 0.1 M KHCO₃ aqueous solution. The role of the topological carbon defects is analyzed in ECR. Then the carbon-based material enriched with topological defects is selected to serve as a substrate material to investigate the heterojunction effect of Pt and topological carbon defects. Both experimental characterizations and theoretical simulations reveal that the strong Pt-defect interaction can modify the electronic structure and charge distribution on the interface of the catalyst. Different Pt-defect coupling catalysts are prepared and the influence of the topological carbon defects on Pt are analyzed. Pt supported on DPC (Pt-DPC) catalyst achieves a 55 mV positive shift of half-wave potential for ORR in O2 saturated 0.1 M HClO4 electrolyte compared with commercial Pt catalyst on graphitized carbon at 25 °C and 101 kPa.

View record

Electrocatalysts for voltage reversal tolerant anodes in proton exchange membrane fuel cells and CO2 reduction to formate (2020)

Catalyst durability in renewable energy systems (including CO₂ electroreduction and Hydrogen fuel cells) is vital to the overall lifetime of the systems. To protect hydrogen fuel cells during cell voltage reversal, oxygen evolution reaction (OER) catalysts (typically RuO₂ or IrO₂) are added to the anode of proton exchange membrane fuel cells (PEMFCs). In this thesis, the durability of these OER catalysts was investigated by measuring the mass changes of heat-treated IrOx powders (350, 450 and 550 °C) drop cast on an electrochemical quartz crystal microbalance (EQCM). IrOx catalysts showed difference in frequency response due to the differential uptake of water and formation of oxyhydroxide species during cyclic voltammetry (CV) experiments (1.2, 1.4 and 1.6 to 0.05 V vs. RHE) confirmed by XPS. Platinum on carbon catalyst (Pt/C) suffered from carbon corrosion during potential holds at 1.8 and 2.0 V. The addition of IrOx powders to Pt/C protected the layer against carbon corrosion creating a simulated reversal tolerant anode.Additionally, OER catalysts were ranked by OER activity and dissolved Ir³⁺ in the electrolyte after an ex situ accelerated stress test (AST) in a representative PEMFC anode environment. The ex situ results are compared with reversal times obtained in a single cell PEMFC subjected to anode accelerated stress test (AAST). Generally, catalysts with higher OER mass activity and Ir³⁺ dissolution had longer reversal times. Heat treatment of unsupported IrOx increased OER durability in the fuel cell anode environment.Catalyst instability strongly affects the viability of electroreduction of CO₂ (ERC) systems as well. To improve the durability and efficiency of ERC catalysts, five Bimetallic Sn-Pb catalyst compositions were electrodeposited (from fluoroborate or oxide media) on two carbon supports. Sn majority catalysts with 15 to 35% Pb generated stable faradaic efficiencies (FE) up to 95% during constant potential electrolysis whereas pure Sn experienced an extensive (up to 30%) decrease in FE. After electrolysis, XRD analysis showed a SnO₂ phase present on 35% Pb catalysts but not on pure Sn catalysts. It is proposed that the presence of Pb in Sn majority catalysts stabilized SnO₂ and enhanced faradaic efficiency durability during ERC.

View record

Novel microporous layers with improved interfacial characteristics for PEM fuel cells (2018)

High efficiencies and reduced greenhouse gas emissions promote proton exchange membrane fuel cells (PEMFCs) as a promising energy conversion technology. However, its widespread commercial application is hampered by certain cost, performance and durability limitations. The interface between the MPL (microporous layer) and the cathode CL (catalyst layer) plays an important role in a PEMFC’s overall performance, since it houses the reaction sites for the oxygen reduction reaction. The interface may furthermore significantly affect mass transport behavior, ohmic contributions and the hydration state of the membrane at different humidities. The main objective of the study was therefore to advance PEMFC research through the development of alternative MPLs offering dual-functional improvements: enhanced interfacial characteristics and improved operational flexibility via suitability for low cathode humidity applications. Alternative MPLs were evaluated based on extensive material characterization and single cell performance testing. Graphene was demonstrated to be a promising alternative. The material displays beneficial interfacial characteristics (a stacked planar morphology, superior conductivity, adhesive behaviour, and improved electrical connectivity with the CL) and furthermore results in improvements in the kinetic and ohmic polarization regions, compared to the conventional CB (carbon black) MPL. Although graphene MPLs also suffer from mass transport limitations, the problem can be addressed through the addition of CB. The addition increases the MPL’s water permeability, which helps to establish a balance between water removal (for the prevention of flooding) and water retention (for membrane hydration) at high and low RH (relative humidity). For graphene tested under one-dimensional control, this results in synergistic performance enhancements, showing a 30% and 80% increase in the maximum power density at 100% and 20% cathode RH. In addition to increased water permeability, other common effects resulting from the creation of CB composites (also observed for reduced graphene oxide and graphite) include decreased surface wettability and through-plane resistance. For the application to low loaded CCMs (0.1 mg cm-²), the potential to improve performance with graphene-based MPLs appears restricted by the catalyst loading itself. Nevertheless, graphene helps to improve performance preservation of low loaded CCMs at low humidity conditions, as also demonstrated for conventionally loaded CCMs (0.4 mg cm-²).

View record

Bifunctional oxygen reduction/evolution catalysts for rechargeable metal-air batteries and regenerative alkaline fuel cells (2017)

The electrocatalysis of oxygen reduction and evolution reactions (ORR and OER, respectively) on the same catalyst surface is among the long-standing challenges in electrochemistry with paramount significance for a variety of electrochemical systems including regenerative fuel cells and rechargeable metal-air batteries. Non-precious group metals (non-PGMs) and their oxides, such as manganese oxides, are the alternative cost-effective solutions for the next generation of high-performance bifunctional oxygen catalyst materials. Here, initial stage electrocatalytic activity and long-term durability of four non-PGM oxides and their combinations, i.e. MnO₂, perovskites (LaCoO₃ and LaNiO₃) and fluorite-type oxide (Nd₃IrO₇), were investigated for ORR and OER in alkaline media. The combination of structurally diverse oxides revealed synergistic catalytic effect by improved bifunctional activity compared to the individual oxide components. Next, the novel role of alkali-metal ion insertion and the mechanism involved for performance promotion of oxide catalysts were investigated. Potassium insertion in the oxide structures enhanced both ORR and OER performances, e.g. 110 and 75 mV decrease in the OER (5 mAcm-²) and ORR (-2 mAcm-²) overpotentials (in absolute values) of MnO₂-LaCoO₃, respectively, during galvanostatic polarization tests. In addition, the stability of K⁺ activated catalysts was improved compared to unactivated samples. Further, a factorial design study has been performed to find an active nanostructured manganese oxide for both ORR and OER, synthesized via a surfactant-assisted anodic electrodeposition method. Two-hour-long galvanostatic polarization at 5 mAcm-² showed the lowest OER degradation rate of 5 mVh-¹ for the electrodeposited MnOx with 270 mV lower OER overpotential compared to the commercial γ-MnO₂ electrode. Lastly, the effect of carbon addition to the catalyst layer, e.g. Vulcan XC-72, carbon nanotubes and graphene-based materials, was examined on the ORR/OER bifunctional activity and durability of MnO₂ LaCoO₃. The highest ORR and OER mass activities of -6.7 and 15.5 Ag-¹ at 850 and 1650 mVRHE, respectively, were achieved for MnO₂-LaCoO₃-multi_walled_carbon_nanotube-graphene, outperforming a commercial Pt electrode. The factors affecting the durability of mixed-oxide catalysts were discussed, mainly attributing the performance degradation to Mn valence changes during ORR/OER. A wide range of surface analyses were employed to support the presented electrochemical results as well as the proposed mechanisms.

View record

Hydrogen peroxide electrosynthesis in solid polymer electrolyte (spe) reactors with and without power co-generation (2017)

For applications that require small amounts of H₂O₂ or have economically difficult transportation means, an alternate, on-site H₂O₂ production method to the current industrial anthraquinone auto-oxidation process is needed. Thus far neutral production of H₂O₂ has been limited to bench-top laboratory scaled research with low yield of H₂O₂ [1]. To produce neutral H₂O₂ on-site and on-demand for drinking water purification, the electroreduction of oxygen at the cathode of a solid polymer electrolyte (SPE) cell could be a possible solution. The work presented here has utilized a SPE cell operating in either fuel cell mode (power generating) or electrolysis mode (power consuming) to produce H₂O₂. The SPE cell reactor is operated with a continuous flow of cathode carrier water flowing through the cathode to remove the product H₂O₂. Two catalysts were chosen for further study in this work, one is the inorganic cobalt-carbon composite catalyst, to be used in both fuel cell mode and electrolysis mode operation. The other is the riboflavin-anthraquinone-carbon composite catalyst, to be used in only the electrolysis mode operation. Through parametric experiments in both modes of operation, the Co-C catalyst was able to achieve peroxide production rate of ~200 μmol hr-¹ cm-² and 4 mW cm-² operating at a cell temperature of 60°C with a current density of 30 mA cm-² and 30% current efficiency in fuel cell mode operation. Long term recycle experiments over a period of 72 hours showed an accumulated H2O2 concentration of over 1400 ppm. Investigation of both catalysts in electrolysis mode operation showed that the AQ-C catalyst achieved maximum H₂O₂ production of 580 μmol hr-¹ cm-² operating at 40°C and a current density of 240 mA cm-² with an 8% current efficiency; while the Co-C catalyst had a maximum H₂O₂ production rate of 360 μmol hr-¹ cm-² operated at 240 mA cm-² with 8% current efficiency. Long term recycle study of both catalysts in electrolysis mode generated maximum H₂O₂ concentrations of over 3000 ppm in 72 hours. Water sample analysis showed no degradation of the catalysts in either mode of operation.

View record

Adsorption of a carboxylated silane on gold : characterization and application to PDMS-based electrochemical cells (2016)

Integrated sensing and biosensing microfluidic systems often require sealing between polydimethylsiloxane (PDMS), glass, and gold interfaces. Studying substances that can self-organize onto glass and gold surfaces may achieve these goals and pave the way for new technological advances. Work presented in this thesis focuses on characterizing the adsorption of N-[(3-trimethoxysilyl)propyl]ethylene-diamine triacetic acid (or TMS-EDTA) on Au and applying this knowledge to construct leak-free PDMS-based electrochemical cells. First, surface analysis of TMS-EDTA-modified Au surfaces was conducted using various techniques. Water contact angle measurements and X-ray photoelectron spectroscopy confirm that the carboxylated silane can chemically modify Au surfaces. Atomic force microscopy studies indicate that a uniform surface coverage with monolayer thickness is formed. Infrared spectroscopy studies indicate that there is little evidence of siloxane cross-linking. Surface plasmon resonance results suggest that the carboxylates on TMS-EDTA-modified Au are available for streptavidin immobilization. Second, electrochemistry was used to determine the Gibbs free energies of adsorption of TMS-EDTA on Au under aqueous conditions. Electrochemical differential capacitance measurements reveal that the potential-dependent free energies of adsorption are ∼ - 20 to - 30 kJ/mol (for potentials between - 0.5 and 0.2 V) in the complex electrolyte solution used. Furthermore, at highly negative potentials ( ∼ - 1.1 V), TMS-EDTA adsorbs minimally onto the Au surface. Third, PDMS surfaces were functionalized to present primary amino groups, and glass or gold slides were functionalized to present carboxyl groups. Strong bonding was achieved by bringing the two surfaces in contact and reacting at room temperature. Shear tests reveal that the novel carboxyl-amine bonding strategy achieved a comparable bond strength as the conventional methods. Subsequently, TMS-EDTA was applied to construct leak-free PDMS-based electrochemical cells. Pressure leak tests were conducted to provide a more realistic measure of the bond strengths under aqueous conditions. A method to electrochemically remove the adsorbed TMS-EDTA layer off of the Au electrode, while maintaining the sealed cell chamber, was also developed. The characterization studies and fabrication strategy presented have led to the development of leak-free PDMS-based electrochemical devices that are suitable for sensing and biosensing applications.

View record

Development and characterization of activated biochar as electrode material for capacitive deionization (2016)

Biochar, a by-product of biomass pyrolysis, was investigated as a carbon-based electrode material for a water treatment method based on electrostatic adsorption/desorption of ions in electric double layers (EDLs) formed on the charged electrodes (capacitive deionization, CDI). Surface area, porous structure, and functional groups of biochar were developed, and corresponding effects on EDL capacitive performance were studied. A novel method was explored to tailor the micro- and meso-porous structures of activated biochar by exploiting the interaction between pre-carbonization drying conditions and carbonization temperature (475–1000 C) in a thermo-chemical process (KOH chemical activation). The mechanism of porosity development was investigated; results suggest that the conversion of KOH to K₂CO₃ under different drying conditions has a major role in tailoring the structure. The resultant surface area, micro- and meso-pore volumes were: 488–2670 m² g-¹, 0.04–0.72 cm³ g-¹, and 0.05–1.70 cm³ g-¹, respectively. Tailored biochar samples were investigated using physico-chemical surface characterization and electrochemical methods. For electrochemical testing, activated biochar was sprayed onto Ni mesh current collectors using Nafion® as binder. The majorly microporous activated biochar showed promising capacitances between 220 and 245 F g-¹ when 0.1 mol L-¹ NaCl/NaOH was used as the electrolyte. Addition of mesoporous structure resulted in significantly reduced electrode resistance (up to 80%) and improved capacitive behaviour due to enhanced ion transport within the pores. CDI of NaCl and ZnCl₂ solutions was investigated in a batch-mode unit through the use of tailored biochar electrodes. For NaCl removal, all samples showed promising capacity (up to 5.13 mg NaCl g-¹) and durability through four consecutive cycles. In contrast, in the case of ZnCl₂, the microporous sample showed a considerable drop in removal capacity (>75%) from cycle 1 to 4, whereas the combined micro- and mesoporous sample exhibited relatively small electrosorption capacity. Interestingly, the sample with mostly mesoporous structure has shown the highest removal capacity (1.15 mg ZnCl₂ g-¹) and durability for Zn²⁺ removal. These results emphasize the importance of tailoring the porous structure of biochar as a function of the specific size of adsorbate ions to improve the CDI performance.

View record

High-yield production of graphene sheets by graphite electro-exfoliation for application in electrochemical power sources (2016)

This thesis first aims at developing an electrochemical approach for low temperature, simple, and cost-effective synthesis of graphene microsheets (GNs) using graphitic electrodes in ionic liquid (IL) medium. The second major focus involves the products application as cathode-modifying microporous layers (MPLs) in proton exchange membrane fuel cells (PEMFCs) as well as anode-modifying materials in microbial fuel cells (MFCs). For the electrochemical exfoliation, a novel IL/acetonitrile electrolyte is introduced, and investigated with low concentration of ionic liquids. Using iso-molded graphite rod as the anode, up to 86% of exfoliation was achieved with the majority of the products as graphene flakes in addition to smaller quantities of carbonaceous particles and rolled sheets. Moreover, the simultaneous anodic and cathodic GN production was developed here with a synergistic exfoliation effect. When graphitic anode and cathode were subjected to a constant cell potential, up to 3 times higher exfoliation yields were generated compared to single-electrode studies on each side (~6-fold improvement in total). Thorough materials characterization confirmed the production of ultrathin GNs (
View record

Development of a swiss-roll mixed-reactant fuel cell (2014)

Capital and operating costs of fuel cell systems must be reduced before they can be competitive with conventional energy conversion technologies. This dissertation concerns the development of an unconventional fuel cell aimed at meeting that challenge.Presented here, for the first time, is a novel cylindrical Swiss-roll mixed-reactant fuel cell (SR-MRFC) that eliminates expensive and failure-prone components of conventional fuel cells. The proof-of-concept of the SR-MRFC was performed both in monopolar and bipolar architectures. In the monopolar case 3D anodes with platinum or with osmium catalysts were coupled to a gas-diffusion MnO₂ cathode in a 20×10-⁴ m² single-cell SR-MRFC, operated with a two-phase mixture of 1 M NaBH₄/2M NaOH(aq) + O₂(g). Instead of a Nafion® membrane, a porous diaphragm was employed. At 323 K, 105 kPa(abs), the peak superficial power densities of the SR-MRFC with the platinum and osmium anode catalysts were up to respectively 2230 and 1880 W m−² with good performance stability during 3 hr continuous operation. These values are the highest power densities ever reported for MRFCs operating under similar conditions and match the highest reported values for conventional dual chamber PEM direct borohydride fuel cells. Scale up of the single-cell SR-MRFC to 100×10-⁴ m² and 200×10-⁴ m² gave corresponding peak superficial power densities of 900 and 700 W m-², while the 20×10-4 m² bipolar reactors produced peak volumetric power densities of 267 and 205 kW m-³.This work also explored the feasibility of electroreduction of N₂O on Pt and Pd in the cathode of a MRFC to generate electricity from N₂O in the tail gases of industrial processes. Here the SR-MRFC was operated using two-phase fuel + oxidant mixtures of 1 M NaBH₄ / 2M NaOH(aq) + N₂O(g) and 0.5 M CH₃OH/2 M NaOH(aq) + N₂O(g). At 323 K, 105 kPa(abs) the peak superficial power densities for the mixed NaBH₄- and MeOH-N₂O systems were respectively 340 W m-² (Pt anode/Pd cathode) and 38 W m-² (PtRu anode/Pd cathode). This work demonstrates for the first time that co-generation of electricity and abatement of N₂O may potentially compete with thermochemical processes of N₂O capture currently under development.

View record

Development of the Direct Borohydride Fuel Cell Anode (2012)

Direct borohydride fuel cells (DBFC) are a promising technology for meeting increasing energy demands of portable electronic applications. The objective of this dissertation was to contribute to the understanding of borohydride (BH₄⁻) electro-oxidation and the development of the DBFC anode; a component which can influence both the performance and cost of a DBFC system. The first part of the investigation involves the elucidation of the BH₄⁻ electro-oxidation mechanism on Pt. The BH₄⁻ electro-oxidation mechanism was studied by correlating the results obtained by the electrochemical quartz crystal microbalance technique (EQCM) and the rotating disk electrode technique (RDE) with density functional theory (DFT) calculations from the literature. It was found that BH₄⁻ electro-oxidation on Pt resulted in the adsorption of reaction intermediates, such as BH₂OHad and BOHad, which required high oxidizing potentials to desorb/ oxidize from the catalyst surface. It was also found that the BH₄⁻ oxidation mechanisms (Langmuir – Hinshelwood versus Eley - Rideal) were dictated by the availability of Pt-sites and the competitive adsorption of OH⁻ and BH₄⁻.The second part involves an investigation of the performance of three different carbon black supported anode catalysts: Pt, PtRu, and Os, with a focus on Os catalysts. Fundamental electrochemical methods combined with fuel cell experiments revealed that osmium nanoparticles are kinetically superior and stable catalysts for BH₄⁻ electro-oxidation compared to Pt and PtRu. It was also found that supported Os electrocatalysts appear to favour the direct oxidation of BH₄⁻ in comparison to Pt, and PtRu electrocatalysts. The final section of this dissertation focuses on the effect of electrocatalyst support and anode design on the performance of the DBFC anode. It was found that the Vulcan® XC-72 supported catalyst alleviated mass transfer related problems associated with hydrogen generation from BH₄⁻ hydrolysis. The most significant improvement was obtained when using the graphite substrate supported catalysts (three-dimensional anodes). Fuel cell studies revealed power densities of 103 mW cm⁻² to 130 mW cm⁻² achieved by 1.7 mg cm⁻² Os and ~1 mg cm⁻² PtRu three-dimensional electrodes respectively at 333 K, using an O₂ oxidant at 4.4 atm (abs), and a 0.5 M NaBH₄ – 2 M NaOH anolyte composition.

View record

Colloidal Electrodeposition of Pt-Ru and Pd Nanostructures on Three-Dimensional Substrates: Application to Direct Methanol and Direct Formic Acid Fuel Cell Anodes (2009)

No abstract available.

Master's Student Supervision

Theses completed in 2010 or later are listed below. Please note that there is a 6-12 month delay to add the latest theses.

Selectivity determination of anodic electrocatalysts for seawater electrolysis (2024)

Hydrogen production from seawater electrolysis has the potential to revolutionize the green energy industry. However, it suffers from a multitude of issues, such as the salts and compounds in seawater damaging the catalysts and electrolyzer components. In particular, corrosive hypochlorite formed at the anode during seawater electrolysis from the chloride oxidation reaction competes with the preferred oxygen evolution reaction. The methods used in the field to determine a catalyst's selectivity for forming hypochlorite or oxygen can yield erroneously high oxygen selectivity because of the decay of hypochlorite. The stability of hypochlorite was examined in the presence of metal ions of commonly used anode electrocatalysts in seawater electrolysis. The metal ions, in particular Ru³⁺ and Ni²⁺, catalyze the decomposition of hypochlorite. Elevated temperatures, e.g., 40 ℃, also cause hypochlorite to decay rapidly. The rotating ring-disc electrode technique was used to characterize IrO₂, NiO, Co₃O₄, RuO₂, Pt/C and PtRu electrocatalysts in situ at near-neutral pH with linear scanning voltammetry, potentiostatic and galvanostatic experiments. Increasing chloride concentration decreases the selectivity for oxygen production, and increasing temperature increases the selectivity for oxygen production. Bubbles formed during the formation of oxygen decrease the selectivity for oxygen production as hypochlorite formation preferentially occurs on the bare catalyst, and increasing chloride concentration decreases the selectivity for oxygen evolution reaction (OER). PtRu is discovered as a promising anode electrocatalyst for seawater electrolysis with excellent selectivity in the presence of chloride; increasing chloride concentration from 0.1 to 1 M caused a threefold increase in the OER current density on PtRu.

View record

A comparative study of the ferric-ferrous and potentiostatic dissolution of chalcopyrite using scanning electrochemical microscopy and surface wetting analysis (2023)

The current work investigates the dissolution of chalcopyrite (CuFeS₂) under two different leaching scenarios using scanning electrochemical microscopy (SECM): (1) leaching in the presence of ferric-ferrous ions (“ferric leaching”) and (2) leaching by the application of a potential without ferric-ferrous ions (“potentiostatic leaching”). Ferric leaching processes have reported a solid elemental sulfur product layer that impedes chalcopyrite dissolution. However, potentiostatic leaching tests have reported a copper sulfide layer as the product that forms during dissolution in the absence of ferric-ferrous.In this work, we used the SECM in two ways: (1) to detect the species released during dissolution in the two scenarios using tip CVs and (2) map the conductivity of the surface under the different conditions. Four ferric-ferrous molar ratios in sulfuric acid solution were used in the ferric leaching scenario: 1:1, 10:1, 100:1 and 1000:1, and the chalcopyrite mixed potentials from these tests were applied to a separate sample potentiostatically in pure sulfuric acid. The tip CVs identified Cu²⁺ and Fe²⁺ released in both leaching scenarios. However, in the potentiostatic leaching case, a CuS product was determined to form at the tip, which was not observed in the ferric leaching case. Diagnostic tests determined that the CuS formed from a copper-thiosulfate complex, with the thiosulfate ion being the intermediate soluble sulfur species released during chalcopyrite dissolution. Once, the CuS-type layer forms on chalcopyrite, in the presence of ferric, it is further oxidized to form a sulfur-rich copper-deficient layer.Contact angle measurements show that the chalcopyrite surfaces produced during ferric leaching are relatively more hydrophobic compared to the potentiostatically leached samples. This is because the sulfur-rich layer in the ferric leaching scenarios is hydrophobic in nature. CuS, from the potentiostatic case, has more holes than electrons and is perceived to have a net positive charge on its surface. These holes attract the water dipole with the negatively charged end oriented toward the surface to flatten the droplet, yielding a lower contact angle and enhancing hydrophilicity. These results support the understanding that mechanistic outcomes from amperometric techniques cannot ultimately be used to explain the results from industrial ferric leaching processes.

View record

Cathode development for all-solid-state lithium sulfur batteries (2023)

EV production is currently dominated by lithium-ion technology; however, precious metal scarcity and price increases have pushed for alternative chemistries to be researched. Presently, the research of lithium metal-based batteries has increased having higher energy densities than traditional lithium-ion batteries (LIBs). The use of sulfur as the active cathode material has gained attention due to the high gravimetric capacity of sulfur (1672 mA h gˉ¹) and its abundance in the Earth’s crust. One of the biggest obstacles solid state lithium sulfur batteries faces, is the utilization and accessibility of sulfur during cycling. Due to sulfur’s low electrical (10ˉ³ S cmˉ¹) and ionic conductivity (10ˉ⁹ S cmˉ¹), Li+ and electron transport is limited, and over time hinders the cell’s capacity. Furthermore, a volumetric change during cycling are observed which pose concerns to the mechanical integrity of the cathode. Carbon supports as well as additives have been explored to promote transport, aid during volume changes, and maximize active material utilization during cycling. This study aimed to evaluate how the deposition method of sulfur onto reduced graphene oxide (rGO), as the carbon support, changed the electrochemical performance of the active material. The examined methods of sulfur deposition include an acetone method as solvent infiltration, sulfur-ethylene diamine (S-EDA) complex as reaction deposition, as well as dry ball milling (DBM) method as mechanical intrusion. The influence of heat treatment and sulfur content was also analyzed to gain insights towards the morphological and electrochemical changes of the cathode. The variation of sulfur deposition methods yielded different electrochemical results proving the synthesis method chosen can alter the arrangement and connection of sulfur on rGO. The incorporation of heat treatment above sulfur’s melting temperature after each synthesis method helped increase the dispersion of sulfur on rGO and minimized crystalline agglomerates. The Acetone method showed minimal losses during synthesis and had a high discharge current density of -0.150 mA cmˉ². Increasing the sulfur content deposited on rGO also showed to have a negative effect on the electrochemical performance of rGO with 40% sulfur deposited on rGO showing the highest initial discharge capacity at 1270 mAh gˉ¹.

View record

Electrode design for reversible CO₂ reduction and formate oxidation (2023)

Scalable carbon dioxide (CO₂) utilization solutions are urgently needed as a result of the continual rise in atmospheric CO₂ concentration brought on by the extensive usage of fossil fuels. To address these issues, the emerging field of electrochemical technologies offers promising solutions for scalable CO₂ utilization. This thesis investigates the design of high-performance bifunctional electrocatalysts for the CO₂ reduction reaction to formate, and formate oxidation reaction in a CO₂ redox flow battery (CRB), in a goal to reduce CO₂ emissions while simultaneously storing renewable energy.A CO₂/formate redox pair at the negative electrode is employed in the CRB. Herein, molecular approaches to heterogenous catalysis are explored for improving the performance of PdSnO₂-based bifunctional catalysts by incorporating polyethyleneimine (PEI) groups to the catalyst layer to increase CO₂ adsorption, stabilize key reaction intermediates, and improve intrinsic catalytic properties. Experimental tests on a variety of electrochemical cells show that PEI-incorporated PdSnO₂ catalysts show superior electrochemical performance compared to pristine PdSnO₂ catalysts. In preliminary batch cell tests, PEI modified catalysts show an increase in formate faradaic efficiency during charge by up to 60% at a 20 mA/cm² current density and increases in peak power densities during battery discharge by 15%. Additionally, under flow cell conditions, the incorporation of PEI to bare PdSnO₂ also shows enhanced discharge power densities and much improved stabilities.The catalytic performance is also further examined in relation to PEI loading, current density, and CO₂ flow rate. Surface characterization techniques including SEM, XPS, XRD and contact angle analysis were performed on several as-prepared and electro-reduced catalytic samples. XPS confirmed the addition of PEI groups in the catalytic layers. It was found that while PEI modification can improve several catalytic properties, it can exacerbate challenges such as flooding and salt precipitation on the electrode surface, especially under flow cell conditions. Despite these difficulties, the bifunctional performance of PdSnO₂ catalysts can be enhanced with PEI modifications and shows good prospects for sustainable energy storage, CO₂ utilization, and mitigating climate change impacts. 

View record

Development of scanning electrochemical microscopy for product selective screening of catalysts for carbon dioxide electroreduction to formate (2021)

The current work deals with the development of scanning electrochemical microscopy (SECM) as a product selective catalyst screening tool for CO₂ electroreduction to formate reaction (CO2RF) in aqueous media. CO2RF is a proposed route for utilizing CO₂ and surplus electrical energy produced by intermittent renewable sources. In CO2RF devices, CO₂ is electrochemically converted to formic acid or to a solution of formate ions. The resulting product can be either sold on the market, used for H₂ storage, or oxidized back to CO₂ to recover the electricity in direct liquid fuel cells. Our goal is to develop SECM for the simultaneous characterization of multiple CO₂ electroreduction (CO2RR) catalysts, probing their electrocatalytic activity in a product selective manner. To illustrate our method, we studied tin oxide-based catalyst, one of the most promising CO2RF catalyst. We submitted these catalysts to an electroreduction pre-treatment at −1.25 and −3 VAg/AgCl, respectively yielding a smooth oxide rich surface and an oxide poor surface covered in nanoparticles (30 to 70 nm diameter). The creation of spherical nanoparticles by electroreduction of tin oxide at −3 VAg/AgCl in an aqueous carbonate solution has, to our knowledge, never been reported. These two pre-treated catalysts, in conjunction with the un-pretreated surface, were simultaneously characterized by SECM, determining their CO2RF electrocatalytic activity relative to each other. The cyclic voltammetry (CV) tip detection mode provided product selective activity data for three different reaction products: formate, CO and H₂. We demonstrated that pre-electroreduction at −1.25 VAg/AgCl formed a surface with improved selectivity toward CO2RF. We also discussed the effect of SECM experimental parameters on the success of CO2RR catalyst characterization, as well as the challenges and limitations of the method. Our development in SECM opens the door to automated screening of CO2RR catalyst, which dovetails with the recent advances in model-based computational catalyst screening. While high screening throughput can be achieved using these various theoretical methods, they depend on experimental catalyst characterization and screening to validate their models. By automating the slowest step of the process, the experimental bottleneck on catalyst screening can hopefully be alleviated.

View record

Lowering the energy consumption of zinc electrowinning by electrocatalysis of the oxygen evolution reaction using manganese oxides (2020)

Zinc is employed in a wide range of commercial applications including galvanizing iron and steel and production of various metal alloys. In hydrometallurgical processes, zinc electrowinning from sulfate-based electrolytes is the last step of zinc extraction in which high purity metallic zinc is electrodeposited from a highly acidic solution on an aluminum cathode. The electrowinning stage is very energy-intensive and responsible for approximately 60% of the power requirement of a zinc refinery. Inside the electrowinning cell, oxygen evolution reaction (OER) overpotential on conventional lead-silver (Pb-Ag) anodes contributes to nearly 25% of the overall cell potential and places a heavy financial burden on zinc refining plants. Thus, improving the energy efficiency of electrowinning by lowering the OER overpotential is of primary significance to the zinc refineries.This study aimed to develop and evaluate novel anodes in order to lower the OER overpotential within the zinc electrowinning process. The novel anodes were prepared by electrodeposition of manganese oxides (MnOx) on industrially provided Pb-Ag substrate using various potentiodynamic and galvanostatic polarization techniques. The anodic electrocatalytic activity of the baseline and MnOx electrodeposited Pb-Ag electrodes was investigated in a manganese (II)-containing sulfuric acid electrolyte using linear scan voltammetry and 72-hour galvanostatic electrolysis at 500 amperes per meter squared current density. Additionally, the baseline and novel anodes were studied within the full-cell electrowinning setup by the means of 24-hour galvanostatic electrolysis at 500 amperes per meter squared current density. The electrolyte composition and operating conditions were selected such that to be directly applicable to the industrial zinc electrowinning process.The MnOx electrodeposited Pb-Ag anodes reduced the OER overpotential by a maximum of 155 and 113 mV in the absence and presence of chloride ions. Investigation of the novel electrodes in the full-cell zinc electrowinning operation corroborated the half-cell experiments, revealing a maximum of 133 mV reduction in overall cell potential. The surface morphology and elemental composition of the novel anodes were investigated using SEM/EDX, XRD, and ICP-OES. This work demonstrated that the MnOx electrodeposited Pb-Ag anodes reveal improved electrocatalytic activity and have great capacity to lower the energy consumption of the conventional zinc electrowinning process.

View record

Organic Redox Catalysts for Oxygen Electroreduction to Hydrogen Peroxide: An Application to Drinking Water Treatment (2012)

Conventional H₂O₂ production entails an energy and capital intensive Riedl-Pfleiderer process, which is advantageous based on the economy of scale, yet it generates large amounts of toxic waste. The electrochemical synthesis of H₂O₂ can potentially emerge in small and remote applications, where the transportation and handling of concentrated H₂O₂ can be avoided. The commercial Dow-Huron electrolysis cell has shown some success in the pulp and paper industry. However, its highly caustic product (pH > 13) may limit its wide-spread application. Electrocatalytically, the two electron reduction of O₂ in near neutral or acidic media has proven challenging. In addition to cobalt macrocycle-based catalysts, quinone-based redox catalysts have also been successfully demonstrated as viable electrocatalysts. The present work reports the synthesis of a novel riboflavinyl-anthraquinone (RF-AQ) compound which showed redox catalytic activity for O₂ reduction to H₂O₂. Cyclic voltammetry with a rotating ring-disk electrode assembly was employed to characterize the catalyst. Chromoamperommetry experiments in a batch electrolysis cell were performed, using 0.5 M H₂SO₄ saturated with O₂, up to 24 hours at 21°C and 1barabs to demonstrate the longer term H₂O₂ synthesis. Modifications of the Vulcan XC72 by RF-AQ adsorption increased the onset potential of the O₂ reduction reaction by up to 50 mV compared to Vulcan XC72 alone. A H₂O₂ selectivity of up to 85 ± 5% was observed for the RF-AQ catalyst. Chronoamperommetry, via constant potential control at 0.1V vs. RHE, with the 10 wt% RF-AQ catalyst (composite loading of 2.5 mg cm⁻²) generated H₂O₂ with an initial rate (in two hours) of 21 µmol hr⁻¹ cm⁻² (normalized by the electrode geometric area) and accumulated up to 425 µmol cm⁻² (normalized by the electrode area) in 24 hours with a current density of about 1.3 mA cm⁻² at 70 ± 5% current efficiency. While the unmodified Vulcan XC72, with a similar catalyst weight loading and the same cathode potential, generated H₂O₂ with an initial rate of 6 µmol hr⁻¹ cm⁻² (normalized by electrode area) and accumulated only up to 140 µmol cm⁻² (normalized by electrode area) in 24 hours with a current density of about 0.55 mA cm⁻² at 55 ± 5% current efficiency.

View record

Anode catalyst layer engineering for the direct formic acid fuel cell (2011)

Direct formic acid fuel cells (DFAFC) are promising alternatives to hydrogen proton exchange membrane fuel cells for microelectronic applications. Compared to direct methanol fuel cell (DMFC), the main advantages of direct formic acid fuel cell (DFAFC) are higher theoretical open circuit voltage (1.45 V at 298 K), lower fuel cross over towards cathode and reasonable power densities at room temperature that make DFAFCs a viable alternative for micropower applications. The operation of DFAFCs on Pd-based catalysts at ambient temperature showed lower fuel permeation from anode to cathode that resulted in better fuel utilization when running on high formic acid concentrations (~10M). However, Pd suffers an unacceptable loss of performance with time that decreases the cell power density by about 50% in a few hours. The aim of the present work is to create an extended reaction zone anode structure to improve the utilization of the catalyst and to modify the electrode surface characteristics in order to reduce performance losses. The novel catalyst deposition technique involved electroless (chemical) deposition of Pd particles directly onto the carbon paper substrate (AvCarbTM P50) in the presence of Nafion® solution. It was found that the use of 4.66 g L⁻¹ of pure Nafion® as an additive to the electroless bath and Shipley pre-treatment resulted in 1.6 mg cm⁻² and 0.07 mg cm⁻² Pd and Sn mass loadings respectively with Pd average particle size of 0.45 to 0.55 μm. When pre-treating in nitric acid solution, the surface coverage was found to be uniform with dense particulate-like structure. The surface nitric acid pre-treatment method in conjunction with 2.46 g L⁻¹ Nafion® additive in the electroless solution were resulted in 4.5 mg cm⁻² Pd mass loading on AvCarbTM P50 and enhanced electrochemical performance at current densities larger than 500 A m⁻² at 333 K . Comparing the Pd/C and PdSn/C performances in DFAFC tests, the Pd/C anode with higher Pd mass loading (4.5 mg cm⁻²) and OCV stayed fairly stable on ~ 0.55 V up to 3.5 hours of constant current draw(100 A m⁻² at 333 K).

View record

Characterization of structural degradation in a polymer electrolyte membrane fuel cell cathode catalyst layer (2010)

This study investigated the structural degradation of a polymer electrolyte membrane fuel cell (PEMFC) due to carbon corrosion and ionomer degradation. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and polarization analyses were completed to characterize and correlate the structural degradation to the performance. Accelerated stress tests (AST) were used to produce the different known degradation mechanisms. Both failure mechanisms had unique fingerprints on the performance degradation. The carbon corrosion results showed a clear thinning of the cathode catalyst layer (CCL) and gas diffusion carbon sub-layer, and a reduction in the effective platinum surface area caused by the carbon support oxidation. The degradation of the CCL and carbon sub-layer altered the water management, as evidenced by an increase of the voltage losses associated with oxygen mass transport and CL ohmic resistance. The ionomer degradation AST showed that greater ionomer in the CCL resulted in greater platinum content in the membrane and a higher fluoride washout rate, suggesting the higher ionomer content facilitated the mass transfer of contaminants (such as dissolved platinum and iron) into the membrane. It is proposed that H2O2 was produced at the anode, diffused into the membrane, and decomposed at the platinum and/or iron sites bound in the membrane structure. The decomposition products attacked the ionomer both in the bulk phase and CCL causing: i) membrane thinning which exacerbated H2 crossover, ii) lower membrane conductivity, and iii) CL structure degradation, resulting in increased reaction penetration into the CL and decreased effective oxygen diffusivity due to changes in CL water content. A method using an electrochemical quartz microbalance (EQCM) was investigated to further evaluate ionomer degradation. Mimicking the ionomer films in the CCL on the EQCM would enable a quantitative method to further evaluate the degradation reactions and overall mechanism. While this technique was not fully developed, background on the EQCM and the work to date is presented as a starting point for future development.

View record


If this is your researcher profile you can log in to the Faculty & Staff portal to update your details and provide recruitment preferences.


Learn about our faculties, research and more than 300 programs in our Graduate Viewbook!