Os eletrocatalisadores Pt/C e Pt-Terras Raras/C (terras raras = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Lu) foram preparados (20% em massa e razão atômica Pt-TR de 50:50) pelo método de redução por álcool, usando H2PtCl6.6H2O (Aldrich) e Terras Raras Cl3.xH2O (Aldrich) como fonte de metais, etileno glicol como solvente e agente redutor e, o carbono Vulcan XC72, como suporte. Os catalisadores foram caracterizados por espectroscopia de energia dispersiva de raios X (EDX), análises de difração de raios X (DRX) e microscopia de transmissão eletrônica (TEM). As análises por EDX mostraram que as razões atômicas dos diferentes eletrocatalisadores Pt-TR/C preparados foram similares às composições nominais de partida. Em todos os difratogramas, observa-se um pico largo em aproximadamente 2 = 25o o qual foi associado ao suporte de carbono Vulcan XC72 e quatro outros picos de difração em aproximadamente 2 = 40o, 47o, 67o e 82o os quais são associados aos planos (111), (200), (220) e (311), respectivamente, da estrutura cúbica de face centrada (CFC) de platina e suas ligas. Para os eletrocatalisadores Pt-TR/C também foram observadas fases nos difratogramas de raios X referentes aos óxidos de terras raras. Foram preparados eletrocatalisadores Pt-La/C com diferentes razões atômicas. Micrografias de transmissão eletrônica apresentaram uma razoável distribuição das partículas de Pt no suporte de carbono com algumas aglomerações, o que está de acordo com os resultados de difração de raios X. O desempenho para a oxidação de CO, metanol e etanol foi investigada através de voltametria cíclica, cronoamperometria e espectroscopia no infravermelho com transformada de Fourier. A atividade eletrocatalítica dos eletrocatalisadores Pt-TR/C, em especial PtLa/C, foram maiores que do Pt/C. A investigação por espectroscopia no infravermelho com transformada de Fourier para a oxidação de etanol com os eletrocatalisadores PtLa/C mostrou que o acetoaldeído e o ácido acético foram os principais produtos formados. O eletrocatalisador PtLa/C (30:70) apresentou melhores resultados para a reação de redução de oxigênio, oxidação de metanol e etanol, e a temperaturas superiores a 30°C para oxidação de monóxido de carbono. / PREPARATION AND CHARACTERIZATION OF PT-RARE EARTH/C ELECTROCATALYSTS FOR PEM FUEL CELLS

L’objectif principal de ce travail de thèse était d’évaluer les propriétés électro catalytiques de différents composés moléculaires vis-à-vis de la réduction électrochimique basse température du dioxyde de carbone, en vue d’applications dans des cellules d’électrolyse à électrolyte polymère solide. Après avoir mesuré les performances de métaux modèles (cuivre et nickel) servant de référence, nous avons testé les performances de quelques composés moléculaires à base de nickel. Le rôle catalytique de ces différents composés a été mis en évidence en mesurant les courbes intensité-potentiel dans différents milieux. Nous avons évalué l’importance de la source en hydrogène dans le mécanisme réactionnel. Les produits de réduction du dioxyde de carbone formés dans le mélange réactionnel ont été analysés par chromatographie en phase gazeuse. Nous avons ensuite abordé la possibilité de développer des cellules d’électrolyse à électrolyte polymère solide. Nous avons testé des cellules utilisant soit des anodes à eau liquide pour le dégagement d’oxygène, soit des anodes à hydrogène gazeux. L’utilisation de complexes moléculaires à base de nickel à la cathode a permis d’abaisser le potentiel de la cathode et de réduire le CO₂ mais la réaction de dégagement d’hydrogène reste prédominante. / The main objective of this research work was to put into evidence the electrocatalytic activity of various molecular compounds with regard to the electrochemical reduction of carbon dioxide, at low temperature, in view of potential application in PEM cells. First, reference values have been measured on copper and nickel metals. Then the performances of some molecular compounds have been measured. The electrochemical activity of these different compounds has been put into evidence by recording the current-potential relationships in various media. The role of a hydrogen source for the reduction processes has been evaluated. The formation of reduction products has been put into evidence and analyzed by gas phase chromatography. Then, a PEM cell has been developed and preliminary tests have been performed. PEM cells with either an oxygen-evolving anode or a hydrogen-consuming anode have been tested. Using nickel molecular complexes, it has been possible to lower the potential of the cathode and to reduce CO₂ but the parasite hydrogen evolution reaction was found to remain predominant.

Os eletrocatalisadores Pt/C e Pt-Terras Raras/C (terras raras = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, and Lu) foram preparados (20% em massa e razão atômica Pt-TR de 50:50) pelo método de redução por álcool, usando H2PtCl6.6H2O (Aldrich) e Terras Raras Cl3.xH2O (Aldrich) como fonte de metais, etileno glicol como solvente e agente redutor e, o carbono Vulcan XC72, como suporte. Os catalisadores foram caracterizados por espectroscopia de energia dispersiva de raios X (EDX), análises de difração de raios X (DRX) e microscopia de transmissão eletrônica (TEM). As análises por EDX mostraram que as razões atômicas dos diferentes eletrocatalisadores Pt-TR/C preparados foram similares às composições nominais de partida. Em todos os difratogramas, observa-se um pico largo em aproximadamente 2 = 25o o qual foi associado ao suporte de carbono Vulcan XC72 e quatro outros picos de difração em aproximadamente 2 = 40o, 47o, 67o e 82o os quais são associados aos planos (111), (200), (220) e (311), respectivamente, da estrutura cúbica de face centrada (CFC) de platina e suas ligas. Para os eletrocatalisadores Pt-TR/C também foram observadas fases nos difratogramas de raios X referentes aos óxidos de terras raras. Foram preparados eletrocatalisadores Pt-La/C com diferentes razões atômicas. Micrografias de transmissão eletrônica apresentaram uma razoável distribuição das partículas de Pt no suporte de carbono com algumas aglomerações, o que está de acordo com os resultados de difração de raios X. O desempenho para a oxidação de CO, metanol e etanol foi investigada através de voltametria cíclica, cronoamperometria e espectroscopia no infravermelho com transformada de Fourier. A atividade eletrocatalítica dos eletrocatalisadores Pt-TR/C, em especial PtLa/C, foram maiores que do Pt/C. A investigação por espectroscopia no infravermelho com transformada de Fourier para a oxidação de etanol com os eletrocatalisadores PtLa/C mostrou que o acetoaldeído e o ácido acético foram os principais produtos formados. O eletrocatalisador PtLa/C (30:70) apresentou melhores resultados para a reação de redução de oxigênio, oxidação de metanol e etanol, e a temperaturas superiores a 30°C para oxidação de monóxido de carbono. / PREPARATION AND CHARACTERIZATION OF PT-RARE EARTH/C ELECTROCATALYSTS FOR PEM FUEL CELLS

The greening of air transport is the driver for developing technologies to reduce the environmental impact of aviation with the aim of halving the amount of carbon dioxide (COଶ) emitted by air transport, cutting specific emissions of nitrogen oxides (NO୶) by 80% and halving perceived noise by the year 2020. Fuel Cells (FC) play an important role in the new power generation field as inherently clean, efficient and reliable source of power especially when comparing with the traditional fossil-fuel based technologies. The project investigates the feasibility of using an electric hybrid system consisting of a fuel cell and battery to power a small model aircraft (PiperCub J3). In order to meet the desired power requirements at different phases of flight efficiently, a simulation model of the complete system was first developed, consisting of a Proton Exchange Membrane hybrid fuel cell system, 6DoF aircraft model and neural network based controller. The system was then integrated in one simulation environment to run in real-time and finally was also tested in hardware-in-the-loop with real-time control. The control strategy developed is based on a neural network model identification technique; specifically Model Reference Control (MRC), since neural network is well suited to nonlinear systems. To meet the power demands at different phases of flight, the controller controls the battery current and rate of charging/discharging. Three case studies were used to validate and assess the performance of the hybrid system: battery fully charged (high SOC), worst case scenario and taking into account the external factors such as wind speeds and wind direction. In addition, the performance of the Artificial Neural Network Controller was compared to that of a Fuzzy Logic controller. In all cases the fuel cell act as the main power source for the PiperCub J3 aircraft. The tests were carried-out in both simulation and hardware-in-the-loop.

The greening of air transport is the driver for developing technologies to reduce the environmental impact of aviation with the aim of halving the amount of carbon dioxide (COଶ) emitted by air transport, cutting specific emissions of nitrogen oxides (NO୶) by 80% and halving perceived noise by the year 2020. Fuel Cells (FC) play an important role in the new power generation field as inherently clean, efficient and reliable source of power especially when comparing with the traditional fossil-fuel based technologies. The project investigates the feasibility of using an electric hybrid system consisting of a fuel cell and battery to power a small model aircraft (PiperCub J3). In order to meet the desired power requirements at different phases of flight efficiently, a simulation model of the complete system was first developed, consisting of a Proton Exchange Membrane hybrid fuel cell system, 6DoF aircraft model and neural network based controller. The system was then integrated in one simulation environment to run in real-time and finally was also tested in hardware-in-the-loop with real-time control. The control strategy developed is based on a neural network model identification technique; specifically Model Reference Control (MRC), since neural network is well suited to nonlinear systems. To meet the power demands at different phases of flight, the controller controls the battery current and rate of charging/discharging. Three case studies were used to validate and assess the performance of the hybrid system: battery fully charged (high SOC), worst case scenario and taking into account the external factors such as wind speeds and wind direction. In addition, the performance of the Artificial Neural Network Controller was compared to that of a Fuzzy Logic controller. In all cases the fuel cell act as the main power source for the PiperCub J3 aircraft. The tests were carried-out in both simulation and hardware-in-the-loop.

Ce travail de thèse s'inscrit dans le cadre de la durabilité des PEMFC et s'intéresse plus particulièrement à la dégradation des électrocatalyseurs de type Pt/C qui sont utilisés dans leurs électrodes. L'objectif visé était la détermination des mécanismes responsables de leur dégradation, par combinaison d'expériences d'électrochimie en cellule à trois électrodes, de microscopie électronique en transmission et à balayage, et de spectrométrie de masse (DEMS). Dans un premier temps nous avons mis en évidence que les méthodes de caractérisation employées peuvent influencer les dégradations observées. Ainsi, la morphologie des nanocatalyseurs Pt/C peut-être altérée par l'observation MET elle même, comme d'ailleurs par la séquence de mesures par CO-stripping. / This thesis is part of the durability of PEMFC and is particularly interested in the degradation of electrocatalysts of type Pt / C that are used within their electrodes. The objective was to determine mechanisms responsible for their degradation, by combining experiments in electrochemical cell with three electrodes, transmission electron microscopy and scanning, and mass spectrometry (DEMS). Initially we have shown that the characterization methods used can influence the degradation observed. Thus, the morphology of Pt nanocatalysts / C may be altered by the TEM observation itself, as does the sequence of measurements by CO-stripping.

Cette thèse porte sur l’étude et le développement d’électrocatalyseurs à base d’iridium pour la réaction de dégagement de dioxygène (OER) dans les électrolyseurs à membrane échangeuse de protons. En raison de la dégradation marquée des électrocatalyseurs en conditions OER, nous nous sommes particulièrement intéressés à la recherche d’un compromis optimal entre activité catalytique et stabilité. Différents électrocatalyseurs (supportés sur noir de carbone, supportés sur oxydes métalliques dopés et non-supportés) ont été synthétisés et caractérisés par des méthodes électrochimiques et physico-chimiques, notamment par spectroscopie photoélectronique X, microscopie électronique en transmission à localisation identique et spectrométrie de masse à plasma à couplage inductif. Les électrocatalyseurs supportés sont les moins stables en conditions OER, notamment du fait de l’agglomération, la coalescence, la dissolution et le détachement des nanoparticules d’oxyde d’iridium. Ces deux derniers mécanismes de dégradation sont exacerbés par la corrosion des supports carbonés et la dissolution des éléments composant les supports oxydes métalliques dopés. Les électrocatalyseurs non-supportés offrent ainsi le meilleur compromis entre activité et stabilité. Les degrés d’oxydation Ir(III) et Ir(V) ont été identifiés comme les plus actifs pour l’OER en électrolyte acide tandis que l’oxyde Ir(IV) est le plus stable, l’espèce la moins stable étant l’iridium métallique Ir(0). La dégradation des couches catalytiques en cellule d’électrolyse PEM ne semble impacter que très peu les performances globales d’électrolyse par rapport à la dégradation des collecteurs de courant. / This thesis focuses on the study and the development of iridium-based electrocatalysts for the oxygen evolution reaction (OER) in proton exchange membrane water electrolyzers. This work investigates in particular electrocatalyst degradation phenomena and aims at reaching an optimal OER activity-stability ratio. Various electrocatalysts (supported on high-surface area carbon, supported on doped-metal oxides and unsupported) have been synthetized and characterized by electrochemical and physico-chemical methods such as X-ray photoelectron spectroscopy, identical-location transmission electron microscopy and inductively coupled plasma mass spectrometry. Supported electrocatalysts feature stability limitations in OER conditions as revealed by agglomeration, coalescence, dissolution, and detachment of iridium oxide nanoparticles, these last two degradation mechanisms being amplified by corrosion of the carbon supports and dissolution of the elements composing the doped metal oxide supports. Unsupported electrocatalysts currently represent the best compromise between OER activity and stability. Ir(III) and Ir(V) oxides were shown to be the most active towards the OER while Ir(IV) oxide is the most stable, the least stable species being metallic iridium Ir(0). In real PEM water electrolyzers, the global electrolysis performance seems to be less impacted by the degradation of catalytic layers than the degradation of current collectors.

Hydrogen gas (H2), that is not produced from fossil oil or natural gas, is expected to become a cornerstone in the energy transition strategy in Europe. The recent years, technological and economic advances in the electrolyzer area, along with political and corporate support, have put H2 at the forefront of many countries’ climate change agenda. Consequently, green H2 is poised to play a large role in the coming energy transition to combat climate change. The possible advantages of integrating H2 production with a combined heat and power plant, or CHP, is investigated in this study. More precisely, the water electrolysis is carried out based on the purified flue gas condensate water and excess heat is recovered as district heating. A comparison of today’s three most common electrolyzer technologies was made, where Proton Exchange Membrane, or PEM, technology was chosen for this project, mainly for its high purity of H2 gas, robust construction, and the ability to run it as a fuel cell. Based on a mass and energy balance, a model including the integration of a PEM with a generic CHP plant was developed. The model was made modifiable, making it possible to change governing parameters, to be able to investigate different possible scenarios. Production flows, losses and other relevant data was calculated from the model. Operational data for the PEM electrolyzer were collected from several manufacturers where a mean value of the data was used as a base-case for the calculations. Based on literature and consulting experts, several assumptions were made, for example the selling price of H2 and the price for electricity. From the base-case were two cases made: a linear and non-linear case. The linear case uses the same input data each year for 20 years, while the non-linear case uses a changing input data each year for 20 years. Calculations were based on an electrolyzer size of 1,4 MW, where auxiliary equipment consumed additional 0,04 MW, resulting in a total energy consumption of 1,44 MW. An operational temperature of 80°C was assumed along with an operational pressure of 5 and 30 bar for the anode and cathode respectively. This resulted in an H2 production flow of 26 kg/h, a process water requirement of 0,2 m3/h, and a possible heat recovery amount of 0,34 MWh with a relevant temperature for the use in district heating. The study shows that the condensate-water at E.ON could provide for ~4000 hours of operation in the wintertime. To enable full operation all year around, a purchase of tap water would be necessary. The economical calculations resulted in an H2 production cost of 53 SEK/kg for the linear case and 58 SEK/kg for the non-linear case. The linear case showed a positive internal rate of return, or IRR, of 1,7%, while the non-linear case resulted in IRR < -25%. A sensitive analysis was made to examine governing parameters. The results of the sensitivity analysis showed that the largest driving variables, that significantly affect the IRR, are the price for electricity and the selling price for H2. The largest OPEX cost was found to be the price of electricity. The results showed that it is feasible to produce H2 at E.ON Örebro in a resource efficient way under certain circumstances, correlated to the electricity and H2 market. With a low electricity price and a selling price of ~50 SEK/kg for H2, good profitability is expected.  It is also clear that future work should focus the areas of O2 usage, infrastructure, and market investigation for a more definitive conclusion.

I detta examensarbete utforskas påverkan av partikelstorleken hos Pt-katalysatorer på kolbärare på syrereduktionen i polymerelektrolytmembran (PEM)-bränsleceller. Den elektrokemiskt aktiva ytarean, aktiviteten för syrereduktion och tillhörande degraderingshastigheter för de undersökta katalysatorerna beräknas och jämförs. Experimenten utfördes med hjälp av en metod som kallas ”roterande skivelektrod med tunn film” i en syra-vatten-lösning. Den katalytiska aktiviteten beräknades med Koutecky-Levichs ekvation. Resultaten visar att filmkvaliteten är avgörande för att kunna göra en bedömning av syrereduktionssaktiviteten. En homogen distribution av Pt-nanopartiklar är nödvändig för att få en korrekt och pålitlig katalytisk aktivitet. Vidare utvecklas en metodik för utvärdering av filmkvaliteten baserad på den diffusionsbegränsade strömtätheten och på potentialen vid halva topphöjden. Mätningen av syrereduktionsaktiviteten genomfördes enbart med prov vars filmkvalitet godkändes med avseende på denna metodik och den erhållna aktiviteten jämfördes vid 0.9 V vs. RHE. De undersökta katalysatorerna uppvisar snarlik aktivitet för syrereduktionsreaktionen, vilket överensstämmer med att också de uppmätta elektrokemiskt aktiva ytareorna för de olika katalysatorerna är snarlika. Förlusten av elektrokemiskt aktiv ytarea visar sig vara beroende av partikelstorleken och mindre partiklar uppvisar en högre degraderingshastighet. Rapporten avslutas med en diskussion om avvikelserna från tidigare studier och möjligheter för vidare studier. / In this thesis, the particle size effect of carbon-supported Pt catalysts on the oxygen reduction reaction in polymer electrolyte membrane fuel cells is studied. The electrochemically active surface area and the oxygen reduction reaction activities and the associated degradation rate of the investigated carbon-supported Pt catalysts are computed and compared. The experiments were conducted by a method called thin-film rotating disk electrode in an aqueous acid solution, and the catalytic activity was computed using the Koutecky-Levich equation. The results show that thin-film quality is crucial in the oxygen reduction reaction activity measurement. A homogeneous distribution of Pt nanoparticles is necessary for obtaining correct and reliable catalytic activities. Furthermore, in this thesis, a methodology based on the diffusion-limited current density and the half-wave potential for thin-film quality evaluation is developed. The oxygen reduction reaction activity measurement was only applied to samples with good film quality, and the obtained activity results were compared at 0.9 V vs. RHE. The investigated carbon-supported Pt catalysts display similar oxygen reduction reaction activities, due to the fact that the measured electrochemically active surface area results for the particle sizes are similar. The degradation rate was studied in a platinum dissolution test and the results show a particle size-dependent electrochemically active surface area loss. Smaller particles show a faster and larger degradation rate. At the end of the thesis, deviations in this work from existing work are discussed, and possibilities for future work are presented.

In this thesis, ammonia (NH3) decomposition was assessed as a fuel processing technology for producing on-demand hydrogen (H2) for portable and distributed fuel cell applications. This study was motivated by the present lack of infrastructure to generate H2 for proton exchange membrane (PEM) fuel cells. An overview of past and recent worldwide research activities in the development of reactor technologies for portable and distributed hydrogen generation via NH3 decomposition was presented in Chapter 2. The objective was to uncover the principal challenges relating to the state-of-the-art in reactor technology and obtain a basis for future improvements. Several important aspects such as reactor design, operability, power generation capacity and efficiency (conversion and energy) were appraised for innovative reactor technologies vis-à-vis microreactors, monolithic reactors, membrane reactors, and electrochemical reactors (electrolyzers). It was observed that substantial research effort is required to progress the innovative reactors to commercialization on a wide basis. The use of integrated experimental-mathematical modelling approach (useful in attaining accurately optimized designs) was notably non-existent for all reactors throughout the surveyed openliterature. Microchannel reactors were however identified as a transformative reactor technology for producing on-demand H2 for PEM cell applications. Against this background, miniaturized H2 production in a stand-alone ammonia-fuelled microchannel reactor (reformer) washcoated with a commercial Ni-Pt/Al2O3 catalyst (ActiSorb® O6) was demonstrated successfully in Chapter 3. The reformer performance was evaluated by investigating the effect of reaction temperature (450–700 °C) and gas-hourly-space-velocity (6 520–32 600 Nml gcat -1 h-1) on key performance parameters including NH3 conversion, residual NH3 concentration, H2 production rate, and pressure drop. Particular attention was devoted to defining operating conditions that minimised residual NH3 in reformate gas, while producing H2 at a satisfactory rate. The reformer operated in a daily start-up and shut-down (DSS)-like mode for a total 750 h comprising of 125 cycles, all to mimic frequent intermittent operation envisaged for fuel cell systems. The reformer exhibited remarkable operation demonstrating 98.7% NH3 conversion at 32 600 Nml gcat -1 h-1 and 700 °C to generate an estimated fuel cell power output of 5.7 We and power density of 16 kWe L-1 (based on effective reactor volume). At the same time, reformer operation yielded low pressure drop (<10 Pa mm-1) for all conditions considered. Overall, the microchannel reformer performed sufficiently exceptional to warrant serious consideration in supplying H2 to low-power fuel cell systems. In Chapter 4, hydrogen production from the Ni-Pt-washcoated ammonia-fuelled microchannel reactor was mathematically simulated in a three-dimensional (3D) CFD model implemented via Comsol Multiphysics™. The objective was to obtain an understanding of reaction-coupled transport phenomena as well as a fundamental explanation of the observed microchannel reactor performance. The transport processes and reactor performance were elucidated in terms of velocity, temperature, and species concentration distributions, as well as local reaction rate and NH3 conversion profiles. The baseline case was first investigated to comprehend the behavior of the microchannel reactor, then microstructural design and operating parameters were methodically altered around the baseline conditions to explore the optimum values (case-study optimization). The modelling results revealed that an optimum NH3 space velocity (GHSV) of 65.2 Nl gcat -1 h-1 yields 99.1% NH3 conversion and a power density of 32 kWe L-1 at the highest operating temperature of 973 K. It was also shown that a 40-μm-thick porous washcoat was most desirable at these conditions. Finally, a low channel hydraulic diameter (225 μm) was observed to contribute to high NH3 conversion. Most importantly, mass transport limitations in the porouswashcoat and gas-phase were found to be negligible as depicted by the Damköhler and Fourier numbers, respectively. The experimental microchannel reactor produced 98.2% NH3 conversion and a power density of 30.8 kWe L-1 when tested at the optimum operating conditions established by the model. Good agreement with experimental data was observed, so the integrated experimental-modeling approach used here may well provide an incisive step toward the efficient design of ammonia-fuelled microchannel reformers. In Chapter 5, the prospect of producing H2 via ammonia (NH3) decomposition was evaluated in an experimental stand-alone microchannel reactor wash-coated with a commercial Cs-promoted Ru/Al2O3 catalyst (ACTA Hypermec 10010). The reactor performance was investigated under atmospheric pressure as a function of reaction temperature (723–873 K) and gas-hourly-space-velocity (65.2–326.1 Nl gcat -1 h-1). Ammonia conversion of 99.8% was demonstrated at 326.1 Nl gcat -1 h-1 and 873 K. The H2 produced at this operating condition was sufficient to yield an estimated fuel cell power output of 60 We and power density of 164 kWe L-1. Overall, the Ru-based microchannel reactor outperformed other NH3 microstructured reformers reported in literature including the Ni-based system used in Chapter 3. Furthermore, the microchannel reactor showed a superior performance against a fixed-bed tubular microreactor with the same Ru-based catalyst. Overall, the high H2 throughput exhibited may promote widespread use of the Ru-based micro-reaction system in high-power applications. Four peer-reviewed journal publications and six conference publications resulted from this work. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2015