Variable renewable energy and green hydrogen demand is expected to increase within the European union in attempts to mitigate climate change. A high penetration of variable renewable energy can result in volatile power prices affecting the profitability of such actors. At the same time southern Sweden suffers from high power prices and could benefit from additional generation. If offshore wind power is used for hydrogen production during low price hours and sold to the market during high price hours, it may be beneficial to invest in electrolysis. This thesis investigates the profitability and conditions of green hydrogen production in the south of Sweden, together with social and economic benefits that comes with it. A model consisting of electrolysis powered directly from an offshore wind farm is analyzed for maximum profit. A linear optimization program is used to investigate the optimal setup of installed electrolysis together with 500MW offshore wind power, subjected to investment costs, market limitations and constraints. Results show that investing in electrolysis according to hydrogen demand and price can increase the overall profitability, while at the same time keeping the production cost of green hydrogen at similar levels as hydrogen produced from natural gas. / Målet att minska klimatpåverkan förväntas öka efterfrågan på förnybar energi och grön vätgas inom den Europeiska Unionen. En hög andel av varierbar energi kan resultera i volatila energipriser som påverkar lönsamheten för sådana aktörer. Samtidigt lider södra Sverige av höga elpriser och kan dra nytta av ytterligare produktion. Om energin från havsbaserad vindkraft används för vätgasproduktion under lågpristimmar och säljs till marknaden under högpristimmar kan det vara fördelaktigt att investera i elektrolys för vätgasproduktion. Detta examensarbete undersöker lönsamheten och förutsättningarna för att producera grön vätgas i södra Sverige, tillsammans med de sociala och ekonomiska fördelar som kan medfölja. En modell bestående av elektrolys som drivs direkt från en havsbaserad vindkraftspark analyseras för maximal vinst. Ett linjärt optimeringsprogram används för att undersöka den bästa kombinationen av installerad elektrolys tillsammans med 500MW havsbaserad vindkraft. Begränsningar i from av investeringskostnader, energibehov och efterfrågan avgör lönsamheten. Resultatet visar att investeringar i elektrolys kan öka den totala lönsamheten samtidigt som produktionskostnaden för grön vätgas hamnar i nivå med kostnader för vätgas framställt ur naturgas.

No description available.

High-temperature Co-electrolysis of H2O and CO2 in a solid-oxide electrolyser (Co-SOE) for syngas production is a high-efficiency renewable electricity conversion and storage method part of the Power-to-X technologies. Syngas, a mixture of H2, CO and CO2, is a critical building block to make several chemical and synthesis fuels. The thesis aimed to model the Co-electrolysis process in a steady-state process modelling tool called Aspen Plus. The model was designed at thermoneutral mode and four cases with electrolysis temperatures of 700 °C, 750 °C, 800 °C and 850°C. The results from the model were used to perform an economic assessment and check the feasibility of Co-SOE. The analysis included calculation of Net Present Value (NPV), Internal Rate of Return (IRR) and the Levelised cost of Syngas (LCOS). The LCOS from Co-SOE was compared to the benchmark technology of syngas production in a Reverse Water Gas Shift (RWGS) reactor. The H2 feed to the RWGS reactor was assumed to be obtained from a Proton Exchange Membrane Electrolyser(PEME). A sensitivity analysis was performed to check the effect of electricity price, electrolyser stack price, electrolyser lifetime, CO2 feed price, by-product O2 revenue and discount rate on the LCOS. The LCOS was calculated to be 0.697, 0.727, 0.752 and 0.783 €/kg at 700 °C, 750 °C, 800 °C and 850 °C, respectively, increased with temperature due to increased electricity consumption at thermoneutral mode. The average LCOS from Co-SOE was 18.5% cheaper than the benchmark technology due to the high investment in the PEME and low conversion efficiency of the RWGS process. There was a trade-off between LCOS and system efficiency due to the effect of internal methanation occurring on the cathode side of the SOE. 750 °C was found to be the optimum design temperature to minimise the LCOS and maximise the efficiency. LCOS was most sensitive to electricity price, followed by O2 revenue and discount rate, while other parameters were less significant. The thesis also discussed key challenges to overcome in the future development of the Co-SOE technology. Co-SOE was found to be a promising technology for green syngas production. However, challenges concerning low stack lifetime, high capital investment and high cost of electricity have yet to be overcome to demonstrate it at a commercial scale.

Den globala ekonomin är idag starkt kopplad till utsläpp av växthusgaser samtidigt som det finns en stark enighet bland världens ledande länder att kraftigt minska de globala utsläppen i enlighet med Parisavtalet. Vätgas som produceras från förnyelsebara energikällor anses utgöra en nyckelroll för ett antal olika applikationsområden de kommande decennierna, där bland transportsektorn. Trots att framställningsprocessen bygger på väl utvecklad teknik finns det än idag väldigt få storskaliga produktionsanläggningar av grön vätgas, men teknikutvecklingen inom området är skyndsam. Rederi AB Gotland är idag Sveriges äldsta rederi och således en av de största aktörerna inom Gotlands transportsektorn. Företaget ser idag över möjligheten för att driftsätta Sveriges första storskaliga vätgasdrivna gods- och passagerarfartyg, GotlandHorizon, vilket är en viktig del i företagets miljöarbete. Huvudsakligen avser företaget attvätgasen produceras lokalt på Gotland, vilket föranleder till en rad olika tekniska utmaningarrelaterade till elproduktion, vätgasframställning och distributionssystem. Med bakgrund av detta har en förstudie tillsammans med Uppsala universitet och projektet “Vätgasbaserad färjetrafik” genomförts för att påvisa och kartlägga viktiga aspekter kring ett framtida produktionssystem av grön vätgas samt kartlägga vilka tekniska lösningar som inom tidsramen för projektet är tekniskt genomförbara. Resultatet av förstudien ska kunna användas som grund för utformning av framtida beräkningsmodeller. Av förstudien framgår det att vattenelektrolys i kombination med en utbyggnation av vindkraft teoretiskt kan möta både det efterfrågade elbehovet för elektricitet och således Gotland Horizons vätgasbehov. Det uppskattade elbehovet för framställning av vätgas genom vattenelektrolys motsvarar dock Gotlands idag totala energikonsumtion, vilket såldes utgör en storutmaning. En annan viktig faktor för processen är en tillförlitlig processvattenförsörjning. Gotland har de senaste åren haft en problematisk grundvattensituation samt att dricksvattenproduktionen på Gotland är begränsad. I studien har de viktiga aspekterna kring utformningen av produktionssystemets analyserats. De ekonomiska aspekterna har också redovisats för att ligga till grund för en optimeringsmodell för vidare analys och optimering av produktionssystemet. Av de beräkningsmodeller som genomförts påvisas att både havsbaserad- samt landbaserad vindkraft kan tillgodose behovet av elproduktion för vattenelektrolys, det är snarare en fråga om hur systemet ska optimeras samt vilka synergieffekter som respektive system kan medförasom bestämmer systemets utformning. Solenergi har ansetts vara tekniskt möjligt men till bakgrund av att efterfrågan på elektricitet året runt är hög anses anläggningen bli orealistiskt stor. Också aspekter gällande produktionssystemet utformning, centraliserat eller decentraliserats, har diskuterats. Till bakgrund av de stora ekonomiska storskalsfördelarna som uppskattas för elektrolysörer inom de kommande åren anses ett centraliserat produktionssystem vara det mest tänkbara utifrån ett ekonomiskt perspektiv. Det har också konstaterats att havsbaserade vätgaspipelines kan bli aktuellt vid havsbaserad vätgasproduktion, det för att minimera kapitalkostnaderna för distributionen av energivektor, vilket skulle kunna minska produktionskostnaderna för vätgas från havsbaserad vindkraft. / The global economy today is strongly linked to greenhouse gas emissions while there is a strong consensus among the world's leading countries to significantly reduce global emissions in accordance with the Paris Agreement. Hydrogen produced from renewable energy sources is considered to play a key role within a several different application areas in the coming decades, including the transport sector. Even though the production process is based on welldeveloped technology, there are still very few large-scale production facilities of green hydrogen, but technological development in the field is rapid. Rederi AB Gotland is today Sweden's oldest shipping company and thus one of the largest players in Gotland's transport sector. The company is currently reviewing the possibility of commissioning Sweden's first large-scale hydrogen-powered freight and passenger vessel, Gotland Horizon, which is an important part of the company's environmental work. Mainly, the company intends that the hydrogen is produced locally on Gotland, which leads to a variety of technical challenges related to electricity production, hydrogen production and distribution systems. With this background, a feasibility study together with Uppsala University and the project "Hydrogen-based ferry traffic" has been carried out to demonstrate and map important aspects of a future production system of green hydrogen and to map which technical solutions within the time frame of the project are technically feasible. The results of the feasibility study can be used as a basis for designing future calculation models. The feasibility study shows that water electrolysis in combination with an expansion of wind power can theoretically meet both the demanded electricity demand for electricity and thus Gotland Horizon's hydrogen needs. However, the estimated electricity demand to produce hydrogen through water electrolysis corresponds to Gotland's current total energy consumption, which was sold poses a major challenge. Another important factor for the process is a reliable process water supply. In recent years, Gotland has had a problematic groundwater situation and the drinking water production on Gotland is limited. In the study, the important aspects of the design of the production system have been analyzed. The economic aspects have also been accounted for to form the basis for an optimization model for further analysis and optimization of the production system. From the calculation models carried out, it is shown that both offshore and onshore wind power can meet the need for electricity production for water electrolysis, it is rather a question of how the system should be optimized and what synergies each system can bring that determine the design of the system. Solar energy has been considered technically possible, but given that the demand for electricity all year round is high, the plant is considered to be unrealistically large. Aspects of the design of the production system, centralised or decentralised, have also been discussed. Considering the large economic economies of scale appreciated for electrolysers in the coming years, a centralized production system is considered the most conceivable from an economic perspective. It has also been recognized that offshore hydrogen pipelines may be relevant in offshore hydrogen production, in order to minimize the capital costs of energy vector distribution, which could reduce the production costs of hydrogen from offshore wind.

Vätgas kan framställas från förnybara energikällor genom vattenelektrolys med anjonbytande membran (AEMWE). AEMWE har vissa fördelar jämfört med traditionell alkalisk vattenelektrolys och elektrolysmed protonledande membran. Till exempel finns det möjlighet att använda alkalisk elektrolyt (även rent vatten) och billiga platinagruppsmetallfria katalysatorer tillsammans med ett anjonbytesmembran. Den största utmaningen med tekniken är att uppnå utmärkt och stabil prestanda för membran och elektroder. AemionTM anjonbytande membran (AEMs) av olika tjocklek, vattenupptag och kapacitet undersöktes i ett AEMWE system med 5 cm2 elektrodarea. Elektrokemisk prestanda hos dessa kommersiella AEM studerades med hjälp av porösa nickel elektroder. Bland de undersökta membranen visade AF2-HWP8-75-X stabil prestanda med en högfrekvent resistans (HFR) på 90 mΩ•cm2 och kunde nå en strömtäthet på 0,8 A/cm2 vid 2,38 V med 1 M KOH vid 60 ˚C.  AEMWE med AF2-HWP8-75-X och olika elektrodkombinationer undersöktes under samma driftsförhållanden. En elektrodkombination med Raney-Ni och NiFeO som katod respektive anod visade bäst prestanda under utvärderingen och gav en strömtäthet på 1,06 och 3,08 A/cm2 vid 2,00 respektive 2,32 V. KOH-lösningens temperatur och koncentration sänktes till 45 ˚C respektive 0,1 M för att undersöka effekten av driftsparametrar på flödescellens prestanda. Flödescellen uppvisade god stabilitet under de nya driftsförhållandena, men dess prestanda minskade avsevärt. Den nådde en strömtäthet på 0,8 A/cm2 vid 2,25 V. / Hydrogen can be produced from renewable energy sources using a novel anion exchange membrane water electrolysis (AEMWE) system. AEMWE has some benefits over the currently used state-of-the-art alkaline and proton exchange membrane water electrolysis systems. For instance, there is a possibility of using alkaline electrolytes (even pure water) and low-cost platinum-group-metal free catalysts together with an ion exchange membrane. However, the main challenge is that the AEMWE system should show excellent and stable performance, depending on the stability of the membrane and the electrodes. AemionTM anion exchange membranes (AEMs) of different thickness and water uptake capacity were investigated using a 5 cm2 AEMWE system. The electrochemical behaviour of these commercial AEMs was studied using nickel (Ni) felt electrodes. Among the investigated AEMs, the AF2-HWP8-75-X showed stable performance with a high frequency resistance (HFR) of 90 mΩ•cm2 and was able to reach a current density of 0.8 A/cm2 at 2.38 V using 1 M KOH at 60 ˚C.  AEMWE systems based on AF2-HWP8-75-X and different electrode combinations were examined under the same operating conditions. An electrode combination with Raney-Ni and NiFeO as cathode and anode, respectively, showed the best performance during the degradation test and provided a current density of 1.06 and 3.08 A/cm2 at 2.00 and 2.32 V, respectively. The operating temperature and concentration of the KOH solution were reduced to 45 ˚C and 0.1 M, respectively, to study the effect of operating parameters on the flow cell performance. The flow cell showed good stability under the new operating conditions, but its performance was reduced significantly. It reached a current density of 0.8 A/cm2 at 2.25 V.

[ES] En la presente tesis se han desarrollados estudios sobre reactores de membrana de alta temperatura. Entre estos se puede diferenciar entre un trabajo experimental y un trabajo de simulación. En el bloque experimental se han desarrollado electrodos basados en cobre para reactores de membrana electroquímicos tubulares de alta temperatura basados en electrolitos protónicos. Para depositar estos electrodos sobre los tubos se han desarrollado diferentes técnicas. Se ha optimizado el método dip-coating para depositar un cermet basado en cobre utilizando la misma cerámica que el electrolito de los soportes tubulares. Las condiciones con las que se llevó a cabo el proceso de dip-coating provocan disminuciones de varios ordenes de magnitud en la resistencia de polarización del electrodo final. Se trata de un método que es muy sensible a posibles defectos en electrolito, como pequeñas grietas o poros, ya que el cobre del electrodo depositado se introduce por estos defectos reaccionando con el níquel del electrodo interno. Asimismo, se ha empleado el método de sputtering para depositar cobre metálico sobre soportes tubulares electroquímicos. Aumentar la temperatura de deposición genera mejores fijaciones electrodo-electrolito. Las celdas con el cobre depositado a alta temperatura mostraron resistencias de polarización inferiores a 0.1 ¿·cm^2. En el bloque de simulaciones mediante métodos de elementos finitos se han desarrollado diferentes modelos para la caracterización de los fenómenos que tienen lugar en reactores de membrana de alta temperatura. Se ha estudiado: (i) la permeación de oxígeno a través de una membrana de conducción iónica-electrónica mixta; (ii) la electrólisis del agua utilizando celdas basadas en conductores protónicos de alta temperatura; (iii) la integración de una celda protónica para la extracción de hidrógeno en un reformador de metano; (iv) la integración de una celda de conductividad co-iónica en la deshidroaromatización de metano en un reactor de lecho catalítico. El modelo de permeación de oxígeno a través de una membrana de conductividad mixta se ajustó a datos experimentales. El modelo ajustado ha permitido caracterizar la importancia del efecto dilutivo y de arrastre sobre el transporte de oxígeno a través de la membrana. Se ha observado que, aunque el efecto de arrastre tenga menor importancia que el dilutivo, su efecto es importante ya que previene la formación de concentraciones de polarización. El estudio de electrolizadores que utilizan conductores protónicos sólidos de alta temperatura ha permitido estudiar el efecto del escalado en este proceso y evaluar la eficiencia en el almacenamiento de energía. El modelo de un reactor de membrana electroquímico basado en conductores protónicos integrado en un reformador de metano ha permitido comprobar que la demanda térmica del proceso se cubre por el efecto Joule y la electrocompresión del hidrógeno. Se ha comprobado como el coarsening observado en las partículas de níquel no limita la extracción de hidrógeno para la celda estudiada. Un último modelo fue construido para estudiar un reactor de membrana para el proceso de deshidrogenación de metano utilizando una celda co-iónica. El modelo fue validado utilizando datos experimentales. Se utilizó el modelo validado para realizar estudios para analizar posibles limitaciones del proceso. Finalmente, se ha comprobado que el desplazamiento del equilibrio de reacción mediante la extracción de hidrógeno se frena debido a limitaciones cinéticas. / [CA] Esta tesi presenta resultats sobre reactors de membrana a alta temperatura. Dos blocs diferenciades poden ser identificats: (i) treball experimental; (ii) treball de modelat. En el bloc experimental, elèctrodes basats en coure han siguts optimitzats per a tubular cells de conductor protòniques. La deposició de la capa basada en coure es va fer amb diferents tècniques. La tècnica de dip-coating ha sigut usada per a depositar una capa de cermet basada en coure. Aquesta tècnica es molt sensible a les condicions amb les que es desenvolupa la deposició perquè causa canvis de varis ordres de magnitud en la resistència de polarització del elèctrode. A més, la tècnica de sputtering ha sigut triada per a depositar coure. Per a depositar correctament la capa de coure, altes temperatures durant la deposició foren requerides. El elèctrode optimitzat presenta resistències de polarització inferiors a 0.1 ¿·cm2. En el treball de modelat, la metodologia de elements finits va ser utilitzada per a modelar diferents fenòmens concernits a reactors de membrana de elevada temperatura. La permeació de oxigen per membranes de conducció mixta ha sigut modelada per a avaluar la importància de la dilució i del arrossegament. Els resultats mostren que, encara que el efecte dilutiu es predominant, el efecte del arrossegament no pot ser depreciat. Un adequat arrossegament del oxigen permeat es necessari per evitar polaritzacions en la concentració del oxigen els quals limitarien la permeació. El efecte del arrossegament es major quan el gas portador es mes pesat. El model per estudiar un procés de electròlisis basat en conductors protòniques a elevada temperatura ha permès estudiar l'efecte de l'escalat de aquest procés i avaluar l'eficiència en l'emmagatzemament d'energia. Modelant un reformador de membrana protònica ha permès comprovar la microintegració tèrmica de tots el fenòmens que tenen lloc en aquest procés. Aquest procés compren les reaccions de reformat, extracció electroquímica de hidrogen i electrocompressió del hidrogen generat. La electrocompressió del hidrogen és un procés isoterma que allibera la energia demanda en forma de calor. El model ha permès comprovar que l'engrossiment de les partícules de níquel no limita l'extracció de hidrogen. Un últim model va ser construït per estudiar l'extracció de hidrogen en un reactor de membrana per al procés de dehidroaromatizatió de metà. El reactor de membrana utilitza materials co-iòniques per l'extracció de hidrogen de la càmera de reacció. Aquest model va ser validat amb resultats experimentals. El model va mostrar que no hi ha limitacions amb la difusió del hidrogen. A més, el desplaçament del equilibri mediant l'extracció de hidrogen està limitat per la baixa activitat cinètica del procés. / [EN] In this thesis several studies were developed about membranes reactor at high temperature. Two differentiated blocks could be identified: (i) experimental works; (ii) modelling works. In the experimental block, electrodes based on copper was developed for tubular protonic based cells. The deposition of the copper layer on the tubes was developed by different techniques. Dip-coating method was optimized to a copper-based cermet on the tube. Conditions of the dip-coating procedure has a critical impact in the final performance of the electrochemical cell whose supposes several orders of magnitude in the polarization resistance. It is a sensitive process with the defect of the tube as shows the copper spread over these defects. Additionally, sputtering technique was used to deposit copper layer on the tube. High temperature is required to achieve suitable attachments copper-tube. This high temperature deposited layer present polarization resistances lower than 0.1 ¿·cm2. In the modelling block, finite element methodology was used to build different models to study different phenomena concerning membrane reactors at high temperature. It was studied: (i) the oxygen permeation across a mixed ionic and electronic conducting membrane; (ii) water electrolysis based on high temperature protonic cells; (iii) hydrogen extraction from a steam methane reforming using a protonic cell; (iv) the intensification of the methane dehydromatization reactor using co-ionic membrane. Oxygen permeation model was built to evaluate the effect of the dilutive and the sweep contribution over the permeation process. The fitted model allowed the importance of the dilutive and sweep effect over the oxygen permeation. Although the sweep effect present lower influence in the oxygen transport across the membrane, its effect prevents concentration polarization limitations. Modelling the protonic cell based electrolysis allowed to study the effect of the scale up in this process and to evaluate the efficiency in the energy storing in form of hydrogen. Modelling protonic membrane reformer allowed checking the thermal microintegration of all the heats which take place in the setup. The electrocompression of hydrogen is an isothermal phenomenon which releases the demanded energy as heat. The model allowed to check the coarsening of the Ni particles does not limit the hydrogen extraction for the studied cell. A final model was built to study a catalytic membrane reactor for the methane dehydroaromatization using co-ionic conducting cells. The model was validated using experimental data. Additionally, different studies were performed to analyze possible limitation in the process. Results show that there are no hydrogen diffusion limitations in this process. Additionally, the shift of the equilibrium by extracting hydrogen has to be stopped because kinetic limitations. / Catalán Martínez, D. (2019). Development of electrocatalytic layers and thermo-fluid dynamic evaluation for high temperature membrane reactors [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/135278

A major problem in the quantitative analysis of AC voltammetric data has been the variance in results between laboratories, often resulting from a reliance on "heuristic" methods of parameter estimation that are strongly dependent on the choices of the operator. In this thesis, an automatic method for parameter estimation will be tested in the context of experiments involving electron-transfer processes in solution-phase. It will be shown that this automatic method produces parameter estimates consistent with those from other methods and the literature in the case of the ferri-/ferrocyanide couple, and is able to explain inconsistency in published values of the rate parameter for the ferrocene/ferrocenium couple. When a coupled homogeneous reaction is considered in a theoretical study, parameter recovery is achieved with a higher degree of accuracy when simulated data resulting from a high frequency AC voltammetry waveform are used. When surface-confined reactions are considered, heterogeneity in the rate constant and formal potential make parameter estimation more challenging. In the final study, a method for incorporating these "dispersion" effects into voltammetric simulations is presented, and for the first time, a quantitive theoretical study of the impact of dispersion on measured current is undertaken.

Understanding the factors influencing the ET characteristics of redox proteins confined at an electrochemical interface is of fundamental importance from both pure (fundamental science) and applied (biosensory) perspectives. This thesis reports on progress made in the emerging field of coupled electrochemical characterization and optical imaging in moving the analysis of redox-active films to molecular scales. More specifically the combination of cyclic voltammetry and wide-field Total Internal Reflection (TIRF) microscopy, here named ‘Fluorescent Cyclic Voltammetry’ (FCV), was applied to monitoring the response of surface-confined redox active proteins at submonolayer concentrations. The combined submicrometre spatial resolution and photon capture efficiency of an inverted TIRF configuration enabled the redox reactions of localized populations of proteins to be directly imaged at scales down to a few hundreds of molecules. This represents a 6-9 orders of magnitude enhancement in sensitivity with respect to classical current signals observed in bioelectrochemical analysis. Importantly, measurements of redox potentials at this scale could be achieved from both natural and artificially designed bioelectrochemical fluorescent switches and shed fundamental light on the thermodynamic and kinetic dispersion within a population of surface confined metalloproteins. The first three chapters of this thesis provide an overview of the relevant literature and a theoretical background to both the rapidly expanding fields of electroactive monolayers bioelectrochemistry and TIRF imaging. The initial design and construction of a robust electrochemically and optically addressable fluorescent switch, crucial to the applicability of FCV is reported in chapter 5. The generation of optically transparent, and chemically modifiable electrode surfaces suitable for FCV are also described. Chapter 6 describes the response of the surface confined azurin-based switch. Analysis of the spatially-resolved redox reaction of zeptomole samples in various conditions enables the mapping of thermodynamic dispersion across the sampled areas. In chapter 7 the newly developed FCV detection method was extended to investigate more complex bioelectrochemical systems containing multiple electron transferring redox centres and responding optically at different wavelengths. This approach provides a platform for spectral resolution of different electrochemical processes on the same sample. Finally in chapter 8 an electrochemical procedure is proposed for investigating the kinetic response of redox proteins using a fundamentally new methodology based on interfacial capacitance. In using variations in the surface chemistry to tune the rate of electron transfer, the approach was shown to be a robust and facile means of characterising redox active films in considerably more detail than possible through standard electrochemical methodologies. Ultimately, it can be applied to probe dispersion within protein populations and represents a powerful means of analysing molecular films more generally.

Herein, the influence of protonation and adsorption upon the redox and electrocatalysis of quinone species - specifically anthraquinone derivatives – is investigated. Through the comparison of the measured rate constants of one-electron reductions of a family of quinones in acetonitrile at both graphite and gold electrodes, it was confirmed that the redox potential indirectly influences the rate of electron transfer in a manner consistent with the potential-dependence of the density of states. In aqueous media, the voltammetric response of both anthraquione-2-sulfonate (AQMS) and anthraquinone-2,6-disulfonate (AQDS) was measured over the full aqueous pH range. A model is provided which is able to describe not just the variation in the formal potential but also the peak height as a function of pH. Importantly, this model predicts that the formal potential for the first (Ef1) and second (Ef2) electron transfers are comparable in magnitude (E^θ _f2−E^_θf1 equals -15mV for AQMS and -36mV for AQDS). This quantitative model is then further extended to consider the situation in which the system is not fully buffered, giving insight into the change of pH at the electrode surface during experimentation. Adsorption to graphitic electrodes can impart a strong influence on the measured voltammetric response. It is demonstrated that through the pre-exposure of a newly prepared graphitic electrode to organic solvents, these adsorption processes can be predominantly blocked. Moreover, it is shown that the electroactivity of the electrode is not significantly altered. This thesis also highlights two cases in which adsorption of the electroactive species may be used to positive effect. First, the surface adsorption of anthraquinone-2-monosulfonate is studied on a graphite electrode, where it is demonstrated that the heterogeneity of the electrode surface may be probed through studying the electrochemical response of the adsorbed species. From this work it is concluded that the rate of electron transfer at the graphitic basal plane is 2-3 orders of magnitude lower than that observed on the edge plane sites. Second, the co-adsorption of DNA and anthraquinone-2-monosulfonate is used as an indirect method to measure the solution phase concentration of DNA (LOD = 8.8μM). The reduced form of anthraquinone is also known to readily reduce oxygen. Through the use of a boron-doped diamond electrode it was possible to directly study the anthraquinone mediated reduction mechanism. Significantly, the voltammetric response indicates the reduction of the oxygen via the semi-quinone intermediate (kf = 4.8 × 10⁹ mol⁻¹ dm³ s⁻¹) is over two orders of magnitude faster than the reaction involving the di-reduced form (kf = 1 × 10⁷ mol⁻¹ dm³ s⁻¹). More importantly, this work provides voltammetric evidence for the existence of the semi-quinone species. This work is subsequently extended through the investigation of the poorly soluble anthraquinone derivative quinizarin. Not only is it possible to detect voltammetrically this biologically relevant species to concentrations as low as 5nM (100ppt), but the methodology also allows the electrochemistry of the quinizarin species to be probed, something which was not previously possible.

[NiFe] hydrogenases are metalloenzymes that act as highly efficient molecular electrocatalysts for the interconversion of protons and molecular hydrogen. Unlike any other known molecular electrocatalyst, the members of a subgroup of respiratory membrane-bound [NiFe] hydrogenases are able to maintain H₂ catalysis in the sustained presence of O₂. This O₂-tolerance depends on the ability to respond to oxidative inactivation by O₂ by exclusively forming rapidly reactivated active site states, thus implying a catalytic cycle in which O₂ acts as a competing substrate to H₂. Using isotope ratio mass spectrometry it is proven that the O2-tolerant Escherichia coli Hydrogenase 1 responds to O₂ attack by acting as a four-electron oxidoreductase, catalysing the reaction 2 H₂ + O₂ → 2 H₂O, equivalent to hydrogen combustion. Special features of the enzyme’s electron relay system enable delivery of the required electrons. A small fraction of the H₂O produced arises from side reactions proceeding via reactive oxygen species, an unavoidable consequence of the presence of low-potential relay centres that release electrons from H₂ oxidation. While the ability to fully reduce O₂ to harmless H₂O at the active site to generate the rapidly reactivated state Ni-B, determines if a hydrogenase is O₂-tolerant, the ratio of oxidative inactivation to reductive reactivation rates determines how tolerant the enzyme is. It is shown by protein film electrochemistry that the (αβ)₂ dimeric assembly of Hyd-1 plays an important role in O₂-tolerance by aiding reactivation of one catalytic unit through electron transfer from the other. The teamwork between two redundant partners implicates a new role for dimerisation and represents a new example of cooperativity in biology. Finally, the non-natural amino acid p-azido-L-phenylalanine was synthesised and incorporated into Hyd-1, testing the possibility of introducing labels at specific sites.