As the cost of solar energy continues to drop, the major hurdle limiting the widespread use of intermittent renewable solar energy is the lack of efficient and cost-effective energy storage. Electrochemical technologies, such as electrolyzers, photoelectrochemical cells, and fuel cells, have the potential to compensate for solar energy intermittency on a large scale, by converting excess solar energy into storable solar fuels, such as hydrogen (H2), which can be converted back to electrical energy at a later time. However, improvements in the efficiency and lifetime of these technologies, in particular the electrocatalysts, are necessary for their commercialization. During operation, efficiency losses result from energetic penalties (overpotentials) associated with several processes occurring at or near the electrocatalyst/electrolyte (ohmic resistance, kinetic barriers, and mass transport limitations). These losses can be further exacerbated due to electrocatalyst durability issues such as dissolution, agglomeration, detachment, and poisoning. A major challenge in electrocatalysis field is developing methods to mitigate these losses without adversely affecting the electrocatalytic stability, selectivity, and/or activity. One promising solution is an oxide-encapsulated electrocatalyst architecture, which has been shown to improve electrocatalyst durability and provide mechanisms for controlling reaction pathways. Previous studies on oxide-encapsulated electrocatalysts, in which metal catalysts are fully or partially covered by ultrathin layers of permeable oxide films, have mostly focused on supported nanoparticles because of their high electrochemically active surface area per catalyst loading. However, these nanoparticle-based architectures tend to have poorly defined and/or non-uniform structures which make it difficult to understand and elucidate structure-property-relationships. This dissertation investigates well-defined oxide-coated electrocatalysts, which serve as model platforms for gaining a fundamental understanding of kinetic and transport phenomena that underlie their operation. This dissertation presents three studies which highlight the versatile functionalities of oxide-encapsulated electrocatalysts to improve the electrocatalyst stability, selectivity, and activity in different electrochemical systems. This dissertation demonstrates the ability of room temperature synthesized silicon oxide (SiOx)-encapsulated Pt electrocatalysts to: i) stabilize nanoparticles and improve electron transfer, ii) mitigate catalyst poisoning and control reaction pathways through selective transport, and iii) alter reaction energetics associated with catalysis at the buried interface. First, this dissertation establishes the ability of room temperature synthesized SiOx coatings to stabilize nanoparticle electrocatalysts by mitigating electrocatalyst migration, coalescence, and detachment on metal-insulator-semiconductor (MIS) photoelectrodes for solar-driven water splitting. Metallic Pt nanoparticles are inherently unstable on the insulating support due to poor physical adhesion and electronic coupling between Pt and SiO2. To overcome this issue, a room temperature UV ozone synthesis process was used to deposit 2-10 nm thick SiOx overlayers on top of electrodeposited Pt nanoparticles to stabilize Pt on the electrode surface. The photoelectrodes containing oxide-encapsulated electrocatalysts exhibit superior durability and electron transfer (ohmic) properties compared to the photoelectrode that lacked the SiOx encapsulation. While this study demonstrates that the oxide-encapsulated electrocatalyst architecture improves the stability of electrocatalytic nanoparticles deposited on insulating materials, it does not elucidate how reactants and products transport through the SiOx barrier to reach the Pt surface. In order to gain a better understanding of kinetic and transport phenomena that govern performance of oxide-encapsulated electrocatalysts, the following studies investigate model electrodes consisting of continuous SiOx overlayers of uniform thickness deposited onto smooth Pt thin films. This planar electrode geometry allows for simple and unambiguous characterization of structure-property relationships. The next study systematically evaluates the influence of SiOx thickness on the HER performance to understand species transport through SiOx. Through detailed characterization and electroanalytical tests, it is shown that proton and H2 transport occur primarily through the SiOx coating such that the HER occurs at the buried Pt|SiOx interface. Importantly, the SiOx nanomembranes were found to exhibit high selectivity for proton and H2 transport compared to Cu2+, a model HER poison. Leveraging this property, it is shown that SiOx–encapsulation can enable poison-resistant operation of Pt HER electrocatalysts. This oxide-encapsulated architecture offers a promising approach to enhancing electrocatalyst stability while incorporating advanced catalytic functionalities such as poison resistance or tunable reaction selectivity. The final study demonstrates ability of SiOx overlayers to alter reaction energetics associated with catalysis at the buried interface. Carbon monoxide (CO), methanol, and ethanol oxidation reactions are studied for their relevance in direct alcohol fuel cell applications. Oxide-supported catalysts have been shown to enhance alcohol oxidation by promoting CO oxidation at metal/oxide interfacial regions through the so-called bifunctional mechanism, in which hydroxyls on the oxide facilitate the removal of adsorbed CO−intermediates from active sites. A key advantage of the oxide-encapsulated electrocatalyst design compared to oxide–supported nanoparticles is that the former maximizes the density of metal/oxide interfacial sites. This study shows that the SiOx overlayer provides proximal hydroxyls, in the form of silanol groups, which can enhance CO and alcohol oxidation through unique interactions at the buried Pt|SiOx interface. Overall, this dissertation highlights the potential of using oxide-encapsulated electrocatalysts for stable, selective, and efficient electrochemical production and use of solar fuels.

Solar energy has the potential to meet all of society’s energy demands, but challenges remain in storing it for times when the sun is not shining. Electrolysis is a promising means of energy storage which applies solar-derived electricity to drive the production of chemical fuels. These so-called solar fuels, such as hydrogen gas produced from water electrolysis, can be fed back to the grid for electricity generation or used directly as a fuel in the transportation sector. Solar fuels can be generated by coupling a photovoltaic (PV) cell to an electrolyzer, or by directly converting light to chemical energy using a photoelectrochemical cell (PEC). Presently, both PV-electrolyzers and PECs have prohibitively high capital costs which prevent them from generating hydrogen at competitive prices. This dissertation explores the design of membraneless electrolyzers and PECs in order to simplify their design and decrease their overall capital costs. A membraneless water electrolyzer can operate with as few as three components: A cathode for the hydrogen evolution reaction, an anode for the oxygen evolution reaction, and a chassis for managing the flows of a liquid electrolyte and the product gas streams. Absent from this device is an ionically conducting membrane, a key component in a conventional polymer electrolyte membrane (PEM) electrolyzer that typically serves as a physical barrier for separating product gases generated at the anode and cathode. These membranes can allow for compact and efficient electrolyzer designs, but are prone to degradation and failure if exposed to impurities in the electrolyte. A membraneless electrolyzer has the opportunity to reduce capital costs and operate in non-pristine environments, but little is known about the performance limitations and design rules that govern operation of membraneless electrolyzers. These design rules require a thorough understanding of the thermodynamics, kinetics, and transport processes in electrochemical systems. In Chapter 2, these concepts are reviewed and a framework is provided to guide the continuum scale modeling of the performance of membraneless electrochemical cells. Afterwards, three different studies are presented which combine experiment and theory to demonstrate the mechanisms of product transport and efficiency loss. Chapter 3 investigates the dynamics of hydrogen bubbles during operation of a membraneless electrolyzer, which can strongly affect the product purity of the collected hydrogen. High-speed video imaging was implemented to quantify the size and position of hydrogen gas bubbles as they detach from porous mesh electrodes. The total hydrogen detected was compared to the theoretical value predicted by Faraday’s law. This analysis confirmed that not all electrochemically generated hydrogen enters the gas phase at the cathode surface. In fact, significant quantities of hydrogen remain dissolved in solution, and can result in lower product collection efficiencies. Differences in bubble volume fraction evolved along the length of the cathode reflect differences in the local current densities, and were found to be in agreement with the primary current distribution. Overall, this study demonstrates the ability to use in-situ HSV to quantitatively evaluate key performance metrics of membraneless electrolyzers in a non-invasive manner. This technique can be of great value for future experiments, where statistical analysis of bubble sizes and positions can provide information on how to collect hydrogen at maximum purity. Chapter 4 presents an electrode design where selective placement of the electrocatalyst is shown to enhance the purity of hydrogen collected. These “asymmetric electrodes” were prepared by coating only one planar face of a porous titanium mesh electrode with platinum electrocatalyst. For an opposing pair of electrodes, the platinum coated surface faces outwards such that the electrochemically generated bubbles nucleate and grow on the outside while ions conduct through the void spacing in the mesh and across the inter-electrode gap. A key metric used in evaluating the performance of membraneless electrolyzers is the hydrogen cross-over percentage, which is defined as the fraction of electrochemically generated hydrogen that is collected in the headspace over the oxygen-evolving anode. When compared to the performance of symmetric electrodes – electrodes coated on both faces with platinum – the asymmetric electrodes demonstrated significantly lower rates of cross-over. With optimization, asymmetric electrodes were able to achieve hydrogen cross-over values as low as 1%. These electrodes were then incorporated into a floating photovoltaic electrolysis device for a direct demonstration of solar driven electrolysis. The assembled “solar fuels rig” was allowed to float in a reservoir of 0.5 M sulfuric acid under a light source calibrated to simulate sunlight, and a solar to hydrogen efficiency of 5.3% was observed. In Chapter 5, the design principles for membraneless electrolyzers were applied to a photoelectrochemical (PEC) cell. Whereas an electrolyzer is externally powered by electricity, a PEC cell can directly harvest light to drive an electrochemical reaction. The PEC reactor was based on a parallel plate design, where the current was demonstrated to be limited by the intensity of light and the concentration of the electrolyte. By increasing the average flow rate of the electrolyte, mass transport limitations could be alleviated. The limiting current density was compared to theoretical values based off of the solution to a convection-diffusion problem. This modeled solution was used to predict the limitations to PEC performance in scaled up designs, where solar concentration mirrors could increase the total current density. The mass transport limitations of a PEC flow cell are also highly relevant to the study of CO2 reduction, where the solubility limit of CO2 in aqueous electrolyte can also limit performance.

Renewable energy for energy production, like Solar, is turning out to be very pertinent in today's world [1]. It is very clear that Solar Energy is going to emerge as one of the key sources of energy in future. Moreover, the storage option is going to play an essential role to the future deployment of solar power plants. Concentrated solar power plants with thermal storage, photovoltaic plants integrated with battery energy storage, and hybrid plants are attractive solutions to obtain a stable and dispatchable energy production. Investors or policymakers usually find it challenging to come up with the most feasible solar storage technology because they need to consider techno-economic feasibility, and at the same time, from a market or administrative perspective as well. So, this thesis study will address the key problem which is aimed at investors or policymakers since there is a need to choose the best solar storage technology at a utility level in future based on so many attributes. The thesis project was carried out in two phases which includes forecast modelling & estimations and techno-economic assessment of virtual plants. These two phases helped to address various questions in relation to the problem statement of this study. The entire thesis study broadly covered seven countries spanning across four major regions around the world. The first phase of the thesis, forecast modelling estimations shows how the seven countries will look in future (2020 – 2050) with respect to installed capacity and costs for PV, CSP, and BESS technologies. Some major results from phase 1 include, in low-cost estimates, China will remain to be the market leader in PV & CSP by 2050. In U.S.A and India, the installed costs of PV are projected to decline by 70% by 2050. By 2050, the installed costs of Solar Tower technology are estimated to drop by about 65% in China and Spain. In U.S.A, the prices of BESS technology are likely to fall by around 58 – 60 % by 2050. In the second phase of thesis study, a techno-economic evaluation of virtual plants addressed the aspects which are to be considered for a solar project if it is deployed in future across seven specific countries. Results from this analysis helps investors or policymakers to choose the cheapest solar storage technology at a utility level across seven specific countries in future (2020 – 2050). Key results from this analysis show that, in the U.S.A, by 2050, PV+BESS will be the cheapest storage technology for 4 – 10 storage hours. Addition of another renewable technology will add up more viability to the comparison. In China, Hybrid will be the cheapest storage technology for 4 – 8 hrs by 2050. There is huge potential for deployment of CSP & hybrid plants in future than PV. In South Africa, CSP will be the cheapest storage technology by 2050 for 4 – 10 hours of storage. It is assumed that deployment of BESS projects at utility level starts from 2025 in South Africa. Beyond this, market forces analysis was carried out which offers insights especially for the policymakers of how various drivers and constraints are influencing each solar technology across the specific countries in future. Overall, the entire thesis study provides guidelines/insights to investors or policy makers for choosing the best solar storage technology in future at a utility scale for a particular country. / Förnybar energi för energiproduktion, liksom Solar, visar sig vara mycket relevant i dagens värld [1]. Det är mycket tydligt att solenergi kommer att framstå som en av de viktigaste energikällorna i framtiden. Dessutom kommer lagringsalternativet att spela en väsentlig roll för den framtida distributionen av solkraftverk. Koncentrerade solkraftverk med värmelagring, solcellsanläggningar integrerade med batterilagring och hybridanläggningar är attraktiva lösningar för att få en stabil och skickbar energiproduktion. Investerare eller beslutsfattare brukar tycka att det är utmanande att komma på den mest genomförbara solcellstekniken eftersom de måste överväga teknikekonomisk genomförbarhet, och samtidigt, ur ett marknads- eller administrativt perspektiv också. Så denna avhandlingsstudie kommer att ta itu med nyckelproblemet som riktar sig till investerare eller beslutsfattare eftersom det finns ett behov av att välja den bästa solenergilagringstekniken på en användningsnivå i framtiden baserat på så många attribut. Avhandlingsprojektet genomfördes i två faser som inkluderar prognosmodellering och uppskattningar och teknikekonomisk bedömning av virtuella anläggningar. Dessa två faser hjälpte till att ta itu med olika frågor i samband med problemstudien i denna studie. Hela avhandlingsstudien omfattade i stort sju länder som sträcker sig över fyra stora regioner runt om i världen. Den första fasen i avhandlingen, prognosmodelleringsuppskattningar visar hur de sju länderna kommer att se ut i framtiden (2020 - 2050) med avseende på installerad kapacitet och kostnader för PV-, CSP- och BESS -teknik. Några viktiga resultat från fas 1 inkluderar, i lågkostnadsuppskattningar, att Kina kommer att vara marknadsledande inom PV och CSP år 2050. I USA och Indien beräknas de installerade kostnaderna för PV minska med 70% år 2050. Av 2050 beräknas de installerade kostnaderna för Solar Tower -teknik sjunka med cirka 65% i Kina och Spanien. I USA kommer priserna på BESS -teknik sannolikt att sjunka med cirka 58 - 60 % år 2050. I den andra fasen av avhandlingsstudien behandlade en teknikekonomisk utvärdering av virtuella anläggningar de aspekter som ska övervägas för ett solprojekt om det används i framtiden i sju specifika länder. Resultaten från denna analys hjälper investerare eller beslutsfattare att välja den billigaste solenergilagringstekniken på en användningsnivå i sju specifika länder i framtiden (2020 - 2050). Viktiga resultat från denna analys visar att i USA, år 2050, kommer PV+BESS att vara den billigaste lagringstekniken på 4 - 10 lagringstimmar. Tillägg av en annan förnybar teknik kommer att öka jämförbarheten. I Kina kommer Hybrid att vara den billigaste lagringstekniken i 4-8 timmar fram till 2050. Det finns en enorm potential för distribution av CSP & hybridanläggningar i framtiden än PV. I Sydafrika kommer CSP att vara den billigaste lagringstekniken år 2050 för 4 - 10 timmars lagring. Det antas att distributionen av BESS -projekt på verktygsnivå börjar från 2025 i Sydafrika. Utöver detta genomfördes marknadskravsanalys som ger insikter speciellt för beslutsfattarna om hur olika drivkrafter och begränsningar påverkar varje solteknik i de specifika länderna i framtiden. Sammantaget ger hela avhandlingsstudien riktlinjer/insikter till investerare eller beslutsfattare för att välja den bästa solenergitekniken i framtiden i en nyttoskala för ett visst land.