Making solar fuels by artificial photosynthesis

In order for solar energy to serve as a primary energy source, it must be paired with energy storage on a massive scale. At this scale, solar fuels and energy storage in chemical bonds is the only practical approach. Solar fuels are produced in massive amounts by photosynthesis with the reduction of CO(2) by water to give carbohydrates but efficiencies are low. In photosystem II (PSII), the oxygen-producing site for photosynthesis, light absorption and sensitization trigger a cascade of coupled electron-proton transfer events with time scales ranging from picoseconds to microseconds. Oxidative equivalents are built up at the oxygen evolving complex (OEC) for water oxidation by the Kok cycle. A systematic approach to artificial photo synthesis is available based on a ""modular approach"" in which the separate functions of a final device are studied separately, maximized for rates and stability, and used as modules in constructing integrated devices based on molecular assemblies, nanoscale arrays, self-assembled monolayers, etc. Considerable simplification is available by adopting a ""dyesensitized photoelectrosynthesis cell"" (DSPEC) approach inspired by dye-sensitized solar cells (DSSCs). Water oxidation catalysis is a key feature, and significant progress has been made in developing a single-site solution and surface catalysts based on polypyridyl complexes of Ru. In this series, ligand variations can be used to tune redox potentials and reactivity over a wide range. Water oxidation electrocatalysis has been extended to chromophore-catalyst assemblies for both water oxidation and DSPEC applications.

Synthetic strategies to nanostructured photocatalysts for CO2 reduction to solar fuels and chemicals

Artificial photosynthesis represents one of the great scientific challenges of the 21st century, offering the possibility of clean energy through water photolysis and renewable chemicals through CO2 utilisation as a sustainable feedstock. Catalysis will undoubtedly play a key role in delivering technologies able to meet these goals, mediating solar energy via excited generate charge carriers to selectively activate molecular bonds under ambient conditions. This review describes recent synthetic approaches adopted to engineer nanostructured photocatalytic materials for efficient light harnessing, charge separation and the photoreduction of CO2 to higher hydrocarbons such as methane, methanol and even olefins.

Materiali ceramici a struttura Aurivillius per la produzione di solar fuels

Solar fuels from CO2 is a topic of current large scientific and industrial interest. In particular, photo-electrochemical cells (PECs) represent today one of the most promising technology for storing sun energy as chemical bonds exploiting carbon dioxide as starting reagent. In this thesis, the possibility of using Aurivillius-type compounds for the production of solar fuels was deeply investigated. Aurivillius-type perovskites, with general formula Bi(n+1)Fe(n-3)Ti3O(3n+3), were synthesized and fully characterized to study the influence of the number of perovskite layers as well as of the synthesis parameters onto their final properties. In particular, 8 different systems were considered increasing the amount of iron and, as a consequence, the number of perovskite layers. These compounds were synthesized through a standard solid-state reaction method as well as via a sol-gel technique and characterized by XRD, SEM and BET analyses. The band gap value and the photocatalytic activity towards Rhodamine B decomposition were assessed as well. For each system, a screen-printing ink was formulated to be deposited as photo-electrodes onto transparent conducting supports. The photo-electrodes were morphologically characterized by XRD and SEM analysis, and their electrochemical properties (cyclic and linear voltammetry, EIS, Mott-Schottky analysis) were determined. Finally, the most promising materials were tested as photo-cathode inside PEC cell under different illumination conditions, to quantify their ability to convert CO2. The obtained results show the potentiality of Aurivillius-type compounds as innovative material for carbon dioxide photo-electrochemical reduction.

A New Reactor Concept for Efficient Solar-Thermochemical Fuel Production

We describe and analyze the efficiency of a new solar-thermochemical reactor concept, which employs a moving packed bed of reactive particles produce of H-2 or CO from solar energy and H2O or CO2. The packed bed reactor incorporates several features essential to achieving high efficiency: spatial separation of pressures, temperature, and reaction products in the reactor; solid-solid sensible heat recovery between reaction steps; continuous on-sun operation; and direct solar illumination of the working material. Our efficiency analysis includes material thermodynamics and a detailed accounting of energy losses, and demonstrates that vacuum pumping, made possible by the innovative pressure separation approach in our reactor, has a decisive efficiency advantage over inert gas sweeping. We show that in a fully developed system, using CeO2 as a reactive material, the conversion efficiency of solar energy into H-2 and CO at the design point can exceed 30%. The reactor operational flexibility makes it suitable for a wide range of operating conditions, allowing for high efficiency on an annual average basis. The mixture of H-2 and CO, known as synthesis gas, is not only usable as a fuel but is also a universal starting point for the production of synthetic fuels compatible with the existing energy infrastructure. This would make it possible to replace petroleum derivatives used in transportation in the U. S., by using less than 0.7% of the U. S. land area, a roughly two orders of magnitude improvement over mature biofuel approaches. In addition, the packed bed reactor design is flexible and can be adapted to new, better performing reactive materials.

Molecular and hybrid systems for solar-to-chemical energy conversion

My Ph.D. thesis was dedicated to the exploration of different paths to convert sunlight into the shape of chemical bonds, by the formation of solar fuels. During the past three years, I have focused my research on two of these, namely molecular hydrogen H2 and the reduced nicotinamide adenine dinucleotide enzyme cofactor NAD(P)H. The first could become the ideal energy carrier for a truly clean energy system; it currently represents the best chance to liberate humanity from its dependence on fossil fuels. To address this, I studied different systems which can achieve proton reduction upon light absorption. More specifically, part of my work was aimed to the development of a cost-effective and stable catalyst in combination with a well-known photochemical cycle. To this extent, I worked on transition metal oxides which, as demonstrated in this work, have been identified as promising H2 evolution catalysts, showing excellent activity, stability, and previously unreported versatility. Another branch of my work on hydrogen production dealt with the use of a new class of polymeric semiconductor materials to absorb light and convert it into H2. The second solar fuel mentioned above is a key component of the most powerful methods for chemical synthesis: enzyme catalysis. The high cost of the reduced forms prohibits large-scale utilization, so artificial photosynthetic approaches for regenerating it are being intensively studied. The first system I developed exploits the tremendous reducing properties of a scarcely known ruthenium complex which is able to reduce NAD+. Lastly, I sought to revert the classical role of the sacrificial electron donor to an active component of the system and, to boost the process, I build up an autonomous microfluidic system able to generate highly reproducible NAD(P)H amount, demonstrating the superior performance of microfluidic reactors over batch and representing another successful photochemical NAD(P)H regeneration system.

A química de coordenação e a produção de combustíveis solares

Life on earth depends on the absorption and conversion of solar energy into chemical bonds, i.e. photosynthesis. In this process, sun light is employed to oxidize water into oxygen and reducing equivalents used to produce fuels. In artificial photosynthesis, the goal is to develop relatively simple systems able to mimic photosynthetic organisms and promote solar-to-chemical conversion. The aim of the present review was to describe recent advances in the application of coordination compounds as catalysts in some key reactions for artificial photosynthesis, such as water splitting and CO2 reduction.

V-substituted In2S3: an intermediate band material with photocatalytic activity in the whole visible light range

We proposed in our previous work V-substituted In2S3 as an intermediate band (IB) material able to enhance the efficiency of photovoltaic cells by combining two photons to achieve a higher energy electron excitation, much like natural photosynthesis. Here this hyper-doped material is tested in a photocatalytic reaction using wavelength-controlled light. The results evidence its ability to use photons with wavelengths of up to 750 nm, i.e. with energy significantly lower than the bandgap (=2.0 eV) of non-substituted In2S3, driving with them the photocatalytic reaction at rates comparable to those of non-substituted In2S3 in its photoactivity range (λ ≤ 650 nm). Photoluminescence spectra evidence that the same bandgap excitation as in V-free In2S3 occurs in V-substituted In2S3 upon illumination with photons in the same sub-bandgap energy range which is effective in photocatalysis, and its linear dependence on light intensity proves that this is not due to a nonlinear optical property. This evidences for the first time that a two-photon process can be active in photocatalysis in a single-phase material. Quantum calculations using GW-type many-body perturbation theory suggest that the new band introduced in the In2S3 gap by V insertion is located closer to the conduction band than to the valence band, so that hot carriers produced by the two-photon process would be of electron type; they also show that the absorption coefficients of both transitions involving the IB are of significant and similar magnitude. The results imply that V-substituted In2S3, besides being photocatalytically active in the whole visible light range (a property which could be used for the production of solar fuels), could make possible photovoltaic cells of improved efficiency.

Facile synthesis of hierarchical Cu2O nanocubes as visible light photocatalysts

Hierarchically structured Cu2O nanocubes have been synthesized by a facile and cost-effective one-pot, solution phase process. Self-assembly of 5 nm Cu2O nanocrystallites induced through reduction by glucose affords a mesoporous 375 nm cubic architecture with superior visible light photocatalytic performance in both methylene blue dye degradation and hydrogen production from water than conventional non-porous analogues. Hierarchical nanocubes offer improved accessible surface active sites and optical/electronic properties, which act in concert to confer 200–300% rate-enhancements for the photocatalytic decomposition of organic pollutants and solar fuels.

Engineering interfacial silicon dioxide for improved metal-insulator-semiconductor silicon photoanode water splitting performance

Silicon photoanodes protected by atomic layer deposited (ALD) TiO2 show promise as components of water splitting devices that may enable the large-scale production of solar fuels and chemicals. Minimizing the resistance of the oxide corrosion protection layer is essential for fabricating efficient devices with good fill factor. Recent literature reports have shown that the interfacial SiO2 layer, interposed between the protective ALD-TiO2 and the Si anode, acts as a tunnel oxide that limits hole conduction from the photoabsorbing substrate to the surface oxygen evolution catalyst. Herein, we report a significant reduction of bilayer resistance, achieved by forming stable, ultrathin (<1.3 nm) SiO2 layers, allowing fabrication of water splitting photoanodes with hole conductances near the maximum achievable with the given catalyst and Si substrate. Three methods for controlling the SiO2 interlayer thickness on the Si(100) surface for ALD-TiO2 protected anodes were employed: (1) TiO2 deposition directly on an HF-etched Si(100) surface, (2) TiO2 deposition after SiO2 atomic layer deposition on an HF-etched Si(100) surface, and (3) oxygen scavenging, post-TiO2 deposition to decompose the SiO2 layer using a Ti overlayer. Each of these methods provides a progressively superior means of reliably thinning the interfacial SiO2 layer, enabling the fabrication of efficient and stable water oxidation silicon anodes.

Sintesi e caratterizzazione di CaCu3Ti4O12 (CCTO) per applicazioni in fotoelettrocatalisi

A promising strategy to mitigate both the energy crisis and global warming is the development of solar fuels and chemicals using as feedstock CO2 in combination with simple molecules such as water. This process stores the solar energy into chemical bonds, leading to a carbon-neutral approach of fuels and chemicals production. Aim of this thesis was the synthesis and characterization of CaCu3Ti4O12 (CCTO)- based compounds to be used as visible light photocatalyst for CO2 to chemical conversion. Different compositions were produced doping CCTO with increasing concentration of iron into the perovskite’s A site in order to identify the materials with the highest photo- and photoelectrocatalytic properties. The most promising compositions were used to produce photoelectrodes by screen printing that were characterized by linear and cyclic voltammetry, impedance spectroscopy and Mott-Schottky analysis to evaluate the electrical conductivity and calculate the flat band potential and the number of charge carriers in the samples. The photoelectrodes were then tested in a photoelectrochemical (PEC) cell for the conversion of CO2 into fuel and chemicals. The results obtained confirm that CCTO-based materials can be considered promising materials for carbon dioxide photo-electrochemical reduction.

Environmental analysis of a Concentrated Solar Power (CSP) plant hybridised with different fossil and renewable fuels

The environmental performance of a 50 MW parabolic trough Concentrated Solar Power (CSP) plant hybridised with different fuels was determined using a Life Cycle Assessment methodology. Six different scenarios were investigated, half of which involved hybridisation with fossil fuels (natural gas, coal and fuel oil), and the other three involved hybridisation with renewable fuels (wheat straw, wood pellets and biogas). Each scenario was compared to a solar-only operation. Nine different environmental categories as well as the Cumulative Energy Demand and the Energy Payback Time (EPT) were evaluated using Simapro software for 1 MWh of electricity produced. The results indicate a worse environmental performance for a CSP plant producing 12% of the electricity from fuel than in a solar-only operation for every indicator, except for the eutrophication and toxicity categories, whose results for the natural gas scenario are slightly better. In the climate change category, the results ranged between 26.9 and 187 kg CO2 eq/MWh, where a solar-only operation had the best results and coal hybridisation had the worst. Considering a weighted single score indicator, the environmental impact of the renewable fuels scenarios is approximately half of those considered in fossil fuels, with the straw scenario showing the best results, and the coal scenario the worstones. EPT for solar-only mode is 1.44 years, while hybridisation scenarios EPT vary in a range of 1.72 -1.83 years for straw and pellets respectively. The fuels with more embodied energy are biomethane and wood pellets.

Surface Plasmon-Induced Band Gap in the Photocurrent Response of Organic Solar Cells

A 260 nm layer of organic bulk heterojunction blend of the polymer poly(3-hexylthiophene) (P3HT) and the fullerene [6,6]-phenyl C(61)-butyric (PCBM) was spin-coated in between aluminum and gold electrodes, respectively, on top of a laser inscribed azo polymer surface-relief diffraction grating. Angle-dependent surface plasmons (SPs) with a large band gap were observed in the normalized photocurrent by the P3HT-PCBM layer as a function of wavelength. The SP-induced photocurrents were also investigated as a function of the grating depth and spacing.

Performance of a solar energy powered falling film evaporator with film promoter

A solar energy powered failing film evaporator with film promoter was developed for concentrating diluted solutions (industrial effluents). The procedure proposed here does not emit CO(2), making it a viable alternative to the method of concentrating solutions that uses vapor as a heat source and releases CO(2) from burning fuel oil in a furnace, in direct opposition to the carbon reduction agreement established by the Kyoto protocol. This novel device consists of the following components: a flat plate solar collector with adjustable inclination, a film promoter (adhering to the collector), a liquid distributor, a concentrate collector. and accessories. The evaporation rate of the device was found to be affected both by the inclination of the collector and by the feed flow. The meteorological variables cannot be controlled, but were monitored constantly to ascertain the behavior of the equipment in response to the variations occurring throughout the day. Higher efficiencies were attained when the inclination of the collector was adjusted monthly, showing up to 36.4% higher values than when the collector remained in a fixed position. (c) 2008 Elsevier Ltd. All rights reserved.

Central de produção de energia eléctrica a partir de energia solar térmica

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica