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At least 19 records

Metal–Carbodithioate-Based 3D Semiconducting Metal–Organic Framework: Porous Optoelectronic Material for Energy Conversion

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate"(-CS 2 ) n M" linkage chemistry, entailing augmented metal-linker electronic communication. The stronger ligand field and higher covalent character of metal-carbodithioate linkages-when combined with spirofluorene-derived organic struts and nickel-(II) ion-based nodes-provided a stable, semiconducting 3D-porous MOF, Spiro-CS 2 Ni. This MOF lacks long-range ordering and is defined by a flexible structure with non-aggregated building units, as suggested by reverse Monte Carlo simulations of the pair distribution function obtained from total scattering experiments. The solvent-removed "closed pore"material recorded a Brunauer-Emmett-Teller area of similar to 400m 2 /g, where the "open pore" form possesses90 wt % solvent-accessible porosity. Electrochemical measurements suggest that Spiro-CS 2 Ni possesses a band gap of 1.57 eV(sigma = 10 -7 S/cm at -1.3 V bias potential),which can be further improved by manipulating the d-electron configuration through an axial coordination (ligand/substrate), the latter of which indicates usefulness as an electrocatalyst and/or a photoelectrocatalyst(upon substrate binding). Transient-absorption spectroscopy reveals a long-lived photo-generated charge-transfer state (τ CR = 6.5 mu s) capable of chemical transformation under a biased voltage. Spiro-CS 2 Ni can endure a compelling range of pH(1-12 for weeks) and hours of electrochemical and photoelectrochemical conditions in the presence of water and organic acids. We believe this work provides crucial design principles for low-density, porous,light-energy-conversion materials.

36 MATERIALS SCIENCE↗

Nanostructured Solar Irradiation Control Materials for Solar Energy Conversion

Tailoring the solar absorptivity (alpha(sub s)) and thermal emissivity (epsilon(sub T)) of materials constitutes an innovative approach to solar energy control and energy conversion. Numerous ceramic and metallic materials are currently available for solar absorbance/thermal emittance control. However, conventional metal oxides and dielectric/metal/dielectric multi-coatings have limited utility due to residual shear stresses resulting from the different coefficient of thermal expansion of the layered materials. This research presents an alternate approach based on nanoparticle-filled polymers to afford mechanically durable solar-absorptive and thermally-emissive polymer nanocomposites. The alpha(sub s) and epsilon(sub T) were measured with various nano inclusions, such as carbon nanophase particles (CNPs), at different concentrations. Research has shown that adding only 5 wt% CNPs increased the alpha(sub s) and epsilon(sub T) by a factor of about 47 and 2, respectively, compared to the pristine polymer. The effect of solar irradiation control of the nanocomposite on solar energy conversion was studied. The solar irradiation control coatings increased the power generation of solar thermoelectric cells by more than 380% compared to that of a control power cell without solar irradiation control coatings.

Kang, Jinho↗

Application of ultrathin TiO 2 layers in solar energy conversion devices

Abstract A vital pursuit in solar energy research is to achieve high efficiency and long‐term stability in energy conversion devices. Coating or sandwiching an ultrathin layer of TiO 2 onto active solar components has been demonstrated to be a remarkably effective and facile strategy to improve their stability. The TiO 2 film acts as a protection layer and enhances solar energy conversion efficiency by passivating surface recombination sites or facilitating electron transport. To date, numerous efforts have been devoted to applying ultrathin TiO 2 layers in various kinds of solar energy conversion devices. In this study, we review deposition techniques, characterization methods of the resulting ultrathin TiO 2 layer, as well as its applications in dye‐sensitized solar cells, organic–inorganic hybrid solar cells, and photoelectrochemical cells.

36 MATERIALS SCIENCE↗

Infrared transmissive concentrated photovoltaics for coupling solar electric energy conversion to solar thermal energy utilization

The use of photovoltaic (PV) cells to convert solar energy to electricity is becoming increasingly prevalent; however, there are still significant limitations associated with the widespread adoption of PV cells for electricity needs. There is a clear need for a high efficiency solar power system that supplies electricity at a competitive cost and that provides for an on-demand supply of electricity as well as energy storage. By combining aspects of concentrated solar power and concentrated photovoltaics, the present invention provides a device that enables the conversion of sunlight to electricity at very high efficiencies and that enables the transmission of thermal energy to heat storage devices for later use. The disclosed device enables transmissive CPV through the use of a multijunction PV cell mounted on a transparent base. The use of a multijunction cell allows for highly efficient absorption of light above the bandgap of the lowest bandgap subcell. The transparent base permits transmission of a high percentage of the remaining light below the bandgap of the lowest bandgap subcell. The present invention also discloses a method of generating electricity through the use of a transmissive CPV device. Sunlight is concentrated onto one or more surfaces of the device. High energy light is absorbed by a multijunction PV cell and converted directly to electricity, while low energy light is transmitted through the device into a thermal storage device, which may then be coupled to a heat engine to generate dispatchable electricity.

Escarra, Matthew David↗

Understanding and controlling the fundamental photochemistry of protonic solar energy conversion (Final Scientific/Technical Report)

The selectivity and activity of most fuel-forming reactions are tunable by the concentration of electrons, holes, protons, and/or hydroxides. That is one reason why traditional solar energy conversion processes are used to drive these reactions, where light directly increases the concentration of electrons and holes. We, instead, took a different approach, using light to increase the concentration of protons and/or hydroxides. For this, we leveraged photophysical and solid-state physics theories, techniques, and design strategies previously developed for the study of traditional solar energy conversion processes. We designed and fabricated several materials platforms based on molecular photoacid and photobase dyes coupled with ion-exchange polymer membranes and assessed their fundamental photoelectrochemistry. We demonstrated control over built-in electric potentials, photovoltages, proton-transfer kinetics, and efficiency limits to our approach. Understanding the basic science of these dye-sensitized protonic membranes and their photochemical mechanisms is of use to the DOE-relevant processes of solar photochemical fuel formation, solar photodialytic desalination, and solar cells. Moreover, functional materials that we developed from this project may be of use to several broad-reaching fields and may provide the foundation for a completely new, inexpensive, and robust solar energy conversion technology.

14 SOLAR ENERGY↗

Harnessing surface plasmons for solar energy conversion

NASA research on the feasibility of solar-energy conversion using surface plasmons is reviewed, with a focus on inelastic-tunnel-diode techniques for power extraction. The need for more efficient solar converters for planned space missions is indicated, and it is shown that a device with 50-percent efficiency could cost up to 40 times as much per sq cm as current Si cells and still be competitive. The parallel-processing approach using broadband carriers and tunable diodes is explained, and the physics of surface plasmons on metal surfaces is outlined. Technical problems being addressed include phase-matching sunlight to surface plasmons, minimizing ohmic losses and reradiation in energy transport, coupling into the tunnels by mode conversion, and gaining an understanding of the tunnel-diode energy-conversion process. Diagrams illustrating the design concepts are provided.

Anderson, L. M.↗

Photoelectrochemical materials for solar energy conversion

Research and development on semiconductors for applications in solar energy conversion has witnessed rapid growth over the past several decades. With the aim of producing chemical fuels from sunlight, intense research efforts have focused on the discovery of semiconductors with crystalline structures and chemical compositions that have the potential to satisfy the complex set of required photoelectrochemical properties. This chapter focuses on the foundational structure-property relationships of selected oxide and nitride semiconductors relevant to their uses as n-/p-type photoelectrodes and as photocatalysts. Their solid-state structures and compositions are described, with a special emphasis on strategies proven effective at targeting suitable band gaps with strong visible-light absorption, efficient charge separation and diffusion of charge carriers, and optimal band edge energies for driving surface redox reactions for water splitting.

O’Donnell, Shaun↗

Insolation data for solar energy conversion derived from satellite measurements of earth radiance

Detailed knowledge of the irradiance of the sun at ground locations is essential for the design and evaluation of solar energy conversion systems. The primary source of such data is the global network of weather stations. Such stations are often too far apart and for most locations the data available are only daily total irradiance or monthly averages. Solar energy conversion programs require insolation data with considerably higher geographical and temporal resolution. Meteorological satellites gather routinely extensive data on the energy reflected and scattered into space by the earth-atmosphere system. A program has been initiated to use such data for deriving ground insolation for energy conversion. Some of the preliminary results of this program will be discussed.

Thekaekara, M. P.↗

Electron/hole selectivity in organic semiconductor contacts for solar energy conversion (Final Report)

Four major and accomplishments for the project "Electron/hole selectivity in organic semiconductor contacts for solar energy conversion.'' are reported. The first is a development of a model describing the contact-determined behavior of a solar cell. The most basic solar cell consists of an intrinsic (pure) semiconductor that acts as an absorber to which contacts are made that provide the asymmetry needed to create a driving force (voltage) for the directional flow of electrons (current), in other words, to convert sunlight into electrical energy. The asymmetry at the contacts comes from the different rate at which electrons and holes, the charge carriers generated by illumination, are collected. We developed a model that describes the ideal current-voltage, and hence energy converting properties, of an ideal photovoltaic that is entirely determined by the kinetics for these charge collection processes. Second, we measured how organic semiconductor interfacial layers impact contact electron and hole transfer rates at semiconductor interfaces and described how these concepts do or do not determine the open-circuit voltage of a solar cell. The work clearly controverts common general misconceptions about the action of contact interfacial layers, such as the idea that improved selectivity for one carrier over the other results from decreased recombination, and quantitatively demonstrates how specific interfacial layer materials act to improve the efficiency of a solar cell. Third, we measured the sub-band gap external quantum efficiency (EQE) of a series of organometal halide perovskite (“perovskite”) solar cells. These measurements quantified band-tailing and revealed defect states, which can cause recombination, that correlate with composition, performance, and hysteresis. Finally, we developed a semiconductor bipolar membrane that uses light to pump ions. This structure is unique among systems that drive ion gradients using light in that it is designed to pump salt rather than one sign of ion; it is a photochemical salt pump.

14 SOLAR ENERGY↗

Tandem photovoltaic solar cells and increased solar energy conversion efficiency

Tandem photovoltaic cells, as proposed by Jackson (1955) to increase the efficiency of solar energy conversion, involve the construction of a system of stacked p/n homojunction photovoltaic cells composed of different semiconductors. It had been pointed out by critics, however, that the total power which could be extracted from the cells in the stack placed side by side was substantially greater than the power obtained from the stacked cells. A reexamination of the tandem cell concept in view of the development of the past few years is conducted. It is concluded that the use of tandem cell systems in flat plate collectors, as originally envisioned by Jackson, may yet become feasible as a result of the development of economically acceptable solar cells for large scale terrestrial power generation.

Loferski, J. J.↗

Solar energy conversion using surface plasmons for broadband energy transport

A new strategy for efficient solar energy conversion based on parallel processing with surface plasmons is introduced. The approach is unique in identifying: (1) a broadband carrier with suitable range for energy transport, and (2) a technique to extract more energy from the more energetic photons, without sequential losses or unique materials for each frequency band. The aim is to overcome the fundamental losses associated with the broad solar spectrum and to achieve a higher level of spectrum splitting than has been possible in semiconductor systems.

Anderson, L. M.↗

Development of low-cost silicon crystal growth techniques for terrestrial photovoltaic solar energy conversion

Because of the growing need for new sources of electrical energy, photovoltaic solar energy conversion is being developed. Photovoltaic devices are now being produced mainly from silicon wafers obtained from the slicing and polishing of cylindrically shaped single crystal ingots. Inherently high-cost processes now being used must either be eliminated or modified to provide low-cost crystalline silicon. Basic to this pursuit is the development of new or modified methods of crystal growth and, if necessary, crystal cutting. If silicon could be grown in a form requiring no cutting, a significant cost saving would potentially be realized. Therefore, several techniques for growth in the form of ribbons or sheets are being explored. In addition, novel techniques for low-cost ingot growth and cutting are under investigation.

Zoutendyk, J. A.↗

Thermodynamic limits to the efficiency of solar energy conversion by quantum devices

The second law of thermodynamics imposes a strict limitation to the energy converted from direct solar radiation to useful work by a quantum device. This limitation requires that the amount of energy converted to useful work (energy in any form other than heat) can be no greater than the change in free energy of the radiation fields. Futhermore, in any real energy conversion device, not all of this available free energy in the radiation field can be converted to work because of basic limitations inherent in the device itself. A thermodynamic analysis of solar energy conversion by a completely general prototypical quantum device is presented. This device is completely described by two parameters, its operating temperature T sub R and the energy threshold of its absorption spectrum. An expression for the maximum thermodynamic efficiency of a quantum solar converter was derived in terms of these two parameters and the incident radiation spectrum. Efficiency curves for assumed solar spectral irradiance corresponding to air mass zero and air mass 1.5 are presented.

Buoncristiani, A. M.↗

Advanced solar energy conversion

An atomic iodine laser, a candidate for the direct solar pumped lasers, was successfully excited with a 4 kW beam from a xenon arc solar simulator, thus proving the feasibility of the concept. The experimental set up and the laser output as functions of operating conditions are presented. The preliminary results of the iodine laser amplifier pumped with the HCP array to which a Q switch for giant pulse production was coupled are included. Two invention disclosures - a laser driven magnetohydrodynamic generator for conversion of laser energy to electricity and solar pumped gas lasers - are also included.

Lee, J. H.↗

Silicon Schottky photovoltaic diodes for solar energy conversion

Various factors in Schottky barrier solar cell fabrication are evaluated in order to improve understanding of the current flow mechanism and to isolate processing variables that improve efficiency. Results of finger design, substrate resistivity, surface finishing and activation energy studies are detailed. An increased fill factor was obtained by baking of the vacuum system to remove moisture.

Anderson, W. A.↗

BiVO 4 –Liquid Junction Photovoltaic Cell with 0.2% Solar Energy Conversion Efficiency

BiVO 4 is an important photoanode material for water oxidation, but its photoelectrochemistry regarding the triiodide/iodide redox couple is not well understood. Here, we use a combination of open circuit potential measurements, photoelectrochemical scans, and liquid surface photovoltage spectroscopy (SPS) to confirm that BiVO 4 /triiodide/iodide electrolyte contacts produce up to 0.55 V photovoltage under 23 mW/cm –2 illumination from a 470 nm LED. Inspired by these results, we construct FTO/BiVO 4 /KI(I 2 ) aq /Pt sandwich photoelectrochemical cells from electrochemically grown 0.5 × 0.5 cm 2 BiVO 4 and Mo-doped BiVO 4 films. Under AM 1.5 illumination, the devices have up to 0.22% energy conversion efficiency, 0.32 V photovoltage, and 1.8 mA cm –2 photocurrent. Based on SPS, hole transfer to iodide is sufficiently fast to prevent the competing water oxidation reaction. Mo doping increases the incident photon-to-current efficiency to up to 55% (at 425 nm under front illumination) by improving the BiVO 4 conductivity, but this comes at the expense of a lower photovoltage resulting from recombination at the Mo defects and a detrimental Schottky junction at the interface with FTO. Additional photovoltage losses are caused by the offset between the BiVO 4 valence band edge and the triiodide/iodide electrochemical potential and by electron back transfer to iodide at the FTO back contact (shunting). Overall, this work provides the first example of a BiVO 4 –liquid photovoltaic cell and an analysis of its limitations. Finally, even though the larger band gaps of metal oxides constrain their solar energy conversion efficiency, their transparency to visible light and deep valence bands makes them suitable for tandem photovoltaic devices.

14 SOLAR ENERGY↗

Tracking Photochemical and Photophysical Processes for Solar Energy Conversion Via Multidimensional Visible and Vibrational Spectroscopic Methods

This project was motivated by an overarching goal to elucidate the mechanism of energy and electron transfer that governs the efficient charge separation in photosystem I (PSI) complexes. PSI is a natural light harvesting complex that drives oxygenic photosynthesis in plants, algae, and cyanobacteria. It uses ~300 tightly packed chlorophylls (Chls) to absorb photons, transfer the excitation energy to the reaction center (RC), and generate a charge separated state with near unity quantum efficiency (QE). A better understanding of the mechanism of energy transfer and charge separation in PSI is required for understanding the high QE of natural light harvesting complexes, and it could lead to the further development of artificial photosynthetic systems for solar energy conversion. We applied two-dimensional electronic spectroscopy (2DES) to different cyanobacterial photosystem I complexes to map energy transfer pathways to gain insight into the efficient light harvesting of PSI. We interpreted the 2DES spectra through a global analysis procedure, finding two ultrafast equilibration processes involving red-shifted Chl states. The analysis procedure is general and can be readily applied to other natural and artificial light harvesting systems. In addition to investigating PSI complexes, we also performed measurements on model systems to establish general data analysis procedures for interpreting 2D spectra.

14 SOLAR ENERGY↗