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At least 271 records · Page 15

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NASA NTRS1979

Future production of hydrogen from solar energy and water - A summary and assessment of U.S. developments

The paper examines technologies of hydrogen production. Its delivery, distribution, and end-use systems are reviewed, and a classification of solar energy and hydrogen production methods is suggested. The operation of photoelectric processes, biophotolysis, photocatalysis, photoelectrolysis, and of photovoltaic systems are reviewed, with comments on their possible hydrogen production potential. It is concluded that solar hydrogen derived from wind energy, photovoltaic technology, solar thermal electric technology, and hydropower could supply some of the hydrogen for air transport by the middle of the next century.

Hanson, J. A.↗

NASA NTRS1982

A study of the photocatalytic effects of aqueous suspensions of platinized semiconductor materials on the reaction rates of candidate redox reactions

The effectiveness of powdered semiconductor materials in photocatalyzing candidate redox reactions was investigated. The rate of the photocatalyzed oxidation of cyanide at platinized TiO2 was studied. The extent of the cyanide reaction was followed directly using an electroanalytical method (i.e. differential pulse polarography). Experiments were performed in natural or artificial light. A comparison was made of kinetic data obtained for photocatalysis at platinized powders with rate data for nonplatinized powders.

Miles, A. M.↗

NASA NTRS1992

Heterogeneous photocatalytic oxidation of atmospheric trace contaminants

A two year study to examine the feasibility of using heterogeneous photocatalysis for spacecraft air purification was begun at North Carolina State University on November 1, 1990. The original grant proposal included examination of the rates of destruction of anticipated spacecraft-generated air contaminants, including alcohols, aldehydes, chlorinated compounds, as well as trace levels of volatile compounds containing nitrogen, sulfur, and silicon. The progress made in the second six month period of 5/1/91-11/1/91 is discussed.

Ollis, David F.↗

NASA NTRS2009

Measuring the Photocatalytic Breakdown of Crystal Violet Dye using a Light Emitting Diode Approach

A simple method to estimate the photocatalytic reactivity performance of spray-on titanium dioxide coatings for transmissive glass surfaces was developed. This novel technique provides a standardized method to evaluate the efficiency of photocatalytic material systems over a variety of illumination levels. To date, photocatalysis assessments have generally been conducted using mercury black light lamps. Illumination levels for these types of lamps are difficult to vary, consequently limiting their use for assessing material performance under a diverse range of simulated environmental conditions. This new technique uses an ultraviolet (UV) gallium nitride (GaN) light emitting diode (LED) array instead of a traditional black light to initiate and sustain photocatalytic breakdown. This method was tested with a UV-resistant dye (crystal violet) applied to a titanium dioxide coated glass slide. Experimental control is accomplished by applying crystal violet to both titanium dioxide coated slides and uncoated control slides. A slide is illuminated by the UV LED array, at various light levels representative of outdoor and indoor conditions, from the dye side of the slide. To monitor degradation of the dye over time, a temperature-stabilized white light LED, whose emission spectrum overlaps with the dye absorption spectrum, is used to illuminate the opposite side of the slide. Using a spectrometer, the amount of light from the white light LED transmitted through the slide as the dye degrades is monitored as a function of wavelength and time and is subsequently analyzed. In this way, the rate of degradation for photocatalytically coated versus uncoated slide surfaces can be compared. Results demonstrate that the dye absorption decreased much more rapidly on the photocatalytically coated slides than on the control uncoated slides, and that dye degradation is dependent on illumination level. For photocatalytic activity assessment purposes, this experimental configuration and methodology minimizes many external variable effects and enables small changes in absorption to be measured. This research also compares the advantages of this innovative LED light source design over traditional mercury black light systems and non- LED lamp approaches. This novel technology begins to address the growing need for a standard method that can assess the performance of photocatalytic materials before deployment for large scale, real world use.

Ryan, Robert E.↗

NASA NTRS2009

An LED Approach for Measuring the Photocatalytic Breakdown of Crystal Violet Dye

A simple technique to assess the reactivity of photocatalytic coatings sprayed onto transmissive glass surfaces was developed. This new method uses ultraviolet (UV) gallium nitride (GaN) light-emitting diodes (LEDs) to drive a photocatalytic reaction (the photocatalytic breakdown of a UV-resistant dye applied to a surface coated with the semiconductor titanium dioxide); and then a combination of a stabilized white light LED and a spectrometer to track the dye degradation as a function of time. Simple, standardized evaluation techniques that assess photocatalytic materials over a variety of environmental conditions, including illumination level, are not generally available and are greatly needed prior to in situ application of photocatalytic technologies. To date, much research pertaining to this aspect of photocatalysis has been limited and has focused primarily on laboratory experiments using mercury lamps. Mercury lamp illumination levels are difficult to control over large ranges and are temporally modulated by line power, limiting their use in helping to understand and predict how photocatalytic materials will behave in natural environmental settings and conditions. The methodology described here, using steady-state LEDs and time series spectroradiometric techniques, is a novel approach to explore the effect of UV light on the photocatalytic degradation of a UV resistant dye (crystal violet). GaN UV LED arrays, centered around 365 nm with an adjustable DC power supply, are used to create a small, spatially uniform light field where the steady state light level can be varied over three to four orders of magnitude. For this study, a set of glass microscope slides was custom coated with a thinly sprayed layer of photocatalytic titanium dioxide. Crystal violet was then applied to these titanium-dioxide coated slides and to uncoated control slides. The slides were then illuminated at various light levels from the dye side of the slide by the UV LED array. To monitor dye degradation on the slides over time, a temperature-stabilized white light LED was used to illuminate the opposite side of the slides. As the dye degraded, the amount of light from the white light LED transmitted through the slide was monitored with a spectrometer and subsequently analyzed to determine and compare the rate of dye degradation for photocatalytically coated versus uncoated slide surfaces. The long-term stability of the spectrometer/white light LED combination, which required only a single reference spectra to be taken for a time series sequence of several hours, enabled accurate measurements of transmitted light over time. Time series transmission curves were generated and results demonstrated that over time the transmission increased much more rapidly on the coated slides than on the control slides. This experimental configuration and methodology for photocatalytic activity measurement minimizes many external variable effects and allows low light level studies to be performed. This study also compares the advantages of this novel LED light source design to traditional mercury lamp systems and non-LED lamp approaches that have conventionally been used. The methodology and experimental design research summarized in this abstract is partly funded by the Department of Homeland Security, Science and Technology Directorate, and by the NASA Stennis Space Center Innovative Partnerships Program.

Ryan, Robert E.↗

NASA NTRS2007

Photocatalytic/Magnetic Composite Particles

Photocatalytic/magnetic composite particles have been invented as improved means of exploiting established methods of photocatalysis for removal of chemical and biological pollutants from air and water. The photocatalytic components of the composite particles are formulated for high levels of photocatalytic activity, while the magnetic components make it possible to control the movements of the particles through the application of magnetic fields. The combination of photocatalytic and magnetic properties can be exploited in designing improved air- and water treatment reactors.

Wu, Chang-Yu↗

NASA NTRS2011

Radiation-Resistant Hybrid Lotus Effect for Achieving Photoelectrocatalytic Self-Cleaning Anticontamination Coatings

An experiment involving radiation-resistant hydrophobic coatings is planned for space exposure and experimental testing on the International Space Station (ISS) in 2011. The Lotus biocide coatings are designed for supporting space exploration missions. This innovation is an antibacterial, anti-contamination, and self-cleaning coating that uses nano-sized semiconductor semimetal oxides to neutralize biological pathogens and toxic chemicals, as well as to mitigate dust accumulation (see figure). The Lotus biocide coating is thin (approximately microns thick), lightweight, and the biocide properties will not degrade with time or exposure to biological or chemical agents. The biocide is stimulated chemically (stoichiometric reaction) through exposure to light (photocatalysis), or by an applied electric field (electrocatalysis). The hydrophobic coating samples underwent preliminary high-energy proton and alpha-ray (helium ion) irradiations at the Lawrence Berkeley National Laboratory 88" cyclotron and demonstrated excellent radiation resistance for a portion of the Galactic Cosmic Ray (GRC) and Solar Proton spectrum. The samples will undergo additional post-flight studies when returned to Earth to affirm further the radiation resistance properties of the space exposed coatings.

Taylor, Edward W.↗

NASA NTRS2012

Visible Light Responsive Catalysts Using Quantum Dot-Modified Ti02 for Air and Water Purification

The method of photocatalysis utilizing titanium dioxide, TiO2, as the catalyst has been widely studied for trace contaminant control for both air and water applications because of its low energy consumption and use of a regenerable catalyst. Titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors and are a setback for the technology for space application due to the possibility of Hg contamination. The development of a visible light responsive (VLR) TiO2-based catalyst could lead to the use of solar energy in the visible region (approx.45% of the solar spectrum lies in the visible region; > 400 nm) or highly efficient LEDs (with wavelengths > 400 nm) to make PCO approaches more efficient, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts; those that are available still have poor activity in the visible region compared to that in the UV region. Thus, this study was aimed at the further development of VLR catalysts by a new method - coupling of quantum dots (QD) of a narrow band gap semiconductor (e.g., CdS, CdSe, PbS, ZnSe, etc.) to the TiO2 by two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications, using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems serve as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, type of quantum dots, and dosage of quantum dots.

Coutts, Janelle L.↗

NASA NTRS2013

Studying the Use of Photocatalytic Coatings to Increase Building/Structure Sustainability and Cleanliness at NASA Stennis Space Center

TiO2 coated surfaces demonstrated both visually through photographic representation, and quantitatively, through reflectance measurements that they improved upon the current state of cleanliness upon the surfaces that they were applied to. TiO2 has the potential to both maintain and increase building s sustainability and the overall appearance of cleanliness TiO2 coated slides degraded soot under UV light compared to soot samples on plain uncoated slides under the same conditions Degradation of soot by photocatalysis was far more apparent than degradation of soot by UV light alone This demonstration provides the foundation for a laboratory model that could be used to simulate real world applications for photocatalytic materials Additional research is required to better understand the full potential of TiO2

Underwood, Lauren↗

NASA NTRS2014

Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.

visible light↗

NASA NTRS2014

Visible-Light Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

visible light↗

NASA NTRS2015

Visible-Light-Responsive Catalyst Development for Volatile Organic Carbon Remediation Project

Photocatalysis is a process in which light energy is used to 'activate' oxidation/reduction reactions. Unmodified titanium dioxide (TiO2), a common photocatalyst, requires high-energy UV light for activation due to its large band gap (3.2 eV). Modification of TiO2 can reduce this band gap, leading to visible-light-responsive (VLR) photocatalysts. These catalysts can utilize solar and/or visible wavelength LED lamps as an activation source, replacing mercury-containing UV lamps, to create a "greener," more energy-efficient means for air and water revitalization. Recently, KSC developed several VLR catalysts that, on preliminary evaluation, possessed high catalytic activity within the visible spectrum; these samples out-performed existing commercial VLR catalysts.

Technology Portfolio System↗

NASA NTRS2016

Photocatalytic Conversion of CO2 on Mars

Light on Mars shows potential for providing the energy means necessary for enhanced In-Situ Resource Utilization (ISRU). Through photocatalysis, the energy barrier required to convert CO2 is lowered and CH4 production is favorable.

Photoreactor↗

DOE OSTI2024

Oxidizing Role of Cu Cocatalysts in Unassisted Photocatalytic CO 2 Reduction Using p-GaN/Al 2 O 3 /Au/Cu Heterostructures

Not Available

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DOE OSTI2021

Dynamic Control of Photocatalytic Proton Reduction through the Mechanical Actuation of a Hydrogel Host Matrix

This paper describes a photocatalytic hydrogen evolution system that is dynamically and reversibly responsive to the pH of the surrounding solution through actuation of a micro-hydrogel (microgel) matrix that hosts the photocatalysts (CdSe/CdS nanorods). Here, the reversible actuation occurs within 0.7 s (swelling) and 1.7 s (contraction). A ΔpH of 0.01 relative to the pK a of the tertiary amine on the microgel polymer (7.27) results in a reversible change in the average diameter of the microgel hosts by a factor of 2.5 and a change in the photocatalytic turnover frequency (TOF) by a factor of five. Kinetic isotope effect and photoluminescence quenching experiments reveal that the scavenging of the photoexcited hole by sulfite ions is the rate-limiting step and leads to the observed response of the TOF to pH through actuation of the microgel. Molecular dynamics simulations quantify a greater local concentration of sulfite hole scavengers for pH < pK a .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Highly Active Rutile TiO 2 Nanocrystalline Photocatalysts

The controllable synthesis of rutile TiO 2 single crystal particles with the preferential orientation of {111} facets still remains a scientific and technological challenge. Here, we developed a facile route for fabrication of rutile TiO 2 nanorod crystals (RTiO 2 NRs) having high ratios of oxidative {111} to reductive {110} surfaces. RTiO 2 NRs were synthesized using a peroxo-titanium complex (PTC) approach, which was controlled by changing the Ti/H 2 O 2 ratio. The thus obtained RTiO 2 NRs revealed a high tendency to agglomerate through orientation-dependent attachment along the {110} facets. This resulted in an increased {111}/{110} surface ratio and led to a markedly improved photocatalytic activity of RTiO 2 NR aggregates. The reported findings illustrate the rich potential of the herein proposed facile and energy-efficient synthesis of nanostructured rutile TiO 2 -based photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Shapeshifting Nanocatalyst for CO2 Conversion

The conversion of CO2 into high-value chemicals through a photoreduction reaction in water is a promising route to reduce the dependence on fossil fuels. Enhancing selectivity toward hydrocarbons or alcohols can be achieved by Ag-Cu alloys. However, the stabilized surface state created by Ag-Cu interactions is still poorly understood. In this work, multi-modal in situ X-ray experiments reveals underlying mechanisms and the evolution of Ag-Cu nanoparticles under CO2 reduction reaction (CO2RR) conditions. Both morphological and chemical changes of Ag and Cu species induced by diffusion mechanics are tracked during nanocatalyst operation. The initial spheroid Ag-Cu nanoparticles are composed of a Cu-rich shell and Ag-rich core. The reduction treatment promotes Ag migration toward the surface. During photocatalytic CO2 reduction reaction, Cu atoms migrate back to the surface, forming Ag-Cu-O species. The study observes the surface oxidation of Cu(0) to Cu+ and the presence of Ag at the sub-surface region. Furthermore, nanoparticles change their shape, decreasing their specific surface area, driven by Cu diffusion during the CO2 photoreduction reaction. The results provide invaluable insights into the dynamic restructuring of the catalyst under reaction conditions and into the active species responsible for CO2 conversion.

CO2 reduction reaction↗

DOE OSTI2022

Dicyanobenzothiadiazole (DCBT) Organic Dye as a Visible Light Absorbing Strong Photoinduced Oxidant with a 16 Microsecond Long–Lived Excited State

Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar energy conversion and long–lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6–dicyano[2,1,3]benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady–state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. Finally, the long–lived excited state photosensitizer is well–suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water–soluble photosensitizer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗