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At least 73 records · Page 4

Conversion of laser energy to chemical energy by the photoassisted electrolysis of water

Ultraviolet irradiation of the n-type semiconductor TiO2 crystal electrode of an aqueous electrochemical cell evolves O2 at the TiO2 electrode and H2 at the Pt electrode. The gases are typically evolved in a 2:1 (H2:O2) volume ratio. The photoassisted reaction seems to require applied voltages, but values as low as 0.25 V do allow the photoassisted electrolysis to proceed. Prolonged irradiation in either acid or base evolves the gaseous products in amounts which clearly demonstrate that the reaction is catalytic with respect to the TiO2. The wavelength response of the TiO2 and the correlation of product yield and current are reported. The results support the claim that TiO2 is a true photoassistance agent for the electrolysis of water. Minimum optical storage efficiencies of the order of 1 percent can be achieved by the production of H2.

Wrighton, M. S.

Innovative techniques for the production of energetic radicals for lunar processing including cold plasma processing of local planetary ores

Hydrogen reduction of ilmenite has been studied by a number of investigators as a potential means for recovery of oxygen from lunar soil. Interest in this process has always rested with the simplicity of the flow diagram and the utilization of established technology. Effective utilization of hydrogen in the reduction process at temperatures of 1200 C and below has always been disappointing and, as such, has led other investigators to focus attention on other systems. Effective utilization of hydrogen in the reduction of ilmenite can be significantly enhanced in the presence of a non-equilibrium hydrogen plasma. Ilmenite at solid specimen temperatures of 600 C to 970 C were reacted in a hydrogen plasma. Those experiments revealed that hydrogen utilization can be significantly enhanced. At a specimen temperature of 850 C the fraction of H2 reacted was 24 percent compared to the 7 percent theoretical limit calculated with thermodynamic theory for the same temperature. An added advantage for a hydrogen plasma involves further reduction of TiO2. Reduction of the iron oxide in ilmenite yields TiO2 and metallic iron as by products. Titanium forms a number of oxides including TiO, Ti2O3, Ti3O5 and the Magneli oxides (Ti4O7 to Ti50O99). In conventional processing of ilmenite with hydrogen it is possible to reduce TiO2 to Ti7O13 within approximately an hour, but with poor utilization of hydrogen on the order of one mole of H2 per thousand. In the cold or non-equilibrium plasma TiO2 can be rapidly reduced to Ti2O3 with hydrogen utilization exceeding 10 percent. Based on design considerations of the plasma reactor greater utilization of the hydrogen in the reduction of TiO2 is possible.

Bullard, D.

Lunar mare volcanism: Mixing of distinct, mantle source regions with KREEP-like component

Mare basalts comprise less than 1% of the lunar crust, but they constitute our primary source of information on the moon's upper mantle. Compositional variations between mare basalt suites reflect variations in the mineralogical and geochemical composition of the lunar mantle which formed during early lunar differentiation (4.5-4.4 AE). Three broad suites of mare basalt are recognized: very low-Ti (VLT) basalts with TiO2 less than 1 wt%, low-Ti basalts with TiO2 = 2-4 wt%, and high-Ti basalts with TiO2 = 10-14 wt%. Important subgroups include the Apollo 12 ilmenite basalts (TiO2 = 5-6 wt%), aluminous low-Ti mare basalts (TiO2 = 2-4 wt%, Al2O3 = 10-14 wt%), and the newly discovered Very High potassium (VHK) aluminous low-Ti basalts, with K2O = 0.4-1.5 wt%. The mare basalt source region has geochemical characteristics complementary to the highlands crust and is generally thought to consist of mafic cumulates from the magma ocean which formed the felsic crust by feldspar flotation. The progressive enrichment of mare basalts in Fe/Mg, alkalis, and incompatible trace elements in the sequence VLT basalt yields low-Ti basalt yields high-Ti basalt is explained by the remelting of mafic cumulates formed at progressively shallower depths in the evolving magma ocean. This model is also consistent with the observed decrease in compatible element concentrations and the progressive increase in negative Eu anomalies.

Shervais, John W.

Dimmable Electronic Ballast for a Gas Discharge Lamp

Titanium dioxide (TiO2) is the most efficient photocatalyst for organic oxidative degradation. TiO2 is effective not only in aqueous solution, but also in nonaqueous solvents and in the gas phase. It is photostable, biologically and chemically inert, and non-toxic. Low-energy UV light (approximately 375 nm, UV-A) can be used to photoactivate TiO2. TiO2 photocatalysis has been used to mineralize most types of organic compounds. Also, TiO2 photocatalysis has been effectively used in sterilization. This effectiveness has been demonstrated by its aggressive destruction of microorganisms, and aggressive oxidation effects of toxins. It also has been used for the oxidation of carbon monoxide to carbon dioxide, and ammonia to nitrogen. Despite having many attractive features, advanced photocatalytic oxidation processes have not been effectively used for air cleaning. One of the limitations of the traditional photocatalytic systems is the ballast that powers (lights) the bulbs. Almost all commercial off-the-shelf (COTS) ballasts are not dimmable and do not contain safety features. COTS ballasts light the UV lamp as bright as the bulb can be lit, and this results in shorter bulb lifetime and maximal power consumption. COTS magnetic ballasts are bulky, heavy, and inefficient. Several iterations of dimmable electronic ballasts have been developed. Some manifestations have safety features such as broken-bulb or over-temperature warnings, replace-bulb alert, logbulb operational hours, etc. Several electronic ballast boards capable of independently lighting and controlling (dimming) four fluorescent (UV light) bulbs were designed, fabricated, and tested. Because of the variation in the market bulb parameters, the ballast boards were designed with a very broad range output. The ballast boards can measure and control the current (power) for each channel.

Raducanu, Marius

Enhancing mobility and interface state engineering via UV-ozone treatment in BEOL-compatible ultrathin TiO 2 transistors

It has emerged as a potential candidate to improve the performance of monolithic-three-dimensional (M3D) integration of fused logic and memories through low-temperature in situ synthesis of high-performance metal–oxide–semiconductor (MOS) transistors. Here, we report the demonstration of the BEOL-compatible low thermal budget (350 °C) fabrication process of ultrathin-TiO2 transistors by the combination of RTA and UV-ozone treatment (RTA-UVOz). UV–ozone (UVOz) treatment of TiO2 anatase films significantly enhances stability, boosting ION current and field effect mobility (μ FE ) by two times of magnitude in TiO2 TFTs. UV ozone treatment helps to eliminate pre-existing oxygen vacancies and carbon contamination on TiO2 channels even at low temperature (100 °C), resulting in high-quality channel/dielectric interfaces with low interface states (D it ). During UVOz treatment, oxygen species (O x ) passivate the oxygen vacancies ($V$$^{2+}_{o}$), and hence low concentration of $V$$^{2+}_{o}$ would be left for ionization/de-ionization under PBS/NBS, leading to improved bias stress stability. Furthermore, the TiO 2 TFTs with thin ZrO 2 gate dielectric exhibited excellent performance including a lower subthreshold swing (SS) of 98 mV/dec with high drive I ON current ∼ 4.5 μA/μm, a high I ON /I OFF > 10 9 , and mobility μFE of 7 cm 2 /V-s under a battery powered voltage of 1 V. UV–ozone treatment enables high-performance, CMOS-compatible TiO 2 transistors with a low thermal budget, ideal for next-generation flexible, energy-efficient electronics.

BEOL

Photoproduction of I2, Br2, and Cl2 on n-semiconducting powder

The photosynthetic production of Br2 and Cl2 and the photocatalytic production of I2 from aqueous solutions of the respective halide ions in the presence of platinized semiconducting n-TiO2 powder are reported. Reactions were produced in 2-3 M oxygen-saturated aqueous solutions of KI, KBr or NaCl containing Pt-TiO2 powder which were irradiated by a high-pressure mercury lamp at a power of 400 mW/sq cm. Halogens are found to be produced in greater quantities when platinized TiO2 powders are used rather than pure TiO2, and rates of halogen production are observed to increase from Cl2 to Br2 to I2. The presence of the synthetic reactions producing Br2 and Cl2 with a net influx of energy indicates that an effective separation of the photoproduced electron-hole pair occurs in the semiconductor. Quantum efficiencies of the reaction, which increase with decreasing solution pH, are found to be as high as 30%, implying a solar-to-chemical energy conversion efficiency between 0.03% and 3% for the case of chlorine production. It is concluded that the photoproduction of halogens may be of practical value if product halogens are efficiently removed from the reaction cell.

Reichman, B.

Interaction of hydrogen chloride and water with oxide surfaces. III - Titanium dioxide

The adsorption of hydrogen chloride and water vapors on five TiO2 powders in both the anatase and rutile crystalline forms was studied as a function of temperature, pressure, and outgas conditions. The adsorbents were characterized utilizing X-ray powder diffraction, scanning electron microscopy, surface area analysis, indicator method, microelectrophoresis, XPS, and infrared spectroscopy. It was found that both outgas temperature and adsorption temperature influenced the adsorption of water vapor on TiO2, while water vapor adsorption on TiO2 was completely reversible. It is argued that the number of hydroxyl groups present on the surface determines the adsorption capacity of water on the different titanium dioxides. It was found that heats of immersion in water were affected significantly by outgas temperature. Hydrogen chloride adsorption isotherms at 30 C measured on TiO2 after outgassing at 100-400 C showed that a part of the total HCl adsorbed was irreversibly adsorbed. The highest HCl adsorption capacity per unit area was exhibited by anatase, while pure rutile exhibited the lowest adsorption capacity.

Siriwardane, R. V.

Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738

Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

Fryburg, G. C.

Lunar resources: Oxygen from rocks and soil

The first set of hydrogen reduction experiments to use actual lunar material was recently completed. The sample, 70035, is a coarse-grained vesicular basalt containing 18.46 wt. percent FeO and 12.97 wt. percent TiO2. The mineralogy includes pyroxene, ilmenite, plagioclase, and minor olivine. The sample was crushed to a grain size of less than 500 microns. The crushed basalt was reduced with hydrogen in seven tests at temperatures of 900-1050 C and pressures of 1-10 atm for 30-60 minutes. A capacitance probe, measuring the dew point of the gas stream, was used to follow reaction progress. Experiments were also conducted using a terrestrial basalt similar to some lunar mare samples. Minnesota Lunar Simulant (MLS-1) contains 13.29 wt. percent FeO, 2.96 wt. percent Fe2O3, and 6.56 wt. percent TiO2. The major minerals include plagioclase, pyroxene, olivine, ilmenite, and magnetite. The rock was ground and seived, and experiments were run on the less than 74- and 500-1168-micron fractions. Experiments were also conducted on less than 74-micron powders of olivine, pyroxene, synthetic ilmenite, and TiO2. The terrestrial rock and mineral samples were reduced with flowing hydrogen at 1100 C in a microbalance furnace, with reaction progress monitored by weight loss. Experiments were run at atmospheric pressure for durations of 3-4 hr. Solid samples from both sets of experiments were analyzed by Mossbauer spectroscopy, petrographic microscopy, scanning electron microscopy, tunneling electron microscopy, and x-ray diffraction. Apollo 17 soil 78221 was examined for evidence of natural reduction in the lunar environment. This sample was chosen based on its high maturity level (I sub s/FeO = 93.0). The FeO content is 11.68 wt. percent and the TiO2 content is 3.84 wt. percent. A polished thin section of the 90-150 micron size fraction was analyzed by petrographic microscopy and scanning electron microscopy.

Allen, C. C.

Mariner 10 multispectral images of the eastern limb and farside of the moon

We present the first analysis of Mariner 10 multispectral image data for the eastern limb and farside of the moon. A new, rigorous calibration of these data is used that provides results that are consistent with independently derived data sets. From these newly calibrated data, a color ratio image (0.48/0.58 micron) is produced to show relative TiO2 abundances in mare units on the eastern limb and farside of the moon. Our results indicate that the farside lunar mare deposits examined have TiO2 contents that are intermediate to low (2.5 pct TiO2) relative to mare deposits on the nearside. We find no evidence for areally extensive deposits of either very low titanium or high to very high titanium basalts in these portions of the moon. Our findings support previous interpretations that the source regions for lunar mare basalts are laterally heterogeneous. Additionally, examination of highland units reveals a relatively blue region that corresponds with a previously proposed cryptomare, suggesting enhanced TiO2 for this unit. Finally, based on these Mariner 10 data, telescopic spectral data, Galileo multispectral image data, and lunar meteorite analyses we speculate that volcanism in farside mare deposits did not include high titanium basalts.

Robinson, Mark S.

Lunar phase function effects on spectral ratios used for resource assessment

Groundbased telescopic CCD images of 36 selected locations on the moon were obtained in five 'standard' bandpasses at 12 phase angles ranging from -78 deg to +75 deg to measure phase function effects on the ratio values used to quantify the abundance of TiO2 and qualitatively indicate soil maturity. Consistent with previous studies, we find that the moon is 'bluer' at small phase angles, but that the effect on the ratio values for TiO2 abundance for the phase angles of our data is on the order of the measurement uncertainties throughout the range of abundances found in the mare. The effect is more significant as seen from orbiting spacecraft over a range of selenographic latitude. Spectral ratio images (400/560 and 400/730 nm) were used to map the abundance of TiO2 using the empirical relation found by Charlette et al from analysis of returned lunar soils. Additionally, the 950/560 and 950/730 nm image ratios were used to define the regions of mature mare soil in which the relation is valid. Although the phase function dependence on wavelength was investigated and quantified for small areas and the integrated disc, the effect specifically on TiO2 mapping was not rigorously determined. For consistency and convenience in observing the whole lunar front side, our mapping utilized images taken -15 deg less than alpha less than 15 deg when the moon was fully illuminated from earth; however, this includes the strong opposition peak.

Larson, S. M.

Airing Out Anthrax

The AiroCide TiO2 is an air-purifier that kills 93.3 percent of airborne pathogens that pass through it, including Bacillus anthraci, more commonly known as anthrax. It is essentially a spinoff of KES Science & Technology, Inc.'s Bio-KES system, a highly effective device used by the produce industry for ethylene gas removal to aid in preserving the freshness of fruits, vegetables, and flowers. The TiO2-based ethylene removal technology that is incorporated into the company's AiroCide TiO2 and Bio-KES products was first integrated into a pair of plant-growth chambers known as ASTROCULTURE(TM) and ADVANCED ASTROCULTURE(TM). Both chambers have housed commercial plant growth experiments in space on either the Space Shuttle or the International Space Station. The AiroCide TiO2 also has a proven record of destroying 98 percent of other airborne pathogens, such as microscopic dust mites, molds, and fungi. Moreover, the device is a verified killer of Influenza A (flu), E. coli, Staphylococcus aureas, Streptococcus pyogenes, and Mycoplasma pneumoniae, among many other harmful viruses.

Source record

Self-Cleaning Coatings and Materials for Decontaminating Field-Deployable Land and Water-Based Optical Systems

This technology exploits the organic decomposition capability and hydrophilic properties of the photocatalytic material titanium dioxide (TiO2), a nontoxic and non-hazardous substance, to address contamination and biofouling issues in field-deployed optical sensor systems. Specifically, this technology incorporates TiO2 coatings and materials applied to, or integrated as a part of, the optical surfaces of sensors and calibration sources, including lenses, windows, and mirrors that are used in remote, unattended, ground-based (land or maritime) optical sensor systems. Current methods used to address contamination or biofouling of these optical surfaces in deployed systems are costly, toxic, labor intensive, and non-preventative. By implementing this novel technology, many of these negative aspects can be reduced. The functionality of this innovative self-cleaning solution to address the problem of contamination or biofouling depends on the availability of a sufficient light source with the appropriate spectral properties, which can be attained naturally via sunlight or supplemented using artificial illumination such as UV LEDs (light emitting diodes). In land-based or above-water systems, the TiO2 optical surface is exposed to sunlight, which catalyzes the photocatalytic reaction, facilitating both the decomposition of inorganic and organic compounds, and the activation of superhydrophilic properties. Since underwater optical surfaces are submerged and have limited sunlight exposure, supplementary UV light sources would be required to activate the TiO2 on these optical surfaces. Nighttime operation of land-based or above-water systems would require this addition as well. For most superhydrophilic self-cleaning purposes, a rainwater wash will suffice; however, for some applications an attached rainwater collector/ dispenser or other fresh water dispensing system may be required to wash the optical surface and initiate the removal of contaminates. Deployment of this non-toxic,non-hazardous-technology will take advantage of environmental elements (i.e. rain and sunlight), increase the longevity of unattended optical systems, increase the amount of time between required maintenance, and improve the long-term accuracy of sensor measurements.

Ryan, Robert

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

Multifunctional Surface Treatment for Self-Sterilization and CO2 Sequestration for Sustainable Space Exploration

A long-term human space presence is dependent on maintaining a safe living environment. Disinfecting surfaces is essential to protecting astronauts from potential pathogens, as well as structural components of the habitat from damaging biofilms. Developing a surface coating that utilizes readily available light has the potential to provide sterilization with additional functionality. Titanium dioxide (TiO2) is a commonly used photocatalyst owing to its efficiency, economic feasibility, and safety to humans. TiO2 photocatalyst modified with other metals such as copper or iron could allow for self-sterilization, photocatalytic memory, and photoreduction of carbon dioxide (CO2) to fuels on Mars. Sustainable design of the photocatalyst should account for the resources available, specifically within the Martian and Lunar regolith. This project reviews the current technologies to design a TiO2 photocatalyst which can be incorporated into a space habitat’s inner lining.

Human Space Exploration

Characterizing the surface compositions of supported bimetallic PtSn clusters: Effects of cluster-support interactions and surface adsorbates

PtSn bimetallic clusters on TiO2(110) and highly oriented pyrolytic graphite (HOPG) surfaces have been characterized by scanning tunneling microscopy, low energy ion scattering (LEIS), Xray photoelectron spectroscopy, and temperature programmed desorption (TPD); density functional theory (DFT) calculations have also been performed to better understand adsorption of CO and D2 on the PtSn surfaces. On TiO2 at coverages of 2 ML of Pt and 2 ML of Sn, exclusively bimetallic clusters are formed for both orders of deposition because clusters of the first metal completely cover the surface such that all atoms of the second metal are incorporated into the existing clusters. In contrast, on HOPG, the high mobility and weak cluster-support interactions on HOPG result in much larger 2 ML monometallic clusters (~30 Å high) that do not completely cover the surface, and deposition of the second metal produces larger clusters as well as smaller ones. Despite the difference in cluster morphologies for the different orders of deposition and supports, the LEIS experiments demonstrate that in all cases, the PtSn clusters are rich in Sn at the surface, as expected based on the lower surface free energy for Sn compared to Pt. Furthermore, the +0.2 eV shift in the Sn(3d5/2) binding energy observed on all surfaces in the presence of Pt is consistent with PtSn alloy formation. Deposition of 2 ML of Sn on TiO2 produces two-dimensional clusters with oxidation of Sn and reduction of titania at the clustersupport interface, but addition of Pt to the Sn clusters causes Sn to diffuse away from this interface, leaving Sn in the metallic state. TPD experiments on 2 ML Pt/TiO2 with increasing coverages of Sn show that the number of adsorption sites for D2 sharply decreases to nearly zero at 0.5 ML, while CO adsorption decreases to zero only at much higher Sn coverages of 2 ML. DFT studies for Sn modified Pt surfaces and bulk structures demonstrate that for CO adsorption at low Sn coverages (<0.25 ML), the strong Pt-CO interactions induce diffusion of Pt to the cluster surface and the formation of a bulk Pt3Sn alloy, whereas D2 adsorption does not lead to interactions with the Pt surface that are strong enough to induce alloy formation. A single Sn adatom prevents D2 adsorption on four neighboring Pt atoms via site-blocking and the donation of electron density to Pt.

Li, Fangliang

A contactless in situ EFISH method for measuring electrostatic potential profile of semiconductor/electrolyte junctions

In photoelectrochemical cells, promising devices for directly converting solar energy into storable chemical fuels, the spatial variation of the electrostatic potential across the semiconductor–electrolyte junction is the key parameter that determines the cell performance. In principle, electric field induced second harmonic generation (EFISH) provides a contactless in situ spectroscopic tool to measure the spatial variation of electrostatic potential. However, the total second harmonic generation (SHG) signal contains the contributions of the EFISH signals of semiconductor space charge layer and the electric double layer, in addition to the SHG signal of the electrode surface. The interference of these complex quantities hinders their analysis. In this work, to understand and deconvolute their contributions to the total SHG signals, bias-dependent SHG measurements are performed on the rutile TiO2(100)–electrolyte junction as a function of light polarization and crystal azimuthal angle (angle of the incident plane relative to the crystal [001] axis). A quadratic response between SHG intensity and the applied potential is observed in both the accumulation and depletion regions of TiO2. The relative phase difference and amplitude ratio are extracted at selected azimuthal angles and light polarizations. At 0° azimuthal angle and s-in–p-out polarization, the SHG intensity minimum has the best match with the TiO2 flatband potential due to the orthogonal relative phase difference between bias-dependent and bias-independent SHG terms. We further measure the pH-dependent flatband potential and probe the photovoltage under open circuit conditions using the EFISH technique, demonstrating the capability of this contactless method for measuring electrostatic potential at semiconductor–electrolyte junctions.

Chemistry

Towards Spatial Control of Reaction Selectivity on Photocatalysts using Area Selective Atomic Layer Deposition on Model Dual Site Electrocatalyst Platform

Photocatalytic water splitting is a promising route to low-cost H2; however, this approach is currently limited by solar-to-hydrogen (STH) conversion efficiencies in the sub-10% range. Z-scheme water splitting, in which H2 and O2 evolving particles are operated in separate compartments and electronically coupled by a soluble redox mediator, offers improvements in STH efficiency but introduces high rates of undesired side and back reactions. Nanoscopic oxide coatings (e.g., CrOx, and SiOx) have previously been used to selectively block undesired reactants from reaching active sites; however, a coating encapsulating the entire photocatalyst particle limits activity as the particle can no longer facilitate both half reactions. In contrast to photodeposition, which may produce non-uniform overlayers due to the difficulty of controlling local electrochemical reactivity on the surface, area-selective atomic layer deposition (AS-ALD) can be used to deposit conformal ultrathin oxide coatings while preserving access to non-growth areas of a substrate surface. To develop this technique for Z-scheme photocatalysts, we performed AS-ALD of TiO2 on a dual site planar electrocatalyst based on interdigitated arrays of Pt and Au. Self-assembled monolayers of 1-octadecanethiol (ODT) were used to block growth on the Au array, resulting in a patterned surface in which only the Pt sites were encapsulated with TiO2. These electrocatalysts demonstrated localized reaction selectivity for hydrogen evolution reaction (HER) over the TiO2/Pt sites, while the uncoated Au sites retained activity towards Fe(II)/Fe(III) redox (FeRR). Under independent potential control, these microelectrodes showed that selectively deposited TiO2 coatings can suppress the rate of back reactions on neighboring active sites by an order of magnitude compared to uncoated control samples.

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