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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Effective interactions of the open bosonic string via field theory

Abstract We describe a method to extract an effective Lagrangian description for open bosonic strings, at zero transcendentality. The method relies on a particular formulation of its scattering amplitudes derived from color-kinematics duality. More precisely, starting from a (DF) 2 + YM quantum field theory, we integrate out all the massive degrees of freedom to generate an expansion in the inverse string tensionα′. We explicitly compute the Lagrangian terms through$$ \mathcal{O} $$ O (α′ 4 ), and target the sector of operators proportional toF 4 to all orders inα′.

Physics↗
DOE OSTI2016

Oxidation of Cyclohexene Catalyzed by Nanoporous Au(Ag) in Liquid Phase

Nanoporous gold with minor silver content has been identified as a new type of gold based catalyst for selective oxidation of cyclohexene with molecular oxygen in liquid. By oxidation of the leached nanoporous gold foils in ozone, the minor silver content was oxidized in this paper to form silver oxide nanoclusters on the surface of nanoporous gold. With further treatment in methanol, the surface silver oxide was reduced and surface alloy was formed on gold ligaments. Both nanoporous gold treated with ozone only and the one with ozone and then methanol are very active for selective oxidation of cyclohexene with molecular oxygen in liquid of cyclohexene with a turn-over-frequency (TOF) of 0.55–0.99 molecules per surface Au atom per second under a solvent-free and initiator- free condition. The total selectivity for production of 2-cyclohexene-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide was increased from 57.5 % to 80.8 % by an additional treatment of nanoporous gold in methanol after activation in zone. Finally, the correlation of catalytic selectivity for the production of the three products and corresponding surface chemistry of ligament suggests that (1) the formed Au–Ag alloy surface is favorable for the formation of 2-cyclohexen-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide and (2) the surface silver oxide is favorable for the production of cyclohexenyl hydroperoxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Ultrafast Laser Welding and Terahertz Time-domain Spectroscopy of Soda Lime Silicate Glass

Joining and welding techniques of similar and dissimilar materials have reached their limits due to the inflexibility of adapting dielectric materials, e.g., glasses and ceramics, reproducibility for transparent materials, and cycle process time. The ability to join pieces of glasses using laser irradiation allows rapid processing of vacuum insulating glass (VIG) for a widening range of commercial energy-efficient applications. We have used a 1064-nm laser wavelength with 15 picoseconds pulse width and a 155-kHz repetition rate to weld commercial plate glass pieces. The welded samples were characterized via x-ray fluorescence (XRF), time-of-flight secondary ion mass spectrometry (TOF–SIMS), polarimetry, and terahertz time-domain spectroscopy (THz-TDS) to determine the integrity of the weld and chemical changes in the welded areas. Our data shows no significant changes in glass chemistry and structure on average over nano- to micro-scales occurred from the welding process within the limits of the characterization tools. Our results demonstrate successful welding of glass plates without significant changes in the glass chemistry, structure, or properties in the laser-modified region or strains in the bulk glass.

Matthies, Kathleen [ORNL] (ORCID:0009000213135441)↗
DOE OSTI2018

Biosynthesis, Microstructural Characterisations and Investigation of In-Vitro Mutagenic and Eco-Toxicological Response of a Novel Microbial Exopolysaccharide Based Biopolymer

A modified microbial polysaccharide based biopolymer has been investigated as a potential candidate towards development of sustainable biomaterials and bioplastics. An in-depth study was carried out to biosynthesize, characterize and assess any possible mutagenic potential and ecotoxicity of the microbial polysaccharide biopolymer. Microstructural investigations using confocal microscopy, Fourier transform (FT)-Raman depth profile mapping and scanning electron microscopy (SEM) of the biosynthetically modified polysaccharide revealed internal structural perturbations, as well as occlusion of granular pores by extraneous materials. The Raman 3D mapping depth profile along with time-of-flight (MALDI-TOF) mass spectrometry also indicated important structural and surface modifications, which could be correlated to the production of microbial exopolysaccharides and secondary metabolites. The study then looked into any possible genetic mutation and ecological risks associated with the biosynthetically modified polysaccharide through the investigation of genotoxicity and ecotoxicity. The genotoxicity study was carried out through bacterial reverse gene mutation (Ames) test by using two different strains (TA98 and TA100) of bacteria. The results did not indicate any mutagenic effect against either of the strains used for the biopolymer samples and was found to be genotoxically safe. Ecotoxicity tests, carried out using bioluminescent bacteria Vibrio fisheri further indicated no ecotoxicity within the given experimental conditions. The study measured the half maximal effective concentration (EC50) to cause a 50% decrease in the light output of the bacteria, a measure of ecotoxicological response of the biopolymer. Overall, results from this study indicated that the novel biopolymer was genotoxically and ecotoxically safe, which offers immense potential for future use of this biopolymer.

36 MATERIALS SCIENCE↗
DOE OSTI2018

A Novel Hyperbranched Polymeric Flocculant for Waste-Water Treatment

Cationic hyperbranched oligomer poly(N-acryloyl-1,2-diaminoethane hydrochloride) (HADE) was firstly synthesized by Michael addition reaction. And then, a series of cationic flocculants poly(acrylamide/N-acryloyl-1,2-diaminoethane hydrochlorides) (PAM-HADEs) with hyperbranched structure was prepared from HADE as macro-monomer and acrylamide (AM). The structures of PAM-HADEs were characterized by Fourier transform infrared spectrometry, {sup 1}H and {sup 13}C nuclear magnetic resonance spectroscopy, gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF). And the properties were systematically evaluated by intrinsic viscosity, zeta potential and hydrodynamic radius. The mechanism of the cationic hyperbranched copolymer used in water treatment was extensively studied via a jar test in which the transmittance of the supernatant, settling time, and average floc size were used to evaluate the flocculability. Compared with the linear flocculant poly (acrylamide/liner-N-acryloyl-1,2-diaminoethane hydrochloride) (PAM-LADE), the novel hyperbranched polymeric flocculants exhibited outstanding flocculability which were reflected by shorter settlement time, high transmittance and large floc size. The primary cause that PAM-HADEs owned excellent flocculability is the more stretching configuration and less chains entanglement of PAM-HADEs in waste-water due to their hyperbranched structure compared with that of the linear PAM-LADE which exhibited curly coil configuration. On the other hand, abundant and exposed cationic terminal groups of PAM-HADEs originated from their hyperbranched structure also hint higher flocculation capacity. At optimum dosages of the polymer, the transmittance of the supernatant is less at low and high pH values, indicating that the natural pH (pH 7.29) of the suspension is the most appropriate pH for the flocculation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Chromatographic isolation of vanadyl porphyrins from heavy oil resins

A broad fraction of petroleum vanadyl porphyrins of high spectral purity was isolated from heavy oil resins with high vanadium content using a two-step chromatographic method. At the first step, the primary concentrate of vanadyl porphyrins was separated from the resins on the silica gel column. At the second step, it was further purified by the gradient elution through the column packed with sulfo-cationite. According to UV—VIS spectroscopy, this technique allows one to isolate up to 70% of vanadyl porphyrins with the spectral purity corresponding to the best results of other purification methods providing only narrow fractions of vanadyl porphyrins of comparable purity. Deoxophylloerythroetioporphyrin (DPEP) and etioporphyrin (Etio) series of vanadyl porphyrins with the carbon number range of C{sub 28}—C{sub 42} and DPEP/ Etio ratio equal to 1.18 were identified by MALDI-TOF mass-spectrometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

SUDA: A SUrface Dust Analyser for Compositional Mapping of the Galilean Moon Europa

Abstract The Surface Dust Analyser (SUDA) is a mass spectrometer onboard the Europa Clipper mission for investigating the surface composition of the Galilean moon Europa. Atmosphereless planetary moons such as the Galilean satellites are wrapped into a ballistic dust exosphere populated by tiny samples from the moon’s surface produced by impacts of fast micrometeoroids. SUDA will measure the composition of such surface ejecta during close flybys of Europa to obtain key chemical signatures for revealing the satellite’s composition such as organic molecules and salts, history, and geological evolution. Because of their ballistic orbits, detected ejecta can be traced back to the surface with a spatial resolution roughly equal to the instantaneous altitude of the spacecraft. SUDA is a Time-Of-Flight (TOF), reflectron-type impact mass spectrometer, optimized for a high mass resolution which only weakly depends on the impact location. The instrument will measure the mass, speed, charge, elemental, molecular, and isotopic composition of impacting grains. The instrument’s small size of$268 ~\mathrm {mm} \times 250 ~\mathrm {mm} \times 171$ 268 mm × 250 mm × 171 $~\mathrm {mm}$ mm , radiation-hard design, and rather large sensitive area of 220 cm 2 matches well the challenging demands of the Clipper mission.

Astronomy & Astrophysics↗
DOE OSTI2019

Evaluation of the Structure and Biological Activities of Condensed Tannins from Acanthus ilicifolius Linn and Their Effect on Fresh-Cut Fuji Apples

Condensed tannins (CT{sub S}) have been isolated and purified from leaves of Acanthus ilicifolius Linn. And their structures were investigated by three methods: {sup 13}C nuclear magnetic resonance ({sup 13}C NMR), reversed-phase high-performance liquid chromatography (RP-HPLC), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The results showed that the CT{sub S} were a mixture of catechin/epicatechin, galatechin/epicatechin, and amphicin/epigalin, and that the polymer chain lengths were 3-mers to 14-mers. Antityrosinase activities and antioxidant activities of the CT{sub S} from A. ilicifolius leaves were further studied. The IC{sub 50} of the CT{sub S} on mushroom tyrosinase activity was determined to be 19.7 ± 0.13 μg/mL, and inhibition type analyses indicated that the CT{sub S} were mixed type inhibitors and their inhibition CT{sub S} was reversible. The CT{sub S} from A. ilicifolius leaves also exhibited potential antioxidant activity. The IC{sub 50} of DPPH and ABTS scavenging activities were 104 ± 0.894 μg/mL and 86 ± 0.616 μg/mL, respectively. And the FRAP value was 758.28 ± 2.42 mg AAE/g. In addition, we found that the CT{sub S} from A. ilicifolius leaves had an excellent effect on preserving the quality of fresh-cut apples by preventing apples from browning through reducing polyphenol oxidase activities in apples.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Improving the Sensitivity of Mass Spectrometry by Using a New Sheath Flow Electrospray Emitter Array at Subambient Pressures

Arrays of chemically etched emitters with individualized sheath gas capillaries have been developed to enhance electrospray ionization (ESI) at subambient pressures. By including an emitter array in a subambient pressure ionization with nanoelectrospray (SPIN) source, ionization and transmission efficiency can be maximized allowing for increased sensitivity in mass spectrometric analyses. The SPIN source eliminates the major ion losses at conventional ESI-mass spectrometry (MS) interface by placing the emitter in the first vacuum region of the instrument. To facilitate stable electrospray currents in such conditions we have developed an improved emitter array with individualized sheath gas around each emitter. The utility of the new emitter arrays for generating stable multi-electrosprays at subambient pressures was probed by coupling the emitter array/SPIN source with a time of flight (TOF) mass spectrometer. The instrument sensitivity was compared between single emitter/SPIN-MS and multi-emitter/SPIN-MS configurations using an equimolar solution of 9 peptides. An increase in sensitivity correlative to the number of emitters in the array was observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Characterization of ZnO Nanoparticles using Superconducting Tunnel Junction Cryodetection Mass Spectrometry

Zinc oxide (ZnO) nanoparticles coated with either n-octylamine (OA) or α-amino poly(styrene-co-acrylonitrile) (PSAN) ligands (L) have been analyzed using laser desorption/ionization and matrix assisted laser desorption/ionization (MALDI) time-of-flight (TOF) superconducting tunnel junction (STJ) cryodetection mass spectrometry. STJ cryodetection has the advantage of high m/z detection and allows for the determination of average molecular weights and dispersities for 500–600 kDa ZnO-L nanoparticles. The ability to detect the relative energies deposited into the STJs has allowed for investigation of ZnO-L metastable fragmentation. ZnO-L precursor ions gain enough internal energy during the MALDI process to undergo metastable fragmentation in the flight tube. These fragments produced a lower energy peak, which was assigned as ligand-stripped ZnO cores whereas the individual ligands were at too low of an energy to be observed. From these STJ energy resolved peaks, the average weight percentage of inorganic material making up the nanoparticle was determined, where ZnO-OA and ZnO-PSAN nanoparticles are comprised of ~62% and ~68% wt ZnO, respectively. In one example, grafting densities were calculated based on the metastable fragmentation of ligands from the core to be 16 and 1.1 nm{sup –2} for ZnO-OA and ZnO-PSAN, respectively, and compared with values determined by thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). .

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Temperature Dependence of Ar{sub n}{sup +} Cluster Backscattering from Polymer Surfaces: a New Method to Determine the Surface Glass Transition Temperature

In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to study the intensity variations of the backscattered Ar{sub n}{sup +} clusters as a function of temperature for several amorphous polymer surfaces (polyolefins, polystyrene, and polymethyl methacrylate). For all these investigated polymers, our results show a transition of the ratio Ar{sub 2}{sup +}/(Ar{sub 2}{sup +} + Ar{sub 3}{sup +}) when the temperature is scanned from –120 °C to +125 °C (the exact limits depend on the studied polymer). This transition generally spans over a few tens of degrees and the temperature of the inflection point of each curve is always lower than the bulk glass transition temperature (T{sub g}) reported for the considered polymer. Due to the surface sensitivity of the cluster backscattering process (several nanometers), the presented analysis could provide a new method to specifically evaluate a surface transition temperature of polymers, with the same lateral resolution as the gas cluster beam. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

Multivariate Analysis of MALDI Imaging Mass Spectrometry Data of Mixtures of Single Pollen Grains

Mixtures of pollen grains of three different species (Corylus avellana, Alnus cordata, and Pinus sylvestris) were investigated by matrix-assisted laser desorption/ionization time-of-flight imaging mass spectrometry (MALDI-TOF imaging MS). The amount of pollen grains was reduced stepwise from > 10 to single pollen grains. For sample pretreatment, we modified a previously applied approach, where any additional extraction steps were omitted. Our results show that characteristic pollen MALDI mass spectra can be obtained from a single pollen grain, which is the prerequisite for a reliable pollen classification in practical applications. MALDI imaging of laterally resolved pollen grains provides additional information by reducing the complexity of the MS spectra of mixtures, where frequently peak discrimination is observed. Combined with multivariate statistical analyses, such as principal component analysis (PCA), our approach offers the chance for a fast and reliable identification of individual pollen grains by mass spectrometry. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

Dual-Channel Enzymatic Inhibition Measurement (DEIM) Coupling Isotope Substrate via Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry

A novel dual-channel enzymatic inhibition measurement (DEIM) method was developed to improve the repeatability with light/heavy isotope substrates, producing reliable relative standard deviations (< 3%) by employing acetylcholinesterase (AChE) as the model enzyme. The matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) was adapted for enzyme-inhibited method due to its good salt-tolerance and high throughput; meanwhile, dual-channel enzymatic reactions were performed to improve the repeatability of each well. The acetylcholinesterase inhibition measurement was conducted by mixing the quenched enzyme reaction solution of blank group (with heavy isotope as substrate) and experimental group (with light isotope as substrate), of which the inhibition rate might be affected by isotope effects. Hence, inverse study and Km measurement were implemented to validate the method. The inverse study shows similar inhibition rate (68.9 and 70.3%) and the Km of isotope substrates are analogous (0.139 and 0.135 mM), which demonstrated that the novel method is feasible to AChE inhibition measurement. Finally, the method was applied to herb extracts, half of which exhibit inhibition to AChE. The precise dual-channel enzymatic inhibition measurement (DEIM) method could be regarded as a promising approach to potential enzyme inhibitor screening. .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Integration of High-Resolution Mass Spectrometry with Cryogenic Ion Vibrational Spectroscopy

We describe an instrumental configuration for the structural characterization of fragment ions generated by collisional dissociation of peptide ions in the typical MS{sup 2} scheme widely used for peptide sequencing. Structures are determined by comparing the vibrational band patterns displayed by cryogenically cooled ions with calculated spectra for candidate structural isomers. These spectra were obtained in a linear action mode by photodissociation of weakly bound D{sub 2} molecules. This is accomplished by interfacing a Thermo Fisher Scientific Orbitrap Velos Pro to a cryogenic, triple focusing time-of-flight photofragmentation mass spectrometer (the Yale TOF spectrometer). The interface involves replacement of the Orbitrap’s higher-energy collisional dissociation cell with a voltage-gated aperture that maintains the commercial instrument’s standard capabilities while enabling bidirectional transfer of ions between the high-resolution FT analyzer and external ion sources. The performance of this hybrid instrument is demonstrated by its application to the a{sub 1}, y{sub 1} and z{sub 1} fragment ions generated by CID of a prototypical dipeptide precursor, protonated L-phenylalanyl-L-tyrosine (H{sup +}-Phe-Tyr-OH or FY-H{sup +}). The structure of the unusual z{sub 1} ion, nominally formed after NH{sub 3} is ejected from the protonated tyrosine (y{sub 1}) product, is identified as the cyclopropane-based product is tentatively identified as a cyclopropane-based product. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2019

Plasma-Based Ambient Desorption/Ionization Mass Spectrometry for the Analysis of Liquid Crystals Employed in Display Devices

Liquid-crystal displays (LCDs) are the most frequently used display technology worldwide these days. Due to the rather complex manufacturing process and purity requirements for the chemicals used, quality control and display failure analysis are important analytical tasks. Currently, the state-of-the-art techniques (e.g., high-performance liquid chromatography (HPLC), gas chromatography (GC) coupled to mass spectrometry (MS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), or high-resolution microscopy) are costly and time-consuming. Hence, a new pathway to precisely analyze liquid-crystalline materials and LCDs in their native state is reported. A new approach for direct analysis via plasma-based ambient desorption/ionization mass spectrometry (ADI-MS) offers an inexpensive and faster alternative. In this study, direct analysis in real time (DART), the low-temperature plasma (LTP) probe, and flowing atmospheric-pressure afterglow (FAPA) ADI sources coupled to high-resolution mass spectrometry (HR-MS) are compared based on their capabilities and performance for liquid-crystal analysis. These sources enable direct analyte desorption from a sample surface at ambient conditions and ionize the vaporized analyte molecules in a subsequent step. Primarily, the ionization capabilities of the three ADI sources are compared for individual liquid-crystal standards, mixtures of liquid crystals (LCs), and complex liquid crystal/additive mixtures applied in commercially available LCDs. Furthermore, direct surface analysis from a glass substrate is also performed with ADI-MS to compare their applicability to this type of sample matrix. .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Deformation mechanisms of a 20Mn TWIP steel investigated by in situ neutron diffraction and TEM

The deformation mechanisms and associated microstructure changes during tensile loading of an annealed twinning-induced plasticity (TWIP) steel with the chemical composition of Fe–20Mn–3Si–3Al–0.045C (wt.%) were systematically investigated using in situ time-of-flight (TOF) neutron diffraction in combination with postmortem transmission electron microscopy (TEM). The initial microstructure of the investigated alloy consists of equiaxed austenitic grains with the initial α´-phase of ~7% in volume. In addition to dislocation slip, twinning and two kinds of martensitic transformations from the austenite to α´- and epsilon martensites were observed as the main deformation modes during the tensile deformation. In situ neutron diffraction provides a powerful tool to establish the deformation mode map for elucidating the role of different deformation modes in different strain regions. The critical stress is 520 MPa for the martensitic transformation from the austenite to α´-martensite, whereas a higher stress (>600 MPa) is required for actuating the deformation twin and/or the martensitic transformation from -martensite. Both epsilon- and α´-martensites act as the hard phases whereas mechanical twinning contributes to both strength and ductility of the studied steel. TEM observations confirmed that the twinning process was facilitated by the parent grains orientated with <111> or <110> parallel to the loading direction. The nucleation and growth of twins are attributed to the pole and self-generation formation mechanisms, as well as the stair-rod cross-slip mechanism.

in situ neutron diffraction↗
DOE OSTI2022

Olefin methylation over iron zeolites and the methanol to hydrocarbons reaction

The effect of olefin addition to a stream of dimethyl ether on the methanol homologation reaction is investigated using iron-substituted zeolites Fe-beta and Fe-ZSM-5. The reaction was investigated using plug-flow microreactors in the temperature range of 240–400 °C, at a total pressure of 0.239 MPa and a WHSV of 6.12 (g DME/ gcat -hr). For Fe-beta (Si/Fe= 9.2) catalysts, isobutene co-feeding almost doubles dimethyl ether (DME) consumption rate and shifts selectivity towards larger olefins with carbon numbers from 5 to 7. Addition of isobutene above 6.3%, however, resulted in a reduction of DME consumption rates, an effect assigned to the replacement of surface methoxy groups for adsorbed olefins in the zeolite pores. Below a temperature of 340 °C hydride-transfer rates are negligible; reaction rates are stable for over 5.5 h and the products consist almost exclusively of olefins and a small amount of methane. Above 360 °C the onset of catalytic hydride transfer processes is observed leading to fast catalyst deactivation rates and an increase in the concentration of aromatic species. Iron ZSM-5 (Si/Fe = 21.4) catalysts under similar reaction conditions consumes methanol faster than Fe-beta at approximately three times the TOF (on a per iron basis). The Fe-ZSM-5 catalyst was selective to a distribution of products (C5 to C8) as compared to Fe-beta which was selective to primarily C5 and C7. Co-feeding larger olefins (2-methyl-2-butene, 2,3-dimethyl-2-butene, 2,3,3-trimethyl-1-butene, and 2,4,4-trimethyl-2-pentene) at a 3.9% olefin concentration over Fe-beta changed selectivity towards cracking products (C4 compounds such as isobutene). As the size of the olefin increases, a reduction of DME consumption rate is also observed. Here these results show that co-feeding olefins with DME over Fe-zeolites is a promising route to increase methylation rates at relatively low temperatures producing larger branched olefins and that the product distribution is highly dependent on the zeolite pore size and structure of the olefin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Highly active subnanometer Rh clusters derived from Rh-doped SrTiO 3 for CO 2 reduction

Here, sub-nanometer Rh clusters derived from Rh-doped SrTiO 3 , demonstrated by in-situ X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements, are applied as highly active catalysts for CO 2 reduction. Compared to the supported Rh/SrTiO 3 , the catalyst synthesized by a doping-segregation method exhibits a higher space-time yield (STY) to CO with a selectivity of 95% for CO 2 reduction by hydrogen; it also shows a higher activity with a larger turnover frequency (TOF) for CO 2 reduction by ethane. According to the in-situ diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) experiments, the higher CO selectivity for CO 2 hydrogenation is attributed to the lower CO binding strength resulted by the strong interactions (e.g., charge transfer) between Rh atoms and the oxide support with surface defects. The superior activity is suggested to be originated from the cooperative effect between the highly dispersed sub-nanometer Rh clusters for efficient dissociation of H 2 /C 2 H 6 and the reconstructed SrTiO 3 with oxygen vacancies for preferential adsorption/activation of CO 2 . Finally, the doping-segregation method provides a unique opportunity to tune the size of active metal clusters and the physicochemical properties of the oxide support, offering the potential for applications in a variety of chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗