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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 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Robust palladium hydride catalyst for electrocatalytic formate formation with high CO tolerance

Palladium is unique in the electrocatalytic reduction of CO 2 to formate because of its low or even near-equilibrium onset potential. However, the inevitably produced CO molecules poison and deactivate the catalyst surface, resulting in an insufficient operating lifetime (<30 min) for conventional and optimized Pd catalysts. In this work, we present a hydrogen-rich Palladium hydride catalyst (PdH0.5/C) derived from a one-step solvothermal synthesis. This catalyst showed a 93.1 % faradaic efficiency towards formate at – 0.4 V (vs RHE). The working lifetime reached a record of 4 h, which was ~15 times longer than a commercial Pd catalyst and outperformed all previous Pd-based electrocatalysts for CO 2 -HCOO – conversion. The high CO tolerance was attributed to the selectivity improvement induced by lattice hydrogen and the weak CO adsorption strength on diverse active sites (i.e. kink, step, and terrace). Isotopic analysis revealed a direct participation of the lattice hydrogen in the protonation of CO 2 molecules in formate formation.

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

In-situ monitoring of atomically dispersed Pt sites supported on OMS-2 during CO 2 activation

Atomically dispersed catalysts have drawn great interest lately, as they showcase a high density of active sites, selectivity, and high turnover frequencies in oxidation chemistry due to labile oxygen activation. In contrast, the applications of these catalysts have lagged in reduction reactions due to the ambiguity caused by the sintering and restructuring of active sites. To bridge this gap, the evolution of Pt 4+ isomorphically substituted into an octahedral molecular sieve structure (OMS-2) under reductive conditions was correlatively characterized using multiple in-situ analytical techniques such as ambient pressure X-ray photoelectron spectroscopy, environmental transmission electron microscopy, and solid-state nuclear magnetic resonance. The surface dynamics of the Pt single atoms were revealed during the Reverse Water Gas Shift (RWGS) reaction, where the active sites were identified as two-coordinated platinum single atoms. Under reaction, we show nonbinding atoms adjacent to the single atoms restructured the motif of the single atoms to Pt 2+ via ion mobility of potassium, increasing the activation energy by 25.6 kJ/mol. Here, this work also highlights the potential for increased stability of the single atom sites via isomorphic substitution of the metal oxide support, since the Pt-OMS-2 catalyst retained activity for about 33 h before deactivation, after which nanoparticles were observed in TEM images. This work offers a new perspective in single atom synthesis using the metal oxide as the host for the single atom site, instead of adatoms on the surface

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

Heterostructured nano-catalysts with efficient metal-oxide interfaces unlock high-performance direct methanol protonic ceramic fuel cells

Direct methanol protonic ceramic fuel cells (PCFCs) are attractive due to their low cost, convenient storage, and high volumetric energy density, as well as their suitability for transportation. However, the poor coking tolerance of conventional nickel-based anodes leads to their susceptibility to severe carbon deposition and significant deactivation after long-term exposure to hydrocarbons. Herein, we report a nano-catalyst of Ce 0.6 Ni 0.2 Cu 0.2 O 2 with a heterogeneous structure that is spontaneously reduced into a Ce 0.6 Ni 0.2-x Cu 0.2-x O 2-δ (CeNCO) oxide framework interfaced with a nano NiCu alloy (denoted as NC/CeNCO) under operating conditions, as confirmed by analyses of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. A Ni-BaCe 0.7 Y 0.06 Yb 0.06 Zr 0.06 Hf 0.06 Gd 0.06 O 3-δ anode-supported PCFC employing the NC/CeNCO metal-oxide catalyst achieved a peak power density of 1.11 W cm −2 and operational stability of about 100 h at 700 °C when fueled by 35 % CH 3 OH-15 % H 2 O-50 % N 2 . In conclusion, the enhanced performance and coking resistance are attributed to the efficient interfaces of Ni, Cu, and ceria-based oxide in NC/CeNCO for CH 3 OH reforming, as confirmed by analyses of electrochemical performance and Raman spectroscopy with density functional theory calculations, revealing that these interfaces can enhance CH 3 OH activation and promote efficient OH-mediated carbon removal via COH intermediates.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2018

High catalytic performance of Fe-Ni/Palygorskite in the steam reforming of toluene for hydrogen production

The inexpensive and abundant material, palygorskite, was used as a promising catalyst support to prepare Fe-Ni/Pal catalysts. Catalytic steam reforming of toluene as a biomass tar model compound over these catalysts was investigated in a fixed-bed reactor under different parameters, including reaction temperatures and S/C molar ratios. The stability and lifetime of Fe 3 Ni 8 /Palygorskite catalyst was evaluated under optimal conditions and its kinetic parameters were determined as well. The fresh and used catalysts were characterized using X-ray diffraction (XRD), H 2 temperature-programmed reduction (H 2 -TPR), transmission electron microscopy (TEM), and Raman spectra. The results showed that the Fe 3 Ni 8 /Palygorskite catalyst with high dispersion was successfully prepared and exhibited superior catalytic performance compared with those of the monometallic catalysts (Fe 3 /Palygorskite and Ni 8 /Palygorskite) and the bare Palygorskite. Increasing the reaction temperature from 500 °C to 700 °C was beneficial for the toluene conversion and gaseous yields. The catalytic activity of Fe 3 Ni 8 /Palygorskite varied distinctly with the increase of S/C molar ratio and reached maximum at the the S/C molar ratio of 1.0. The apparent activation energy of 41.55 kJ mol -1 and the pre-exponential factor of 1.35 × 10 3 m 3 kg -1 h -1 were obtained for Fe 3 Ni 8 /Palygorskite in kinetic studies under optimal reaction conditions, respectively. Here, the carbon deposition analysis of the used catalysts revealed that the formation of graphitic carbon rather than amorphous carbon was the main reason for the deactivation of Fe 3 Ni 8 /Palygorskite catalysts. When ceased the injection of steam into the reaction system, the graphitic carbon would be accelerating formed on the surface of the Fe 3 Ni 8 /Palygorskite and decreased its catalytic activity for toluene conversion. But owing to the water gas shift reaction, the catalytic activity of Fe 3 Ni 8 /Palygorskite seemed to recover gradually to its optimum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Assessments of data centers for provision of frequency regulation

There are numerous opportunities for data centers to participate in demand response programs considering their large energy capacities, flexible working environments and workloads, redundant design and operation, etc. As a type of demand response, frequency regulation requires fast response, and its potential is not fully explored by data centers yet. This paper proposes a synergistic control strategy for data center frequency regulation which uses both IT and cooling systems. It combines power management techniques at the server level with control of the chilled water supply temperature to track the regulation signal from the electrical market. A frequency regulation flexibility factor is also proposed to increase the IT capacity for frequency regulation. The performance of the control strategy is studied through numerical simulations using an equation based object-oriented Modelica platform designed for data centers. Simulation results show that with well-tuned control parameters, data centers can provide frequency regulation service in both regulation up and down. The performance of data centers in providing frequency regulation service is largely influenced by the regulation capacity bid, frequency regulation flexibility factor, workload condition, and cooling mode of the cooling system, and not significantly influenced by the time constant of chillers. In addition, compared with a server-only control strategy, the proposed synergistic control strategy can provide an extra regulation capacity of 3% of the design power when chillers are activated. Here, when chillers are deactivated, both strategies have a similar regulation capacity.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2020

Oxidation kinetic modelling of Fe-based oxygen carriers for chemical looping applications: Impact of the topochemical effect

Chemical looping is a promising technology for fossil fuel utilization due to its high fuel conversion efficiency with in-situ CO 2 capture capability. Metal oxide are used as oxygen carriers (OCs) and circulate between a fuel reactor and an air reactor to perform reduction and oxidation reactions, respectively. In general, OC exiting the fuel reactor is not reduced fully to its metallic state due to many factors including carbon deposition and OC deactivation. Therefore, the effect of the initial reduction state on the OC oxidation in the air reactor is a significant parameter for consideration in developing the oxidation kinetic model. The objective of this work is to develop a physically significant kinetic model that applies to the oxidation of both initially fully and partially reduced OC with air. For this study, 1.5 mm Fe-based OC particle supported with TiO 2 was used as the model OC particle due to its complex multistep reaction nature. The oxidation kinetics were experimentally investigated in a thermogravimetric analyzer (TGA). Results indicate a significant difference in the oxidation rate profile for the OCs when oxidized from an initially fully reduced compared to an initially partially reduced state. Elemental mapping via energy-dispersive X-ray spectroscopy (EDS) reveals a shrinking-core type topochemical pattern across the OC particle, which was identified to be the cause of the dependency of kinetics on the initial reduction state. A generalized kinetic model was developed based on the observed shrinking-core behavior without presuming any rate-determining steps and experimentally validated over a broad range of temperatures (800–1000 °C) and oxygen concentrations (5, 7, 10, and 15 mol%). Impacts of particle porosity, size, and core-shell structure on the OC oxidation kinetics were analyzed in the developed oxidation kinetic model to suggest methods of improving the oxidation rate of the OC without modifying the chemical composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Starved Escherichia coli preserve reducing power under nitric oxide stress

Nitric oxide (NO) detoxification enzymes, such as NO dioxygenase (NOD) and NO reductase (NOR), are important to the virulence of numerous bacteria. Pathogens use these defense systems to ward off immune-generated NO, and they do so in environments that contain additional stressors, such as reactive oxygen species, nutrient deprivation, and acid stress. NOD and NOR both use reducing equivalents to metabolically deactivate NO, which suggests that nutrient deprivation could negatively impact their functionality. To explore the relationship between NO detoxification and nutrient deprivation, we examined the ability of Escherichia coli to detoxify NO under different levels of carbon source availability in aerobic cultures. We observed failure of NO detoxification under both carbon source limitation and starvation, and those failures could have arisen from inabilities to synthesize Hmp (NOD of E. coli) and/or supply it with sufficient NADH (preferred electron donor). We found that when limited quantities of carbon source were provided, NO detoxification failed due to insufficient NADH, whereas starvation prevented Hmp synthesis, which enabled cells to maintain their NADH levels. This maintenance of NADH levels under starvation was confirmed to be dependent on the absence of Hmp. Intriguingly, these data show that under NO stress, carbon-starved E. coli are better positioned with regard to reducing power to cope with other stresses than cells that had consumed an exhaustible amount of carbon. -- Highlights: •Carbon source availability is critical to aerobic E. coli NO detoxification. •Carbon source starvation, under NO stress, preserves intracellular NADH levels. •Preservation of NADH depends on starvation-dependent inhibition of Hmp induction.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

MiR-223 modulates hepatocellular carcinoma cell proliferation through promoting apoptosis via the Rab1-mediated mTOR activation

Hepatocellular carcinoma (HCC) is a common digestive malignancy. MiR-223, a well-identified miRNA, exhibits diverse properties in different cancers. In this study, we demonstrated that miR-223 could suppress cell growth and promote apoptosis in HepG2 and Bel-7402 HCC cell lines. We screened and identified a novel miR-223 target, Ras-related protein Rab-1(Rab1). Upregulation of miR-223 would specifically and markedly down-regulate Rab1 expression. In addition, miR-223-overexpressing subclones showed significant cell growth inhibition by increasing cell apoptosis in HepG2 and Bel-7402 cells. To identify the mechanisms, we firstly investigated the mTOR pathway and found that pmTOR, p70S6K and Bcl-2 were dramatically down-regulated after miR-223 transfection, while no changes in the level of Bax was visualized. Furthermore, our data showed that the anti-tumor effects arising from miR-223 transfection in HCC cells may be due to the deactivation of mTOR pathway caused by the suppression of Rab1 expression when miR-223 is overexpressed. In summary, our results indicate that miR-223 functions as a tumor suppressor and plays a critical role in inhibiting the tumorigenesis and promoting the apoptosis of HCC through the mTOR signaling pathway in vitro. By targeting Rab1, miR-223 efficiently mediates the mTOR pathway. Given these, miR-223 may be a potential therapeutic target for treating HCC. - Highlights: • miR-223 is downregulated in hepatocellular carcinomas. • Rab1 is a novel downstream target of miR-223. • miR-223 suppressed cell growth and enhanced apoptosis in HepG2 and Bel-7402 cells. • miR-223 modulated mTOR signaling pathway by targeting Rab1.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Inhibition of Notch signaling pathway using γ-secretase inhibitor delivered by a low dose of Triton-X100 in cultured oral cancer cells

Highlights: • A novel method is developed to deliver γ-secretase inhibitor DAPT using a low dose of Triton-X100. • This approach effectively blocks the cleavage of Notch1 receptor. • The elimination of Notch1 intracellular domain from cell nuclei is confirmed. • Notch1 signaling blockade in mRNA level is demonstrated upon applying this delivery system. How to effectively delivering therapeutic agents, including γ-secretase inhibitors (GSIs), into live cells, remains a significant challenge. This study assessed the effect of Notch signaling inhibition by examining levels of the Notch1 intracellular domain (N1ICD) in cultured oral cancer cells analyzed with random stitched images (2D) and 3D visualizations using confocal microscopy and quantitative gene analysis. Substantially, we have developed a novel method to assist the delivery of γ-secretase inhibitor, DAPT, into live cells in the presence of an effective minimum concentration of Triton-X100 (0.001%) without damaging cell activity and membrane integrity assessed with cell proliferation assays. The images obtained in this study showed that DAPT alone could not block the γ-secretase inhibitor despite inhibiting cell growth. Further analysis of quantitative gene expressions of Notch signaling canonical pathway to verify the effectiveness of the novel method for delivering inhibitor into live cells, displayed deregulation of Notch1, Delta-like ligand 1 (DLL1) and hairy and enhancer of split 1 (Hes1). Our data suggest that Notch1/Hes1 signaling pathway is deactivated using DAPT with a low dose of Triton-X100 in this cancer cells. And the finding also suggests that Notch1 could be engaged by DLL1 to promote differentiation in oral cancer cells. Using this approach, we demonstrate that Triton-X100 is a promising and effective permeabilization agent to deliver γ-secretase inhibitor DAPT into live oral epithelial cells. This strategy has the potential to implicate in the treatment of cancer diseases.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Kinetic profiles of photocurrents in cells expressing two types of channelrhodopsin genes

Highlights: • Expression of an additional channelrhodopsin gene compensates ChR2 function. • Two channelrhodopsins can coexist in a cell without affecting their function. • Sensitivity to low light intensity is enhanced by expressing two channelrhodopsins. • Turning-ON and turning-OFF constants are prolonged in dual gene expression. Channelrhodopsin-2 (ChR2), a light-activated cation-selective ion channel, has been widely used as a tool in optogenetic research. ChR2 is specifically sensitive to wavelengths less than 550 nm. One of the methods to expand the sensitivity of a channelrhodopsin to a wider range of wavelengths is to express another channelrhodopsin in the cells by the transduction of an additional gene. Here, we report the characteristic features of cells expressing two types of channelrhodopsins, each having different wavelength sensitivities. In HEK293 cells stably expressing ChR2, photocurrents were elicited at stimuli of 400–550 nm, and the wavelength sensitivity range was expanded by the additional transduction of the modified Volvox channelrhodopsin-1 (mVChR1) gene, which has broad wavelength sensitivities, ranging from 400 to 600 nm. However, the photocurrent at 550 nm was lower than that of the mVChR1-expressing cell; moreover, the turning-on and turning-off constants were delayed, and the deactivation rates were decreased. Meanwhile, the response to lower light intensity was improved by the additional gene. Thus, the transduction of an additional gene is a useful method to improve the light and wavelength sensitivities, as well as photocurrent kinetic profiles, of channelrhodopsins.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

The role of ozone in the formation and structural evolution of graphene oxide obtained from nanographite

Chemical exfoliation of graphite under strong oxidizing conditions yields graphene oxide nanosheets with oxy functional groups on the carbon basal plane. The importance of ozone in the chemical oxidation mechanism of graphite by the widely-used Hummers' method has been largely overlooked. Herein we demonstrate that the ozonolysis of graphite leads to the formation of secondary epoxy and perox-ymonosulfate ester functional groups arising from a rotationally hindered Criegee intermediate and sulfuric acid, in a strongly favored thermodynamic process. This mechanistic step is followed by formation of adjacent epoxy and hydroxy groups as major functionalities on graphene oxides via a radical process, and leaves a significant amount of unreacted peroxides well above levels previously recognized. The thermal decomposition of graphene releases sulfur oxygen species (SO 2 and SO), but does not appear to release ozone even if this reaction pathway is moderately favored thermodynamically. Here we propose anew structural model for graphene oxide based on detailed chemical and spectroscopic data that provides insight into observed chemical reactivity and physical properties, including the antimicrobial activity and protein deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Role of surface diffusion in formation of unique reactivity for graphite oxidation: Time-resolved measurements in a pulsed diffusion reactor

Quantification of oxidation kinetics is essential to develop graphitic materials for diverse applications: from refractories found in gas-cooled nuclear reactors to catalysts needed for chemical manufacturing. In this work, using well-defined highly oriented pyrolytic graphite, low-pressure isotopic transient experiments combined with controlled annealing periods, we resolve the role of surface diffusion and quantify oxidation kinetics with nanomole-precision. We observe an unexpected increase in reactivity following annealing which is explained by the role of surface diffusion increasing the probability for trapping mobile oxygen at more reactive edge sites. Here, the locus of adsorption and spillover to the basal plane is distinct from the trapping location creating a more active oxygen species. Isotopic products reflect the population dynamics of oxygen added at the edge and surface diffusion that relocates basal plane oxygen to more reactive edge sites. Since this process proceeds in parallel with direct oxidation reactions, it is not likely to be observed using steady-state or conventional ‘bulk’ characterization techniques. Our unique time-resolved non-equilibrium measurement in a well-defined transport regime, enables observation of three distinct behaviors: short-term deactivation due to the balance of rates in oxygen supply/product formation, reactivity increases due to surface diffusion and longer-term reactivity increase with oxygen accumulation.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Role of Pt during hydrodeoxygenation of biomass pyrolysis vapors over Pt/HBEA

1.3 wt% Pt/HBEA and HBEA were studied as catalysts for the hydrodeoxygenation of pine pyrolysis vapors at 500 °C. Both catalysts showed high initial conversion of oxygenated pyrolysis products into aromatic hydrocarbons, while Pt/HBEA showed higher stability in terms of hydrocarbon productivity and deferred breakthrough of oxygenated compounds. Among 1-, 2- and 3-ring aromatic hydrocarbons, Pt/HBEA had a significantly higher selectivity than HBEA towards unalkylated aromatics (e.g., benzene) as compared to the corresponding alkylated aromatics (e.g., toluene and xylene). Additionally, Pt addition to HBEA decreased coke deposition and improved resistance to pore and acid site blockage as determined by TPO, N 2 physisorption, and NH 3 TPD. The ability of Pt to promote cleavage and hydrogenation of methoxy and methyl groups was observed by increased methane production over Pt/HBEA relative to HBEA. A progressive decrease in the methane production over Pt/HBEA correlated with deactivation in terms of reduced benzene formation, breakthrough of oxygenated products, and increased formation of polynuclear aromatics and their degree of substitution, which indicate coke formation. In conclusion, the increased methane yield and suppressed coke formation with the addition of Pt is attributed to hydrogen spillover, through which hydrogen activated on Pt can subsequently migrate to the HBEA support to reverse the coke-forming hydrogen abstraction reaction.

09 BIOMASS FUELS↗
DOE OSTI2022

Low temperature ethanol steam reforming: Selectivity control with lithium doping of Pt/m-ZrO 2

Lithium promoted 2%Pt/m-ZrO 2 catalysts previously observed to exhibit higher rates for the low temperature water-gas shift (LTS) were tested for the ethanol steam reforming with the aim of exploring the potential tuning of the selectivity. Characterization of catalysts having optimized Li content (0.5–0.75%Li) for LTS exhibited (a) weakened C—H bonding of formate, a proposed intermediate in the LTS mechanism, as shown by a shift in the ν(CH) band to lower wavenumbers, (b) a relatively low extent of blocking of Pt, as measured by the ν(CO) band intensity of Pt-CO, (c) increased basicity as measured by CO 2 temperature-programmed desorption with mass spectrometry, but not so high as to strongly inhibit CO 2 product removal, and finally (d) no evidence of electron transfer from Li to Pt. Here, for this study, the same catalysts were tested for ethanol steam reforming (ESR). Results show that Li could likewise weaken the C—C bond of the acetate intermediate, the analog of formate in LTS, and facilitate decarboxylation over decarbonylation altering the selectivity in favor of methanation. This trend was confirmed by fixed bed reaction testing, in-situ infrared spectroscopy experiments of transient ESR, and temperature-programmed ESR using MS. The Li-doped catalysts may be used to pre-reform ethanol prior to feeding to a methane steam reformer to increase the overall H 2 selectivity of the process. DRIFTS of steady state ESR revealed that deactivation occurs through losses in the Pt-support interface, thereby hindering the turnover of the acetate intermediate.

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

Shifting the MLCT of d 6 metal complexes to the red and NIR

Light-active d 6 -coordination compounds hold great promise for light energy conversion, sensors and therapeutic applications. However, the activity in the red-to-NIR spectral region is highly desirable to convert solar light more efficiently, use low-cost red-light sources and activate these chromophores in biological tissue environment. Due to their versatility, tunability and broad intense absorption, d 6 -coordination compounds with metalto-ligand charge transfer (MLCT) transitions are especially interesting. This review article offers a comprehensive collection of strategies to tune MLCT excited states in d 6 metal complexes and gives insights on group 6 to group 9 transition metals and their respective state-of-the-art MLCT engineering towards red-shifted absorption and emission properties with long-lived excited states. Strategies comprise lowering the π* level of the ligands, destabilizing and mixing of the metal-based HOMO, switching within a group of transition metals, matrix effects and insights into dealing with excited state deactivation in the context of the energy gap law.

Metal to ligand charge transfer (MLCT)↗
DOE OSTI2019

In-situ hydrogenation of bio-oil/bio-oil phenolic compounds with secondary alcohols over a synthesized mesoporous Ni/CeO 2 catalyst

Mesoporous ceria, which was synthesized under supercritical conditions, was found to be an effective support material of Ni catalyst for the in-situ hydrogenation of m-cresol (a representative compound of bio-oil) using secondary alcohols of 2-propanol (2-PrOH) and 2-butanol (2-BuOH) as a hydrogen source (H-donor) to produce 3-methylcyclohexanol, 3-methylcyclohexene, and methylcyclohexane under a H2 gas-free atmosphere. The activities of different metal catalysts (Ni, Cu, and Co) for the in-situ hydrogenation of m-cresol were examined using 2-PrOH as a H-donor. Total and effective conversion of m-cresol achieved only over Ni/CeO 2 because of its fair catalytic properties, as determined by N2 adsorption-desorption, hydrogen temperature-programmed reduction, ammonia temperature-programmed desorption, X-ray diffraction, and transmission electron microscopy. The dependence of Ni/CeO2 performance on the reaction time (4-6 h) and Ni loading (3-9 wt%) was examined from the in-situ hydrogenation of m-cresol with 2-PrOH. The deactivation test of Ni/CeO 2 was performed by reusing the spent catalyst, which was then regenerated through successive oxidation and reduction, several times in the m-cresol transformation employing 2-PrOH as a H-donor. In addition to m-cresol, other phenolic model compounds of bio-oil, such as anisole, phenol, and guaiacol, were also treated by in-situ hydrogenation with 2-PrOH over Ni/CeO 2 . Although this catalyst was effective for phenol and guaiacol transformation, it was relatively ineffective for anisole conversion. The in-situ hydrogenation of crude bio-oil with 2-PrOH and 2-BuOH was accomplished over the Ni/CeO 2 catalyst, resulting in a refined bio-oil with a 37.5-38.9% lower oxygen content and a high heating value (HHV) of up to 25 MJ/kg.

09 BIOMASS FUELS↗
DOE OSTI2019

Engineering stable Pt nanoparticles and oxygen vacancies on defective TiO 2 via introducing strong electronic metal-support interaction for efficient CO 2 photoreduction

This work for the first time reports the promoting effect of strong electronic metal-support interaction (EMSI) in Pt/TiO 2 -V O (V O : oxygen vacancy) for gas-phase CO 2 photoreduction. A novel in-situ surface hydrogenation was developed to prepare hydrogenated Pt/TiO 2 -V O in a continuous, high throughput diffusion flame aerosol reactor. The combined results of various characterization techniques confirmed the presence of EMSI between Pt and defective TiO 2 -V O resulted in the enhanced electronic density of Pt nanoparticles. Both the modulated electronic structure of Pt and surface oxygen vacancies simultaneously promoted the activation of surface adsorbed carbon intermediates and facilitated the separation of photogenerated charges, eventually boosting the photocatalytic activity of Pt/TiO 2 -V O . The optimized Pt/TiO 2 -V O demonstrated a high quantum yield of 1.49% with high CH 4 selectivity (81%), which rendered 5.8- and 1.2-fold enhancements over its counterparts of TiO 2 -V O and Pt/TiO 2 . More importantly, the EMSI also played a critical role in preserving the surface metallic Pt 0 and oxygen vacancies, and in sustaining high activity of the Pt/TiO 2 -V O , whereas rapid catalytic deactivation are observed for both TiO 2 -V O and Pt/TiO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗