Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “catalyst”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Anion Exchange Membrane Water Electrolysis Using a Catalyst-Coated Membrane Cathode

A catalyst-coated membrane (CCM) approach to electrode fabrication for high pH water electrolysis offers enhanced interfacial contact between the catalyst layer and the membrane surface in comparison to the catalyst-coated substrate (CCS) electrode configuration. The CCM facilitates enhanced ionic and water transport between the cathode and the anion exchange membrane (AEM). This advantage is particularly significant with AEM water electrolysis (compared to proton exchange membrane water electrolysis) because the cathode typically operates under dry conditions and relies solely on diffusive water transport across the AEM from the liquid-fed anode. This study presents a direct performance comparison between CCS and CCM cathode configurations using identical hydrogen evolution reaction (HER) catalysts and other components. The use of a pseudo-reference electrode integrated into the membrane electrode assembly enabled detailed analysis of the CCM cathode polarization behavior. Surface characterization provided insight into the degradation mechanisms associated with the CCM configuration. Optimization of the cathode ionomer cross-link density improved both the cathode polarization performance and the electrolysis device durability. Further optimization of the HER catalyst loading in the CCM cathode resulted in additional gains in the electrolysis efficiency. Collectively, these findings offer valuable guidance for the design and fabrication of high-performance, durable AEM electrolysis CCMs.

Water electrolysis↗
DOE OSTI2022

Functional CeO x nanoglues for robust atomically dispersed catalysts

Single-atom catalysts make exceptionally efficient use of expensive noble metals and can bring out unique properties. However, applications are usually compromised by limited catalyst stability, which is due to sintering. Although sintering can be suppressed by anchoring the metal atoms to oxide supports, strong metal–oxygen interactions often leave too few metal sites available for reactant binding and catalysis, and when exposed to reducing conditions at sufficiently high temperatures, even oxide-anchored single-atom catalysts eventually sinter. Here we show that the beneficial effects of anchoring can be enhanced by confining the atomically dispersed metal atoms on oxide nanoclusters or ‘nanoglues’, which themselves are dispersed and immobilized on a robust, high-surface-area support. We demonstrate the strategy by grafting isolated and defective CeO x nanoglue islands onto high-surface-area SiO 2 ; the nanoglue islands then each host on average one Pt atom. Further, we find that the Pt atoms remain dispersed under both oxidizing and reducing environments at high temperatures, and that the activated catalyst exhibits markedly increased activity for CO oxidation. We attribute the improved stability under reducing conditions to the support structure and the much stronger affinity of Pt atoms for CeO x than for SiO 2 , which ensures the Pt atoms can move but remain confined to their respective nanoglue islands. The strategy of using functional nanoglues to confine atomically dispersed metals and simultaneously enhance their reactivity is general, and we anticipate that it will take single-atom catalysts a step closer to practical applications.

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

Transitioning Rationally Designed Catalytic Materials to Real 'Working' Catalysts Produced at Commercial Scale: Nanoparticle Materials

Catalyst design, from idea to commercialization, requires multi-disciplinary scientific and engineering research and development over 10-20 year time periods. Historically, the identification of new or improved catalyst materials has largely been an empirical trial-and-error process. However, advances in computational capabilities (new tools and increased processing power) coupled with new synthetic techniques have started to yield rationally-designed catalysts with controlled nano-structures and tailored properties. This technological advancement represents an opportunity to accelerate the catalyst development timeline and to deliver new materials that outperform existing industrial catalysts or enable new applications, once a number of unique challenges associated with the scale-up of nano-structured materials are overcome.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Hydrogen generation via ammonia decomposition on highly efficient and stable Ru-free catalysts: approaching complete conversion at 450 °C

We report Hydrogen (H 2 ) is a prospective zero-carbon and high-energy-density fuel alternative to fossil fuels for generating power and clean energy. Ammonia (NH 3 ) is a promising H 2 (17.7%) carrier, which can easily overcome the challenges associated with H 2 storage and transportation. Thermocatalytic ammonia decomposition reaction (ADR) is an effective way to produce clean H 2 but it relies on the use of expensive and rare ruthenium (Ru)-based catalysts at elevated temperatures (>500 °C), hence is not sustainable and economically feasible. Herein, we report a synergistic strategy to design a heterostructured Ru-free catalyst, consisting of CoNi alloy nanoparticles well-dispersed on a MgO–CeO 2 –SrO mixed oxide support with potassium promotion. The resulting K–CoNi alloy –MgO–CeO 2 –SrO catalyst presents 97.7% and 87.5% NH 3 conversion efficiency at 450 °C at gas hourly space velocities (GHSVs) of 6000- and 12 000-mL h -1 g cat -1 , respectively. At 500 °C, the H 2 production rate (57.75 mmol g cat -1 min -1 ) becomes comparable to that of most of the reported Ru-based catalysts. The catalyst stability has been successfully demonstrated in both a fixed-bed reactor under high pressure (120 h at 5.0 bar) and a membrane reactor prototype (600 h at 1.5 bar) at 500 °C. High-temperature in situ XPS analysis, temperature-programmed desorption/reduction, and density functional theory calculations have been carried out to elucidate the possible active sites and performance enhancement mechanisms. This work highlights the importance of constructing optimal interfaces between active metal nanoparticles and oxide support for boosting the NH 3 to H 2 conversion efficiency and long-term stability.

25 ENERGY STORAGE↗
DOE OSTI2016

Directed plant cell-wall accumulation of iron: Embedding co-catalyst for efficient biomass conversion

Plant lignocellulosic biomass is an abundant, renewable feedstock for the production of biobased fuels and chemicals. Previously, we showed that iron can act as a co-catalyst to improve the deconstruction of lignocellulosic biomass. However, directly adding iron catalysts into biomass prior to pretreatment is diffusion limited, and increases the cost of biorefinery operations. Recently, we developed a new strategy for expressing iron-storage protein ferritin intracellularly to accumulate iron as a catalyst for the downstream deconstruction of lignocellulosic biomass. In this study, we extend this approach by fusing the heterologous ferritin gene with a signal peptide for secretion into Arabidopsis cell walls (referred to here as FerEX). The transgenic Arabidopsis plants. FerEX. accumulated iron under both normal and iron-fertilized growth conditions; under the latter (iron-fertilized) condition, FerEX transgenic plants showed an increase in plant height and dry weight by 12 and 18 %, respectively, compared with the empty vector control plants. The SDS- and native-PAGE separation of cell-wall protein extracts followed by Western blot analyses confirmed the extracellular expression of ferritin in FerEX plants. Meanwhile, Perls' Prussian blue staining and X-ray fluorescence microscopy (XFM) maps revealed iron depositions in both the secondary and compound middle lamellae cell-wall layers, as well as in some of the corner compound middle lamella in FerEX. Remarkably, their harvested biomasses showed enhanced pretreatability and digestibility, releasing, respectively, 21 % more glucose and 34 % more xylose than the empty vector control plants. These values are significantly higher than those of our recently obtained ferritin intracellularly expressed plants. This study demonstrated that extracellular expression of ferritin in Arabidopsis can produce plants with increased growth and iron accumulation, and reduced thermal and enzymatic recalcitrance. Here, the results are attributed to the intimate colocation of the iron co-catalyst and the cellulose and hemicellulose within the plant cell-wall region, supporting the genetic modification strategy for incorporating conversion catalysts into energy crops prior to harvesting or processing at the biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2019

Highly Stable Oxygen Electrodes Enabled by Catalyst Redistribution through an In Situ Electrochemical Method

Here, in this work, for the first time an in situ electrochemical pretreatment approach to fabricate a highly reversible oxygen electrode with redistributed ultrafine RuO 2 catalysts on a carbon nanotube (CNT) matrix is reported. The optimally pretreated RuO 2 /CNT oxygen electrodes demonstrate an extremely stable cycling life, 800 times with non-Li metal anode, under a capacity-limited protocol of 800 mAh g −1 in an ether-based electrolyte in an O 2 environment. The highly stable activity of ultrafine RuO 2 catalysts in oxygen reduction and evolution processes originates from the synergetic effect of greatly reduced size of catalyst (<2 nm) and uniform redistribution of catalyst particles after the in situ electrochemical pretreatment process. The pretreatment method discovered in this work can not only significantly enhance the activity/efficiency of the catalysts used for air electrodes but can also be widely applied to other electro-catalysis systems.

25 ENERGY STORAGE↗
DOE OSTI2024

Reductive Depolymerization of Lignin to Aromatic Compounds over Promoted Nickel Catalysts in Sub– and Supercritical Methanol

The use of γ-Al 2 O 3 -supported Ni catalysts promoted with either Cu or Fe was investigated for the reductive catalytic fractionation (RCF) of hybrid poplar in methanol at 200 and 250 °C. The effectiveness of lignin depolymerization was quantified in terms of the lignin oil production, the quantity and distribution of identifiable monomers present in the lignin oil, and the yield of residual solids. All of the Ni-based catalysts tested provided improved yields of lignin oil and monomers, along with reduced char formation, relative to blank (sans catalyst) runs. The highest monomer yield of 51 % was obtained at 250 °C over a 20 wt.% Ni-5 wt.% Cu/Al 2 O 3 catalyst, the improved performance obtained through Cu promotion being attributed to the ability of Cu to facilitate NiO reduction, resulting in an increased amount of Ni 0 on the catalyst surface and, consequently, improved hydrogenation activity. Finally, the main monomers formed were propanol-, propyl- and propenyl-substituted guaiacol and syringol, the S/G ratio of the products corresponding closely to that in the native lignin.

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

Correlating Catalyst Design and Discharged Product to Reduce Overpotential in Li-CO 2 Batteries

Li-CO 2 batteries with dual efficacy for greenhouse gas CO 2 sequestration and high energy output have been regarded as a promising electrochemical energy storage technology. However, battery feasibility has been hampered by inferior electrochemical performance due to large overpotentials and low cyclability primarily caused by the difficult decomposition of ultra-stable Li 2 CO 3 during charge. The use of cathode catalysts has been highlighted as a promising solution and catalyst properties, as well as the nature of discharge products, are closely correlated with electrochemical performance. Here, the catalyst design strategies that include active site enrichment, electrical transport enhancement, and mass transfer improvement are summarized. Catalyst effects on product decomposition are then subsequently introduced, while product geometry and chemical composition will be explored, with an emphasis on the formation/decomposition of Li 2 C 2 O 4 instead of Li 2 CO 3 . Building on previous research, future directions that facilitate improvements in catalyst design are put forward to reinforce the fundamental development of Li-CO 2 batteries.

25 ENERGY STORAGE↗
DOE OSTI2017

Control of the properties of catalysts for methane aromatization by synthesizing ZSM-5 zeolites with different crystallite sizes

MFI zeolite materials (ZSM-5) with crystal sizes in the range from 0.10 to 1.70 μm have been synthesized. Acidic and surface properties, phase and morphological composition of the prepared zeolites have been studied by the IR sprectroscopy, nitrogen porosimetry, XRD, and scanning electron microscopy. Increasing crystal size was shown to decrease the general acidity of the zeolite. Synthesized zeolites served as supports for molybden-containing catalysts for methane aromatization prepared by using the solid phase synthesis approach. Diffuse reflectance IR spectroscopy, thermoprogrammed desoption of ammonia and {sup 27}Al NMR spectroscopy were used to characterize the physicochemical properties of the catalysts. An increase in the crystallite size of the zeolite favors a decrease in the acidity of the catalysts and inhibits the formation of alumina molybdate during the catalyst preparation. As a result, a tendency to coke formation is suppressed and the performance of the catalysts in methane aromatization improved: methane conversion and aromatic hydrocarbon yield increase.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Recovery of Platinum Group Metals from Spent Catalysts Using Iron Chloride Vapor Treatment

The recovery of platinum group metals (PGMs) from spent automobile catalysts is a difficult process because of their relatively low contents in the scrap. In this study, to improve the efficiency of the existing recycling techniques, a novel physical concentration method involving treatment with FeCl{sub 2} vapor has been examined. The reactions occurring between typical catalyst components and FeCl{sub 2} vapor are discussed from the thermodynamic point of view, and the validity of the proposed technique was experimentally verified. The obtained results indicate that the vapor treatment at around 1200 K (927 °C) can effectively alloy PGMs (Pt, Pd, and Rh) with Fe, resulting in the formation of a ferromagnetic alloy. It was also confirmed that cordierite and alumina (the major catalyst components) remained unreacted after the vapor treatment, while ceria species were converted into oxychlorides. The samples simulating the automobile catalyst were also subjected to magnetic separation after the treatment with FeCl{sub 2} vapor; as a result, PGMs were successfully extracted and concentrated in the form of a magnetic powder. Thus, the FeCl{sub 2} vapor treatment followed by magnetic separation can be utilized for recovering PGMs directly from spent catalysts as an effective pretreatment for the currently used recycling methods.

36 MATERIALS SCIENCE↗
DOE OSTI2017

A re-examination of the catalyst activation and temperature hysteresis in methane combustion on Pt/Al 2 O 3

Methane combustion is an industrially important reaction that has been extensively studied. Supported Pt catalysts on Al 2 O 3 exhibit excellent activity in this reaction owing to their Csingle bondH bond activation capability. Pt/Al 2 O 3 catalyst remains almost inactive until the conversion increases abruptly at the ignition temperature (T ign ). The temperature hysteresis behavior has been reported, where after ignition, as the temperature is lowered below T ign , the catalyst continues to exhibit high activity. The activation has been previously attributed to the removal of adsorbed oxygen on Pt sites at T ign , while the hysteresis has been explained by the local temperature elevation caused by the reaction heat. Here in this work, this behavior was re-examined at a small scale in a fixed-bed flow reactor over a range of pre-treatment and reaction mixture conditions. Low-temperature activation was achieved by pre-treating the catalyst with CH 4 . Carefully designed control experiments yielded observations that cannot be rationalized by the existing theory, suggesting that it is incomplete. Based on these new results, we propose a more comprehensive theory describing the active sites in the oxidation reaction as methane-derived adsorbed carbon active sites, and their formation as the controlling factor in the catalyst activation. The hysteresis can be better explained by the enhanced stability of active sites under reaction conditions. In situ infrared spectroscopy and mass spectrometry studies were conducted in a flow cell, providing strong evidence supporting the theory. The dissociative adsorption of CH 4 was studied under a variety of pre-treatment conditions, and proved to be responsible for the active site formation. The fundamental understanding obtained in this work contributes significant insights to the understanding of reaction mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Redox oxide@molten salt as a generalized catalyst design strategy for oxidative dehydrogenation of ethane via selective hydrogen combustion

Here, the current study demonstrates a redox oxide @ molten salt core-shell architecture as a generalized redox catalyst design strategy for chemical looping – oxidative dehydrogenation of ethane. 17 combinations of redox active oxides and molten salts were prepared, evaluated, and characterized. X-ray diffraction indicates that the redox oxides and molten salts are fully compatible, forming separate and stable phases. X-ray photoelectron spectroscopy demonstrates that the molten salts aggregate at the redox oxide surface, forming a core-shell structure to block the non-selective sites responsible for CO x formation. Up to ~74% single-pass olefin yields were achieved using the proposed redox catalyst design strategy. Statistical analyses of the performance data indicate the potential to achieve up to 86.7% single-pass yield by simply optimizing the operating conditions using the redox catalysts reported in this study. Meanwhile, the generalizability of the catalyst design strategy offers exciting opportunities to further optimize the composition and performance of the redox catalysts for ethane ODH under a chemical looping scheme with significantly reduced energy consumption and CO 2 emissions.

03 NATURAL GAS↗
DOE OSTI2016

Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO 2 supports

In this study, we investigated the impact of ZrO 2 on the performance of palladium-based oxidation catalysts with respect to low-temperature activity, hydrothermal stability, and sulfur tolerance. Pd supported on ZrO 2 and SiO 2 were synthesized for a comparative study. Additionally, in an attempt to maximize the ZrO 2 surface area and improve sulfur tolerance, a Pd support with ZrO 2 -dispersed onto SiO 2 was studied. The physicochemical properties of the catalysts were examined using ICP, N 2 sorption, XRD, SEM, TEM, and NH 3- , CO 2- , and NO x- TPD. The activity of the Pd catalysts were measured from 60 to 600 °C in a flow of 4000 ppm CO, 500 ppm NO, 1000 ppm C 3 H 6 , 4% O 2 , 5% H 2 O, and Ar balance. The Pd catalysts were evaluated in fresh, sulfated, and hydrothermally aged states. Overall, the ZrO 2 -containing catalysts showed considerably higher CO and C 3 H 6 oxidation activity than Pd/SiO 2 under the reaction conditions studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Activity and stability of mesoporous CeO 2 and ZrO 2 catalysts for the self-condensation of cyclopentanone

Metal oxides containing acid-base pairs are widely used as catalysts for aldol condensation reactions, but they are often prone to secondary condensation and fast deactivation. In this contribution, high-surface area mesoporous CeO 2 and ZrO 2 have been synthesized and tested as catalysts for the self-condensation of cyclopentanone, an attractive molecular building block for several biomass upgrading strategies. Here, the catalytic activity, stability, and overall kinetics behavior of these two catalysts have been compared in the liquid phase. A detailed kinetics analysis shows that on both oxides, the reaction is controlled by the initial unimolecular α-H abstraction step, in which cyclopentanone forms the crucial enolate intermediate. Subsequently, the enolate couples with another cyclopentanone molecule in a bimolecular C-C coupling step. CO 2 -TPD analysis and site titration with probe molecules indicate that initially the most active catalyst is the mesoporous ZrO 2 sample with strong base character. However, this catalyst exhibits a very rapid deactivation. By contrast, the mesoporous CeO 2 prepared in this study has lower basicity strength, which results in lower initial activity, but enhanced stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Crystallographic dependence of CO 2 hydrogenation pathways over HCP-Co and FCC-Co catalysts

We report efficient conversion of CO 2 is of great significance for sustainable supply of chemicals and fuels. While Co-based catalysts are known to be effective for CO hydrogenation in Fischer-Tropsch synthesis, they work very differently in CO 2 hydrogenation. This study reveals a crystallographic dependence of reaction pathways for CO 2 hydrogenation on Co catalyst showing a new type of structure sensitivity and structure-activity-selectivity relationship for CO 2 conversion to chemicals and fuels. The experimental work on CO 2 conversion including steady-state isotopic transient kinetic analysis (SSITKA) using 13 C-labeled CO 2 shows a preferential CH 4 formation over HCP-Co but dominant CO formation over FCC-Co. The density functional theory calculations indicate that CO 2 does dissociate directly into chemisorbed CO * and O * on both HCP-Co and FCC-Co, but the CO * intermediates on HCP-Co prefer to be hydrogenated to form CH 4 whereas the CO* on FCC-Co preferentially desorb to form CO. The significantly altered adsorption strength of CO * due to the presence of chemisorbed O * and CO 2 * species on the catalyst surface is responsible for the mechanistic disconnection in product selectivity between the CO 2 and CO hydrogenation over Co catalysts. This study also shows that the addition of K to Co diminishes the direct impact of Co crystal structure, but improves the selectivity to C 2 + hydrocarbons along with higher CO 2 conversion. This seems to result from another pathway originating from HCOO* intermediate from bonding interaction of surface Co atoms with carbon in CO 2 , leading to the formation of CH x * whose coupling subsequently give rises to C 2 + products. The present study sheds new light into the crystallographic structural sensitivity of CO 2 hydrogenation towards the rational design of more selective catalysts for CO 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Multi-atom Pt and PtRu catalysts for high performance AEMFCs with ultra-low PGM content

To reduce the platinum group metal (PGM) loading in anion exchange membrane fuel cells (AEMFCs), it is important to transition to catalysts with very low PGM content, and eventually to catalysts that are completely PGM-free. Here, in this work, four supported low-PGM Pt and PtRu catalysts were prepared using a new, simple, scalable technique: Controlled Surface Tension (CST) method. CST allows for a high density of very small multi-atom clusters. Catalysts were physically characterized using a wide array of techniques and tested for their ORR and HOR activity both ex-situ and integrated into operating AEMFCs. The PGM loading was reduced by a factor of 14 while achieving comparable performance to commercial catalysts. AEMFCs were also assembled with ultralow PGM loading (0.05 mgPGM cm -2 ), where PtRu anodes were paired with Fe–N–C cathodes to achieve a specific power of 25 W/mg PGM (40 W/mg Pt ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels

NREL's thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient route to completely biogenic pyrolysis-based fuel precursors, fuels, and value-added chemicals depending on catalyst and process conditions. A near term pathway being developed uses these liquids for co-processing with petroleum feedstocks to assess biogenic carbon incorporation in hydrocarbon fuel feedstocks for potential refinery use. In this work, the impact of feedstock and catalyst on catalytic fast pyrolysis oil (CFPO) composition was determined with the oils then assessed for biogenic fuel production via FCC (fluidized catalytic cracking) co-processing. Biomass vapors were generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce clean vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled to a custom pyrolyzer system designed to produce consistent-composition pyrolysis vapors as feed to the DCR. Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available modified zeolite-based catalysts to produce CFPOs. These upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and simulated distillation (SIMDIS) to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. These exploratory vapor-phase-upgrading results demonstrated the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The FCC co-processing results demonstrated the feasibility of using CFPOs with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.

biogenic carbon↗
DOE OSTI2020

Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗