In-situ Characterization of Metal/Oxide Catalysts for CO2 Conversion: From Fundamental Aspects to Real Catalysts Design
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36 MATERIALS SCIENCE↗
SEARCH · Engineering Papers
Results for “catalyst characterization”
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Characterization and catalytic behavior of Fischer-Tropsch catalysts derived from different cobalt precursors
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99 GENERAL AND MISCELLANEOUS↗
The Development of Catalysts for Upgrading of Pyrolysis Vapor for Refinery Feedstocks and Intermediates (CRADA Final Report)
Catalytic fast pyrolysis (CFP) is a versatile technology platform to convert biomass into fungible hydrocarbon transportation fuels and chemical co-products. Key technical barriers to reaching this goal include increasing the product yields and achieving the desired fuel properties for gasoline, diesel, and jet range fuels or blendstocks that would be suitable for introduction into existing refinery unit operations. Overcoming these barriers will require durable catalysts that are effective at upgrading and stabilizing biomass pyrolysis vapors. Towards these goals, this CRADA leveraged NREL experience as a leader in biomass pyrolysis research and Johnson Matthey's (JM) experience as a leader in the production of advanced catalytic materials. The scope spanned CFP catalyst development, characterization, multi-scale reaction testing, and computational modeling. CRADA benefits to DOE, Participant, and U.S. Taxpayer: Assists laboratory in achieving programmatic scope, Uses the laboratory’s core competencies. The purpose of this CRADA was to develop and deploy catalysts for biomass CFP to help achieve cost-competitive biofuels and bio-based products. This was accomplished through a close collaboration between biomass conversion researchers at NREL and catalyst development researchers at JM. Summary of Research Results: Focus Area 1. Foundational research on catalytic conversion and deactivation: Key interactions between pyrolysis vapors and heterogeneous catalysts were probed through catalyst characterization, model compound reaction testing, and atomistic-scale computational modeling. Catalyst development focused on multifunctional materials, which include zeolites, oxides, carbides, and nitrides. Computational modeling identified reaction mechanisms and elucidated surface chemistry to test hypotheses regarding mechanisms of deoxygenation, coupling, cracking, dehydration, coke formation, hydrogen transfer, and aromatic ring reactions. This information was used to design multifunctional catalysts to increase product yields, control product selectivity, and reduce deactivation during CFP and downstream processing steps. The results served to increase fundamental understanding of key catalyst attributes and durability features for the upgrading of biomass pyrolysis vapors. Model compound experiments confirmed the importance of metal-acid bifunctionality for the deoxygenation of lignin-derived phenolic species under hydrodeoxygenation conditions. This insight led to the development of catalysts such as Pt/TiO2 and Mo2C, which were confirmed as high-performing materials during subsequent bench-scale experiments using biomass-derived pyrolysis vapors. This focus area also led to the identification of important catalyst deactivation mechanisms associated with the deposition of inorganic contaminants such as potassium. The molecular-level insight from model compound experiments and computational modeling, shown in Figure 1, informed the development of regeneration procedures that have been shown to be effective for restoration of > 90% of initial catalyst activity. This understanding has subsequently been translated to other catalyst systems, including zeolite materials that can be operated without requirements for co-fed hydrogen.
09 BIOMASS FUELS↗
In-situ and ex-situ comparison of the electrochemical oxidation of SO 2 on carbon supported Pt and Au catalysts
Electrochemical characterizations are performed using thin films and commercial carbon supported platinum and gold catalysts for sulfur dioxide oxidation, the primary electrochemical oxidation reaction in the Hybrid-sulfur (HyS) thermochemical process. Electrochemical evaluation of metal thin films qualitatively confirms the higher activity of Au over Pt, AuPt, Pd, and Ir for the electrochemical oxidation of SO 2 . Ex-situ testing, using rotating disk electrode (RDE), shows an earlier onset potential for Au/C at low sulfuric acid concentrations (C ≤ 3.5 M) and a higher turnover frequency than Pt/C at sulfuric acid concentrations ranging from 3.5 M to 9 M. In-situ electrolysis experiments using low catalyst loadings (0.1 mg Au cm –2 , a factor of ≥5 lower than typical loadings) confirm that Au nanoparticles exhibit higher current densities and greater stability than Pt nanoparticles. This is consistent with the thin film screening studies, which showed higher activity with increasing gold content in AuPt thin films. Here, this work reveals an alternative material to state-of-the-art Pt to lower the energy needs and aid the HyS cycle in reaching the target of $2/kg H 2 set forth by the Department of Energy to achieve economic feasibility of large-scale hydrogen generation.
08 HYDROGEN↗
Can Li: A Career in Catalysis
Prof. Can Li is distinguished for his seminal achievements in fundamental and applied researches in catalysis, especially in advancing the characterization of catalysts and catalytic reactions related to solar energy conversion and fine chemical synthesis. The scope of his research is wide ranging, and he is leading some of the fields. This account highlights his major scientific achievements in advancing the fundamental sciences of characterizing catalysts and understanding the mechanisms of catalytic reactions by developing in situ spectroscopic techniques (e.g., infrared (IR), ultraviolet (UV), Raman, space- and time-resolved spectroscopies and photoelectric imaging), and applying the obtained knowledge in the rational design and synthesis of catalysts for practical applications in photocatalytic, electrocatalytic and photoelectrocatalytic water splitting and CO 2 reduction, chiral synthesis in nanoreactors and ultradeep desulfurization of fuels, and fine chemical synthesis. In particular, his demonstration of the kiloton scale solar fuel production project will be introduced as a successful model for converting fundamental science into practical and impactful applications to convert CO 2 and water into solar fuels. This account also highlights his services to the catalysis communities and international collaborations for promoting catalysis science worldwide.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NH3-SCR on Cu, Fe and Cu+Fe exchanged Beta and SSZ-13 catalysts: hydrothermal aging and propylene poisoning effects
Cu, Fe and Cu+Fe ion exchanged Beta and SSZ-13 catalysts were prepared by solution ion exchange using commercial NH4/Beta, and NH4/SSZ-13 that was prepared in-house. To study hydrothermal aging effects, Beta supported catalysts were aged hydrothermally at 700 C and SSZ-13 supported catalysts were aged at 750 C. In order to reveal the effects of Fe addition in the co-exchanged catalysts, these catalysts were characterized by means of powder X-ray diffraction (XRD), N2 adsorption-desorption, electron paramagnetic resonance (EPR), 27Al-nuclear magnetic resonance (27Al-NMR) and propylene coking followed with temperature programmed reaction (TPR), and further tested with standard NH3-SCR with and without the presence of propylene. Collectively, the catalyst characterizations and reaction testing indicated minor beneficial effects of Fe addition in Cu,Fe/Beta, where NH3-SCR activity, N2 selectivity and hydrothermal stability were all slightly improved. In contrast, Fe addition did not show apparent beneficial effects in low-temperature SCR for the Cu,Fe/SSZ-13 case. At elevated reaction temperatures, however, the presence of Fe indeed considerably improved NO conversion and N2 selectivity for the hydrothermally aged Cu,Fe/SSZ-13 catalyst in the presence of propylene. The authors from Pacific Northwest National Laboratory (PNNL) gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated for the US DOE by Battelle. The authors from East China University of Science and Technology acknowledge support from National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang also gratefully acknowledges the China Scholarship Council for a Joint-Training Scholarship Program with PNNL.
Wang, Aiyong↗
Activated carbon supported Ni, Fe, and bimetallic NiFe catalysts for CO x -free H 2 production by microwave methane pyrolysis
The goal of this study was to test the effect of metal-impregnated carbon-based catalysts on the conversion of methane to hydrogen gas and solid carbon using microwave reactor technology. Monometallic and bimetallic catalysts on activated carbon supports (Ni/AC, Fe/AC, Ni-Fe/AC) are compared during methane pyrolysis testing. Catalytic methane pyrolysis was carried out in a microwave reactor at reaction temperatures of 600 °C and 800 °C. For comparison, one of the catalysts (Ni-Fe/AC) was tested in a conventionally heated reactor at 800 °C. The prepared catalysts were characterized by X-ray diffraction (XRD), while post-reaction catalysts were characterized by XRD and SEM. During reaction testing, the monometallic Ni/AC catalyst exhibited the best catalytic activity (CH 4 conversion: 46.0 and H 2 yield: 46.9%) when reacted in the microwave reactor, however, it suffered from rapid deactivation from carbon deposition (carbon yield: 0.39 gC/g catalyst). The bimetallic Ni-Fe/AC catalyst was slightly less active (CH 4 conversion: 36.9 and H 2 yield: 40.5%) but it was more resistant to carbon formation (carbon yield: 0.27 gC/g catalyst) suggesting it may have greater long-term stability. The Ni-Fe/AC catalyst was also the most energy efficient as it required the least microwave power to maintain the 800 °C reaction temperature compared to the other catalysts tested. Methane conversion of the bimetallic Ni-Fe/AC at 800 °C under microwave irradiation was three times the conversion under conventional heating at the same reaction temperature. Finally, this work demonstrates the use of microwave-specific catalysts for catalytic methane pyrolysis in a microwave reactor, and can be used as a foundation for further methane pyrolysis process and catalyst optimization for CO x -free H 2 production.
08 HYDROGEN↗
Preparation and Characterization of Model Homotopic Catalysts: Rh Adatoms, Nanoparticles, and Mixed Oxide Surfaces on Fe 3 O 4 (001)
The atomic-level characterization of active sites is essential to understanding the mechanisms behind catalytic reactions. In this study, using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), we follow the morphological changes of a model Rh catalysts supported on Fe 3 O 4 (001) as a function of temperature and Rh coverage. Here, we identify the preparation conditions leading to model catalysts containing homotopic or nearly homotopic Rh species bound as adatoms, small clusters, substitutional within the Fe 3 O 4 (001), and nanoparticles. Adsorbates such as CO and CO 2 are further subsequently used to characterize the properties of different Rh sites. Using temperature programmed desorption (TPD), we demonstrate that adatoms, clusters, and nanoparticles exhibit high-temperature CO desorption (250-600 K). Strong binding on such sites further allows for CO oxidation to CO 2 via the Mars-van-Krevelen mechanism. In contrast, CO 2 was found to interact weakly with all Rh sites. Differences in desorption temperature enable the use of CO and CO 2 as titration methods for nanoparticles and Fe 3 O 4 (001), respectively. A small quantity of CO 2 was found to be reduced to CO on Rh adatoms and clusters.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Research tool development for catalyst, catalyst/ionomer, and ionomer characterization above 100°C (CRADA Final Report)
There is a need to develop experimental tools that address the catalyst and ionomer interface under high-temperature proton-exchange-membrane (HT-PEM) operating conditions (dry, >100°C). These conditions mean traditional water-based measurements for membrane and ionomer properties are insufficient; new ex-situ techniques are required to address and characterize expected novel materials. In this project we develop a microelectrode cell for high temperature kinetics and gas transport properties and ex-situ ionomer thin-film characterization under these conditions. We use baseline Nafion and phosphoric-acid imbibed membranes as prototype materials for measuring the membrane/acid/ionomer systems with Pt microelectrodes and demonstrate feasibility of the tools.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synthesis and characterization of tetrairidium clusters in the metal organic framework UiO-67: Catalyst for ethylene hydrogenation
Not provided.
catalysis (heterogeneous), materials and chemistry↗
Direct Characterization of Atomically Dispersed Catalysts: Nitrogen-Coordinated Ni Sites in Carbon-Based Materials for CO 2 Electroreduction
Metal, nitrogen-doped carbon materials have attracted interest as heterogenous catalysts that contain MN x active sites that are analogous to molecular catalysts. Of particular interest is Ni,N-doped carbon, a catalyst that is active for the electrochemical reduction of CO 2 to CO. Critical to the understanding of these materials is proof of single atomic sites and characterization of the environment surrounding the metal atom; however, directly probing this coordination remains challenging. This challenge is addressed in this study by combining scanning transmission electron microscopy (STEM), single atom electron energy loss spectroscopy (EELS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Through STEM imaging, atomic dispersion of Ni in the carbon framework is confirmed and image analyses are utilized to give semiquantitative estimates of neighbor distance distributions and site densities of Ni atoms. Atomic resolution EELS demonstrates that N and Ni are colocated at the single Ni atom sites suggesting Ni–N coordination. ToF-SIMS reveals a distribution of NiN x C y - fragments that reflect the Ni–N bonding environments within Ni,N-doped carbon. The fragmentation from Ni,N-doped carbon is similar to Ni phthalocyanine, suggesting the existence of heterogenized, molecular-like NiN 4 active sites which motivates future studies that leverage insight from molecular catalysis design to develop next-generation heterogeneous catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Condensed Phase Deactivation of Solid Brønsted Acids in the Dehydration of Fructose to Hydroxymethylfurfural
Catalyst deactivation resulting from the hydrothermal leaching of sulfonic acid residues and the deposition of carbonaceous residues was studied using condensed phase flow reactor experiments along with state-of-the-art solid-state NMR. Several commercially available sulfonic acid-containing heterogeneous Brønsted acids were compared by measuring the rates of sulfonic acid breakdown at hydrothermal flow conditions of 160 °C. Amberlyst 45 was found to show higher hydrothermal stability when compared to both Nafion and Amberlyst 15, with <10% loss in acidity after 48 h. The dehydration reaction of fructose to hydroxymethylfurfural (HMF) was used as a model system to compare deactivation rates from carbon deposition (fouling) to those from sulfur leaching, and deactivation from fouling was shown to be dramatically faster than that from sulfonic acid leaching alone. Fouling rates were then investigated in greater detail by comparing the influence of several factors including reactant, solvent, residence time, and feed concentration. The only successful approach to minimize fouling was the use of a polar aprotic solvent [dimethyl sulfoxide (DMSO)] with dilute (50 mM) reactant streams. In aqueous systems, operating the reactor in a regime with low conversion conditions (short residence times) does not significantly improve the longevity of the catalyst. Spent catalysts were characterized using 13C solid-state NMR spectroscopy enhanced by dynamic nuclear polarization. Additionally, in situ 1H and 13C high-resolution magic angle spinning (HR-MAS) solid-state NMR spectroscopies were used to investigate the solvent influence at the catalyst interface. The HR-MAS NMR studies showed that in polar aprotic solvents, the increased acidity leads to greater selectivity toward HMF; more importantly, that the dehydration products do not readily adhere to the surface in DMSO, in contrast to their behavior in water. The results demonstrate that more active and longer-lived acid catalysts could be obtained by tuning the solvent and surface polarity to allow for efficient desorption of products, thereby reducing the catalyst deactivation that occurs due to fouling.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
α- and β-CoNi binary hydroxides nanostructures: Synthesis, characterization, and application as heterogeneous catalysts
The aim of this study is to show that α- and β-CoNi binary hydroxides nanostructures can be used as heterogeneous catalysts in the oxidation of benzyl alcohol, N-formylation of aniline, and the Claisen–Schmidt condensation. The catalysts were synthesized by hydrothermal method and characterized by XRD, FE-SEM/EDX, FT-IR, TGA, UV–vis and N{sub 2} adsorption-desorption techniques. The α-phase is similar to layered double hydroxide (LDH), while β-phase is isostructural with brucite. In all of the three reactions, the conversion enhanced by increasing the amount of catalysts from 10 to 30 mg, and the catalytic activity of α-phase was better than β-phase. In benzyl alcohol oxidation, the best conversion for α- and β-phases was 90% and 80%, respectively, under solvent-free conditions. In N-formylation, the best yield for both catalysts was obtained 95% in solvent-free conditions. However, the time required for α-phase to reach this amount was a quarter of that for β-phase. For the Claisen–Schmidt condensation, the best yield was obtained at 90 °C, which was 70% and 50% for α- and β-CoNi binary hydroxides, respectively. Both catalysts were stable and subsequent to each step of recovery and reuse, no significant loss in activity was observed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ru-promoted perovskites as effective redox catalysts for CO2 splitting and methane partial oxidation in a cyclic redox scheme
The current study reports AxA’1-xByB’1-yO3- perovskite redox catalysts (RCs) for CO2-splitting and methane partial oxidation (POx) in a cyclic redox scheme. Strontium (Sr) and iron (Fe) were chosen as A and B site elements with A’ being lanthanum (La), samarium (Sm) or yttrium (Y), and B’ being manganese (Mn), or titanium (Ti) to tailor their equilibrium oxygen partial pressures (P_(O_2 ) s) for CO2-splitting and methane partial oxidation. DFT calculations were performed for predictive optimization of the oxide materials whereas experimental investigation confirmed the DFT predicted redox performance. The redox kinetics of the RCs improved significantly by 1 wt.% ruthenium (Ru) impregnation without affecting their redox thermodynamics. Ru impregnated LaFe0.375Mn0.625O3 (A=0, A’=La, B=Mn, and B’=0) was the most promising RC in terms of its superior redox performance (CH4/CO2 conversion >90% and CO selectivity~ 95%) at 800oC. Long-term redox testing over Ru impregnated LaFe0.375Mn0.625O3 indicated stable performance during the first 30 cycles following with a ~25% decrease in the activity during the last 70 cycles. Air treatment was effective to reactivate the redox catalyst. Detailed characterizations revealed the underlying mechanism for redox catalyst deactivation and reactivation. Furthermore, this study not only validated a DFT guided mixed oxide design strategy for CO2 utilization but also provides potentially effective approaches to enhance redox kinetics as well as long-term redox catalyst performance.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Fabrication and Characterization of Iron-Based Catalysts for the Dehydrogenation of Fossil Fuels
For a prosperous and sustainable future, hydrogen is an encouraging solution due to its simple transition for industrial decarbonization and synergy for economic development. Paradoxically, current hydrogen production pathways release substantial amount of greenhouse gases into the atmosphere contributing to climate change. To keep up with increasing demand, hydrogen could be produced through microwave-assisted thermocatalytic dehydrogenation of fossil fuels without emitting carbon dioxide. This requires specified catalysts to meet the requirements of hydrogen yield and selectivity. The objective of the present research is to fabricate, characterize, and compare iron-based alumina (FeAlxOy) catalysts produced via solution combustion synthesis and iron-based catalysts on silicon carbide support (Fe/SiC) produced via incipient wetness impregnation. Heat mode, fuel type, and oxidizer mole ratio were varied for FeAlxOy catalysts, and metal loading was varied for Fe/SiC catalysts. Each resultant product was characterized by X-ray diffraction analysis, scanning electron microscopy, laser diffraction particle size analysis, and Brunauer-Emmett-Teller (BET) surface area analysis. Characterization suggests that fabrication of iron-based alumina nanocomposites through solution combustion synthesis in a muffle furnace using citric acid as the fuel yields the most promising catalyst.
Reyes, Victoria Isabel↗
The effect of CO on CO2 methanation over Ru/Al2O3 catalysts: a combined steady-state reactivity and transient DRIFT spectroscopy study
The reactivity of Ru/Al2O3 catalysts in the hydrogenation of CO/CO2 gas mixtures is investigated in this work. Accordingly kinetic measurements are carried out at process conditions of industrial interest (i.e., at high COx per-pass conversion and with concentrated COx/H2 streams), and the surface species on the catalyst are investigated through transient DRIFTS-MS analysis. The catalyst shows gradual deactivation when the methanation is carried out in the presence of CO in the gas feed at low temperatures (200-300 °C). However, stable performance is observed at higher temperatures, showing CH4 yields even higher than those observed during methanation of a pure CO2 feed. The catalyst deactivation at low temperature is reversible as thermal treatments at temperatures above 350 °C are able to restore the catalytic activity. DRIFTS-MS experiments revealed that CO2 methanation involves a reaction pathway where CO2 is adsorbed as bicarbonate on Al2O3 and successively hydrogenated to methane on Ru, passing through formate and carbonyl intermediates. In the presence of CO at low temperatures, the catalyst shows a higher CO coverage of the Ru sites, a larger formate coverage of alumina sites and the presence of adsorbed carbonaceous species, identified as hydrocarbon and carboxylate species. Carboxylates remain on the surface, effectively blocking adsorption sites thus leading to catalyst deactivation. However, working above the carboxylate decomposition temperature ensures a clean catalyst surface, resulting in stable and high performance in CO/CO2 methanation. Catalyst preparation, characterization and testing activity were carried out with a joint project between the Politecnico di Milano and the Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA), which is gratefully acknowledged. The authors gratefully acknowledge the financial support of the DRIFTS experiments by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. L.F. also acknowledges the Pacific Northwest National Laboratory (PNNL) for the financial support during his permanence as visiting student.
Methanation, Power-to-gas, Ru/Al2O3 catalyst, cata↗
Machine Learning for Challenging EELS and EDS Spectral Decomposition
Scanning transmission electron microscopy (STEM) is one of the primary methods of characterizing heterogenous catalysts due to its unprecedented spatial resolution and the ability to perform imaging and chemical analysis simultaneously at the atomic scale. Here the characterization of heterogenous catalysts that are composed of metal and oxide support, the atomic configurations are often probed by Z-contrast imaging while the chemical distributions can be revealed by using either electron energy loss spectroscopy (EELS) or energy dispersive X-ray spectroscopy (EDS).
47 OTHER INSTRUMENTATION↗
Automated methods for improved characterization of alloy nanoparticle catalysts
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Cullen, David A.↗