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At least 217 records · Page 12

Computational Design of Metal-Exchanged MFI Zeolites for Coupling CO 2 –Ethylene to Form Acrylic Acid

The production of acrylic acid by coupling CO 2 and ethylene is highly desirable, as it uses a C 1 molecule to introduce the carboxylic group into a large commodity chemical, forming an unsaturated carboxylic acid. Molecular complexes have been used as catalysts in the literature for this reaction; however, these homogeneous studies were all limited by low activity and stability, and efficient heterogeneous catalysts remain to be explored. Here, we report density functional theory calculations, through which we investigated metal-exchanged MFI zeolites with metals from 3d, 4d, and 5d series for this reaction. Screening of reaction thermodynamics has shown that Sc, Y, Cr, Mo, W, Mn, Tc, and Re dispersed into MFI zeolites are potential catalysts. We further calculated the activation barriers for the β–H transfer, a key elementary step that normally determines the overall rates, and found the lowest barrier over Sc- and Y-MFI; such a feasible kinetics is attributed to the low electronegativity of Sc and Y that strongly affects the nature of the transition states and the charge redistribution during the β–H transfer. In conclusion, this work thus provides guidelines for designing a zeolite-based catalyst for this valuable reaction and identifies promising metal centers to be used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Tar Reduction for Assistance in Thermal Conversion of Space Waste for Energy Production

The Trash to Gas (TtG) project investigates technologies for converting waste generated during spaceflight into various resources. One of these technologies was gasification, which employed a downdraft reactor designed and manufactured at NASA's Kennedy Space Center (KSC) for the conversion of simulated space trash to carbon dioxide. The carbon dioxide would then be converted to methane for propulsion and water for life support systems. A minor byproduct of gasification includes large hydrocarbons, also known as tars. Tars are unwanted byproducts that add contamination to the product stream, clog the reactor and cause complications in analysis instrumentation. The objective of this research was to perform reduction studies of a mock tar using select catalysts and choose the most effective for primary treatment within the KSC downdraft gasification reactor. Because the KSC reactor is operated at temperatures below typical gasification reactors, this study evaluates catalyst performance below recommended catalytic operating temperatures. The tar reduction experimentation was observed by passing a model tar vapor stream over the catalysts at similar conditions to that of the KSC reactor. Reduction in tar was determined using gas chromatography. Tar reduction efficiency and catalyst performances were evaluated at different temperatures.

energy conversion↗

Fluorine-Tuned Carbon-Based Nickel Single-Atom Catalysts for Scalable and Highly Efficient CO 2 Electrocatalytic Reduction

Electrocatalytic CO 2 reduction is garnering significant interest due to its potential applications in mitigating CO 2 and producing fuel. However, the scaling up of related catalysis is still hindered by several challenges, including the cost of the catalytic materials, low selectivity, small current densities to maintain desirable selectivity. In this study, Fluorine (F) atoms were introduced into an N-doped carbon-supported single nickel (Ni) atom catalyst via facile polymer-assisted pyrolysis. This method not only maintains the high atom utilization efficiency of Ni in a cost-effective and sustainable manner but also effectively manipulates the electronic structure of the active Ni-N 4 site through F doping. The catalyst has also been further optimized by controlling the F states, including convalent and semi-ionic states, by adjusting the fluorine sources involved. Consequently, this catalyst with unique structure exhibited comparable electrocatalytic performance for CO 2 -to-CO conversion, achieving a Faradaic efficiency (FE) of over 99% across a wide potential range and an exceptional CO evolution rate of 9.5 x 10 4 h -1 at -1.16 V vs reversible hydrogen electrode (RHE). It also delivered a practical current of 400 mA cm -2 while maintaining more than 95% CO FE. Experimental analysis combined with density functional theory (DFT) calculations have also shown that F-doping modifies the electron configuration at the central Ni-N 4 sites. In conclusion, this modification lowers the energy barrier for CO 2 activation, thereby facilitating the production of the crucial *COOH intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Developing novel electrodes with ultralow catalyst loading for high-efficiency hydrogen production in proton exchange membrane electrolyzer cells

Hydrogen plays more crucial roles for decarbonizing the planets and meeting the climate challenges because of its high energy density and zero-emission. It can be produced with proton exchange membrane electrolyzer cells (PEMECs) driven by sustainable and renewable energy resources. Although PEMECs have a number of advantages, including high purity production, quick response, and the ability to operate at high pressure facilitating the gas delivering, their performance and cost greatly hinder their commercial-scale applications. To achieve high-efficiency and cost-reduced hydrogen production in PEMECs, we proposed thin engineered liquid/gas diffusion layers (LGDLs) and associated electrodes, i.e., catalyst-coated LGDLs (CCLGDLs), over conventional porous transport layers (PTLs) and catalyst-coated membranes (CCMs). The research approaches in this project are based on material synthesis, in-situ and ex-situ characterizations, component design and treatment, numerical modeling, and cost analysis. The thin and tunable LGDLs (TT-LGDLs) and CCLGDLs were successfully developed with great performance improvement as demonstrated in lab-scale, bench-scale, and system-scale electrolyzer tests. The electrode thickness was reduced from 370 µm to less than 100 µm with simplified fabrication processes. With the catalytically enhanced Ir-based catalyst coating, the as-developed CCLGDLs with a catalyst loading of 0.34 mg Ir /cm 2 achieved a cell performance of 1.77 V at 2 A cm -2 , exhibiting the catalyst mass activity enhanced by >20 times with significant catalyst saving over conventional catalyst cell design. In-situ PEMEC characterizations, including the current distribution mapping and high-speed and multiscale visualizations, were conducted for a deeper understanding of mass transport and electrochemical reactions within an electrolyzer with LGDLs and CCLGDLs. A 2D cell model was developed and validated for the enhanced performance on TT-LGDL through reducing ohmic losses due to nonuniform hydration and water transport. Further, the cost analysis results have shown a path to move beyond equivalency and surpass costs associated with the project baseline. In this project, the design and fabrication of TT-LGDLs and CCLGDLs will contribute to the performance enhancement, manufacturing simplification, and cost reduction for PEMECs and other energy conversion devices, thus shortening their pathways towards commercialization. This project also provides a good foundation for furthering the in-situ reaction interface research.

08 HYDROGEN↗

Recycling polyolefin plastic waste at short contact times via rapid joule heating

Abstract The chemical deconstruction of polyolefins to fuels, lubricants, and waxes offers a promising strategy for mitigating their accumulation in landfills and the environment. Yet, achieving true recyclability of polyolefins into C 2 -C 4 monomers with high yields, low energy demand, and low carbon dioxide emissions under realistic polymer-to-catalyst ratios remains elusive. Here, we demonstrate a single-step electrified approach utilizing Rapid Joule Heating over an H-ZSM-5 catalyst to efficiently deconstruct polyolefin plastic waste into light olefins (C 2 -C 4 ) in milliseconds, with high productivity at much higher polymer-to-catalyst ratio than prior work. The catalyst is essential in producing a narrow distribution of light olefins. Pulsed operation and steam co-feeding enable highly selective deconstruction (product fraction of >90% towards C 2 -C 4 hydrocarbons) with minimal catalyst deactivation compared to Continuous Joule Heating. This laboratory-scale approach demonstrates effective deconstruction of real-life waste materials, resilience to additives and impurities, and versatility for circular polyolefin plastic waste management.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct aromatization of CO 2 via combined CO 2 hydrogenation and zeolite-based acid catalysis

Aromatics, including benzene, toluene, and xylenes (BTX), are essential chemical building blocks and are widely used as solvents, fuel additives, and polymers. With the recent development in CO 2 capture technologies and the progress made in producing H 2 using renewable energy, direct hydrogenation of CO 2 to aromatics via heterogeneous catalysis has emerged as a promising pathway to accomplish the production of aromatics with simultaneous utilization of waste CO 2 . In this review, we focus on recent advances in the nascent field of direct CO 2 aromatization, whereby tandem catalysts composed of CO 2 hydrogenation and aromatization functionalities are designed and deployed. We review two categories of tandem catalysts: catalysts integrating Fe-based/H-ZSM-5 components following RWGS (reverse water-gas shift of CO 2 to CO)-FT (Fischer-Tropsch synthesis of lower olefins)-aromatization pathways, and catalysts combining metal oxide/H-ZSM-5 domains following CO 2 to methanolaromatization pathways. The key parameters that determine the catalytic performance, such as the composition and structure of the Fe-based or metal oxide-based CO 2 conversion catalysts, the properties of H-ZSM-5, and the synergy between the two components, are analyzed to provide insights for the design of efficient tandem catalysts for CO 2 aromatization. In parallel, thermodynamic analyses, mechanistic studies, and density functional theory (DFT) computations for the relevant reaction routes and pathways are discussed to offer improved understanding of CO 2 activation, reaction intermediates, and product formation. In closing, the challenges and prospects for these tandem reactions are addressed to provide suggested paths forward for future research.

10 SYNTHETIC FUELS↗

Sequential Electrochemical Flow Cell for Complex Multicomponent Electrocatalysis

A highly efficient flow cell for sequential electrolysis containing two complete electrochemical cells, capable of generating reactive species at the upstream working electrode and transporting them to the downstream working electrode, is demonstrated. Deconvolution of the intermixed electrode circuits is accomplished through analysis of the inherent resistance of the electrolyte, which allows for precise and independent control of the electrochemical potential at each electrode without altering concentrations of supporting or background electrolyte species. Sequential electrolysis involving oxidation of hydrogen and reduction of the generated protons downstream is demonstrated at nearly 100% efficiency on Pt-decorated dealloyed porous Nb catalysts. The conversion efficiency of the catalysts is discussed in terms of their geometries and active surface composition, elucidating strategies for use of sequential electrolysis cells for fundamental and applied studies.

25 ENERGY STORAGE↗

Liquid organic hydrogen carriers for long-duration energy storage

Liquid organic hydrogen carrier (LOHC) systems are an excellent alternative to pressurized gas and liquid hydrogen storage technologies due to their high volumetric storage capacities and straightforward adaptation to existing infrastructure. Here, we investigate various molecular and heterogenized Ru, Mn, and Fe catalysts for the reversible (de)hydrogenation of polyols. Mn catalysts, Mn-MACHO(Ph) (1) and Mn-MACHO(iPr)BH 4 (2-BH 4 ) were found to maintain catalytic activity for hydrogen production comparable to the Ru analogs, with greater than 98% conversion of 1,4 butanediol and quantitative hydrogen production. Furthermore, to assess the viability of utilizing heterogenized molecular catalysts for 1,4 butanediol (de)hydrogenation, molecular catalysts, Mn-MACHO(Ph), Ru-MACHO(Ph), and Ru-9, were polymerized to form Mn-MACHO-Poly, Ru-MACHO-Poly, and Ru-9-Poly respectively. These catalysts were then used to assess (de)hydrogenation of polyols, ethylene glycol and 1,4 butanediol. These studies reveal that Ru-MACHO-Poly is an efficient dehydrogenation catalyst with 99% conversion and a hydrogen percent yield of 96%. In addition, Ru-MACHO-Poly is a competent hydrogenation catalyst with approximately 98% conversion back to 1,4 butanediol based on quantitative NMR measurements. Overall, the data suggest these molecular and heterogenized catalysts have potential for practical use in polyalcohol-based LOHC systems.

08 HYDROGEN↗

A review of in situ/operando studies of heterogeneous catalytic hydrogenation of CO 2 to methanol

Repurposing CO 2 into chemicals, one of the Carbon Dioxide Removal (CDR) strategies, still faces significant challenges in conversion and energy efficiency due to the lack of effective catalysts and processes. Fundamental understanding through in situ/operando investigations of the reaction mechanisms and catalyst structures is pivotal for developing the efficient catalysts. This paper reviews the past and recent in situ/operando studies of methanol synthesis from heterogeneous CO 2 hydrogenation over a few typical catalysts including Cu-based, oxide-based, and noble-metal-based catalysts. With the development of high-pressure reactors, in situ/operando IR, X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), neutron diffraction and imaging have been used to reveal the surface intermediates and structures of working catalysts under CO 2 hydrogenation conditions. On the one hand, the combined operando techniques shed light on working mechanisms for some catalytic systems. On the other hand, due to the complexity of selective CO 2 hydrogenation reaction and limited sensitivity of current accessible operando techniques to the surface structure of catalysts, it is still murky about the exact nature of the active sites at the surface/interface and how different sites promote different reaction paths. Furthermore, it is concluded that new methodologies for differentiating signals from different sites, and the development of surface-sensitive techniques for high pressure reactions are needed for providing structural descriptors of highly active and selective CO 2 conversion catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Active and Stable Palladium Catalysts on Novel Ceria–Alumina Supports for Efficient Oxidation of Carbon Monoxide and Hydrocarbons

Precious metal catalysts with superior low-temperature activity and excellent thermal stability are highly needed in environmental catalysis field. In this study, a novel two-step incipient wetness impregnation (T-IWI) method was developed for the fabrication of a unique and highly stable CeO 2 /Al 2 O 3 support (CA-T). Pd anchored on CA-T exhibited a much higher low-temperature catalytic activity and superior thermal stability in carbon monoxide (CO) and hydrocarbon (HC) oxidations, compared to Pd anchored on conventional CeO 2 /Al 2 O 3 (CA), which was prepared by a one-step IWI method. After aging treatment at 800 °C, the CO oxidation rate on Pd/CA-T (1.69 mmol/(g Pd s)) at 120 °C was 4.1 and 84.5 times of those on Pd/CA (0.41 mmol/(g Pd s)) and Pd/Al 2 O 3 (0.02 mmol/(g Pd s)), respectively. It was revealed that the CA-T support with well-controlled small CeO 2 particles (ca. 12 nm) possessed abundant defects for Pd anchoring, which created rich Pd-CeO 2 interfaces with strengthened interaction between Pd and CeO 2 where oxygen could be efficiently activated. This resulted in the significantly improved oxidation activity and thermal stability of Pd/CA-T catalysts. The T-IWI method developed herein can be applied as a universal approach to prepare highly stable metal oxide-alumina-based supports, which have broad application in environmental catalyst design, especially for automobile exhaust aftertreatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Structure–Property Relationships for Ammonium Transport through Charged Organogels

Ammonia is a promising carbon-free fuel, but current methods to produce ammonia are energy intensive. New methods are thereby needed, with one promising method being electrochemical nitrogen reduction cells. Efficient cell operation requires robust catalysts but also efficient membrane separators that permit the selective transport of ions while minimizing the transport of the products across the cell. Commercial membranes have an unknown morphology which makes designing improved cells challenging. To address this problem, we synthesized a series of membranes with controlled crosslinking density and chemical composition to understand their impact on ammonium transport. Higher crosslinking density led to lower ammonium permeability. At the highest crosslinking density, similar ammonium permeability was observed independent of the water volume fraction and hydrophobicity of the monomers. These results suggest new directions to develop membranes with reduced ammonium crossover to improve the efficiency of these electrochemical cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Entropy Alloy Catalysis for Ammonia Decomposition

In this set of experiments, the focus is on developing a high entropy alloy catalyst to decompose ammonia into it two basic atomic elements; N2 and H2. 2𝑁𝐻3 ⇌ 𝑁2 + 3𝐻2 This must be done for the purpose of industrial release of ammonia into the atmosphere in a safer, healthier way. The goal behind this project was to create a catalyst with equal efficiency to ruthenium-based catalysts, which are the current industry standard. Using ruthenium at scale is cost prohibitive and is a hinderance to higher adoption of a hydrogen fuel economy.

Qutob, Laila A. [Savannah River National Laborator↗

In situ Formation of Platinum-Carbon Catalysts in Propane Dehydrogenation

The catalytic production of propylene via propane dehydrogenation (PDH) is a key reaction in the chemical industry. By combining operando transmission electron microscopy with density functional theory analysis, we show that the intercalation and ordering of carbon on Pt interstitials to form Pt-C solid solutions is relevant for increasing propylene production. More specifically, we found that at the point of enhanced propylene formation, the structure of platinum nanoparticles is transformed into a transient caesium chloride-type Pt-C polymorph. At more elevated temperatures, the zincblende and rock salt polymorphs seemingly coexist. When propylene production was highest, multiple crystal structures consisting of Pt and carbon were occasionally found to coexist in one individual nanoparticle, distorting the Pt lattice. Catalyst coking was detected at all stages of the reaction, but did initially not affect all particles. These findings could lead to the development of novel synthesis strategies towards tailoring highly efficient PDH catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Durable Thin‐Film Porous Transport Electrodes for High Current Density PEM Water Electrolysis

Proton exchange membrane water electrolyzers rely on relatively expensive Ir-based catalysts for efficient and durable hydrogen production. To reduce system costs, Ir loadings can be reduced if performance and durability are maintained. Sputter deposition is a readily scalable method to synthesize uniform, low-loading catalyst layers with controlled composition. A catalyst applied directly to the porous transport layer can have advantages for performance, manufacturing simplicity, and catalyst recovery. Suitable porous transport layer porosity can minimize activity losses when reducing loadings. Here, methods are presented to deposit metallic Ir as well as amorphous and rutile Ir oxides. The activity and durability of these materials in the porous transport electrode architecture is evaluated. The metallic and amorphous forms have better initial activity, however, operation at 3 A cm −2 with 0.1 mg Ir cm −2 shows that only rutile IrO 2 maintains performance beyond 100 h with a 50 mV improvement after 700 h. A >10x reduced dissolution rate is shown for rutile IrO 2 . With a low-porosity transport layer and 0.4 mg Ir cm −2 , a steady-state voltage decay rate of 6 µV h −1 is achieved. The results demonstrate that sputter-deposited rutile IrO 2 porous transport electrodes with low Ir loading can be operated at high current density to reduce hydrogen production costs.

08 HYDROGEN↗

Thermal Activation of Zirconium(IV) Acetylacetonate Catalysts to Enhance Polyurethane Synthesis and Reprocessing

Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.

Alcohols↗

Ru Single Atoms on One-Dimensional CF@g-C 3 N 4 Hierarchy as Highly Stable Catalysts for Aqueous Levulinic Acid Hydrogenation

Herein, we report a stable catalyst with Ru single atoms anchored on a one-dimensional carbon fiber@graphitic carbon nitride hierarchy, by assembling wet wipes composed of fiber-derived carbon fiber (CF), melamine-derived graphitic carbon nitride (g-C3N4) and RuCl3 before NaBH4 reduction. The atomically dispersed Ru species (3.0 wt%) are tightly attached via N-coordination provided by exterior g-C3N4 nanosheets, and further stabilized by the interior mesoporous CF. The obtained CF@g-C3N4–Ru SAs catalyst can be cycled six times without notable leaching of Ru or loss of GVL yield in the acidic media. This catalyst is more stable than Ru nanoparticles supported on CF@g-C3N4, as well as Ru single atoms anchored on CF and g-C3N4, and proves to be one of the most efficient metal catalysts for aqueous LA hydrogenation to γ-valerolactone (GVL). The isolated Ru atoms by strong N-coordination, and their enhanced electron/mass transfer afforded by the one-dimensional hierarchy, can be responsible for the excellent durability of CF@g-C3N4–Ru SAs under harsh reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Partial-Single-Atom, Partial-Nanoparticle Composites Enhance Water Dissociation for Hydrogen Evolution

The development of an efficient electrocatalyst toward the hydrogen evolution reaction (HER) is of significant importance in transforming renewable electricity to pure and clean hydrogen by water splitting. However, the construction of an active electrocatalyst with multiple sites that can promote the dissociation of water molecules still remains a great challenge. Herein, a partial-single-atom, partial-nanoparticle composite consisting of nanosized ruthenium (Ru) nanoparticles (NPs) and individual Ru atoms as an energy-efficient HER catalyst in alkaline medium is reported. The formation of this unique composite mainly results from the dispersion of Ru NPs to small-size NPs and single atoms (SAs) on the Fe/N codoped carbon (Fe–N–C) substrate due to the thermodynamic stability. The optimal catalyst exhibits an outstanding HER activity with an ultralow overpotential (9 mV) at 10 mA cm -2 (η 10 ), a high turnover frequency (8.9 H 2 s -1 at 50 mV overpotential), and nearly 100% Faraday efficiency, outperforming the state-of-the-art commercial Pt/C and other reported HER electrocatalysts in alkaline condition. Both experimental and theoretical calculations reveal that the coexistence of Ru NPs and SAs can improve the hydride coupling and water dissociation kinetics, thus synergistically enhancing alkaline hydrogen evolution performance.

36 MATERIALS SCIENCE↗

Methane Catalytic Pyrolysis by Microwave and Thermal Heating over Carbon Nanotube-Supported Catalysts: Productivity, Kinetics, and Energy Efficiency

Methane catalytic pyrolysis, which is the reaction to produce hydrogen and carbon without emitting CO 2 , represents an approach for decarbonization using natural gas as an energy resource. In this work, the endothermic pyrolysis reaction was carried out under two heating scenarios: convective thermal heating and microwave-driven irradiative heating. The pyrolysis reaction was conducted at 550-600 °C over carbon nanotube-supported Ni-Pd and Ni-Cu catalysts. On both catalysts, an enhanced methane conversion rate was observed under microwave irradiation. The enhanced catalytic activity was hypothetically caused by the presence of free electrons in the carbon atoms within CNT that enabled the CNT support to absorb microwave energy effectively and to be heated efficiently by microwave. The microwave catalytic pyrolysis has shown improvement in kinetics, where the apparent activation energy dropped from 45.5 kJ/mol under conventional convective heating to 24.8 kJ/mol under microwave irradiation. When the methane conversion rate is increased by 37 %, the microwave power consumption only changed by 10.8 %. The research demonstrated the potential of transforming natural gas to clean hydrogen and value-added carbon in a more energy-efficient way. Process simulation and techno-economic analysis showed that potentially hydrogen minimum selling price of about $1 /kg H 2 could be achieved.

03 NATURAL GAS↗