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At least 1,243 records · Page 69

Developing machine learning for heterogeneous catalysis with experimental and computational data

Machine learning techniques have emerged as a useful tool for identifying complex patterns and correlations in large datasets, such as associating catalyst performance to its physicochemical properties. In the heterogeneous catalysis communities, machine learning models have mostly been developed using high-throughput quantum chemistry calculations, with only a few case studies resulting in experimentally validated catalyst improvements. This limited success may be due to the use of simplified catalyst structures in computational studies and the lack of comprehensive experimental datasets. In this Review, we bring together studies integrating high-throughput approaches and machine learning for the advancement of solid heterogeneous catalysis, leveraging both experimental and computational data. We systematically analyze trends in the field, based on the descriptors used as model input and output; the materials, devices, or reactions investigated; the dataset size; and the overall achievements. Furthermore, for models reporting unitless R 2 values, we compare the performances based on these mentioned trends.

Computational chemistry↗

Tailoring catalyst layer structures for anion exchange membrane fuel cells by controlling the size of ionomer aggreates in dispersion

The development of anion exchange membranes and ionomers plays a critical role in performance of anion exchange membrane fuel cells. However, the optimal design of catalyst layer structures still remains unexplored despite its significance. Herein, the rational design guide is presented for cathode and anode catalyst layers using m-TPN1 ionomer by controlling the size of ionomer aggregates in dispersion and comparing various catalyst layer structures. The size of m-TPN1 aggregates decreases, creating a more uniform ionomer distribution and a larger triple-phase-boundary. As ionomer distribution of the cathode catalyst layer becomes more uniform, the power density of membrane-electrode-assembly is enhanced. Also, the power density at fully humidified condition strongly correlates with the porosity of anode catalyst layer due to the limitation of hydrogen transport at anode by water flooding.

42 ENGINEERING↗

Fine Gradient Electrode and Micro Porous Layer Structures for Improved Heavy Duty Fuel Cells (Final Report)

The commercial deployment of Heavy Duty Fuel Cells(HDFC) for applications such as large trucks (for example, Class 8 capable of carrying 50,000 lb. loads) depends vitally on achieving high efficiency and durability at reasonable costs. Furthermore, the HDFC must operate under practical conditions such as with fuel and air impurities, multiple stop-start cycles, and under the extremes of climate our planet offers – from hot and cold to dry and wet. These conditions place a premium on the stability and utilization of the materials comprising the membrane electrode assemblies (MEAs) powering the fuel cell. and the current catalysts, MicroPorous Layers, and Electrode structures and additives are insufficient for these needs. In Phase I Pajarito and Advent will develop durable electrocatalysts, MicroPorous Layer and electrode additives, and electrode structures for heavy duty fuel cells designed for zero-emission long-haul trucking. The electrocatalyst products are designed to solve the challenging durability and performance needs of fuel cells designed for long life and high efficiency through a combination of uniquely structured designed catalysts as well as new MicroPorous Layers (MPLs) and electrode structure additives. These improved materials will provide Pajarito both an expanded commercial opportunity in electrocatalysts, as well as new markets for MPL and electrode additives. The resulting public benefits include improved economics of fuel cells, a leading zero-emission technology for mobility, as well as reduced reliance on the critical minerals and metals used in the heavy-duty trucks industry. Possible follow-up Phase II and III projects would add full MEA products based on the Phase I efforts catalysts and additives, with full system validation by leading Fuel Cell Truck developers.

08 HYDROGEN↗

Rational Design and Synthesis of Hierarchical Porous Mn–N–C Nanoparticles with Atomically Dispersed MnNx Moieties for Highly Efficient Oxygen Reduction Reaction

Developing transition-metal excluding iron and cobalt–nitrogen–carbon (M–N–C) electrocatalysts for the oxygen reduction reaction (ORR) is critical to substantially promote the development of precious-metal-free metal–air batteries and fuel cells. In the work, Mn–N–C nanoparticles with atomically dispersed MnNx moieties were synthesized by pyrolyzing Mn-ion–dual-pyridine coordinated complex, which was obtained via a simple condensation reaction between 2,6-diamino-pyridine and 2,6-diacetyl-pyridine with MnCl 2 as the Mn source. The precursor features with a characteristic structure of dual-pyridine ligand, which possesses a strong coordinating capability for Mn 2+ , facilitating the formation of highly dispersed nitrogen-coordinated Mn sites (MnN x ). Attributed to the highly active atomic MnN x sites, hierarchical pore structure, and high surface area of the Mn–N–C derived from the new precursor, it exhibits outstanding ORR performance in 0.1 M KOH with an almost direct four-electron reaction path and high selectivity of O 2 into H 2 O (low H2O2 production <3.5%). The half-wave potential of Mn–N–C is 0.88 V vs RHE, which is 20 mV higher than that of commercial Pt/C catalyst and reaches to the level of Fe–N–C catalyst obtained by the same method. Meanwhile, the feasibility of Mn–N–C for practical application is validated by its higher-performance power output in Zn–air battery with a maximum power density of 132 mW cm –2 compared to that of Pt/C (121 mW cm –2 ) using the same catalyst loading of 1.0 mg cm –2 . This work develops a convenient route to develop non-Fe or Co–N–C electrocatalyst for the ORR.

36 MATERIALS SCIENCE↗

Biogas Reforming to Syngas: A Review

Interest in novel uses of biogas has increased recently due to concerns about climate change and greater emphasis on renewable energy sources. Although biogas is frequently used in low-value applications such as heating and fuel in engines or even just flared, reforming is an emerging strategy for converting biogas to syngas, which could then be used to obtain high-value-added liquid fuels and chemicals. Interest also exists due to the role of dry, bi-, and tri-reforming in the capture and utilization of CO 2 . New research efforts have explored efficient and effective reforming catalysts, as specifically applied to biogas. In this paper, we review recent developments in dry, bi-, and tri-reforming, where the CO 2 in biogas is used as an oxidant/partial oxidant. The synthesis, characterization, lifetime, deactivation, and regeneration of candidate reforming catalysts are discussed in detail. The thermodynamic limitation and techno-economics of biogas conversion are also discussed.

09 BIOMASS FUELS↗

Continuous-flow reactor with superior production rate and stability for CO 2 reduction using semiconductor photocatalysts

Semiconductor photocatalyst approaches for solar CO 2 reduction are attractive due to their simplicity but have lagged in efficiency compared to less-integrated photoelectrochemical (PEC) approaches and to electrolysis reactors. We identify poor mass transport and catalyst deactivation as key constraints. To address them, we have developed a continuous-flow photocatalytic reactor system allowing us to control the triple-phase interface on the photocatalyst surface using the liquid and reactant gas flow rates. With the goal of selectively producing CO, the reactor is optimized by controlling the pressure and flow rates of the reactant gas and electrolyte in contact with both sides with the intermediately placed catalyst. In comparison to batch reactors with an immobile photocatalyst bed and gas phase CO 2 or CO 2 purged water, 10–24 times higher production rates are achieved for photocatalysts such as TiO 2 , ZnO, C 3 N 4 , and CdS by simply changing to the designed flow-type photoreactor without any catalyst modification. In addition, CO selectivity (93.2%) and long-term stability (>780 min) using the designed reactor are significantly enhanced compared to using the batch reactors (71.7%, <180 min for reduced 50% activity). Here, we propose that the enhanced mass transport on the photocatalyst surface accelerates the desorption of the initial photolysis product, CO, and prevents the poisoning effect from deactivating photocatalyst activity. This study has the potential to facilitate the utilization of semiconductor-based photocatalytic reactions for achieving superior performance wih gaseous reactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation

Since our initial report in 1976, the oxygen rebound mechanism has become the consensus mechanistic feature for an expanding variety of enzymatic C–H functionalization reactions and small molecule biomimetic catalysts. For both the biotransformations and models, an initial hydrogen atom abstraction from the substrate (R–H) by high-valent iron-oxo species (Fe n =O) generates a substrate radical and a reduced iron hydroxide, [Fe n-1 –OH ·R]. This caged radical pair then evolves on a complicated energy landscape through a number of reaction pathways, such as oxygen rebound to form R–OH, rebound to a non-oxygen atom affording R–X, electron transfer of the incipient radical to yield a carbocation, R + , desaturation to form olefins, and radical cage escape. These various flavors of the rebound process, often in competition with each other, give rise to the wide range of C–H functionalization reactions performed by iron-containing oxygenases. In this review, we first recount the history of radical rebound mechanisms, their general features, and key intermediates involved. We will discuss in detail the factors that affect the behavior of the initial caged radical pair and the lifetimes of the incipient substrate radicals. Several representative examples of enzymatic C–H transformations are selected to illustrate how the behaviors of the radical pair [Fe n-1 –OH ·R] determine the eventual reaction outcome. Finally, we discuss the powerful potential of “radical rebound” processes as a general paradigm for developing novel C–H functionalization reactions with synthetic, biomimetic catalysts. We envision that new chemistry will continue to arise by bridging enzymatic “radical rebound” with synthetic organic chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fully Oxidized Ni–Fe Layered Double Hydroxide with 100% Exposed Active Sites for Catalyzing Oxygen Evolution Reaction

Ni–Fe layered double hydroxides (LDHs) are promising for catalyzing the oxygen evolution reaction (OER) in alkaline media. However, the OER mechanism is highly debated, partially because of the lack of an ideal catalyst with 100% exposed active sites for unambiguous characterization. In this paper, we develop an alcohol intercalation method to prepare ultrathin Ni–Fe LDH with a 1/3 unit-cell thickness and 100% exposed active sites. The ultrathin LDH catalyst exhibits an intrinsic activity similar to the bulk LDH and allows a direct and reliable characterization of the catalyst without any interference from “bulk” inactive species. Operando synchrotron X-ray analysis indicates that the metallic ions in ultrathin Ni–Fe LDH are fully oxidized into tetravalence states at low applied potentials and that the OER occurs on the tetravalent Ni and Fe ions following a decoupled proton/electron mechanism. In conclusion, our findings demonstrate that a full oxidization of metal ions is crucial for highly active NiFe LDHs and that it can be accomplished by engineering ultrathin nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scalable synthesis of supported catalysts using fluidized bed atomic layer deposition

Overcoating layers deposited on the surface of heterogeneous catalysts using atomic layer deposition (ALD) have been shown to increase catalyst activity, lifetime, and selectivity. In this study, we performed Al 2 O 3 ALD and Pd ALD in a commercial fluidized bed reactor on high surface area mesoporous powder supports to create overcoated catalysts with high precursor utilization. We investigated the reaction mechanism for both Al 2 O 3 ALD and Pd ALD using in situ mass spectrometry and developed a mathematical model to understand the precursor saturation behaviors. We characterized the catalyst samples using a variety of techniques to measure the surface area, porosity, composition, and surface chemistry of the overcoated catalysts. Finally, we used propane dehydrogenation as a probe reaction to evaluate the performance of the catalysts prepared by fluidized bed ALD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rational design of septenary high-entropy alloy for direct ethanol fuel cells

Promoting C–C bond cleavage of ethanol by a complete 12-electron (12e) ethanol oxidation reaction (EOR) is a grand challenge for the development of highly efficient direct ethanol fuel cells (DEFCs). Most state-of-the-art catalysts only implement the EOR in an incomplete 4e or 2e pathway because of the poisoning of the catalysts by strongly adsorbed CO, leading to the poor output performance and low cell efficiency of DEFCs. Herein, a septenary PtPdFeCoNiSnMn high-entropy alloy (PtPd HEA) with a PtPd-rich surface but super-low platinum group metals loading was developed. We identified and proved the functions of each element in the PtPd HEA. The DEFCs assembled with the PtPd HEA (0.12 mg PtPd ∙cm -2 ) achieved a maximum power density of 0.72 W cm -2 and a durable operation for 1,200 h, which outperforms state-of-the-art catalysts for DEFCs. This work will be a design principle for nanostructured alloy development for renewable energy and sustainability applications.

25 ENERGY STORAGE↗

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↗

Solar Decarbonization of Paraffin Dehydrogenation Through Particle Heat Carriers (Final Technical Report)

This project focuses on solutions to decarbonize high-temperature catalytic processes using solar thermal heat. The primary project goal is to show the validity of a moving packed bed reactor for propane dehydrogenation using catalyst particles as the heat carrier for the reaction, which can be heated by concentrated solar energy in a particle receiver. This concept, if further developed, may provide a cost-effective pathway for converting lower value gases to important chemical precursors for industrial materials using only renewable energy. The project was divided into six tasks. In Task 1, DFT calculations were performed to understand the role of Pt and Sn in the catalytic dehydrogenation reaction. In Task 2 chemical kinetics measurements were made for several catalyst formulations at high temperatures. In Task 3, the solar absorptance of catalyst particles was compared to the absorptance of commonly used materials in particle receivers. In Task 4, numerical models were developed which could predict performance of the complete system and predict specific temperatures in the system. In Task 5, a prototype system was designed, fabricated, and tested to show the validity of the concept. Task 6 concerned project management activities. Experiments with the prototype showed repeatable thermal performance at temperatures targeted for the reaction. A limited set of tests were done with active catalyst and propane dehydrogenation, showing conversion of propane to propylene with a range of conversions and selectivities. The results are promising, and the prototype designed was reliable during testing, and the team expects that further development of the prototype would yield improved results. A numerical model framework based on coupled fluid and particle mechanics was developed with high computational efficiency using GPU calculations. The model may prove highly useful for evaluating other high-temperature particle systems. However, it was determined that simpler porous media models were good fits for the needs of the current moving packed bed concept. Data showing strong solar absorption of the particles validates the plan of using existing solar particle receivers with only a change in the particle type. Catalyst investigation showed that Pt 1 Sn 3 is the most viable candidate for developing PtSn catalysts for high temperature propane dehydrogenation, considering the balance of activity, selectivity, and deactivation. This project completed an initial study of various factors needed to incorporate a moving bed catalytic reactor for propane dehydrogenation into a concentrated solar thermal particle system. Future developments may allow this technology to be scaled up and help to use solar thermal energy to decarbonize not only the propane dehydrogenation reaction, but other gas-solid catalytic reactions at similar temperatures.

14 SOLAR ENERGY↗

Bosch CO2 reduction unit research and development.

Development of Bosch CO2 reduction units for manned spacecraft application has been in progress for a decade. The Bosch process catalytically reacts CO2 with H2 to produce water and carbon. The water may then be electrolyzed to close the biological oxygen and process hydrogen loops. A critical problem has been to confine the reaction so that carbon does not block flow and stop the process. Reaction isolation within a replaceable catalyst cartridge has been successfully demonstrated. Objectives of the current development program are a 25% reduction in operating power, an 80% reduction in expendable weight, and minimized resupply volume.

Holmes, R. F.↗

Phase segregation reversibility in mixed-metal hydroxide water oxidation catalysts

Achieving stable, low-cost electrocatalysts represents a daunting challenge towards practical water oxidation reactions. Here, we report that a degraded electrocatalyst can be revivified under catalytic operating conditions by manipulating reversible phase segregation. Under the oxygen evolution reaction conditions, Fe segregation develops in the Ni–Fe hydroxide host lat- tice, with the formation of FeOOH, resulting in an interface between the FeOOH and the host lattice. A dynamic metal dissolu- tion–redeposition process accelerates the Fe segregation and formation of the FeOOH secondary phase, resulting in catalyst deactivation. Operando synchrotron spectroscopic and microscopic analyses suggest that the phase segregation is revers- ible between the water oxidation potential and the catalyst reduction potential. Therefore, we have developed an intermittent reduction methodology to revivify the catalytic activity under the operating conditions, enhancing catalyst durability. The pres- ent study highlights that tailoring phase segregation at the catalyst/electrolyte interface constitutes an important strategy for revivifying and stabilizing catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide

Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.

Upchurch, Billy T.↗

Interfacial Engineering of W 2 N/WC Heterostructures Derived from Solid‐State Synthesis: A Highly Efficient Trifunctional Electrocatalyst for ORR, OER, and HER

Abstract To meet the practical demand of overall water splitting and regenerative metal–air batteries, highly efficient, low‐cost, and durable electrocatalysts for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) are required to displace noble metal catalysts. In this work, a facile solid‐state synthesis strategy is developed to construct the interfacial engineering of W 2 N/WC heterostructures, in which abundant interfaces are formed. Under high temperature (800 °C), volatile CN x species from dicyanodiamide are trapped by WO 3 nanorods, followed by simultaneous nitridation and carbonization, to form W 2 N/WC heterostructure catalysts. The resultant W 2 N/WC heterostructure catalysts exhibit an efficient and stable electrocatalytic performance toward the ORR, OER, and HER, including a half‐wave potential of 0.81 V (ORR) and a low overpotential at 10 mA cm −2 for the OER (320 mV) and HER (148.5 mV). Furthermore, a W 2 N/WC‐based Zn–air battery shows outstanding high power density (172 mW cm −2 ). Density functional theory and X‐ray absorption fine structure analysis computations reveal that W 2 N/WC interfaces synergistically facilitate transport and separation of charge, thus accelerating the electrochemical ORR, OER, and HER. This work paves a novel avenue for constructing efficient and low‐cost electrocatalysts for electrochemical energy devices.

Diao, Jinxiang↗

Optimizing hierarchical membrane/catalyst systems for oxidative coupling of methane using additive manufacturing

The advantage of a membrane/catalyst system in oxidative coupling of methane (OCM) compared to conventional reactive systems is that by introducing oxygen to the OCM catalytic sites through a membrane, parasitic gas phase reactions of O 2 (g), responsible for lowering product selectivity, can be avoided. The design and fabrication of membrane/catalyst systems has, however, been hampered by low volumetric chemical conversion rates, high capital cost, and difficulties in codesigning membrane and catalyst properties to optimize the performance. We solve these issues by developing a dual-layer additive manufacturing process, based on phase inversion, to design, fabricate and optimize a hollow fiber membrane/catalyst system for OCM. We demonstrate the approach though a case study using BaCe 0.8 Gd 0.2 O 3-δ (BCG) as the basis of both the catalyst and separation layers. We show that by using the manufacturing approach we can codesign the membrane thickness and catalyst surface area so that the flux of oxygen transport through the membrane and methane activation rates in the catalyst layer match each other. Here, we demonstrate that this “rate matching” is critical for maximizing the performance, with the membrane/catalyst system significantly overperforming conventional reactor designs under identical conditions.

36 MATERIALS SCIENCE↗

Quinone-mediated electrochemical O2 reduction accessing high power density with an off-electrode heterogeneous catalyst

New methods for interconversion of electrical and chemical energy are crucial to address emerging challenges in renewable energy storage and conversion. Dissolved redox mediators provide an effective means to transport electrons (and protons) between an electrode and catalysts that are not in direct physical contact with an electrode. Mediators are widely implemented in biofuel cells, but such devices typically exhibit low power densities. Here, we report the development of a tetrasubstituted quinone mediator that exhibits excellent stability under strongly acidic conditions and supports electrochemical reduction of O2 at an off-electrode heterogeneous cobalt catalyst contained within a packed-bed reactor. Efficient oxidation of the hydroquinone by O2 in the reactor provides the basis for mediator regeneration, and an integrated “flow cathode” system supports high fuel-cell power densities. These results establish the combination of organic mediators with off-electrode heterogeneous catalysts as a versatile platform for development of new electrode-driven chemical redox transformations.

Preger, Yuliya↗