Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “catalyst design”

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 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Electrochemically Determined O–H Bond Dissociation Free Energies of NiO Electrodes Predict Proton-Coupled Electron Transfer Reactivity

Redox reactions at metal oxide (MOx) surfaces are implicated in many catalytic and energy conversion processes. However, the fundamental thermodynamics dictating such interfacial reactivity remain ill-defined, in part because of the frequent involvement of proton as well as electron transfers. Herein, we describe an approach connecting the pH-dependent electrochemical response of MOx thin films with the bond dissociation free energies (BDFEs) of their electroactive surface O-H bonds. Using NiO as a case study, we show that these BDFEs can predict much of the observed proton-coupled electron transfer (PCET) reactivity at the MOx surface. Analyzing the PCET reactivity of MOx materials in terms of BDFEs could enable new approaches for designing more active and efficient catalysts and electrocatalysts for important PCET reactions.

Wise, Catherine F.↗
DOE OSTI2024

Atomic-scale identification of active sites of oxygen reduction nanocatalysts

Heterogeneous nanocatalysts play a crucial role in both the chemical and energy industries. Despite substantial advancements in theoretical, computational and experimental studies, identifying their active sites remains a major challenge. Here we utilize atomic electron tomography to determine the three-dimensional atomic structure of PtNi and Mo-doped PtNi nanocatalysts for the electrochemical oxygen reduction reaction. We then employ the experimental atomic structures as input to first-principles-trained machine learning to identify the active sites of the nanocatalysts. Through the analysis of the structure–activity relationships, we formulate an equation termed the local environment descriptor, which balances the strain and ligand effects to provide physical and chemical insights into active sites in the oxygen reduction reaction. The ability to determine the three-dimensional atomic structure and chemical composition of realistic nanoparticles, combined with machine learning, could transform our fundamental understanding of the active sites of catalysts and guide the rational design of optimal nanocatalysts.

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

Predicting metal–metal interactions. I. The influence of strain on nanoparticle and metal adlayer stabilities

Strain-engineering of bimetallic nanomaterials is an important design strategy for developing new catalysts. In this paper, we introduce an approach for including strain effects into a recently introduced, density functional theory (DFT)-based alloy stability model. The model predicts adsorption site stabilities in nanoparticles and connects these site stabilities with catalytic reactivity and selectivity. Strain-based dependencies will increase the model’s accuracy for nanoparticles affected by finite-size effects. In addition to the stability of small nanoparticles, strain also influences the heat of adsorption of epitaxially grown metal-on-metal adlayers. In this respect, we successfully benchmark the strain-including alloy stability model with previous experimentally determined trends in the heats of adsorption of Au and Cu adlayers on Pt (111). For these systems, our model predicts stronger bimetallic interactions in the first monolayer than monometallic interactions in the second monolayer. We explicitly quantify the interplay between destabilizing strain effects and the energy gained by forming new metal–metal bonds. While tensile strain in the first Cu monolayer significantly destabilizes the adsorption strength, compressive strain in the first Au monolayer has a minimal impact on the heat of adsorption. Hence, this study introduces and, by comparison with previous experiments, validates an efficient DFT-based approach for strain-engineering the stability, and, in turn, the catalytic performance, of active sites in bimetallic alloys with atomic level resolution.

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

Field Scale Testing of the Thermocatalytic Ethylene Production Process Using Ethane and Actual Coal Fired Flue Gas Co 2

This report provides a summary of the work performed and results obtained from a project supported by the US DOE (DE-FE0031713). In this study, Southern Research (SR) completed field-scale demonstration of a rationally designed novel nano-engineered catalyst driven thermochemical process to produce high yield of ethylene by using CO 2 derived from actual coal-fired flue gas and ethane. This process, referred to here as “CO 2 -ODH” due to CO 2 use via oxidative dehydrogenation (ODH) mechanism, follows a modified pathway to classical steam cracking (SC) process of ethylene production thus paving the way for significantly reduced CO 2 footprint, marginally improved thermodynamics, higher product selectivity and lower reaction temperatures.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Development and Demonstration of a Fuel-Efficient, Class 8 Tractor & Trailer Engine System (SuperTruck II)

Navistar presents the SuperTruck II (ST II) Final Report to the Unites States Department of Energy (US DOE), which covers the five Budget Periods (BPs) from 10-1-2016 through 6-30-2022. For ST II, Navistar built on the achievements of the SuperTruck I (ST I) Program as a catalyst to continue critical research, design and development, testing, and operations to reach the ambitious goals of the ST II project. This approach allowed Navistar to continue contributing to the essential needs of our nation for safe, efficient, and cost-effective delivery of goods and services, as we reduced negative environmental effects and improved operational productivity. This document contains information specified in DOE F 4600.2, Final Scientific/Technical Report DOE F 241.3, B. SCIENTIFIC/TECHNICAL REPORTS, explaining how we met and exceeded program requirements. Throughout this Final Report, Navistar extracted information from documents prepared during the project that represent our management, design and development, building, and testing efforts to meet and exceed SuperTruck II project goals. Navistar followed Plan requirements to achieve / exceed Project Objectives: a) >100% improvement in vehicle freight efficiency (FE) (on ton-MPG basis) relative to 2009 baseline with stretch goal of 140% improvement [actual: 170%); b) >55% engine brake thermal efficiency (BTE) demonstrated in operational engine at a 65-mph cruise point on a dynamometer – ≥31% increase from 2009 baseline [actual: 55.20% of combined BTE) ; and c) development and implementation of commercially cost effective technologies (in terms of a simple payback). Technology selection / development path focused on developing technologies applicable for production within 3-year approach, while ensuring technology readiness and cost of ownership for end users. The Program was organized into five budget periods: Requirements / Technology Assessment and Initial Hardware Testing; Technology Development and Concept Readiness Demonstration; Technology Finalization and Validation Tractor / Trailer Fabrication, Integration and Commissioning Demonstration; and Fuel Economy (FE) and Brake Thermal Efficiency (BTE) and Program Completion. Leadership was provided by DOE, with tasks performed by laboratories (Argonne National Laboratory, Lawrence Livermore National Laboratory); partners at Bosch, TPI, Dana, and J.B. Hunt; , and support from University of Michigan and Clemson University. Navistar lead this team with Principal Investigator / Contracting Officer; Project Manager (PM); Vehicle, Engine, and Aftertreatment Engineers; Finance Manager, Technical Program Leads, and Legal/IP; and other key personnel. Work also included personnel in risk management; funding / budget / finance. Work involved analysis, development, testing, and down selection of individual/system engine, aftertreatment, and vehicle technologies, with integration of selected technologies into a prototype vehicle for demonstration of fuel-efficiency gain. Work also included component/integrated system level development of truck and trailer aerodynamics, base engine efficiency, advanced aftertreatment, combustion efficiency, waste heat recovery, hybrid powertrain, reduced rolling resistance, weight reduction, idle reduction, and driver feedback. As ST II progressed, Navistar performed computer-based modeling / simulations of technologies focused on the primary operational areas: Engine, Aftertreatment, and Vehicle. During the ST II Program, the COVID Virus outbreak unexpectedly challenged by the effects of, which affected staffing, scheduling, design, supplies, availability of materials, production procedures, and testing. The DOE responded by extending the program by three quarters to ensure that project tasks were completed for this vital project. Focus continued on analyzing, developing, testing, and down selecting individual-/system-level engine and vehicle technologies for integration of the final selected technologies into a prototype vehicle that would demonstrate fuel-efficiency gains made possible through these technologies. This included component/integrated system-level development of truck and trailer aerodynamics, base engine efficiency, advanced aftertreatment, combustion efficiency, waste heat recovery, solar power, distributed and intelligent vehicle power, hybrid powertrain, reduced rolling resistance, weight reduction, idle reduction, and driver feedback. Throughout the program, function, reliability, and performance at all levels were ensured through testing. Proof of this approach was demonstrated in multiple, on-road demonstrations: Scenario A (Flatland) Fuel Economy, Scenario B (Hilly) Fuel Economy, and City Cycle Tests. Other benefits derived from ST II included new/improved products, publications, patents, and next-step capabilities related to electric/hydrogen vehicles and autonomous driving.

Zukouski, Russ↗
DOE OSTI2024

Catalytic Interconversion of Ammonia and Dinitrogen at Base Metals

Best known as a fertilizer, ammonia is also a carbon-free fuel that produces only benign byproducts, nitrogen and water. Moreover, the synthesis of ammonia from water and nitrogen in the air can be used to store energy from renewable, yet intermittent power sources such as solar and wind. This work develops new molecular electrocatalysts to efficiently extract electrical energy from ammonia, a process which currently is underdeveloped. These studies inspire complementary electrochemical approaches for the synthesis of ammonia from nitrogen by coupling it with the protons ultimately to be derived from acidified water. Careful mechanistic studies that outline the molecular steps involved in these chemical transformations will inform the design of new classes efficient catalysts that interconvert ammonia and nitrogen. Importantly, this study targets molecular electrocatalysts with inexpensive, Earth abundant metals such as iron and copper, consistent with the sustainable use and synthesis of ammonia.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Understanding piezocatalysis, pyrocatalysis and ferrocatalysis

The last decade has witnessed the emergence of the application of piezoelectric and ferroelectric materials for catalytic and photocatalytic applications that harness light, thermal and mechanical energy into chemical reactions. This article surveys the different concepts of pyro- and piezocatalysis and differences with respect to ferrocatalysis and switchable catalysis and delves into the current understanding of the mechanisms underlying piezocatalysis. The outlook for advancing in the surface science studies required for the design of new and better catalysts based on polar electromechanically active materials is discussed in the context of the state of the art experimental studies and potential future nanoscience developments.

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

Block Copolymer-Templated Synthesis of Fe–Ni–Co-Modified Nanoporous Alumina Films

Despite intense interest in the catalytic potential of transition metal oxide heterostructures, originating from their large surface area and tunable chemistry, the fabrication of well-defined multicomponent oxide coatings with controlled architectures remains challenging. Here, we demonstrate a simple and effective swelling-assisted sequential infiltration synthesis (SIS) strategy to fabricate hierarchically porous multicomponent metal-oxide electrocatalysts with tunable bimetallic composition. A combination of solution-based infiltration (SBI) of transition metals, iron (Fe), nickel (Ni), and cobalt (Co), into a block copolymer (PS73-b-P4VP28) template, followed by vapor-phase infiltration of alumina using sequential infiltration synthesis (SIS), was employed to synthesize porous, robust, conformal and transparent multicomponent metal-oxide coatings like Fe/AlO x , Fe+Ni/AlO x , and Fe+Co/AlO x . Electrochemical assessments for the oxygen evolution reaction (OER) in a 0.1 M KOH electrolyte demonstrated that the Fe+Ni/AlO x composite exhibited markedly superior catalytic activity, achieving an impressive onset potential of 1.41 V and a peak current density of 3.29 mA/cm 2 . This superior activity reflects the well-known synergistic effect of alloying transition metals with a trace of Fe, which facilitates OER kinetics. Overall, our approach offers a versatile and scalable path towards the design of stable and efficient catalysts with tunable nanostructures, opening new possibilities for a wide range of electrochemical energy applications.

conformal films↗
DOE OSTI2023

Understanding of Active Sites and Interconversion of Pd and PdO during CH 4 Oxidation

Pd-based catalysts are widely used in the oxidation of CH 4 and have a significant impact on global warming. However, understanding their active sites remains controversial, because interconversion between Pd and PdO occurs consecutively during the reaction. Understanding the intrinsic active sites under reaction conditions is critical for developing highly active and selective catalysts. In this study, we demonstrated that partially oxidized palladium (PdO x ) on the surface plays an important role for CH 4 oxidation. Regardless of whether the initial state of Pd corresponds to oxides or metallic clusters, the topmost surface is PdO x , which is formed during CH4 oxidation. A quantitative analysis using CO titration, diffuse reflectance infrared Fourier-transform spectroscopy, X-ray diffraction, and scanning transmission electron microscopy demonstrated that a surface PdO layer was formed on top of the metallic Pd clusters during the CH 4 oxidation reaction. Furthermore, the time-on-stream test of CH 4 oxidation revealed that the presence of the PdO layer on top of the metallic Pd clusters improves the catalytic activity. Our periodic density functional theory (DFT) calculations with a PdO x slab and nanoparticle models aided the elucidation of the structure of the experimental PdO particles, as well as the experimental C-O bands. The DFT results also revealed the formation of a PdO layer on the metallic Pd clusters. This study helps achieve a fundamental understanding of the active sites of Pd and PdO for CH 4 oxidation and provides insights into the development of active and durable Pd-based catalysts through molecular-level design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Hydrogen-oxygen catalytic ignition and thruster investigation. Volume 1: Catalytic ignition and low pressure thruster evaluations

An experimental and analytical program was conducted to evaluate catalytic igniter operational limits, igniter scaling criteria, and delivered performance of cooled, flightweight gaseous hydrogen-oxygen reaction control thrusters. Specific goals were to: (1) establish operating life and environmental effects for both Shell 405-ABSG and Engelhard MFSA catalysts, (2) provide generalized igniter design guidelines for high response without flashback, and (3) to determine overall performance of thrusters at chamber pressures of 15 and 300 psia (103 and 2068 kN/sq m) and thrust levels of 30 and 1500 lbf, respectively. The experimental results have demonstrated the feasibility of reliable, high response catalytic ignition and the effectiveness of ducted chamber cooling for a high performance flightweight thruster. This volume presents the results of the catalytic igniter and low pressure thruster evaluations are presented.

Johnson, R. J.↗
NASA NTRSDate not supplied

Development of Electrolytic Oxygen Recovery System for Advanced Life Support

The oxygen (O2) recovery system for the International Space Station (ISS) can recover approximately 50 percent of O2 from metabolic carbon dioxide (CO2). Increasing the O2 recovery rate and closing the open loop for future long duration crewed missions in space beyond Low Earth Orbit (LEO) is essential. There are several developmental efforts underway to increase the recovery rate. However, most of these technologies result in a complex, heavy, and power consuming system. The desired exploration O2 recovery system would be reliable and efficient with maximum O2 recovery. Marshall Space Flight Center (MSFC) is currently investigating an electrolytic O2 recovery approach that will increase the O2 recovery to greater than 70 percent as well as lowering the complexity, mass, and power consumption than most other technologies currently under development. The electrolytic O2 recovery system consists of a Microfluidic Electrochemical Reactor (MFECR) that is based on the electrochemical reduction of CO2 to O2 and ethylene (C2H4) using water (H2O) as precursor and operates at standard condition with a theoretical recovery rate of 73 percent. In 2016, NASA’s Game Changing Development Program awarded the University of Texas Arlington (UTA) a grant to initiate the development of the MFECR. Since 2019, MSFC and UTA have been collaborating with the current goals of increasing the O2 recovery efficiency, advancing the technology readiness to a Technology Readiness Level (TRL) 4, and maturing the system to process CO2 of one crew-member. Based on the results from UTA’s initial efforts, the following were identified as key areas of improvement in order to maximize O2 recovery for the system: further development of the anode material and cathode catalyst, model-based cell design optimization, and the addition of a separation system and fuel cell. This paper will present the current developmental efforts of the electrolytic system including MFECR design and overall system enhancements as well as results from single cell stack testing.

Brittany R Brown↗
DOE OSTI2020

IDENTIFICATION OF ADSORBA TION OF ADSORBATE FT-IR BANDS USING IN-SI -IR BANDS USING IN-SITU TECHNIQUES: Pd SPECIATION AND ADSORPTION CHEMISTRY OF Pd-ZEOLITES FOR PASSIVE NOx ADSORPTION

To meet increasingly stringent automotive emissions standards, further improvements in catalytic converter design are necessary. Current automotive catalyst systems are effective at eliminating emission of nitrogen oxides (NOx) once the catalyst reaches operational temperature (~200 °C). NOx emitted at lower catalyst temperatures now comprises most of the NOx released during a typical test cycle. Referred to as “the cold start problem” this issue has come to the forefront of automotive catalyst development, as mitigating these emissions is necessary to further reduce automotive emissions. Passive NOx adsorbers present an appealing solution to the cold start problem, these being a class of materials that chemisorb exhaust components such as NOx, carbon monoxide (CO) and hydrocarbons at near-ambient temperatures, and then desorb these compounds once the downstream catalyst has reached operational temperature. An effective passive NOx adsorber must have several properties: high NOx adsorption at near-ambient temperatures, near-complete NOx desorption at temperatures within the operational range, high thermal stability, and resistance to automotive exhaust components at high temperatures. The potential environmental impact of such a system is substantial, as NOx emissions currently result in the formation of millions of tons of smog and acid rain each year. Pd-exchanged zeolites have shown promise for deployment as Passive NOx adsorbers, though much remains to be understood about their adsorption chemistry and deactivation. In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) provides a convenient probe of adsorbed species, most automotive exhaust components possessing IR-active chemical bonds. By examining the evolution of IR bands under various pretreatments and adsorbates, the overall Pd-speciation and adsorptive zeolite sites of each material can be characterized, and the identities of IR bands can be deduced. In this work, microreactor-MS analysis of the adsorption and desorption behavior of these materials was also examined, these results being coupled with in-situ DRIFTS temperature programmed desorption (TPD) to correlate desorption events with specific adsorbed species. A pair of zeolite frameworks of similar Si/Al ratio but differing pore size were examined, Beta zeolite (BEA) and Chabazite (CHA) representing a medium- and small-pore framework, respectively. The effect of Pd-loading on BEA was examined, as well as the various deactivation pathways and active sites of each material.

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

Correlating Oxidation State and Surface Area to Activity from Operando Studies of Copper CO Electroreduction Catalysts in a Gas-Fed Device

Copyright © 2020 American Chemical Society. The rational design of high-performance electrocatalysts requires a detailed understanding of dynamic changes in catalyst properties, including oxidation states, surface area, and morphology under realistic working conditions. Oxide-derived Cu catalysts exhibit a remarkable selectivity toward multicarbon products for the electrochemical CO reduction reaction (CORR), but the exact role of the oxide remains elusive for explaining the performance enhancements. Here, we used operando X-ray absorption spectroscopy (XAS) coupled with simultaneous measurements of the catalyst activity and selectivity by gas chromatography (GC) to study the relationship between oxidation states of Cu-based catalysts and the activity for ethylene (C2H4) production in a CO gas-fed cell. By utilizing a custom-built XAS cell, oxidation states of Cu catalysts can be probed in device-relevant settings and under high current densities (>80 mA cm-2) for the CORR. By employing an electrochemical oxidation process, we found that the Cu oxidation states and specific ion species do not correlate with C2H4 production. The difference in the CORR activity is also investigated in relation to electrochemical surface area (ECSA) changes. While the hydrogen evolution reaction (HER) activity is positively correlated to the ECSA changes, the increased C2H4 activity is not proportional to the ECSA. Ex situ characterization from microscopic techniques suggests that the changes in the C2H4 activity and selectivity may arise from a morphological transformation that evolves into a more active structure. These comprehensive results give rise to the development of a cell regeneration method that can restore the performance of the Cu catalyst without cell disassembly. Our study establishes a basis for the rational design of highly active electrocatalysts for broad-range reactions in a gas-fed device.

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

New challenges in oxygen reduction catalysis: a consortium retrospective to inform future research

In this perspective, we highlight results of a research consortium devoted to advancing understanding of oxygen reduction reaction (ORR) catalysis as a means to inform fuel cell science. We demonstrate how targeted collaborations between different institutions from academic, national lab, and industry backgrounds and different scientific disciplines like theory, experiment, and characterization can yield unique insights into fuel cell catalysts. We comment on such insights into material designs for platinum-group-metal alloys, transition metal oxides, and non-traditional materials including metal–organic frameworks; systems that have served as the foundational building blocks for our consortium. We also motivate a renewed focus on catalyst durability in light of emerging technological requirements and paths forward in understanding in situ and operando electrochemical stability. Lastly, we describe new frontiers ORR research can take and how emerging artificial intelligence tools can assist researchers in capturing data, selecting new experiments, and guiding characterization to accelerate the design and discovery of fuel cell catalysts. A main goal of sharing this perspective is to discuss the rationale for our future research plans based on our consortium work. However, we also hope to illustrate both the potential impact of a collaborative strategy with the hopes of inspiring a higher degree of Industry-Academia-National Laboratory collaboration and encourage other centers and consortiums to distill and share their findings in a similar perspective-type article. Together we hope to enable the fuel cell research community to engage in a discussion of strategies for research and accelerated development of catalysts with improved activity and stability.

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

Direct methane activation by atomically thin platinum nanolayers on two-dimensional metal carbides

We report efficient and direct conversion of methane to value-added products has been a long-term challenge in shale gas applications. Here, we show that atomically thin nanolayers of Pt with a single or double atomic layer thickness, supported on a two-dimensional molybdenum titanium carbide (MXene), catalyse non-oxidative coupling of methane to ethane/ethylene (C 2 ). Kinetic and theoretical studies, combined with in-situ spectroscopic and microscopic characterizations, demonstrate that Pt nanolayers anchored at the hexagonal close-packed sites of the MXene support can activate the first C–H bond of methane to form methyl radicals that favour desorption over further dehydrogenation and thus suppress coke deposition. At 750 °C and 7% methane conversion, the catalyst runs for 72 hours of continuous operation without deactivation and exhibits >98% selectivity towards C 2 products, with a turnover frequency of 0.2–0.6 s -1 . Our findings provide insights into the design of highly active and stable catalysts for methane activation and create a platform for developing atomically thin supported metal catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Cool GTL for the Conversion of Biogas to Jet Fuel

Cool GTL is a new process under development for conversion of biogas from digestors or CO2 +H2 to high quality drop in jet fuel. Cool GTL is designed to be a streamlined simplified low cost process which can be cost effective for small scale biogas applications. Cool GTL has the advantage that it uses a high activity bi-reforming catalyst, in a streamlined electric reformer design, to make the synthesis gas for a high conversion slurry fischer Tropsch process followed by a trailing wax cracking reactor. In this way high quality jet fuel can be directly produced. Recent experimental test data will be presented showing product quality. The life cycle analysis LCA will also be presented as well.

09 BIOMASS FUELS↗