Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Catalyst synthesis”

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 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Ultrathin platinum nanowire based electrodes for high-efficiency hydrogen generation in practical electrolyzer cells

Significant reduction of noble metal catalyst loading and simplification of electrode fabrication are urgently needed in order to lower the cost of proton exchange membrane electrolyzer cells (PEMECs) for large-scale hydrogen production. Herein, we report an integrated electrode design comprising in-situ grown platinum nanowires (PtNW) on ultrathin titanium liquid/gas diffusion layers (LGDLs) via a cost-effective and green chemical synthesis approach. The ultrathin integrated PtNW electrodes showed a low cell voltage of 1.643 V and high efficiency of 90.08% at 1000 mA cm -2 using about 15 times lower catalyst loadings than a conventional catalyst-coated membrane in PEMEC tests. Ex-situ electrochemical characterizations and microscale visualizations further reveal that PtNW electrodes display highly efficient hydrogen evolution reactions and excellent electrode durability due to high active surface area, favorable bubble detachment, and structural stability. This work provides new insights into catalyst layer design and facile ultrathin electrode fabrication for more compact and low-cost PEM electrolyzers, fuel cells and other systems.

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

Ligand-Guided Growth of Alloyed Shells on Intermetallic Seeds as a Route toward Multimetallic Nanocatalysts with Shape-Control

In this work, shape-controlled core@shell PdCu@PtCu nanoparticles (NPs) were synthesized by seed-mediated co-reduction. Specifically, cubic-shaped NPs were achieved by selecting tetraoctylammonium bromide (TOAB) and triphenylphosphine (TPP) as capping ligands. Their roles were investigated by incorporating independently each ligand into the reaction and analyzing the products by transmission electron microscopy (TEM). This analysis revealed that the quasi-spherical PdCu seeds acquired cubic shapes during the synthesis and directed shell deposition. This process was mediated by TPP, which was central to achieving monodisperse NPs with shape-control. The synthesis conditions were modified to tune both the thickness and composition of the shells. Evaluation of the NPs as catalysts for the electrooxidation of formic acid found that the NPs with the thinnest Pt-rich shells gave the highest specific activity, with the nanocubic shape also enhancing performance with respect to the spherical counterpart. These results highlight the benefits of integrating compositional, architectural, and shape-control all in one NP construct.

36 MATERIALS SCIENCE↗
DOE OSTI2022

CO 2 hydrogenation: Selectivity control of CO versus CH 4 achieved using Na doping over Ru/m-ZrO 2 at low pressure

By doping 1%Ru/m-ZrO 2 with sodium, selectivity tuning between CO and CH 4 during CO 2 hydrogenation was achieved by controlling the relative rates of reverse water-gas shift and CO methanation. By increasing basicity through Na loading: (1) the formate C-H bond is weakened in DRIFTS of adsorbed CO, accelerating C-H bond formation of formate and promoting CO formation at the Ru/m-ZrO 2 interface; and (2) the coverage of Na increases on ensembles of Ru atoms responsible for methanation. Increasing Na content shifts selectivity from CH 4 (useful for synthetic natural gas) to CO, which can be used for Fischer-Tropsch synthesis or methanol-to-gasoline. Electronic modification of formate is likely due to enhanced basicity (strengthening bonding between catalyst and the-CO 2 function of formate and weakening C-H). In conclusion, no electron transfer from Na to Ru was detected in XANES. DRIFTS as a function of time and XPS results showed that Na exacerbates site blocking and deactivation.

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

Carbonate-Catalyzed CO 2 Insertion into Hydrocarbon C-H Bonds (Final Technical Report)

The development of methods to utilize CO 2 as a feedstock for chemical and fuel synthesis is critical for creating renewable alternatives to fossil fuel-based products. This project investigated a class of catalyst materials known as "dispersed carbonates", which are composed of alkali carbonate salts (e.g. potassium carbonate) dispersed in porous support materials. These catalysts react with CO 2 and organic molecules to form chemicals known as carboxylates that have wide applications in the chemical industry. The project used a combination of spectroscopic and reactivity studies to provide fundamental insight into the structure and mechanism of dispersed carbonates in these reactions, leading to variants with greater reactivity. In addition, dispersed carbonates were investigated for CO 2 hydrogenation catalysis, which is critical for processes under development for making sustainable fuels. The dispersed carbonates proved to be highly active and selective catalysts for the reverse water gas shift reaction in which CO 2 is hydrogenated to CO. The dispersed carbonates provide a compelling alternative to conventional metal-based catalysts for reverse water gas shift that could enable new process designs with higher efficiency and lower complexity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

AVIRIS spectra correlated with the chlorophyll concentration of a forest canopy

Imaging spectrometers have many potential applications in the environmental sciences. One of the more promising applications is that of estimating the biochemical concentrations of key foliar biochemicals in forest canopies. These estimates are based on spectroscopic theory developed in agriculture and could be used to provide the spatial inputs necessary for the modeling of forest ecosystem dynamics and productivity. Several foliar biochemicals are currently under investigation ranging from those with primary absorption features in visible to middle infrared wavelengths (e.g., water, chlorophyll) to those with secondary to tertiary absorption features in this part of the spectrum (e.g., nitrogen, lignin). The foliar chemical of interest in this paper is chlorophyll; this is a photoreceptor and catalyst for the conversion of sunlight into chemical energy and as such plays a vital role in the photochemical synthesis of carbohydrates in plants. The aim of the research reported here was to determine if the chlorophyll concentration of a forest canopy could be correlated with the reflectance spectra recorded by the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS).

Kupiec, John↗
DOE OSTI2024

Covalent Triazine-Based Frameworks with Ru-tda Based Catalyst Anchored via Coordination Bond for Photoinduced Water Oxidation

Light-induced water splitting (hν-WS) for the production of hydrogen as a solar fuel is considered a promising sustainable strategy for the replacement of fossil fuels. An efficient system for hν-WS involves a photoactive material that, upon shining light, is capable of separating and transferring charges to catalysts for the hydrogen and oxygen evolution processes. Covalent triazine-based frameworks (CTFs) represent an interesting class of 2D organic light-absorbing materials that have recently emerged thanks to their tunable structural, optical and morphological properties. Typically, catalysts (Cat) are metallic nanoparticles generated in situ after photoelectroreduction of metal precursors or directly drop-casted on top of the CTF material to generate Cat-CTF assemblies. Here, in this work, the synthesis, characterization and photocatalytic performance of a novel hybrid material, Ru-CTF, is reported, based on a CTF structure featuring dangling pyridyl groups that allow the Ru-tda (tda is [2,2':6',2'“-terpyridine]-6,6'”-dicarboxylic acid) water oxidation catalyst (WOC) unit to coordinate via covalent bond. The Ru-CTF molecular hybrid material can carry out the light-induced water oxidation reaction efficiently at neutral pH, reaching values of maximum TOF of 17 h -1 and TONs in the range of 220 using sodium persulfate as a sacrificial electron acceptor.

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

Automated processing of environmental transmission electron microscopy images for quantification of thin film dewetting and carbon nanotube nucleation dynamics

We report scalable production of carbon nanotubes (CNTs) requires catalysts and reaction conditions that provide high nucleation efficiency. In situ characterization methods such as environmental transmission electron microscopy (ETEM) can reveal fundamental mechanisms of synthesis, but to date have primarily provided qualitative observations on small sample sizes. Here, quantitative analysis is performed using high-resolution, high-rate video capture of ETEM experimentation coupled with automated image processing, involving computer vision algorithms and convolutional neural networks. By this approach, we detect distinct nanoparticle formation from an alumina-supported iron thin film and subsequent CNT nucleation from the nanoparticles. The statistical summary of particles in each video shows that, compared to a H 2 -only atmosphere, pretreatment of the catalyst with carbon added to the H 2 atmosphere results in a smaller average particle diameter, a 2-fold increase in particle density (to 5300 particles/μm 2 ), a 3-fold increase in CNT nucleation efficiency (to 92%), and more than a 5-fold increase in CNT density (to 4800/μm 2 ). Addition of carbon during exposure to H 2 is also more effective than NH 3 at dewetting the catalyst film and increasing the CNT nucleation efficiency, in spite of NH 3 being a stronger reducing agent for iron. Insights from this study are applicable to improving CNT yield and productivity in both batch-style and continuous processes.

25 ENERGY STORAGE↗
DOE OSTI2023

Synthesis of PHI-type zeolite harmotome using barium as an inorganic structure-directing agent inspired from natural mineral compositions

Zeolites are nanoporous aluminosilicates widely used as commercial adsorbents, heterogeneous catalysts, and ion-exchange materials due to their unique porosity, acidity, and thermal stability. The vast majority of synthetically-realized zeolite structures are prepared under hydrothermal conditions in alkaline media, and often in the presence of an organic structure-directing agent that facilitates the crystallization of diverse porous networks. Due to economic and environmental disadvantages of organic-based syntheses, it is often desirable to produce zeolites in organic-free media using alkali metal ions as the most commonly employed inorganic structure-directing agents (ISDAs). Here, in this study, we were inspired by the elemental compositions of natural zeolite minerals to examine the use of an alkaline earth metal ion as the ISDA to prepare zeolites with the PHI framework type. Two natural minerals exhibiting this crystal structure are phillipsite and harmotome. Both structures contain sodium and potassium as extra-framework cations, but only harmotome contains barium cations. Here we examined how the combination of alkali and alkaline earth ISDAs promote the formation of PHI-type zeolites. Our findings reveal that each isostructure is prepared under different synthesis conditions where simply adding barium to a growth mixture does not always lead to harmotome formation. Harmotome is formed in more dilute and alkaline growth media; however, time-resolved analyses of zeolite crystallization reveal that harmotome can be synthesized at low temperatures (ca. 65 °C) with rates that are 5-times faster than syntheses of phillipsite. This seemingly indicates that barium reduces the energetic barrier for PHI-type zeolite nucleation in ways that are not fully understood. Moreover, harmotome crystals exhibit an average particle size of ca. 60 nm, which is nearly 40-fold smaller than phillipsite crystals prepared under similar conditions. Collectively, these findings identify routes to control crystallization of PHI-type zeolites and may provide a broader strategy for using the composition of natural zeolite minerals to optimize the preparation of synthetic analogues.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Solid-State Synthesis of Highly Dispersed Nitrogen-Coordinated Single Iron Atom Electrocatalysts for Proton Exchange Membrane Fuel Cells

Fe–N–C with atomically dispersed Fe single atoms is the most promising candidate to replace platinum for the oxygen reduction reaction (ORR) in fuel cells. However, the conventional synthesis procedures require quantities solvents and metal precursors, sluggish adsorption process, and tedious washing, resulting in limited metal doping and uneconomical for large-scale production. Here, for the first time, Fe 2 O 3 is adopted as the Fe precursor to derive abundant single Fe atoms dispersed on carbon surfaces. The Fe–N–C catalyst synthesized by this simple method shows an excellent ORR activity with half-wave potentials of 0.82 and 0.90 V in acidic and alkaline solutions, respectively. A single fuel cell with an optimized Fe–N–C cathode shows a high peak power density of 0.84 W cm –2 . The solid-state transformation synthesis method developed in this study may shed light on mass production of single-atom-based catalysts.

25 ENERGY STORAGE↗
DOE OSTI2020

Status and challenges for the application of platinum group metal-free catalysts in proton-exchange membrane fuel cells

Platinum group metal-free (PGM-free) electrocatalysts are an important class of materials for the sustainable energy economy and significant effort has been made towards developing PGM-free catalysts to replace their costly Pt counterparts in fuel cell electric vehicles. The progress made in activity over the last decade is reviewed, along with synthesis strategies for more controlled active site formation and performance gains achieved through electrode engineering. The increased focus on durability, the growing understanding of degradation mechanisms, and the need for standard performance and accelerated stress test protocols are discussed.

25 ENERGY STORAGE↗
DOE OSTI2021

Microwave-enhanced catalytic ammonia synthesis under moderate pressure and temperature

In this study, an alternative approach based on microwave-enhanced ammonia synthesis for Haber-Bosch process was carried out under moderate pressure of 0.1–0.65 MPa and temperature range of 280–400 °C over a stable CsRu/CeO 2 catalyst. The ammonia production rate is significantly improved under microwave conditions. At 0.65 MPa and 320 °C, maximum ammonia production rate was achieved at H 2 /N 2 ratio of 1/1. Stable performance was obtained in a 6-cycles of startup-shutdown operation for cumulative on-line time of 80 h. The work demonstrates the potential of microwave catalytic technology for the distributed ammonia synthesis using renewable power having intermittent nature of energy supply.

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

Advancements in cerium/titanium metal-organic frameworks: Unparalleled stability in CO oxidation

Due to the excellent catalytic properties of Ce-based materials, the development of thermally stable metal-organic frameworks (MOFs) based on Ce-oxo clusters has attracted significant attention but remains challenging. In this work, we report the synthesis of an unreported Ce 4 Ti 2 -TMA (Ce IV 4 Ti IV 2 O 4 (OH) 4 (C(CH 3 ) 3 COO) 12 ·3H 2 O·3MeCN) cluster, which serves as an ideal source for the assembly of robust Ce/Ti-MOFs. Using this cluster, we constructed two isostructural MOFs, denoted as NU-3000 and NU-3001. Single-crystal X-ray diffraction analysis confirms these MOFs as mesoporous structures with 12-coordinated Ce 3 Ti 3 nodes. Furthermore, structural analysis reveals a plane triangular node structure that likely contributes to the excellent thermal stability of these MOFs. Finally, both MOFs show catalytic activity toward high-temperature (250°C) CO oxidation and maintain significant porosity, emphasizing the thermal stability of these materials under practical catalytic conditions. Furthermore, the straightforward synthesis of thermally robust Ce/Ti-MOFs from the Ce 4 Ti 2 -TMA cluster will pave the way for future Ce/Ti-MOF-based catalyst development.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The high-yield direct synthesis of dimethyl ether from CO 2 and H 2 in a dry reaction environment

Direct dimethyl ether (DME) synthesis from CO 2 and H 2 is considered a promising production route. However, this process is thermodynamically and kinetically restricted by the presence of water as a byproduct. In this study, a water-conduction membrane was incorporated into the direct DME synthesis reactor to generate a dry reaction environment. In the absence of water, the activities of the CO 2 hydrogenation catalyst (CZA) and methanol dehydration catalyst (HZSM-5) were boosted 4- and 10-fold, respectively, and single-pass CO 2 conversion of up to 73.4%, far beyond equilibrium, and DME yields of up to 54.5% were obtained. Moreover, the good protection of the catalysts against fast deactivation was demonstrated.

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

Computational analysis of metal–metal bonded dimetal tetrabenzoate redox potentials in the context of ammonia oxidation electrocatalysis

Metal–metal bonded complexes are promising candidates for catalyzing redox transformations. Of particular interest is the oxidation of ammonia to dinitrogen, an important half reaction for the potential utilization of ammonia as a fuel or hydrogen carrier. This work computationally explores 30 different metal–metal bonded dimers (5 different metal centers and 6 different benzoate ligand derivatives) to explore the tunability of the redox potential when ammonia is bound to the complexes as an axial ligand, modeling the first step in ammonia oxidation electrocatalysis. We calculate the redox potentials of these compounds, making reference to experimental data when appropriate, identifying two degrees of tunability: a coarse adjustment, changing the metal center, allows for a wide range of redox potentials to be accessed (from +1.0 to –2.0 V vs. ferrocene/ferrocenium in acetonitrile solution) and a fine adjustment, the para-substituent of the benzoate derivative, which affects the redox potential in a smaller range based on the electron donating/withdrawing effects of the substituent. Ruthenium and osmium tetrabenzoate catalysts are prime candidates for next generation ammonia oxidation catalysts because their redox potentials fall within the direct ammonia fuel cell “viability zone” bracketed by the thermodynamic potentials of oxygen reduction (ORR) and nitrogen reduction (NRR). Rhodium tetrabenzoate species fall above the ORR potential, suggesting ammonia oxidation promoted by Rh 2 catalysts could instead be used to facilitate hydrogen production through coupling to hydrogen evolution at a cathode. The redox potentials of rhenium and iridium tetrabenzoate catalysts fall below the NRR potential suggesting that these compounds could be further investigated in the context of electrochemical ammonia synthesis. Each redox event studied involves electron transfer from the M–M δ* orbital regardless of choice of metal or benzoate ligand derivative; this leads us to believe that the chemical reactivity of the various studied compounds will be similar in the context of ammonia oxidation.

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

Multiscale modeling and laser diagnostics to reveal non-equilibrium reaction chemistry at a plasma-liquid interface

Low-temperature, atmospheric-pressure plasmas in contact with liquid are at the core of a wide range of applications including water treatment, medicine, materials synthesis, and chemical transformation. In general, plasma-liquid processes are scientifically compelling because reactivity can be produced without a catalyst, in relatively inert molecules, such as air or nitrogen and liquid water, in their native states at ambient conditions. However, reactions at a plasma-liquid interface are extremely complex, occurring at a multiphase, gas-liquid boundary where excited or dissociate gaseous species dissolve and react with solution-phase species, and unique reaction pathways are induced by non-equilibrium chemistry. In particular, detailed knowledge of the physical and chemical processes, including what species are produced in the gas phase and how these species are subsequently transported across and react near the interfacial region, remains largely unanswered. In this project, modeling of the non-equilibrium reaction chemistry at the interface of low-temperature, atmospheric-pressure plasmas and liquid water is developed, supported by advanced laser diagnostics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗