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At least 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Electrical and Spectroscopic Diagnostics as Real‐Time Metallization Indicators During Hydrogen Plasma Smelting Reduction

This study investigates the hydrogen (H 2 ) plasma reduction process of direct-reduced-iron-grade hematite ore at different arc currents (100–200 A) in an Ar–5% H 2 atmosphere at 0.9 bar. Iron ore samples (10 g) were exposed to a plasma arc, and the reduction/metallization kinetics were analyzed over fixed time intervals. Electrical diagnostics revealed that the arc voltage exhibited takeover-mode oscillations which were suppressed at higher currents due to stronger electromagnetic coupling. The voltage dropped significantly as metallization approached ∼95%, linked to increased electrical conductivity of the metallic iron (Fe) in the ore as well as Fe evaporation into the arc, lowering the arc resistance. A simplified Elenbaas–Heller model supported this explanation and confirmed that Fe vapor concentration enhances plasma conductivity. Optical emission spectroscopy focused on the plasma–metal interface revealed the plasma's optically thick nature, as the primary Fe I 526.95 nm line experienced self-absorption. However, weaker Fe I lines (404.58, 438.35 nm) normalized to Ar I 696.5 nm provided a reliable proxy for metallization. These diagnostics, electrical and spectroscopic, effectively track metallization in real-time during H 2 plasma smelting reduction.

08 HYDROGEN↗
DOE OSTI2024

Continuous Flow Photoelectrochemical Reactor with Gas Permeable Photocathode: Enhanced Photocurrent and Partial Current Density for CO 2 Reduction

Photoelectrochemical (PEC) CO 2 reduction using a photocathode is an attractive method for making valuable chemical products due to its simplicity and lower overpotential requirements. However, previous PEC processes have often been diffusion-limited leading to low production rates of the CO 2 reduction reaction, due to inefficient gas diffusion through the liquid electrolyte to the catalyst surface, particularly at high current densities. In this study, a gas-permeable photocathode in a continuous flow PEC reactor is incorporated, which facilitates the direct supply of CO 2 gas to the photocathode-electrolyte interface, unlike dark reaction-based flow reactors. This concept is demonstrated using Ag-TiO 2 on carbon paper, illuminated through a quartz window and flowing liquid electrolyte. CO 2 supply is managed via pressure and flow control on the non-illuminated side of the carbon paper. The photocurrent density is significantly influenced by the flow rates and pressure of CO 2 gas, and the electrolyte flow rates. Compared to the traditional H-cell, the continuous PEC flow reactor achieves ≈10-fold increase in CO faradaic efficiency, 30-fold increase in production rate and 16-fold increase in stability without catalyst modifications. This work provides essential insights into the design and application of continuous gas-liquid flow PEC reactor systems, highlighting their potential for other PEC reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Selective CO 2 Reduction on 2D Mesoporous Bi Nanosheets

The conversion of CO 2 to value-added products using electrical or solar energy represents an attractive means for the capture and utilization of atmospheric CO 2 . Formate is a popular product from CO 2 reduction, but its reaction selectivity is usually unsatisfactory. Tin-based materials have attracted the most attention for formate production at present. Unfortunately, most of them only exhibit moderate selectivity in a narrow and highly cathodic potential window. In this study, it is demonstrated that traditionally under-explored bismuth has a much greater potential for formate production than tin or other materials. Mesoporous bismuth nanosheets are prepared here by the cathodic transformation of atomic-thick bismuth oxycarbonate nanosheets. They enable the selective CO 2 reduction to formate with large current density, excellent Faradaic efficiency (approximate to 100%) over a broad potential window and great operation stability. Moreover, Bi nanosheets are integrated with an oxygen evolution reaction electrocatalyst in full cells, and achieve efficient and robust solar conversion of CO 2 /H 2 O to formate/O 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2025

Selective Electrochemical Reduction of CO 2 to Metal Oxalates in Nonaqueous Solutions Using Trace Metal Pb on Carbon Supports Enhanced by a Tailored Microenvironment

In this work, the electroreduction of carbon dioxide (CO 2 ) to oxalate is enabled by incorporating trace metallic lead (Pb) on carbon‐based supports (CBS) with polymer overlayers. These composite materials serve as an efficient electrocatalytic system for the facile conversion and storage of CO 2 , a pernicious atmospheric pollutant. Results from controlled potential electrolysis experiments indicate that 1) trace metallic Pb on the ppb scale is active toward the reductive coupling of CO 2 to oxalate at comparable Faradaic efficiencies to bulk metallic Pb and 2) polymer encapsulation of this trace metallic Pb leads to promotion of CO 2 reduction (CO 2 R) selectively to metal oxalates over other products such as CO. Importantly, metal oxalates are important alternative cementitious materials and precursors for other materials’ synthesis applications. The solid products undergo rigorous spectroscopic characterization, including 13 CO 2 labeling experiments, to ensure the metal oxalates are in fact produced from CO 2 R. These findings serve as a model for leveraging microenvironment effects to enhance activity and selectivity for CO 2 R using trace‐metal catalysts for carbon utilization and storage technologies.

alternative cementitious materials↗
DOE OSTI2017

Stability of Residual Oxides in Oxide-Derived Copper Catalysts for Electrochemical CO 2 Reduction Investigated with 18 O Labeling

Oxide-derived (OD) Cu catalysts possess high selectivity towards the formation of multi-carbon products (C 2 /C 3 ) for aqueous electrochemical CO 2 reduction (CO 2 R). It has been proposed that a large fraction of the initial oxide can be surprisingly resistant to reduction, and these residual oxides play a crucial catalytic role. The stability of residual oxides was investigated by synthesizing 18 O-enriched OD Cu catalysts and testing them for CO 2 R. These catalysts maintain a high selectivity towards C 2 /C 3 products (ca. 60 %) for up to 5 h in 0.1 m KHCO 3 at -1.0 V vs. RHE. Yet, secondary-ion mass spectrometry measurements show that only a small fraction (<1 %) of the original 18 O content remains, showing that residual oxides are not present in significant amounts during CO 2 R. Moreover, we show that OD Cu can reoxidize rapidly, which could compromise the accuracy of ex situ methods for determining the true oxygen content.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Chelating N-Heterocyclic Carbene Ligands Enable Tuning of Electrocatalytic CO 2 Reduction to Formate and Carbon Monoxide: Surface Organometallic Chemistry

Reported here is the chelate effect as a design principle for tuning heterogeneous catalysts for electrochemical CO 2 reduction. Palladium functionalized with a chelating tris-N-heterocyclic carbene (NHC) ligand (Pd-timtmbMe) exhibits a 32-fold increase in activity for electrochemical reduction of CO 2 to C1 products with high Faradaic efficiency (FE C1 =86 %) compared to the parent unfunctionalized Pd foil (FE=23 %), and with sustained activity relative to a monodentate NHC-ligated Pd electrode (Pd-mimtmb Me ). Here, the results highlight the contributions of the chelate effect for tailoring and maintaining reactivity at molecular-materials interfaces enabled by surface organometallic chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Programmable Exposure of Pt Active Facets for Efficient Oxygen Reduction

Pt-based materials are the state-of-the-art catalysts for oxygen reduction reaction (ORR), but their high cost and scarcity remain the major obstacles for large-scale applications in renewable energy industries. To produce efficient ORR catalysts with low Pt content, PtNi porous films (PFs) with sufficiently exposed Pt active sites were rationally designed through a programmable approach combining electrochemical bottom-up (electrodeposition) and topdown (anodization) processes. The unique dynamic oxygen-bubble template (DOBT) programmably controlled by square-wave potential was utilized to tune the catalyst morphology and expose Pt active facets in PtNi PFs. Here, the surface-bounded species such as hydroxyl anions (OH*, *=surface site) on the exposed PtNi PFs surfaces were adjusted by the applied anodic voltage, further affecting the dynamic oxygen (O 2 ) bubbles adsorption on Pt. As a result, PtNi PF with enriched Pt (111) facets (denoted as Pt 3.5% Ni PF) was obtained, showing prominent ORR activity with an onset potential of 0.92 V (vs. RHE) at an ultra-low Pt loading (0.015 mg cm -2 ). The adsorbed OHads coverage estimation shows fewer OHads on Pt 3.5% Ni PF than other PtNi PFs, indicating that enriched Pt (111) facets in the catalysts enable facilitated O 2 adsorption for oxygen reduction and thus leading to superior ORR activity

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Heat-Treated Aerogel as a Catalyst for the Oxygen Reduction Reaction

Aerogels are fascinating materials that can be used for a wide range of applications, one of which is electrocatalysis of the important oxygen reduction reaction. In their inorganic form, aerogels can have ultrahigh catalytic site density, high surface area, and tunable physical properties and chemical structures—important features in heterogeneous catalysis. Herein, we report on the synthesis and electrocatalytic properties of an iron–porphyrin aerogel. 5,10,15,20-(Tetra-4-aminophenyl)porphyrin (H 2 TAPP) and Fe II were used as building blocks of the aerogel, which was later heat-treated at 600 °C to enhance electronic conductivity and catalytic activity, while preserving its macrostructure. The resulting material has a very high concentration of atomically dispersed catalytic sites (9.7×10 20 sites g –1 ) capable of catalyzing the oxygen reduction reaction in alkaline solution (E onset =0.92 V vs. RHE, TOF=0.25 e – site –1 s –1 at 0.80 V vs. RHE).

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

Transition Metal Nitrides as Promising Catalyst Supports for Tuning CO/H 2 Syngas Production from Electrochemical CO 2 Reduction

The electrochemical carbon dioxide reduction reaction (CO 2 RR) to produce synthesis gas (syngas) with tunable CO/H 2 ratios has been studied by supporting Pd catalysts on transition metal nitride (TMN) substrates. Combining experimental measurements and density functional theory (DFT) calculations, Pd-modified niobium nitride (Pd/NbN) is found to generate much higher CO and H 2 partial current densities and greater CO Faradaic efficiency than Pd-modified vanadium nitride (Pd/VN) and commercial Pd/C catalysts. In-situ X-ray diffraction identifies the formation of PdH in Pd/NbN and Pd/C under CO 2 RR conditions, whereas the Pd in Pd/VN is not fully transformed into the active PdH phase. DFT calculations show that the stabilized *HOCO and weakened *CO intermediates on PdH/NbN are critical to achieving higher CO 2 RR activity. This work suggests that NbN is a promising substrate to modify Pd, resulting in an enhanced electrochemical conversion of CO 2 to syngas with a potential reduction in precious metal loading.

25 ENERGY STORAGE↗
DOE OSTI2022

Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites

Electrochemical CO 2 reduction is a potential approach to convert CO 2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO 2 reduction to CO, and the single-site Ni-N x motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-N x content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.

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

Cylindrical C 96 Fullertubes: A Highly Active Metal-Free O 2 -Reduction Electrocatalyst

A new isolation protocol was recently reported for highly purified metallic Fullertubes D 5h -C 90 , D 3d -C 96 , and D 5d -C 100 , which exhibit unique electronic features. Here, we report the oxygen reduction electrocatalytic behavior of C 60 , C 70 (spheroidal fullerenes), and C 90 , C 96 , and C 100 (tubular fullerenes) using a combination of experimental and theoretical approaches. C 96 (a metal-free catalyst) displayed remarkable oxygen reduction reaction (ORR) activity, with an onset potential of 0.85 V and a halfway potential of 0.75 V, which are close to the state-of-the-art Pt/C benchmark catalyst values. Here we achieved an excellent power density of 0.75 W cm −2 using C 96 as a modified cathode in a proton-exchange membrane fuel cell, comparable to other recently reported efficient metal-free catalysts. Combined band structure (experimentally calculated) and free-energy (DFT) investigations show that both favorable energy-level alignment active catalytic sites on the carbon cage are responsible for the superior activity of C 96 .

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

Inhibition of Alkali Metal Reduction of 1-Adamantanol by London Dispersion Effects

Here, a series of alkali metal 1-adamantoxide (OAd 1 ) complexes of formula [M(OAd 1 )(HOAd 1 ) 2 ], where M=Li, Na or K, were synthesised by reduction of 1-adamantanol with excess of the alkali metal. The syntheses indicated that only one out of every three HOAd 1 molecules was reduced. An X-ray diffraction study of the sodium derivative shows that the complex features two unreduced HOAd 1 donors as well as the reduced alkoxide (OAd 1 ), with the Ad 1 fragments clustered together on the same side of the NaO 3 plane, contrary to steric considerations. This is the first example of an alkali metal reduction of an alcohol that is inhibited from completion due to the formation of the [M(OAd 1 )(HOAd 1 ) 2 ] complexes, stabilized by London dispersion effects. NMR spectroscopic studies revealed similar structures for the lithium and potassium derivatives. Computational analyses indicate that decisive London dispersion effects in the molecular structure are a consequence of the many C–H•••H–C interactions between the OAd 1 groups.

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

Synergistic Porosity and Charge Effects in a Supramolecular Porphyrin Cage Promote Efficient Photocatalytic CO 2 Reduction**

We present a supramolecular approach to catalyzing photochemical CO 2 reduction through second-sphere porosity and charge effects. An iron porphyrin box (PB) bearing 24 cationic groups, FePB-2(P), was made via post-synthetic modification of an alkyne-functionalized supramolecular synthon. FePB-2(P) promotes the photochemical CO 2 reduction reaction (CO 2 RR) with 97 % selectivity for CO product, achieving turnover numbers (TON) exceeding 7000 and initial turnover frequencies (TOF max ) reaching 1400 min -1 . The cooperativity between porosity and charge results in a 41-fold increase in activity relative to the parent Fe tetraphenylporphyrin (FeTPP) catalyst, which is far greater than analogs that augment catalysis through porosity (FePB-3(N), 4-fold increase) or charge (Fe p-tetramethylanilinium porphyrin (Fe-p-TMA), 6-fold increase) alone. In conclusion, this work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Reduction of Propanoic Acid over Pd-Promoted Supported WO x Catalysts

Here, silica-, titania-, and zirconia-supported tungsten oxide catalysts were synthesized by wetness impregnation techniques. When promoted with Pd, these materials catalyzed the reduction of propanoic acid to 1-propanol at 433 K with a selectivity of up to 92% (13.5% conversion) in atmospheric pressure of H 2 . Over Pd-promoted WO x /TiO 2 , the observed orders of reaction were 0.2 in H 2 and 0.7 in propanoic acid, and the apparent activation energy was 54 kJ mol –1 . In situ X-ray absorption spectroscopy of Pd-promoted WO x /SiO 2 revealed a slight reduction of the W from +6 to an average oxidation state of about +5 during H 2 treatment above 473 K. In situ infrared spectroscopy indicated the catalyst surface was covered mostly by propanoate species during reaction. For comparison, supported phosphotungstic acid was also evaluated as a catalyst under identical conditions, yet the resulting high acidity of the catalyst was deleterious to alcohol selectivity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Structure Activity Relationships for Second‐Coordination Sphere Functional Group Dependent CO 2 Reduction by Manganese Bipyridyl Electrocatalysts

Abstract A series of twelve second coordination sphere (SCS) functionalized manganese tricarbonyl bipyridyl complexes are investigated for their electrocatalytic CO 2 reduction properties in acetonitrile. A qualitative and quantitative assessment of the SCS functional groups is discussed with respect to the catalysts’ thermodynamic and kinetic efficiencies, and their product selectivities. In probing a broad scope of functional groups, it is clear that only the aprotic ortho‐arylester SCS is capable of promoting the highly desired low‐overpotential proton‐transfer electron‐transfer (PT‐ET) pathway for selective CO production. The ortho‐phenolic analogues cause an increase in overpotential with a product selectivity favoring H 2 evolution, consistent with a high‐overpotential pathway via the anionic [Mn−H] − intermediate. Alternative aprotic Lewis base functional groups such as trifluoromethyl, morpholine and acetamide are shown to also be capable of intermediate manganese hydride generation. The tertiary amine substituent, 2‐morpholinophenyl, exhibits a desirable product distribution characteristic of syn‐gas (CO : H 2 =30 : 48) with an impressive turnover frequency, while the secondary amine group, 2‐acetamidophenyl, induces a notable shift in selectivity with a faradaic yield of 55 % for the formate (HCO 2 − ) product. In addition to their catalytic properties, cyclic voltammetry and infrared spectroelectrochemistry (IR‐SEC) studies are presented to probe pre‐catalyst electronic properties and the two‐electron reduction activation pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Hydrothermal Synthesis of Platinum-Group-Metal-Free Catalysts: Structural Elucidation and Oxygen Reduction Catalysis

In this paper, a hydrothermal approach to generate a platinum-group-metal-free (PGM-free) Fe-N-C catalyst for the oxygen reduction reaction (ORR) is introduced. The process involves partial carbonization by hydrothermal means followed by thermal treatment to obtain the final catalysts. Detailed X-ray scattering analysis of the glucose-imidazole catalysts (termed as GLU-IMID-C catalysts), obtained for the first time with the use of CarbonXS GUI program, reveals the presence of face-centered cubic (FCC) iron nanoparticles embedded in partially graphitic carbon in all catalyst variations. We also report the physical characterization of these catalysts by using X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area analysis, and transmission electron microscopy. The electrocatalytic behavior of the catalysts towards oxygen reduction is studied separately in acidic and alkaline electrolytes by rotating ring disk electrode measurements. The catalysts exhibit high ORR activity in acidic (0.5 M H 2 SO 4 ) and alkaline (0.1 M KOH) electrolytes. Lastly, a precursor structure-performance relationship of these catalysts and their performance trends in both electrolytes has been discussed in this work.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Enhancing NO Reduction by CO Over NiO/CeO 2 Catalyst by Optimizing the Metal Oxide–Support Interaction

Noble metal catalysts are widely used in three-way catalysts (TWCs) due to their high efficiency, but their scarcity and high cost drive the need for effective, low-cost alternatives. Here, in this work, a series of NiO/CeO 2 catalysts were engineered by modulating the OH content and crystallite size of the CeO 2 support. This approach yielded Ni species ranging from isolated single atoms to small clusters and larger aggregates, with varied NiO/CeO 2 interaction strengths. Evaluation of their performance in NO reduction by CO, CO oxidation, and the water–gas shift reaction revealed that the NiO/CeO 2 -300 catalyst, featuring small CeO 2 crystallites and highly dispersed NiO clusters, delivered superior activity for NO reduction and CO oxidation. It was demonstrated that small NiO clusters, due to their efficient CO adsorption and activation, were more active than Ni single atoms. Furthermore, the presence of water was found to influence the catalyst stability, with NiO clusters less stable than single atoms likely due to the hydroxylation effect leading to the formation of Ni(OH) 2 . Oxygen storage capacity measurements revealed that performance was governed by a combination of CeO 2 crystallite size and the abundance of NiO/CeO 2 interfaces. These findings demonstrated that the catalytic performance of Ni/CeO 2 systems could be maximized by optimizing the Ni nanostructure and its interaction with CeO 2 support, positioning them as a promising, multifunctional nonprecious alternative for three-way catalysis application.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A Co-design Framework for Online Data Analysis and Reduction

Science applications preparing for the exascale era are increasingly exploring in situ computations comprising of simulation-analysis-reduction pipelines coupled in-memory. Efficient composition and execution of such complex pipelines for a target platform is a codesign process that evaluates the impact and tradeoffs of various application- and system-specific parameters. In this article, we describe a toolset for automating performance studies of composed HPC applications that perform online data reduction and analysis. We describe Cheetah, a new framework for composing parametric studies on coupled applications, and Savanna, a runtime engine for orchestrating and executing campaigns of codesign experiments. Furthermore, this toolset facilitates understanding the impact of various factors such as process placement, synchronicity of algorithms, and storage versus compute requirements for online analysis of large data. Ultimately, we aim to create a catalog of performance results that can help scientists understand tradeoffs when designing next-generation simulations that make use of online processing techniques. We illustrate the design of Cheetah and Savanna, and present application examples that use this framework to conduct codesign studies on small clusters as well as leadership class supercomputers.

97 MATHEMATICS AND COMPUTING↗