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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.

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At least 1,315 records · Page 73
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

A review of iron and cobalt porphyrins, phthalocyanines, and related complexes for electrochemical and photochemical reduction of carbon dioxide

This review summarizes research on the electrochemical and photochemical reduction of CO₂ using a variety of iron and cobalt porphyrins, phthalocyanines, and related complexes. Metalloporphyrins and metallophthalocyanines are visible light absorbers with extremely large extinction coefficients. However, yields of photochemically-generated active catalysts for CO₂ reduction are typically low owing to the requirement of a second photoinduced electron. This requirement is not relevant to the case of electrochemical CO₂ reduction. Recent progress on efficient and stable electrochemical systems includes the use of FeTPP catalysts that have prepositioned phenyl OH groups in their second coordination spheres. This has led to remarkable progress in carrying out coupled proton-electron transfer reactions for CO₂ reduction. Such ground-breaking research has to be continued in order to produce renewable fuels in an economically feasible manner.

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

Efficient electrocatalytic conversion of CO 2 to ethanol enabled by imidazolium-functionalized ionomer confined molybdenum phosphide

An effective electrochemical carbon dioxide reduction reaction (eCO 2 RR) requires the discovery of a catalytic system that is highly active and selective for multi-carbon products together with superior CO 2 diffusion at a catalyst layer to minimize the reduction barriers. Here, we found a catalytic system that uses molybdenum phosphide (MoP) nanoparticles covered by imidazolium-functionalized ionomer (Im) that promotes CO 2 diffusion at the catalyst layer toward the catalyst surface, where CO 2 is reduced to ethanol (C 2 H 5 OH). The electrochemical results with the MoP-Im co-catalyst show a C 2 H 5 OH production Faradaic efficiency and a cathodic energy efficiency of 77.4% and 63.3%, respectively, at a potential as low as - 200 mV vs. RHE. The electrochemical experiments along with our physicochemical characterizations indicate that the Im improves CO 2 diffusion and balances water content resulting in a higher CO 2 -to-water ratio at the catalyst layer and fine-tunes the electronic properties of Mo atoms at the MoP surface. Finally, in-situ Raman spectroscopy reveals that a high number of adsorbed *CO intermediates on the surface and a higher binding strength of *CO intermediates on the Mo surface sites in the presence of imidazolium molecules are the main reasons for a superior C-C coupling and thereby the improved C 2 H 5 OH formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Advanced CO 2 Capture Technology for Low Rank Coal IGCC System

The overall objective of the project is to demonstrate the technical and economic viability of a new Integrated Gasification Combined Cycle (IGCC) power plant designed to efficiently process low rank coals. The plant uses an integrated CO 2 scrubber/Water Gas Shift (WGS) catalyst to capture over90 percent capture of the CO 2 emissions, while providing a significantly lower cost of electricity (COE) than a similar plant with conventional cold gas cleanup system based on Selexol TM technology and 90 percent carbon capture. TDA’s system uses a high temperature physical adsorbent capable of removing CO 2 above the dew point of the synthesis gas and a commercial WGS catalyst that can effectively convert CO in The overall objective of the project is to demonstrate the technical and economic viability of a new Integrated Gasification Combined Cycle (IGCC) power plant designed to efficiently process low rank coals. The plant uses an integrated CO 2 scrubber/Water Gas Shift (WGS) catalyst to capture over90 percent capture of the CO 2 emissions, while providing a significantly lower cost of electricity (COE) than a similar plant with conventional cold gas cleanup system based on Selexol TM technology and 90 percent carbon capture. TDA’s system uses a high temperature physical adsorbent capable of removing CO 2 above the dew point of the synthesis gas and a commercial WGS catalyst that can effectively convert CO in bituminous coal the net plant efficiency is about 2.4 percentage points higher than an Integrated Gasification Combined Cycle (IGCC) plant equipped with Selexol TM to capture CO 2 . We also previously completed two successful field demonstrations: one at the National Carbon Capture Center (Southern- Wilsonville, AL) in 2011, and a second demonstration in fall of 2012 at the Wabash River IGCC plant (Terra Haute, IN). In this project, we first optimized the sorbent to catalyst ratio used in the combined WGS and CO 2 capture process and confirmed the technical feasibility in bench-scale experiments. In these tests, we did not observe any CO breakthrough both during adsorption and desorption steps indicating that there is complete conversion of CO to CO 2 and H 2 . The overall CO conversions above 90 percent were observed. The sorbent achieved a total CO 2 loading of 7.82 percent wt. of which 5.68 percent is from conversion of CO into CO 2 . The results of the system analysis suggest that the TDA combined shift and high temperature PSA-based Warm Gas Clean-up technology can make a substantial improvement in the IGCC plant thermal performance for a plant designed to achieve near zero emissions (including greater than 90 percent carbon capture). The capital expenses are also expected to be lower than those of Selexol. The higher net plant efficiency and lower capital and operating costs result in substantial reduction in the COE for the IGCC plant equipped with the TDA combined shift and high temperature PSA-based carbon capture system.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

Effect of gamma radiation on the photocatalytic properties of Cu doped titania nanoparticles

Highlights: • Defective Cu doped TiO{sub 2} powders were prepared by sol-gel route and gamma treatment. • Nanoscale analysis show evidence of internal doping by Cu{sup 2+} in the TiO{sub 2} sublattice. • Catalyst surfaces defect sites improve significantly the photocatalytic efficiency. • (Cu{sup 2+}, V{sub O}{sup -}) cooperative effects promote the photoelectrochemical properties of TiO{sub 2}. - Abstract: The aim of this paper is to study the effect of gamma-rays on structural, physicochemical, optical and photocatalytic performance of TiO{sub 2} nanoparticles doped with different concentrations of copper ranging from 0 to 6 at.%. The powders have been prepared by sol-gel technique and annealed at 400 °C. They were irradiated by gamma-rays with doses varying from 14 to 60 KGy. These investigations confirm the formation of anatase TiO{sub 2} nanoparticles and Cu{sup 2+} ion substitution for Ti{sup 4+} sites within the TiO{sub 2} structure. This study also shows that, once the TiO{sub 2} structure is saturated with copper, a metallic copper segregation is formed at the crystallite surfaces. After gamma irradiation, samples present a crystalline core and a disordered shell structure as a result of the formation of oxygen vacancies. Such oxygen vacancies at the TiO{sub 2} nanocrystal surface lead to a remarkable enhancement of the photocatalytic activity of Cu-doped TiO{sub 2} catalysts.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Origin of High Activity and Durability of Twisty Nanowire Alloy Catalysts under Oxygen Reduction and Fuel Cell Operating Conditions

The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. Here, this report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum–iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ~24% Pt are shown to exhibit the highest mass activity (3.4 A/mg Pt , ~20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40000 cycles and <30% loss after 120000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)-body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions. Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.

25 ENERGY STORAGE↗
DOE OSTI2020

A Comparative Study of Redox Mediators for Improved Performance of Li-Oxygen Batteries.

Redox meditators (RMs) are soluble catalysts located in an electrolyte that can improve the energy efficiency (reduced overpotential) and cyclability of Li-oxygen (Li-O-2) batteries. In this work, 20 RMs within a Li-O-2 system with dimethyl sulfoxide and tetraethylene glycol dimethyl ether electrolytes are studied and their electrochemical features such as redox potential, the separation of cathodic and anodic peaks, and their current intensities are measured using cyclic voltammetry (CV) experiments. Six RMs are selected as "primary" choices based on their electrochemical performance, and stability tests are then performed to examine their electrochemical responses after consecutive cycles. Moreover, galvanostatic cycling tests are performed within a Li-O-2 battery system assembled with selected six RMs for real case consistency investigations. It is found that results from CV to galvanostatic cycling tests are consistent for halides and organometallic RMs, where the former exhibit much higher stability. However, the organic RMs show high reversibility in CV but low in battery cycling results. Density functional theory calculations are carried out to gain more understanding of the stability and redox potentials of the RMs. This study provides comparative information to select the most reliable RMs for Li-O-2 batteries along with new fundamental understanding of their electrochemical activity and stability.

cyclic voltammetry↗
DOE OSTI2019

Electronic Structure Calculations for improving Catalyst Design for Use in the Hybrid Sulfur Cycle

The hybrid sulfur cycle is a promising means for efficient production of large quantities of hydrogen with a small carbon footprint. Furthermore, there is a demonstrated need to design catalysts that are sulfur tolerant and have stability at high temperatures and reduced activation energies. Theoretical calculations can serve as a blueprint for fulfilling these needs by providing fundamental mechanistic insights to guide future experimental studies. Density functional theory was used to calculate the energetics of Pt-Au systems. Adsorption energetics for the unary and binary structures were investigated to provide mechanistic insights for improved catalyst design. Results conclude that adsorption of the SO 2 molecule is further stabilized on the Pt surface with a Pt-0 dative bond compared to Au. Energetics suggest that the adsorbates are more stabilized in the Pt surface due to a stabilization of the S p bands in the electronic structure. Examination of the density of states support the postulation that SO 2 is more weakly bound to Au, thereby leading to better catalytic performance compared to Pt. These results are encouraging and we expect there to be a weakening effect of ligand adsorption on the Pt/Au surfaces when an electric field is applied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Effect of nanostructured carbon support on copper electrocatalytic activity toward CO 2 electroreduction to hydrocarbon fuels

The effect of support on electrocatalytic activity of Cu nanoparticles (NPs) towards CO 2 electroreduction to hydrocarbon fuels (CH 4 and C 2 H 4 ) is investigated for three types of nanostructured carbons: single wall carbon nanotubes (SWNT), graphene (GP) and onion-like carbon (OLC). Cu/SWNT, Cu/GP and Cu/OLC composite catalysts are synthesized and characterized by X-Ray diffraction analysis, transmission electron microscopy and electrochemical surface area measurements. Electrocatalytic activities of the synthesized materials, as measured in an electrochemical cell connected to a gas chromatograph, are compared to that of Cu NPs supported on Vulcan carbon. All four catalysts demonstrate higher activity towards C 2 H 4 generation vs CH 4 , with production of the latter mostly suppressed on Cu NPs supported on nanostructured substrates. Onset potentials for C 2 H 4 vs CH 4 generation are shifted positively by 200 mV for Cu/SWNT, Cu/GP, and Cu/OLC catalysts. The Cu/OLC catalyst is found to be superior to the other two nanostructured catalysts in terms of stability, activity and selectivity towards C 2 H 4 generation. Its faradaic efficiency reached 60% at -1.8 V vs Ag/AgCl. The enhanced activity and stability of Cu/OLC catalyst can be attributed to the unique catalyst design, wherein a shell of OLC surrounds the Cu NPs such that the outer layer acts as a filter that protects the Cu surface from adsorption of undesirable species, enhances its electrocatalytic performance, and improves its viability in CO 2 electroreduction reaction.

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

All-in-one bipolar electrode: A new concept for compact and efficient water electrolyzers

Highly compact and efficient proton exchange membrane electrolyzer cells (PEMECs) are strongly desired for commercializing hydrogen production. Here, a novel concept of all-in-one bipolar electrode (AIOBE) is proposed for high-efficiency and compact PEMECs with the help of 3D printing and sputtering coating. AIOBE ideally integrated catalyst layer (CL)/gas diffusion layer/bipolar plate/current distributor/gasket, which significantly reduced component quantity on the cathode side of PEMECs from 5 to 1, cut down on part weight and volume, and drastically accelerated the fabrication and maintenance processes. Moreover, AIOBE with the micro-scale flat surface and nano-scale rough CL provided an ultralow ohmic resistance (~100 mOhm cm 2 ) and a high catalyst utilization. Finally, AIOBE delivered a practical voltage of 1.62 V and a high energy efficiency of 91% at 1000 mA/cm 2 , and its mass activity (4.48 A/mg Pt ) was 14 times higher than conventional PEMECs. In conclusion, this work provides a new route for developing highly compact electrochemical devices, such as fuel cells, electrolyzers for N 2 reduction and CO 2 conversion, and many more.

3D printing↗
DOE OSTI2025

Hydrogen-rich syngas production from the steam co-gasification of low-density polyethylene and coal refuse

Gasification provides a promising pathway for transforming waste materials into valuable products, such as fuels and chemicals. Here, this study investigates the steam co-gasification of low-density polyethylene (LDPE) and compressed thickener underflow, representative of coal refuse (CR), in a drop tube reactor. The effects of feed blend ratio (0–100 wt% LDPE) and temperature (800–1000 °C) on syngas composition, tar formation, and process efficiency are examined. The high volatility of LDPE makes it more reactive than CR but also promotes the formation of 2–7 ring aromatic tars. Increasing temperature improves carbon conversion efficiency (CCE), cold gas efficiency (CGE), and syngas yield, although the lower heating value (LHV) of syngas decreases. Hydrogen is the dominant gas product, reaching 59 vol% with the H 2 /CO molar ratio ranging from 2.27 to 4.74. Synergistic effects from alkali and alkali earth metals (AAEMs), particularly K and Ca, in CR ash enhance syngas yield by catalyzing char gasification and tar cracking. Hematite (Fe 2 O 3 ) and ash from sub-bituminous/bituminous coals are explored as tar reforming catalysts. Fe 2 O 3 achieves 100 % tar reforming efficiency, while coal ash, with a lower Fe 2 O 3 content (15 wt%), is less effective at cracking polycyclic aromatic hydrocarbons, particularly naphthalene. These findings demonstrate the flexibility of co-gasification, allowing precise tuning of syngas characteristics for specific downstream applications. Further optimization of waste-derived catalysts could enhance the economic viability of gasification in waste-to-energy processes.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Doubly-Charged Negative Ions as Novel Tunable Catalysts: Graphene and Fullerene Molecules Versus Atomic Metals

The fundamental mechanism underlying negative-ion catalysis involves bond-strength breaking in the transition state (TS). Doubly-charged atomic/molecular anions are proposed as novel dynamic tunable catalysts, as demonstrated in water oxidation into peroxide. Density Functional Theory TS calculations have found a tunable energy activation barrier reduction ranging from 0.030 eV to 2.070 eV, with Si 2– , Pu 2– , Pa 2– and Sn 2– being the best catalysts; the radioactive elements usher in new application opportunities. C 60 2– significantly reduces the standard C 60 – TS energy barrier, while graphene increases it, behaving like cationic systems. According to their reaction barrier reduction efficiency, variation across charge states and systems, rank-ordered catalysts reveal their tunable and wide applications, ranging from water purification to biocompatible antiviral and antibacterial sanitation systems.

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

An effective hybrid strategy for converting rice straw to furoic acid by tandem catalysisviaSn-sepiolite combined with recombinantE. coliwhole cells harboring horse liver alcohol dehydrogenase

The upgrading of biomass-derived furfural into high-value bio-based chemicals has attracted interest. In this case, the conversion of rice straw into furfural was firstly performed using tin-loaded sepiolite (Sn-sepiolite) as a catalyst. Acidified solid acid Sn-sepiolite (3.0 wt%) converted alkali-pretreated dewaxed rice straw into furfural at 42.2% yield at 170 °C for 20 min. Moreover, biomass-derived furfural could be completely converted into furoic acid with recombinant immobilized E. coli TS whole-cells within 96 h at pH 7.0 and 30 °C, respectively. Finally, efficient recycling and reuse of the Sn-sepiolite catalyst and immobilized TS whole-cell biocatalyst were developed for the synthesis of furoic acid from rice straw in the one-pot reaction system. In conclusion, an effective one-pot chemo-enzymatic synthesis of furoic acid from renewable biomass was successfully developed using ambient conditions.

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

Carbon Utilization: Electrochemical Approach Using Novel Catalyst and System Integration

The environmental footprint from power generation can be mitigated by capturing emitted carbon dioxide (CO2) and converting it to value-added fuel sources. A multitude of different fuels can be produced from CO2 depending on the chemical reaction catalysts. Typically, these pathways can be developed electrochemically, or through hydrogenation. In recent years the electrochemical reduction of CO2 has grown exponentially, as it has shown potential to decrease atmospheric pollution and provide an additional means of on-demand electricity storage. Formic acid (FA) in particular has industrial applications such as in fuel cells or as a hydrogen storage medium, and requires a lower thermodynamic energy input than any other fuel produced for electrochemical CO2 reduction. However, product selectivity remains a challenge for conventional electrocatalysts, making FA production efficiencies above 50% difficult. To address the challenge of catalytic selectivity, UK CAER employs enzymatic catalysts to facilitate the FA production and minimize unwanted byproducts. Our process couples the catalyst with a charge mediator which is necessary to shuttle electrons, and an electrolyte pH buffer to prevent the catalyst from degrading. Presently, production efficiencies have approached 60% at a rate of over 10 mM FA/hour. System design considerations (flow rate, bulk volume) will also be discussed.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

CO oxidation over a ligand coordinated single site Rh catalyst: identification of the active complex

Single atom catalysis has evolved as a promising strategy to enhance atom utilization efficiency, lower reaction temperatures, and control reaction pathways in heterogeneous catalytic reactions. An important challenge using supported single atom catalysts is the stability of metal single atoms during reactions. Here, we present an approach to stabilize single rhodium atoms on a titania support via a metal–ligand coordination strategy. We explore the reaction activity and mechanism of CO oxidation, as well as the stability under oxidative reaction conditions. Kinetic studies suggest that, with an excess of oxygen in the feed gas, oxygen activation is more facile on defective titania surfaces than on pristine titania surfaces. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis shows that on the pristine titania surface, the 1,10-phenanthroline-5,6-dione (PDO) coordinated Rh catalyst (Rh–PDO/TiO 2 ) catalyzes CO oxidation via the formation of carbonate-like species, which is similar to what occurs on Rh nanoparticle catalysts. However, on the defective titania surface, no carbonate species form for Rh–PDO/def-TiO 2 . The supported Rh–ligand catalysts are also shown to be very stable in such a reaction environment at elevated temperatures, potentially allowing for wide applications.

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

From Metal–Organic Frameworks to Single‐Atom Fe Implanted N‐doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media

Abstract It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal–organic frameworks (MOFs) have been synthesized based on a novel mixed‐ligand strategy to afford high‐content (1.76 wt %) single‐atom (SA) iron‐implanted N‐doped porous carbon (Fe SA ‐N‐C) via pyrolysis. Thanks to the single‐atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized Fe SA ‐N‐C exhibits excellent oxygen reduction activity and stability, surpassing almost all non‐noble‐metal catalysts and state‐of‐the‐art Pt/C, in both alkaline and more challenging acidic media. More far‐reaching, this MOF‐based mixed‐ligand strategy opens a novel avenue to the precise fabrication of efficient single‐atom catalysts.

Jiao, Long↗
DOE OSTI2018

From Metal-Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media [From MOFs to Single Fe Atoms Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media]

Here, it remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal–organic frameworks (MOFs) have been synthesized based on a novel mixed–ligand strategy to afford high–content (1.76 wt %) single–atom (SA) iron–implanted N–doped porous carbon (Fe SA –N–C) via pyrolysis. Thanks to the single–atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized Fe SA –N–C exhibits excellent oxygen reduction activity and stability, surpassing almost all non–noble–metal catalysts and state–of–the–art Pt/C, in both alkaline and more challenging acidic media. More far–reaching, this MOF–based mixed–ligand strategy opens a novel avenue to the precise fabrication of efficient single–atom catalysts.

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

Modification of the Coordination Environment of Active Sites on MoC for High-Efficiency CH 4 Production

Modulating the coordination environment of active sites on catalyst surfaces is crucial to developing effective catalysts and controlling catalysis, but it is highly challenging. Guided by our first-principles calculations, we experimentally accomplish the modification of the coordination environment of active sites on MoC nanoparticle surfaces by anchoring pyridinic N atom rings of holey graphene on Mo atoms. The rings produce electrostatic forces that enable the tuning of the Mo sites' affinity to reaction intermediates, which passivates Mo hollow sites, activates Mo top sites and reduces the over-adsorption of OH on the Mo active sites, as predicted by the calculations. The atomic-level modification is well confirmed by atomic-resolution imaging, high-resolution electron tomography, synchrotron soft X-ray spectroscopy and operando electrochemical infrared spectroscopy. Consequently, the Faradaic efficiency for CO 2 reduction to CH 4 is enhanced from 16% to 89%, a record high efficiency so far, in aqueous electrolyte. Meantime, it also exhibits a negligible activity loss over 50 h.

77 NANOSCIENCE AND NANOTECHNOLOGY↗