Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Co”

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 937 records · Page 52

Improved Microalgal Carbon Utilization Efficiency via Integrated CO 2 Electro-Conversion to Formate and Microalgal Sequestration

This project developed a process to convert industrial carbon dioxide (CO 2 ) emissions into high-value, sustainable products through genetically engineered algae cultivation. While traditional microalgae cultivation depends on sparging CO 2 gas through water, this method is often inefficient because much of the gas escapes into the atmosphere before the algae can consume it. To overcome this challenge, the project designed an integrated system that first uses a CO 2 to formic acid electrolyzer to convert CO 2 into water-soluble formic acid/formate, then introduces formic acid/formate into the algae pond for cultivation, which allows the algae to access and utilize nearly all of the provided carbon, greatly increasing the efficiency of carbon utilization. The project team has successfully scaled up the CO 2 to formic acid electrolyzer from lab-scale to 1000 cm² and demonstrated industrially relevant current densities with the scaled-up electrolyzers using a CO 2 source that simulates industrial CO 2 waste.

42 ENGINEERING↗

Evaluation of microalgae cultivation at air-CO 2 equilibrium pH for improving carbon utilization efficiency

Microalgae are often cultivated at near-neutral pH to optimize growth. However, this results in significant CO 2 loss through outgassing in open-pond cultivation systems, leading to low CO 2 utilization efficiency and higher biomass production costs. One potential solution is algal cultivation at air-CO 2 equilibrium pH, which minimizes CO 2 outgassing but may inhibit growth due to stresses at higher pH levels. In this study, we evaluated the viability of this approach by growing Picochlorum celeri and Tetraselmis striata under outdoor relevant conditions at equilibrium pH. Compared to pH 7 cultures, biomass productivity declined by 35 % for P. celeri and 57 % for T. striata. Although CO 2 outgassing could be minimized, the significant loss in productivity led to a higher overall minimum biomass selling price (MBSP). Increased ammonia toxicity at the higher pH was found to be one of the growth-limiting factors and was mitigated by reducing ammonium fertilizer concentration. This adjustment resulted in a more moderate productivity decline of 13 % (instead of 35 %) for T. striata, and consequently, a lower MBSP was achieved. These findings suggest that equilibrium pH cultivation may be a viable method for reducing CO 2 loss without significantly compromising biomass productivity. Depending on the strain, strategies to mitigate stressors, such as ammonia toxicity, may be necessary.

09 BIOMASS FUELS↗

Identifying Critical Electrode Metrics for Efficient, Selective CO 2 Electrochemical Conversion

Low-temperature electrochemical CO 2 reduction (CO 2 R) in zero-gap membrane electrode assembly (MEA) reactors presents a scalable route to fuels and carbon utilization. However, performance at industrially relevant current densities hinges on mesoscale catalyst layer integration, particularly at the ionomer|catalyst interface. Here, we demonstrate a generalizable in situ electrochemical impedance spectroscopy (EIS) method. We utilize this technique to decouple electrode-level parameters that are correlated to the overall MEA performance. By performing this ex situ EIS method on CO 2 -to-CO catalyst-coated membranes with systematically varied ionomer-to-catalyst (I:C) ratios, we reveal a pronounced dependence of performance, ion transport resistance, and catalyst utilization on the I:C ratio as well as the electrode conditioning. We demonstrate that an optimal I:C ratio exists at which ion transport resistance is minimized and Faradaic efficiency for CO production is maximized. Beyond the electrodes examined, here we compare ion transport resistance to MEA selectivity/Faradaic efficiency obtained in prior studies, revealing a clear correlation between the two. These results suggest that ion transport resistance within the catalyst layer may be a quantitative predictor of MEA performance which underscores the importance of mesoscale integration in achieving scalable CO 2 R technologies.

08 HYDROGEN↗

Metallic Phase-Free Zn-Al Mixed Oxide Dual Function Materials Enable High Co Selectivity in Reactive Carbon Capture From Dilute Streams

Scaling conventional carbon capture and utilization methods can be limited by cost and permitting issues associated with transportation of captured CO2. Reactive carbon capture (RCC), in which a single solid-phase dual function material (DFM) is used to both capture CO2 from dilute streams (e.g., flue gas) and catalytically convert the bound species to products in a single unit operation, has the potential to reduce energy and capital costs by over 50% relative to separate capture and conversion. To incentivize adoption, high-value products such as methanol and CO should be targeted. Appealingly, CO can be produced at atmospheric pressure, thereby lowering overall H2 demand; however, high reaction temperatures (> 600 degrees C) and the use of oxidizable transition metals, such as Ni, are often necessary to drive the reverse water-gas shift (RWGS) during reactive desorption of the bound CO2. The sensitivity of these transition metals to oxygen undercuts their utility in point source RCC. To further derisk RCC, it is essential to develop metallic-phase free DFMs that are insensitive to residual oxygen in flue gas and can achieve selective reactive desorption to CO at moderate pressures (< 400 degrees C). To this end, we have developed K-modified Zn-Al mixed oxides (K/ZnAlOx) to convert captured CO2 to CO with > 97% selectivity and yields up to 53% of captured CO2 at 400 degrees C. Complementary in situ spectroscopy studies revealed the role of K-modification in improving RCC performance of unmodified ZnAlOx. The top performing DFM was also subjected to extended RCC cycling with oxygen co-fed with CO2 during the capture test to assess durability under simulated flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 –Based Dual–Tone Resists for Electron Beam Lithography

The increasing global environmental and energy crisis has urgently motivated the advancement of sustainable materials. Significant effort has been focused on developing new materials to replace the fossil-based resists in the semiconductor industry based on greener sources such as ice, dry ice, small organic molecules, and proteins. Such resist materials, however, have yet to meet the stringent requirements of high sensitivity, high resolution, reliable repeatability, and good compatibility with the current protocols. To this end, CO 2 -based polycarbonates (CO 2 -PCs) obtained from the copolymerization of CO 2 and epoxides are demonstrated as sustainable dual-tone (positive & negative tone) resists for electron beam lithography. By adjusting the chemical structure, developing agent, and molecular weight, the CO 2 -PCs present high sensitivities to electron beam (1.3/120 μC cm -2 ), narrow critical dimensions (29/58 nm), and moderate line edge roughness (4.6/26.7 nm) for negative and positive resists, respectively. Here, a deep understanding of the exposure mechanism of CO 2 -PC resists is provided on the basis of the Fourier transform infrared, Raman, and electron ionization mass spectroscopy. 2D photonic crystal devices are fabricated using the negative and positive CO 2 -PC resists, respectively, and both devices show distinct colors derived from their well-defined nanostructures, indicating the great practical potential of CO 2 -derived electron beam resists.

nanofabrication↗

Decreasing the Overpotential of Aprotic Li-CO 2 Batteries with the In-Plane Alloy Structure in Ultrathin 2D Ru-Based Nanosheets

We report the aprotic Li-CO 2 battery is emerging as a promising energy storage technology with the capability of CO 2 fixation and conversion. However, its practical applications are still impeded by the large overpotential. Herein, the general synthesis of a series of ultrathin 2D Ru-M (M = Co, Ni, and Cu) nanosheets by a facile one-pot solvothermal method is reported. As a proof-of-concept application, the representative RuCo nanosheets are used as the cathode catalysts for Li-CO 2 batteries, which demonstrate a low charge voltage of 3.74 V, a small overpotential of 0.94 V, and hence a high energy efficiency of 75%. Ex/in situ studies and density functional theory calculations reveal that the excellent catalytic performance of RuCo nanosheets originates from the enhanced adsorption toward Li and CO 2 during discharge as well as the elevated electron interaction with Li 2 CO 3 during charge by the in-plane RuCo alloy structure. This work indicates the feasibility of boosting the electrochemical performance of Li-CO 2 batteries by in-plane metal alloy sites of ultrathin 2D alloy nanomaterials.

25 ENERGY STORAGE↗

Constructing Highly Durable Fuel Cell Catalysts Through Integrating Graphitic Shell‐Protected Composite Carbon Support with Gaseous Co Deposition‐Driven PtCo Intermetallics

Metal dissolution, nanoparticle agglomeration, and carbon support corrosion cause significant performance degradation of current PtCo catalysts under acidic and oxidative oxygen reduction reaction. Here, in this study, an integrated strategy is presented to design high-performance Pt 3 Co intermetallic catalysts by regulating gaseous Co deposition-driven diffusion into Pt nanoparticles supported on a composite carbon. The composite carbon is derived from ZIF-8/polyaniline, consisting of a high-surface-area (HSC) core and a protective graphitic shell (GS), which is employed to design 40 wt.% Pt/HSC@GS catalyst. The corresponding membrane electrode assemblies (MEAs) can maintain 1.09 A cm −2 at 0.7 V (20. 7% loss) after 10 000 cycles (1.0–1.5 V for carbon stability) and 1.15 A cm −2 (16.1% loss) after 150 000 cycles (0.60–0.95 V for catalyst stability). A ordered Pt 3 Co intermetallic is synthesized via a gaseous Co-deposition process, which yields a homogeneous Co-rich layer onto the Pt nanoparticles on the composite support, thereby facilitating Co diffusion into Pt crystal during subsequent ordering annealing to form the ordered intermetallic structure. This gaseous deposition leads to a thin carbon layer on PtCo nanoparticles, inhibiting particle growth during the annealing and mitigating Co dissolution under dynamic electrochemical conditions. The PtCo catalyst achieves impressive MEA performance and long-term durability (1.45 A cm −2 at 0.7 V after 120 000 cycles) under heavy-duty conditions.

30 DIRECT ENERGY CONVERSION↗

Single‐Atom Electrocatalysts from Multivariate Metal–Organic Frameworks for Highly Selective Reduction of CO 2 at Low Pressures

Abstract Single‐atom catalysts (SACs) are of great interest because of their ultrahigh activity and selectivity. However, it is difficult to construct model SACs according to a general synthetic method, and therefore, discerning differences in activity of diverse single‐atom catalysts is not straightforward. Herein, a general strategy for synthesis of single‐atom metals implanted in N‐doped carbon (M 1 ‐N‐C; M=Fe, Co, Ni and Cu) has been developed starting from multivariate metal–organic frameworks (MOFs). The M 1 ‐N‐C catalysts, featuring identical chemical environments and supports, provided an ideal platform for differentiating the activity of single‐atom metal species. When employed in electrocatalytic CO 2 reduction, Ni 1 ‐N‐C exhibited a very high CO Faradaic efficiency (FE) up to 96.8 % that far surpassed Fe 1 ‐, Co 1 ‐ and Cu 1 ‐N‐C. Remarkably, the best‐performer, Ni 1 ‐N‐C, even demonstrated excellent CO FE at low CO 2 pressures, thereby representing a promising opportunity for the direct use of dilute CO 2 feedstock.

Jiao, Long↗

Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO 2 Conversion with Carbon‐Based Materials

Abstract Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. We show that Ni, N‐doped carbon (NiPACN), an electrocatalyst for the reduction of CO 2 to CO (CO 2 R), can also selectively catalyze thermal CO 2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO 2 R active site studies. Finally, we construct a generalized reaction driving‐force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO 2 R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

Koshy, David M.↗

Mediated Inner‐Sphere Electron Transfer Induces Homogeneous Reduction of CO 2 via Through‐Space Electronic Conjugation**

Abstract The electrocatalytic reduction of CO 2 is an appealing method for converting renewable energy sources into value‐added chemical feedstocks. We report a co‐electrocatalytic system for the reduction of CO 2 to CO comprised of a molecular Cr complex and dibenzothiophene‐5,5‐dioxide (DBTD) as a redox mediator, which achieves high activity (TOF=1.51–2.84×10 5 s −1 ) and quantitative selectivity. Under aprotic or protic conditions, DBTD produces a co‐electrocatalytic response with 1 by coordinating trans to the site of CO 2 binding and mediating electron transfer from the electrode with quantitative efficiency for CO. This assembly is reliant on through‐space electronic conjugation between the π frameworks of DBTD and the bpy fragment of the catalyst ligand, with contributions from dispersive interactions and weak sulfone coordination.

Hooe, Shelby L.↗

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↗

Bridging Thermal Catalysis and Electrocatalysis: Catalyzing CO 2 Conversion with Carbon-Based Materials

Understanding the differences between reactions driven by elevated temperature or electric potential remains challenging, largely due to materials incompatibilities between thermal catalytic and electrocatalytic environments. In this work, we show that Ni, N-doped carbon (NiPACN), an electrocatalyst for the reduction of CO 2 to CO (CO 2 R), can also selectively catalyze thermal CO 2 to CO via the reverse water gas shift (RWGS) representing a direct analogy between catalytic phenomena across the two reaction environments. Advanced characterization techniques reveal that NiPACN likely facilitates RWGS on dispersed Ni sites in agreement with CO 2 R active site studies. Finally, we construct a generalized reaction driving-force that includes temperature and potential and suggest that NiPACN could facilitate faster kinetics in CO 2 R relative to RWGS due to lower intrinsic barriers. This report motivates further studies that quantitatively link catalytic phenomena across disparate reaction environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and activity of supported bimetallic NiPd nanoparticles: influence of preparation method on CO 2 reduction

Here, bimetallic Ni-Pd and monometallic reference catalysts were prepared by decomposing organometallic precursors, Ni(cod) 2 and Pd 2 (dba) 3 , leading to nanoparticles with sizes ranging from 3 to 6 nm. Two different synthesis procedures were followed: i) solution synthesis using capping ligand (hexadecylamine) followed by impregnation of pre-formed nanoparticles on SiO 2 , called Sol-immobilization (SI); and 2) direct precursor decomposition onto SiO 2 , without stabilizer, called Direct Decomposition (DD). Samples prepared by SI procedure are alloyed bimetallic nanoparticles, whereas samples obtained by DD one show phase segregation. Interestingly, DD samples show better activity for CO 2 hydrogenation into CO (reverse water-gas shift reaction - RWGS) than SI ones. The best compromise between activity for CO 2 activation (at lower temperature) and CO selectivity was achieved with Ni DD and NiPd DD catalysts. Moreover, the addition of palladium increased the concentration of surface undercoordinated sites, which chemisorb CO weakly, thus improving activity and selectivity, in opposition to other samples that chemisorb CO strongly, in multiband configuration. In the presence of Pd, different decomposition rates drive the formation of smaller and more active Ni clusters. The knowledge acquired here on the influence of synthesis conditions on the catalytic properties of Ni-Pd catalysts should guide us to better catalysts for CO 2 transformations into valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Silico Screening of CO 2 –Dipeptide Interactions for Bioinspired Carbon Capture

Carbon capture, sequestration and utilization offers a viable solution for reducing the total amount of atmospheric CO 2 concentrations. On an industrial scale, amine-based solvents are extensively employed for CO 2 capture through chemisorption. Nevertheless, this method is marked by the high cost associated with solvent regeneration, high vapor pressure, and the corrosive and toxic attributes of by-products, such as nitrosamines. An alternative approach is the biomimicry of sustainable materials that have strong affinity and selectivity for CO 2 . Bioinspired approaches, such as those based on naturally occurring amino acids, have been proposed for direct air capture methodologies. In this study, we present a database consisting of 960 dipeptide molecular structures, composed of the 20 naturally occurring amino acids. Furthermore, those structures were analyzed with a novel computational workflow presented in this work that considers certain interaction sites that determine CO 2 affinity. Density functional theory (DFT) and symmetry-adapted perturbation theory (SAPT) computations were performed for the calculation of CO 2 interaction energies, which allowed to limit our search space to 400 unique dipeptide structures. Using this computational workflow, we provide statistical insights into dipeptides and their affinity for CO 2 binding, as well as design principles that can further enhance CO 2 capture through cooperative binding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photochemical CO 2 Reduction Using Rhenium(I) Tricarbonyl Complexes with Bipyridyl-Type Ligands with and without Second Coordination Sphere Effects

In this study, the effect of phenyl, phenol, aniline, amino, and CF 3 substituents of the 2,2'-bipyridine ligand in fac-ReCl(L)(CO) 3 (L=2,2'-bipyridine derivative) catalysts on photochemical CO 2 reduction in dimethylacetamide is examined, in order to understand the structure-function relationships and to compare the catalytic activities with the previously published electrochemical results. All complexes including ReCl(bpy)(CO) 3 have similar excited-state lifetimes and emission spectra, but complex 1 with the Ph-NH 2 moiety exhibits a significantly larger molar absorption coefficient for its metal-to-ligand charge transfer (MLCT) band. All complexes we tested produce CO with only a negligible amount of H 2 and formate in self-sensitized systems in the presence of triethanolamine (TEOA) and in some cases, BIH (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]-imidazole). The presence of the Ph-NH 2 moiety (complex 1) has a beneficial effect on both electrochemical and photochemical activity, allowing a turnover number (TON) of 32 and 120 for photochemical CO production (without and with BIH, respectively). In the case of the Ph-OH group in the second coordination sphere (complexes 4 and 6), these complexes are active for photochemical CO 2 reduction, despite the formation of a stable 6-coordinate Re-OPh intermediate via reductive deprotonation as previously observed under electrochemical conditions. Overall, BIH accelerates the rate of formation of the one-electron reduced species (OERS) of the Re catalysts and allows higher turnover frequency (TOF) and TON for CO formation. The X-ray structures of complexes 1 and 4 were determined to have distorted octahedral Re centres, and show π-π stacking interactions with neighboring molecules as well as intramolecular hydrogen bonds to the internal chloride ligands. The unusually high absorptivity of the MLCT absorption of complex 1 has been explained by TD-DFT calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Downwind dispersion of CO 2 from a major subsea blowout in shallow offshore waters

Growing interest in offshore geologic carbon sequestration (GCS) motivates risk assessment of large-scale subsea CO 2 well blowouts or pipeline ruptures. For major leaks of CO 2 from wells or pipelines, significant fluxes of CO 2 may occur from the sea surface depending on water depth. In the context of risk assessment of human health and safety, we have used previously simulated coupled well-reservoir and water column model results as a source term for dense gas dispersion of CO 2 above the sea surface. The models are linked together by one-way coupling, that is, output of one model is used as input to the next model. These first-of-their-kind coupled flow results are applicable to assessing the hazard of CO 2 to people at and downwind of the sea surface location of emission. Hazard is quantified by plotting the downwind dispersion length (DDL), which we define in the study as the distances from the emission source to the point at which the emitted CO 2 has been diluted to 5% and 1.5% in air by volume. Here results suggest that large-scale blowouts in shallow water (10 m) may cause hazardous CO 2 plumes extending on the order of several hundred meters downwind. Details of the modeling show DDL has a maximum for windspeed (at an elevation of 10 m) of approximately 5 m/s, with smaller DDL for both weaker and stronger winds. This is explained by the fact that wind favors transport but also causes dispersion; therefore there is a certain wind speed that maximizes DDL.

54 ENVIRONMENTAL SCIENCES↗

Simulation study of chemo-mechanical impacts of CO 2 injection in morrow b sandstone reservoir

Here, this study investigates the impacts of geomechanical and geochemical changes on carbon storage in a partially depleted oil reservoir, using results from four different coupled simulation models. Models were used to examine the relative importance of storage mechanisms, and how changing reservoir parameters might affect these mechanisms through time. The study uses data from a Morrowan sandstone reservoir in the Farnsworth Unit (FWU), Ochiltree County, Texas which is currently undergoing CO 2 enhanced oil recovery (EOR). Partially depleted oil reservoirs such as the FWU offer attractive carbon utilization and/or storage targets because of existing infrastructure and economic benefits from incremental oil recovery as well as tax credits. However, prediction of storage capacity or long-term fluid migration in these fields can be difficult because of the wide variation in formation fluids and operational histories that may have undergone. CO 2 injection can cause complex geomechanical and geochemical responses in a reservoir as a result of interplay between dynamic changes in pore pressure, reservoir temperature, fluid composition, and interactions between formation fluids, CO 2 , and reservoir rock. Thus, multiple coupled numerical simulation models must be developed and used to more precisely understand what CO 2 storage mechanisms are most significant, as well as the long-term fate of the stored CO 2 . Our study used results from hydrodynamic, coupled hydro-geomechanical, coupled hydro-geochemical, and coupled hydro-geomechanical-geochemical models to examine how changes in geomechanical and geochemical properties can impact the injectivity or storage capacity of CO 2 . Models simulated historical field operations and then forward-modeled a water-alternate-gas (WAG) operation for 20 years, followed by a 1000-year post-injection monitoring. The work demonstrates that in this specific reservoir, geomechanical impacts appear to be more significant than any geochemical processes, which showed minimal impact on reservoir properties. Furthermore, these simulation scenarios corroborated other studies showing more than 90% of CO 2 injected are being stored and will remain stored in the reservoir. The study was able to draw on a rich set of data from this currently operational project for the work. Because the Morrow is a widespread oil-bearing reservoir in the midcontinent of the United States and is fairly typical of many sandstone reservoirs elsewhere, the study has significance beyond the boundaries of our field area.

58 GEOSCIENCES↗

Positive Co‐Degree Density of Hypergraphs

The minimum positive co-degree of a nonempty r-graph H, denoted $δ^+_{r-1}$ (H), is the maximum k such that if S is an (r-1)-set contained in a hyperedge of H, then is contained in at least distinct hyperedges of H. Given an r-graph F, we introduce the positive co-degree Turán number co + ex(n, F) as the maximum positive co-degree $δ^+_{r-1}$ (H) over all n-vertex r-graphs H that do not contain F as a subhypergraph. In this paper, we concentrate on the behavior of co + ex(n, F) for 3-graphs F. In particular, we determine asymptotics and bounds for several well-known concrete 3-graphs F (e.g. $K^-_4$ and the Fano plane). Here, we also show that, for r-graphs, the limit γ + (F)≔ lim$_{n→∞}$ $\frac{co^+ex(n, F)}{n}$ exists, and “jumps” from 0 to 1/r, that is, it never takes on values in the interval . Moreover, we characterize which r-graphs F have γ + (F) = 0. Our motivation comes primarily from the study of (ordinary) co-degree Turán numbers where a number of results have been proved that inspire our results.

97 MATHEMATICS AND COMPUTING↗