SEARCH · Search NASA

Results for “FORMIC ACID”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 361 records · Page 20

All sources NASA NTRS DOE OSTI

DOE OSTI2015

Assessing photocatalytic power of g-C{sub 3}N{sub 4} for solar fuel production: A first-principles study involving quasi-particle theory and dispersive forces

First-principles quasi-particle theory has been employed to assess catalytic power of graphitic carbon nitride, g-C{sub 3}N{sub 4}, for solar fuel production. A comparative study between g-h-triazine and g-h-heptazine has been carried out taking also into account van der Waals dispersive forces. The band edge potentials have been calculated using a recently developed approach where quasi-particle effects are taken into account through the GW approximation. First, it was found that the description of ground state properties such as cohesive and surface formation energies requires the proper treatment of dispersive interaction. Furthermore, through the analysis of calculated band-edge potentials, it is shown that g-h-triazine has high reductive power reaching the potential to reduce CO{sub 2} to formic acid, coplanar g-h-heptazine displays the highest thermodynamics force toward H{sub 2}O/O{sub 2} oxidation reaction, and corrugated g-h-heptazine exhibits a good capacity for both reactions. This rigorous theoretical study shows a route to further improve the catalytic performance of g-C{sub 3}N{sub 4}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

M2CT-22IN1202096 Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration

Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy-rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling in the AspenOne Suite will be used to determine each component’s sensitivities, costs, inputs, and outputs. Dispatch modeling in the FORCE toolset will optimize the entire system and calculate the NPV for the refinery lifetime. Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2022

M2CT-22IN1202096 Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2012

Structure-Induced Enhancement in Electrooxidation of Trimetallic FePtAu Nanoparticles

Using FePtAu nanoparticles (NPs) as an example, this Communication demonstrates a new structure-control strategy to tune and optimize NP catalysis. The presence of Au in FePtAu facilitates FePt structure transformation from chemically disordered face-centered cubic (fcc) structure to chemically ordered face-centered tetragonal (fct) structure, and further promotes formic acid oxidation reaction (FAOR). The fct-FePtAu NPs have mass activity as high as 2809.9 mA/mg Pt and retain 92.5% of this activity after a 13 h stability test. They become the most efficient NP catalyst ever reported for FAOR. This structure-control strategy can be extended to other multimetallic NP systems, providing a general approach to advanced NP catalysts with desired activity and durability control for practical applications.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2012

COMPLEX ORGANIC MOLECULES AT HIGH SPATIAL RESOLUTION TOWARD ORION-KL. I. SPATIAL SCALES

Here we present high spatial resolution (<1'') observations of molecular emission in Orion-KL conducted using the Combined Array for Research in Millimeter-wave Astronomy. This work was motivated by recent millimeter continuum imaging studies of this region conducted at a similarly high spatial resolution, which revealed that the bulk of the emission arises from numerous compact sources, rather than the larger-scale extended structures typically associated with the Orion Hot Core and Compact Ridge. Given that the spatial extent of molecular emission greatly affects the determination of molecular abundances, it is important to determine the true spatial scale for complex molecules in this region. Additionally, it has recently been suggested that the relative spatial distributions of complex molecules in a source might give insight into the chemical mechanisms that drive complex chemistry in star-forming regions. In order to begin to address these issues, this study seeks to determine the spatial distributions of ethyl cyanide [C{sub 2}H{sub 5}CN], dimethyl ether [(CH{sub 3}){sub 2}O], methyl formate [HCOOCH{sub 3}], formic acid [HCOOH], acetone [(CH{sub 3}){sub 2}CO], SiO, methanol [CH{sub 3}OH], and methyl cyanide [CH{sub 3}CN] in Orion-KL at {lambda} = 3 mm. We find that for all observed molecules, the molecular emission arises from multiple components of the cloud that include a range of spatial scales and physical conditions. Here, we present the results of these observations and discuss the implications for studies of complex molecules in star-forming regions.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2014

Quantum chemical approach for condensed-phase thermochemistry: Proposal of a harmonic solvation model

We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor–liquid equilibration of water and ethanol, and dissolution of gaseous CO{sub 2} in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Active electrochemical interfaces stabilized through self-organized potential oscillations

Some electrochemical systems are known to have higher average efficiency when operated under an oscillatory regime. Given the compromise between activity and stability, the stability of electrochemical interfaces in a self-organized, oscillatory state must be taken into account. Here we evaluate the electro-oxidation of methanol and formic acid on platinum under regular and oscillatory conditions, and study the stability by following the Pt dissolution rates in situ with a stationary probe rotating disk electrode (SPRDE) coupled to an inductively coupled plasma mass spectrometer (ICP-MS). Generally speaking, as the electro-oxidation reaction proceeds, the platinum dissolution rate increases considerably. To guarantee Pt stability, the potential must be kept below 1.0 V vs. RHE. Interestingly, no dissolution is detectable when the electrode potential undergoes temporary self-organization, ensuring a stable and active interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

Highly efficient photochemical HCOOH production from CO{sub 2} and water using an inorganic system

We have constructed a system that uses solar energy to react CO{sub 2} with water to generate formic acid (HCOOH) at an energy conversion efficiency of 0.15%. It consists of an AlGaN/GaN anode photoelectrode and indium (In) cathode that are electrically connected outside of the reactor cell. High energy conversion efficiency is realized due to a high quantum efficiency of 28% at 300 nm, attributable to efficient electron-hole separation in the semiconductor's heterostructure. The efficiency is close to that of natural photosynthesis in plants, and what is more, the reaction product (HCOOH) can be used as a renewable energy source.

36 MATERIALS SCIENCE↗

DOE OSTI2014

A low-temperature processed environment-friendly full-organic carrier collection layer for polymer solar cells

We constructed a concept of the full-organic carrier collection layer (CCL) used for polymer solar cells. The CCL is composed of dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile as hole collection layer (HCL) and chlorine-free solvents (formic acid (FA)) processed 4,7-Diphenyl-1,10-phenanthroline (Bphen) as electron collection layer, exhibiting good solubility, and environmental protection. The FA based device shows ideal power conversion efficiency (3.75%), which is higher than that of control device (3.6%). Besides, the HCL shows a different mechanism in hole extraction by functioning as a charge recombination zone for electrons injected from anode and holes extracted from the donor materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

Behavior of Mercury During DWPF Chemical Process Cell Processing

The Defense Waste Processing Facility has experienced significant issues with the stripping and recovery of mercury in the Chemical Processing Cell (CPC). The stripping rate has been inconsistent, often resulting in extended processing times to remove mercury to the required endpoint concentration. The recovery of mercury in the Mercury Water Wash Tank has never been high, and has decreased significantly since the Mercury Water Wash Tank was replaced after the seventh batch of Sludge Batch 5. Since this time, essentially no recovery of mercury has been seen. Pertinent literature was reviewed, previous lab-scale data on mercury stripping and recovery was examined, and new lab-scale CPC Sludge Receipt and Adjustment Tank (SRAT) runs were conducted. For previous lab-scale data, many of the runs with sufficient mercury recovery data were examined to determine what factors affect the stripping and recovery of mercury and to improve closure of the mercury material balance. Ten new lab-scale SRAT runs (HG runs) were performed to examine the effects of acid stoichiometry, sludge solids concentration, antifoam concentration, form of mercury added to simulant, presence of a SRAT heel, operation of the SRAT condenser at higher than prototypic temperature, varying noble metals from none to very high concentrations, and higher agitation rate. Data from simulant runs from SB6, SB7a, glycolic/formic, and the HG tests showed that a significant amount of Hg metal was found on the vessel bottom at the end of tests. Material balance closure improved from 12-71% to 48-93% when this segregated Hg was considered. The amount of Hg segregated as elemental Hg on the vessel bottom was 4-77% of the amount added. The highest recovery of mercury in the offgas system generally correlated with the highest retention of Hg in the slurry. Low retention in the slurry (high segregation on the vessel bottom) resulted in low recovery in the offgas system. High agitation rates appear to result in lower retention of mercury in the slurry. Both recovery of mercury in the offgas system and removal (segregation + recovery) from the slurry correlate with slurry consistency. Higher slurry consistency results in better retention of Hg in the slurry (less segregation) and better recovery in the offgas system, but the relationships of recovery and retention with consistency are sludge dependent. Some correlation with slurry yield stress and acid stoichiometry was also found. Better retention of mercury in the slurry results in better recovery in the offgas system because the mercury in the slurry is stripped more easily than the segregated mercury at the bottom of the vessel. Although better retention gives better recovery, the time to reach a particular slurry mercury content (wt%) is longer than if the retention is poorer because the segregation is faster. The segregation of mercury is generally a faster process than stripping. The stripping factor (mass of water evaporated per mass of mercury stripped) of mercury at the start of boiling were found to be less than 1000 compared to the assumed design basis value of 750 (the theoretical factor is 250). However, within two hours, this value increased to at least 2000 lb water per lb Hg. For runs with higher mercury recovery in the offgas system, the stripping factor remained around 2000, but runs with low recovery had stripping factors of 4000 to 40,000. DWPF data shows similar trends with the stripping factor value increasing during boiling. These high values correspond to high segregation and low retention of mercury in the sludge. The stripping factor for a pure Hg metal bead in water was found to be about 10,000 lb/lb. About 10-36% of the total Hg evaporated in a SRAT cycle was refluxed back to the SRAT during formic acid addition and boiling. Mercury is dissolved as a result of nitric acid formation from absorption of NO x . The actual solubility of dissolved mercury in the acidic condensate is about 100 times higher than the actual concentrations measured. Mercury metal present in the MWWT from previous batches could be dissolved by this acidic condensate. The test of the effect of higher SRAT condenser temperature on recovery of mercury in the MWWT and offgas system was inconclusive. The recovery at higher temperature was lower than several low temperature runs, but about the same as other runs. Factors other than temperature appear to affect the mercury recovery. The presence of chloride and iodide in simulants resulted in the formation of mercurous chloride and mercurous iodide, respectively, in the offgas system. Actual waste data shows that the chloride content is much less than the simulant concentrations. Future simulant tests should minimize the addition of chloride. Similarly, iodine addition should be eliminated unless actual waste analyses show it to be present; currently, total iodine is not measured on actual waste samples.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Graphene oxide-silica nanohybrids as fillers for PA6 based nanocomposites

Graphene oxide (GO) was prepared by oxidation of graphite flakes by a mixture of H{sub 2}SO{sub 4}/H{sub 3}PO{sub 4} and KMnO{sub 4} based on Marcano's method. Two different masterbatches containing GO (33.3%) and polyamide-6 (PA6) (66.7%) were prepared both via solvent casting in formic acid and by melt mixing in a mini-extruder (Haake). The two masterbatches were then used to prepare PA6-based nanocomposites with a content of 2% in GO. For comparison, a nanocomposite by direct mixing of PA6 and GO (2%) and PA6/graphite nanocomposites were prepared, too. The oxidation of graphite into GO was assessed by X-ray diffraction (XRD), Micro-Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) analyses. All these techniques demonstrated the effectiveness of the graphite modification, since the results put into evidence that, after the acid treatment, interlayer distance, oxygen content and defects increased. SEM micrographs carried out on the nanocomposites, showed GO layers totally surrounded by polyamide-6, this feature is likely due to the strong interaction between the hydrophilic moieties located both on GO and on PA6. On the contrary, no interactions were observed when graphite was used as filler. Mechanical characterization, carried out by tensile and dynamic-mechanical tests, marked an improvement of the mechanical properties observed. Photoluminescence and EPR measurements were carried out onto nanoparticles and nanocomposites to study the nature of the interactions and to assess the possibility to use this class of materials as semiconductors or optical sensors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2016

Quantum mechanical study of CO 2 and CO hydrogenation on Cu(111) surfaces doped with Ga, Mg, and Ti

DFT methods were used to analyze metal (M)-doped Cu(111) surfaces to identify surface alloys that could catalyze the hydrogenation of CO 2 . Here, the adsorption of relevant species for CO 2 /CO hydrogenation were studied on Cu(111) surfaces doped with Ga, Mg, and Ti. Preferred adsorption sites, geometries, and binding energies for relevant intermediates were determined. A systematic study of the thermochemistry of plausible surface reactions for CO 2 /CO hydrogenation on Ga/Cu(111), Mg/Cu(111), and Ti/Cu(111) was performed to postulate reaction mechanisms for the synthesis of formic acid, formaldehyde, and methanol. Our results suggest that Ga/Cu(111) and Mg/Cu(111) surfaces might be promising catalysts for the synthesis of methanol from CO 2 hydrogenation. CO 2 is activated by chemisorption on Mg/Cu(111) and Ti/Cu(111), but the latter surface has a strong interaction with O, which inhibits the last reaction steps and the desorption of the products. Our results demonstrate that the thermochemistry of CO 2 hydrogenation for the synthesis of the different products varies drastically depending on the dopant on Cu(111). Furthermore, our results suggest that the formation energies of HCOO, CH 2 O, CH 3 O, and HCO are good descriptors for catalyst screening.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

Structural and optical characterizations of chemically deposited cadmium selenide thin films

Highlights: {yields} CdSe thin films deposited first time using formic acid as a complexing agent. {yields} The deposited thin films were characterized by XRD, SEM, UV-vis-NIR and electrical techniques. {yields} X-ray diffraction analysis shows presence of zinc blende crystal structure. -- Abstract: Synthesis of cadmium selenide thin films by CBD method has been presented. The deposited film samples were subjected to XRD, SEM, UV-vis-NIR and TEP characterization. X-ray diffraction analysis showed that CdSe film sample crystallized in zinc blende or cubic phase structure. SEM studies reveal that the grains are spherical in shape and uniformly distributed all over the surface of the substrates. The optical band gap energy of as deposited film sample was found to be in the order of 1.8 eV. The electrical conductivity of the film sample was found to be 10{sup -6} ({Omega} cm){sup -1} with n-type of conduction mechanism.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Density functional theory studies of HCOOH decomposition on Pd(111)

Here, the investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO 2 + H 2 and dehydration to CO + H 2 O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easier than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.

36 MATERIALS SCIENCE↗

DOE OSTI2012

DISCOVERY OF THE METHOXY RADICAL, CH{sub 3}O, TOWARD B1: DUST GRAIN AND GAS-PHASE CHEMISTRY IN COLD DARK CLOUDS

We report on the discovery of the methoxy radical (CH{sub 3}O) toward the cold and dense core B1-b based on the observation, with the IRAM 30 m radio telescope, of several lines at 3 and 2 mm wavelengths. Besides this new molecular species we also report on the detection of many lines arising from methyl mercaptan (CH{sub 3}SH), formic acid (HCOOH), propynal (HCCCHO), acetaldehyde (CH{sub 3}CHO), dimethyl ether (CH{sub 3}OCH{sub 3}), methyl formate (CH{sub 3}OCOH), and the formyl radical (HCO). The column density of all these species is {approx_equal}10{sup 12} cm{sup -2}, corresponding to abundances of {approx_equal}10{sup -11}. The similarity in abundances for all these species strongly suggest that they are formed on the surface of dust grains and ejected to the gas phase through non-thermal desorption processes, most likely cosmic rays or secondary photons. Nevertheless, laboratory experiments indicate that the CH{sub 3}O isomer released to the gas phase is CH{sub 2}OH rather than the methoxy one. Possible gas-phase formation routes to CH{sub 3}O from OH and methanol are discussed.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2018

Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds

Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Synergistic Improvement of Carbohydrate and Lignin Processability by Biomimicking Biomass Processing

The sustainability and economic feasibility of modern biorefinery depend on the efficient processing of both carbohydrate and lignin fractions for value-added products. By mimicking the biomass degradation process in white-rote fungi, a tailored two-step fractionation process was developed to maximize the sugar release from switchgrass biomass and to optimize the lignin processability for bioconversion. Biomimicking biomass processing using Formic Acid: Fenton: Organosolv (F 2 O) and achieved high processability for both carbohydrate and lignin. Specifically, switchgrass pretreated by the F 2 O process had 99.6% of the theoretical yield for glucose release. The fractionated lignin was also readily processable by fermentation via Rhodococcus opacus PD630 with a lipid yield of 1.16 g/L. Scanning electron microscope analysis confirmed the fragmentation of switchgrass fiber and the cell wall deconstruction by the F 2 O process. 2D-HSQC NMR further revealed the cleavage of aryl ether linkages (β-O-4) in lignin components. These results revealed the mechanisms for efficient sugar release and lignin bioconversion. The F 2 O process demonstrated effective mimicking of natural biomass utilization system and paved a new path for improving the lignin and carbohydrate processability in next generation lignocellulosic biorefinery.

09 BIOMASS FUELS↗

DOE OSTI2012

A GAS-PHASE FORMATION ROUTE TO INTERSTELLAR TRANS-METHYL FORMATE

The abundance of methyl formate in the interstellar medium has previously been underpredicted by chemical models. Additionally, grain surface chemistry cannot account for the relative abundance of the cis- and trans-conformers of methyl formate, and the trans-conformer is not even formed at detectable abundance on these surfaces. This highlights the importance of studying formation pathways to methyl formate in the gas phase. The rate constant and branching fractions are reported for the gas-phase reaction between protonated methanol and formic acid to form protonated trans-methyl formate and water as well as adduct ion: Rate constants were experimentally determined using a flowing afterglow-selected ion flow tube apparatus at 300 K and a pressure of 530 mTorr helium. The results indicate a moderate overall rate constant of (3.19 {+-} 0.39) Multiplication-Sign 10{sup -10} cm{sup 3} s{sup -1} ({+-} 1{sigma}) and an average branching fraction of 0.05 {+-} 0.04 for protonated trans-methyl formate and 0.95 {+-} 0.04 for the adduct ion. These experimental results are reinforced by ab initio calculations at the MP2(full)/aug-cc-pVTZ level of theory to examine the reaction coordinate and complement previous density functional theory calculations. This study underscores the need for continued observational studies of trans-methyl formate and for the exploration of other gas-phase formation routes to complex organic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗