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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt 3 Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt 3 Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relative to Pt/C and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Selective bond-breaking in formic acid by dissociative electron attachment

We report the results of a joint experimental and theoretical study of dissociative electron attachment to formic acid (HCOOH) in the 6–9 eV region, where H- fragment ions are a dominant product. Breaking of the C–H and O–H bonds is distinguished experimentally by deuteration of either site. We show that in this region H- ions can be produced by formation of two or possibly three Feshbach resonance (doubly-excited anion) states, one of which leads to either C–H or O–H bond scission, while the other can only produce formyloxyl radicals by O–H bond scission. Comparison of experimental and theoretical angular distributions of the anion fragment allows the elucidation of state specific pathways to dissociation.

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

Reactivity of Silanes with ( tBu PONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition

The coordination of tBu PONOP ( tBu PONOP=2,6-bis(ditert-butylphosphinito)pyridine) to different ruthenium starting materials, to generate ( tBu PONOP)RuCl 2 , was investigated in this paper. The resultant ( tBu PONOP)RuCl 2 reactivity with three different silanes was then investigated and contrasted dramatically with the reactivity of ( iPr PONOP)RuCl 2 (DMSO) ( iPr PONOP=2,6-bis(diisopropylphosphinito)pyridine) with the same silanes. The 16-electron species ( tBu PONOP)Ru(H)Cl was produced from the reaction of triethylsilane with ( tBu PONOP)RuCl 2 . Reactions of ( tBu PONOP)RuCl 2 with both phenylsilane or diphenylsilane afforded the 16-electron hydrido-silyl species ( tBu PONOP)Ru(H)(PhSiCl 2 ) and ( tBu PONOP)Ru(H)(Ph 2 SiCl), respectively. Reactions of all three of these complexes with silver triflate afforded the simple salt metathesis products of ( tBu PONOP)Ru(H)(OTf), ( tBu PONOP)Ru(H)(PhSiCl(OTf)), and ( tBu PONOP)Ru(H)(Ph 2 Si(OTf)). Formic acid dehydrogenation was performed in the presence of triethylamine (TEA), and each species proved competent for gas-pressure generation of CO 2 and H 2 . Finally, the hydride species ( tBu PONOP)Ru(H)Cl, ( tBu PONOP)Ru(H)(OTf), and ( tBu PONOP)Ru(H)(PhSiCl 2 ) exhibited faster catalytic activity than the other compounds tested.

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

Microfluidic, One-Batch Synthesis of Pd Nanocrystals on N-Doped Carbon in Surfactant-Free Deep Eutectic Solvents for Formic Acid Electrochemical Oxidation

One of the grand challenges that impedes practical applications of nanomaterials is the lack of robust manufacturing methods that are scalable, cheap, and environmentally friendly. In this work, we address this challenge by developing a microfluidic approach that produces surfactant-free Pd nanocrystals (NCs) uniformly loaded on N-doped porous carbon in a one-batch process. The deep eutectic solvent (DES) prepared from choline chloride and ethylene glycol was employed as a novel synthesis solvent, and its extended hydrogen networks and abundant ionic species effectively stabilize Pd facets and confine nanocrystal sizes without using surfactants. The microreactors provide faster heat exchange and more uniform mass transport, which in combination with DES produced Pd NCs with better-defined shape and predominately exposed Pd (100) facet. Furthermore, we describe that the N-doped functional groups in porous carbon direct dense and uniform heterogeneous growth of Pd NCs in a one-batch process, thereby eliminating a separate catalyst deposition step that is often involved in conventional synthesis. The Pd NCs in the one-batch-produced Pd/C catalysts exhibited a size distribution of similar to ~13 ± 3.5 nm and a high ESCA of 46.0 m 2 /g and delivered 362 mA/mg for formic acid electrochemical oxidation with improved stability, demonstrating the unique potentials of microfluidic reactors and DES for the controllable and scalable synthesis of electrocatalyst materials for practical applications.

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

Choline chloride-formic acid mixture as a medium for the reduction of pertechnetates – electrochemical and spectroscopic studies

In this work, physicochemical properties of the choline chloride (ChCl) and formic acid (FA) mixture (1:2 molar ratio) have been studied over a broad range of temperatures (-140°C – 60 °C). Differential scanning calorimetry has shown that the examined system remains in liquid state at very low temperatures - a glass transition is observed in the range of -125 °C to - 90 °C. The kinematic viscosity, ionic conductivity and the width of the electrochemical window determined for this system revealed its beneficial electrochemical properties. This indicates suitability of ChCl:FA electrolytes in electrochemical measurements. In this non-aqueous electrolyte, the electrochemical reduction of Tc(VII) ions has been studied for the first time. Cyclic voltammetry and chronopotentiometry experiments revealed that the electroreduction of the pertechnetates is a multi-path process which leads to formation of a Tc(IV) ionic form. X-ray absorption spectroscopy of the latter revealed its structure as a TcCl 6 2- complex.

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

Immobilization of highly active bimetallic PdAu nanoparticles onto nanocarbons for dehydrogenation of formic acid

Highly active bimetallic PdAu nanoparticles (NPs) supported on commercial nanocarbons have been prepared through a simple Larginine- mediated synthetic approach. The as-synthesized catalysts have been used for the dehydrogenation of formic acid (FA). Remarkably, the resultant Pd1Au1 NPs immobilized onto MSC-30 carbon achieved a turnover frequency (TOF) value of 8355 h1 at 60 C in aqueous FA solution without addition of sodium formate, much higher than the results of heterogeneous catalysts reported thus far. The simple small-molecule-mediated synthetic methodology developed herein opens a new path for the practical and large-scale development of high-performance catalysts for a wide range of applications.

Hong, Wei↗
DOE OSTI2016

Direction to practical production of hydrogen by formic acid dehydrogenation with Cp*Ir complexes bearing imidazoline ligands

In a Cp*Ir complex with a bidentate pyridyl-imidazoline ligand achieved the evolution of 1.02 m 3 of H 2 /CO 2 gases by formic acid dehydrogenation without any additives or adjustments in the solution system. Furthermore, the pyridyl-imidazoline moieties provided the optimum pH to be 1.7, resulting in high activity and stability even at very acidic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2006

Theoretical Modeling of Formic Acid (HCOOH), Formate (HCOO(-)), and Ammonia (NH(4)) Vibrational Spectra in Astrophysical Ices

Ions embedded in icy grain mantles are thought to account for various observed infrared spectroscopic features, particularly in certain young stellar objects. The dissociation of formic acid (HCOOH) in astrophysical ices to form the formate ion (HCOO(-)) was modeled with density functional theory cluster calculations. Like isocyanic acid (HOCN), HCOOH was found to spontaneously deprotonate when sufficient water is present to stabilize charge transfer complexes. Both ammonia and water can serve as proton acceptors, yielding ammonium (NH4(+)) and hydronium (H3O(+)) counterions. Computed frequencies of weak infrared features produced by stretching and bending modes in both HCOO(-) and HCOOH were compared with experimental and astronomical data. Our results confirm laboratory assignments that a band at 1381 cm(exp -1) can be attributed to the CH bend in either HCOO(-) or HCOOH, but a band at 1349 cm(exp -1) corresponds to CO stretching in HCOO(-). Another feature at 1710 cm(exp -1) (5.85 m) can possibly be assigned to a CO stretching mode in HCOOH, as suggested by experiment, but the agreement is less satisfactory. In addition, we examine and analyze spectroscopic features associated with NH+4, both as a counterion to HCOO(-) or OCN(-) and in isolation, in order to compare with experimental and astronomical data in the 7 m region.

Park, Jin-Young↗
DOE OSTI2021

Hydrogen Bonds and H 3 O + Formation at the Water Interface with Formic Acid Covered Anatase TiO 2

Carboxylic acid-modified TiO 2 surfaces in aqueous environment are of widespread interest, yet atomic-scale understanding of their structure is limited. In this work, we investigate formic acid (FA) on anatase TiO 2 (101) (A-101) in contact with water using density functional theory (DFT) and ab-initio molecular dynamics (AIMD). Isolated FA molecules adsorbed in a deprotonated bridging bidentate (BD) form on A-101 are found to remain stable at the interface with water, with the acid proton transferred to a surface oxygen to form a surface bridging hydroxyl (O br H). With increasing FA coverage, adsorbed monolayers of only BD and successively of alternating monodentate (MD) and BD species give rise to a higher concentration of surface O br H’s. Simulations of these adsorbed monolayers in water environment show that some protons are released from the surface O br H’s to water resulting in a negatively charged surface with nearby solvated H 3 O + ions. These results provide insight into the complex acid-base equilibrium between an oxide surface, adsorbates and water and can also help obtain a better understanding of the wetting properties of chemically modified TiO 2 surfaces.

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

Enrichment of H2 to CO2 ratio using formic acid as a hydrogen carrier - CRADA 581 (Abstract)

The collaboration between PNNL and OCOchem will investigate approaches to enhance the hydrogen (H2) content from a stream of H2 and carbon dioxide (CO2) gases produced in the catalytic decomposition of aqueous formic acid (FA85). OCOchem uses an electrochemical process to generate FA85 from captured CO2 using electricity from renewable resources. The FA85 is a liquid organic hydrogen carrier (LOHC) that provides the opportunity to transport and store hydrogen, in liquid form, at volumetric densities significantly greater than compressed H2 gas, i.e., 50 grams H2/liter FA. PNNL has developed and tested catalytic reactors to release H2 from LOHCs like FA and aqueous formate salts (FS). The H2 released from the LOHC can be oxidized in a proton-exchange membrane fuel cell (PEM-FC) to generate electricity with water as the only by-product. The purpose of the proposed project is to increase the purity of the hydrogen released from the LOHC to enhance the operation efficiency of the PEM FC. The PEM FC in combination with the LOHC provides an approach to demonstrate a portable generator that utilizes hydrogen as the energy carrier instead of conventional diesel generator. The ‘hydrogen generator’ can be used to supply emergency backup power and significantly reduce CO2 emissions relative to a diesel generator.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS1986

Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate

The chemistry of OH in nonprecipitating tropospheric clouds was studied using a coupled gas phase/aqueous phase chemical model. The simulation takes into account the radial dependence of the concentrations of short lived aqueous phase species, in particular, O3(aq) OH(aq). Formic acid is shown to be rapidly produced by the aqueous phase reaction between H2C(OH)2 and OH, but HCOO(-) and OH, but HCOO(-) is in turn rapidly oxidized by OH(aq). The HCOOH concentration in cloud is shown to be strongly dependent on the pH of the cloud water; clouds with pH greater than 5 are not efficient HCOOH sources. A novel mechanism is proposed for the oxidation of S(IV) by OH(aq), with the main product predicted to be peroxymonosulfate, HSO5(-). The latter could contribute significantly to total cloud water sulfur.

Jacob, D. J.↗
DOE OSTI2020

Additive-Free Formic Acid Dehydrogenation Using a Pincer- Supported Iron Catalyst

The iron complex ( iPr PN Me P)Fe(H) 2 (CO) ( iPr PN Me P = CH 3 N(CH 2 CH 2 P i Pr 2 ) 2 ), which features a pincer ligand with a tertiary amine, can give up to 100,000 turnovers for additive-free formic acid dehydrogenation (FADH). This is two orders of magnitude higher than any previously reported base metal system. Furthermore, mechanistic studies reveal the catalytic reaction pathway and provide guidance for the development of improved catalytic systems for additive-free FADH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

A search for formic acid in the upper troposphere - A tentative identification of the 1105-per cm nu-6 band Q branch in high-resolution balloon-borne solar absorption spectra

Infrared solar absorption spectra recorded at 0.02-per cm resolution during a balloon flight from Alamogordo, NM (33 deg N), on March 23, 1981, have been analyzed for the possible presence of absorption by formic acid (HCOOH). An absorption feature at 1105 per cm has been tentatively identified in upper tropospheric spectra as due to the nu-6 band Q branch. A preliminary analysis indicates a concentration of about 0.6 ppbv and 0.4 ppbv near 8 and 10 km, respectively.

Goldman, A.↗
NASA NTRS1984

A Search for Formic Acid in the Upper Troposphere: A Tentative Identification of the 1105-cm(exp -1) nu(sub 6) Band Q Branch in High-Resolution Balloon-Borne Solar Absorption Spectra

Infrared solar absorption spectra recorded at 0.02/cm resolution during a balloon flight from Alamogordo, N.M. (33 deg N), on March 23, 1981, have been analyzed for the possible presence of absorption by formic acid (HCOOH). An absorption feature at 1105/ cm has been tentatively identified in upper tropospheric spectra as due to the nu(sub 6) band Q branch. A preliminary analysis indicates a concentration of approx. = 0.6 ppbv and approx. = 0.4 ppbv near 8 and 10 km, respectively.

Goldman, A.↗
DOE OSTI2020

CO 2 Hydrogenation and Formic Acid Dehydrogenation Using Ir Catalysts with Amide-Based Ligands

In this work, a series of Ir catalysts bearing amide-based ligands generated by a deprotonated amide moiety was prepared with the hypotheses that the strong electron-donating ability of the coordinated anionic nitrogen atom and the proton-responsive OH group near the metal center will improve the catalytic activity for CO 2 hydrogenation and formic acid (FA) dehydrogenation. The effects of the modifications of the ligand architecture on the catalytic activity were investigated for CO 2 hydrogenation at ambient conditions (25 °C with 0.1 MPa H 2 /CO 2 (v/v = 1/1)) and under slightly harsher conditions (50 °C with 1.0 MPa H 2 /CO 2 ) in basic aqueous solutions together with deuterium kinetic isotope effects (KIEs) with selected catalysts. Cp*Ir( L12 )(H 2 O)HSO 4 ( L12 = 6-hydroxy- N -phenylpicolinamidate) that has an anionic coordinating N atom and an OH group in the second coordination sphere, exhibits a turnover frequency (TOF) of 198 h –1 based on the initial 1 h of reaction. This TOF which, to the best of our knowledge, is the highest value ever reported under ambient conditions in basic aqueous solutions. However, Cp*Ir( L10 )(H 2 O)HSO 4 ( L10 = (4-hydroxy- N -methylpicolinamidate) performs better in long-term CO 2 hydrogenation (up to a TON of 14 700 with [Ir] = 10 μM after 348 h and the final formate concentration of 0.643 M with [Ir] = 250 μM) at ambient conditions. Further, the catalytic activity for FA dehydrogenation was examined under three different conditions (pH 1.6, 2.3, and 3.5). The Cp*Ir( L12 )(H 2 O)HSO 4 complex in any of these conditions is less active compared to the picolinamidate catalysts without ortho -OH, owing to its instability. The complex without OH group, Cp*Ir( L8 )(H 2 O)HSO 4 ( L8 = N -phenyl-picolinamidate), exhibits a high TOF (up to 118 000 h -1 ) at 60 °C. Theoretical calculations were performed to examine the catalytic mechanism, and a step-by-step mechanism has been proposed for both CO 2 hydrogenation and FA dehydrogenation reactions. Density functional theory calculations of [Cp*Ir( L3 )(H 2 O)]HSO 4 ( L3 = picolinamidate) and the X-ray structure of the [Cp*Ir( L7 )(H)]·H 2 O ( L7 = N -methylpicolinamidate) complex imply a pH-dependent conformational change from N , N coordination to N , O coordination upon lowering the pH of the aqueous solution.

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

Solution-Phase Synthesis of PdH 0.706 Nanocubes with Enhanced Stability and Activity toward Formic Acid Oxidation

We report palladium is one of the few metals capable of forming hydrides, with the catalytic properties being dependent on the elemental composition and spatial distribution of H atoms in the lattice. Herein, we report a facile method for the complete transformation of Pd nanocubes into a stable phase made of PdH 0.706 by treating them with aqueous hydrazine at a concentration as low as 9.2 mM. Using formic acid oxidation (FAO) as a model reaction, we systematically investigated the structure–catalytic property relationship of the resultant nanocubes with different degrees of hydride formation. The current density at 0.4 V was enhanced by four times when the nanocubes were completely converted from Pd to PdH 0.706 . On the basis of a set of slab models with PdH(100) overlayers on Pd(100), we conducted density functional theory calculations to demonstrate that the degree of hybrid formation could influence both the activity and selectivity toward FAO by modulating the relative stability of formate (HCOO) and carboxyl (COOH) intermediates. Furthermore, this work provides a viable strategy for augmenting the performance of Pd-based catalysts toward various reactions without altering the loading of this scarce metal.

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

Photoionization energetics and dissociation pathways of hydroperoxyethyl formate produced in the reaction of CH 3 CHOO + formic acid

The bimolecular reaction of Criegee intermediates, zwitterionic carbonyl oxide species produced in alkene ozonolysis, with organic acids leads to formation of functional hydroperoxides implicated in the generation of atmospheric aerosols. This theoretical study using high-level explicitly correlated coupled-cluster theory examines the low energy conformers of hydroperoxyethyl formate [HOOCH(CH 3 )OCHO, HPEF] formed in the bimolecular reaction of CH 3 CHOO, a simple alkyl-substituted Criegee intermediate, with formic acid, and the detection of HPEF via photoionization. Here, the vertical and adiabatic ionization energies of HPEF are computed, along with the pathways for dissociative ionization that produce HO 2 or OCHO fragments with daughter ions.

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

Etch Products of Copper Atomic Layer Etching by Oxidation and Formic Acid Vapor

Atomic layer etching (ALE) of metals offers a path to greater control of selectivity, etch rate, and etch profile. However, tailoring a process to meet these demands requires an understanding of the volatile etch product, which is challenging to detect due to low product concentrations and the paramagnetism of many metalorganic products. Here, in this work, several complementary analysis techniques were used to determine the volatile etch product and residual surface species of a Cu ALE process based on plasma oxidation and formic acid vapor etching of the oxidized layer. It was shown that the volatile product was copper formate with a Cu 2+ paramagnetic center, in concordance with prior density functional theory (DFT) calculations. While copper formate tetrahydrate was formed, it was determined that the tetrahydrate product was confined to the surface, with anhydrous copper formate being the volatile etch product.

Smith, Taylor G. [Univ. of California, Los Angeles↗