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All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Titan's Aerosol and Condensation Cloud Properties in the Far-IR Between 2005 and 2010

Analyses of far-IR spectra between 20 and 560 cm(exp -1) (500 to 18 micron) recorded by the Cassini Composite Infrared Spectrometer (CIRS) yield the spectral dependence and the vertical distribution of Titan's photochemical aerosol and ice clouds. Titan's aerosol appears to be well mixed between the surface and an altitude of 300 km, with a spectral shape that does not change with latitude or time. The aerosol exhibits an extremely broad emission feature with a spectral peak at 140 cm(exp -1) (71 micron), which is not evident in laboratory simulated Titan aerosols (tholin). This low- energy aerosol emission feature may arise from low-energy molecules such as polycyclic aromatic hydrocarbons and/or nitrogenated aromatics. Unlike the vertically well-mixed aerosol, Titan's condensate clouds are located in highly restricted altitudes in the lower stratosphere, ranging between 60 and 100 km at low and moderate latitudes, to between 150 and 165 km at high northern latitudes during northern winter. Such clouds are located at altitudes where nitrile vapors are expected to condense and appear to be dominated by HCN and HC3N, which are the two most abundant nitriles in Titan's atmosphere. Associated with this ice cloud is a broad emission feature that spectrally peaks near 160 cm(exp -1) (62.5 micron). This ice composite appears to chemically change with altitude and latitude, probably as a result of differences in vapor abundance and condensation temperature, and the ice cloud appears to be global in extent. Both CIRS and the Huygens Descent Imager and Spectral Radiometer (DISR) show evidence of cloud layering in Titan's lower stratosphere. The 15 km difference in cloud altitude indicated by the two instruments suggests a difference in ice composition. CIRS also indicates a second ice cloud that exists at isolated latitudes and is consistent with hydrocarbon condensation above the tropopause. This cloud exhibits an emission feature that spectrally peaks near 80 cm(exp -1) (125 micron), possibly due to C2H6 ice or dominated by an ethane-acetylene composite ice, given that CzH6 then C2H2 are the two most abundant hydrocarbons next to methane in Titan's atmosphere.

Anderson, Carrie↗
NASA NTRS2011

Titan's Aerosol and Stratospheric Ice Opacities Between 18 and 500 Micrometers: Vertical and Spectral Characteristics from Cassini CIRS

Vertical distributions and spectral characteristics of Titan's photochemical aerosol and stratospheric ices are determined between 20 and 560 per centimeter (500-18 micrometers) from the Cassini Composite Infrared Spectrometer (CIRS). Results are obtained for latitudes of 15 N, 15 S, and 58 S, where accurate temperature profiles can be independently determined. In addition, estimates of aerosol and ice abundances at 62 N relative to those at 15 S are derived. Aerosol abundances are comparable at the two latitudes, but stratospheric ices are approximately 3 times more abundant at 62 N than at 15 S. Generally, nitrile ice clouds (probably HCN and HC3N), as inferred from a composite emission feature at approximately 160 per centimeter, appear to be located over a narrow altitude range in the stratosphere centered at approximately 90 km. Although most abundant at high northern latitudes, these nitrile ice clouds extend down through low latitudes and into mid southern latitudes, at least as far as 58 S. There is some evidence of a second ice cloud layer at approximately 60 km altitude at 58 S associated with an emission feature at approximately 80 per centimeter. We speculate that the identify of this cloud may be due to C2H6 ice, which in the vapor phase is the most abundant hydrocarbon (next to CH4) in the stratosphere of Titan. Unlike the highly restricted range of altitudes (50-100 km) associated with organic condensate clouds, Titan's photochemical aerosol appears to be well-mixed from the surface to the top of the stratosphere near an altitude of 300 km, and the spectral shape does not appear to change between 15 N and 58 S latitude. The ratio of aerosol-to-gas scale heights range from 1.3-2.4 at about 160 km to 1.1-1.4 at 300 km, although there is considerable variability with latitude, The aerosol exhibits a very broad emission feature peaking at approximately 140 per centimeter. Due to its extreme breadth and low wavenumber, we speculate that this feature may be caused by low-energy vibrations of two-dimensional lattice structures of large molecules. Examples of such molecules include polycyclic aromatic hydrocarbons (PAHs) and nitrogenated aromatics. Finally, volume extinction coefficients N chi EPSILON derived from 15 S CIRS data at a wavelength of lambda = 62.5 micrometers are compared with those derived from the 10 S Huygens Descent Imager/Spectral Radiometer (DISR) data at 1.583 micrometers. This comparison yields volume extinction coefficient ratios N chi EPSILON (1.583 micrometers)/N chi EPSILON (62.5 micrometers) of roughly 70 and 20, respectively, for Titan's aerosol and stratospheric ices, The inferred particle cross-section ratios chi EPSILON(1.583 micrometers)/chi EPSILON (62.5 micrometers) appear to be consistent with sub-micron size aerosol particles, and effective radii of only a few microns for stratospheric ice cloud particles.

Anderson, Carrie M.↗
NASA NTRS2005

Corrosion-Prevention Capabilities of a Water-Borne, Silicone-Based, Primerless Coating

Comparative tests have been performed to evaluate the corrosion-prevention capabilities of an experimental paint of the type described in Water-Borne, Silicone-Based, Primerless Paints, NASA Tech Briefs, Vol. 26, No. 11 (November 2002), page 30. To recapitulate: these paints contain relatively small amounts of volatile organic solvents and were developed as substitutes for traditional anticorrosion paints that contain large amounts of such solvents. An additional desirable feature of these paints is that they can be applied without need for prior application of primers to ensure adhesion. The test specimens included panels of cold-rolled steel, stainless steel 316, and aluminum 2024-T3. Some panels of each of these alloys were left bare and some were coated with the experimental water-borne, silicone-based, primerless paint. In addition, some panels of aluminum 2024-T3 and some panels of a fourth alloy (stainless steel 304) were coated with a commercial solvent-borne paint containing aluminum and zinc flakes in a nitrile rubber matrix. In the tests, the specimens were immersed in an aerated 3.5-weight-percent aqueous solution of NaCl for 168 hours. At intervals of 24 hours, the specimens were characterized by electrochemical impedance spectroscopy (EIS) and measurements of corrosion potentials. The specimens were also observed visually. As indicated by photographs of specimens taken after the 168-hour immersion (see figure), the experimental primerless silicone paint was effective in preventing corrosion of stainless steel 316, but failed to protect aluminum 2024-T3 and cold-rolled steel. The degree of failure was greater in the case of the cold-rolled steel. On the basis of visual observations, EIS, and corrosion- potential measurements, it was concluded that the commercial aluminum and zinc-filled nitrile rubber coating affords superior corrosion protection to aluminum 2024-T3 and is somewhat less effective in protecting stainless steel 304.

Calle, Luz Marina↗
NASA NTRS2012

Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗
NASA NTRS2012

Isotopic Anomalies in Primitive Solar System Matter: Spin-State Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15, This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar core. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotop c enrichments measured in carbonaceous meteorites, However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores, We also show that while the nitriles, HCN and HNC, contain the greatest N-15 enrichment, this is not expected to correlate with extreme D emichment. These calculations therefore support the view that Solar System N-15 and D isotopic anomalies have an interstellar heritage, We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗
NASA NTRS2018

Observations of Organic Chemistry on Titan

Titan is the largest moon of Saturn, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Atmospheric photochemistry results in the production of a wide range of complex organic molecules, including hydrocarbons, nitriles, aromatics and species of possible pre-biotic relevance. Studies of Titan's atmospheric chemistry thus provide a unique opportunity to explore the origin and evolution of complex organic matter in a primitive (terrestrial) planetary atmosphere. Underpinned by laboratory measurements, remote and in-situ observations of hydrocarbons, nitriles and oxygen-bearing species provide important new insights in this regard. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new facility, well suited to the study of molecular emission from Titan's upper and middle-atmosphere. This presentation will focus on detection and mapping of rotational emission lines from molecules including HNC, CO, HC3N, CH3CN, C2H3CN and C2H5CN, as well minor isotopologues. Possible chemical formation pathways for these species will be discussed, and the scope for improved understanding of non-aqueous organic chemistry through laboratory experiments and atmospheric/liquid-phase simulations under Titan-like conditions will be examined [5].

Charnley, Steven B.↗
NASA NTRS2014

X-Ray Absorption near Edge Structure Spectroscopic Study of Hayabusa Category 3 Carbonaceous Particles

Analyses with a scanning transmission x-ray microscope (STXM) using x-ray absorption near edge structure (XANES) spectroscopy were applied for the molecular characterization of two kinds of carbonaceous particles of unknown origin, termed category 3, which were collected from the Hayabusa spacecraft sample catcher. Carbon-XANES spectra of the category 3 particles displayed typical spectral patterns of heterogeneous organic macromolecules; peaks corresponding to aromatic/olefinic carbon, heterocyclic nitrogen and/or nitrile, and carboxyl carbon were all detected. Nitrogen-XANES spectra of the particles showed the presence of N-functional groups such as imine, nitrile, aromatic nitrogen, amide, pyrrole, and amine. An oxygen-XANES spectrum of one of the particles showed a ketone group. Differences in carbon- and nitrogen-XANES spectra of the category 3 particles before and after transmission electron microscopic (TEM) observations were observed, which demonstrates that the carbonaceous materials are electron beam sensitive. Calcium-XANES spectroscopy and elemental contrast mapping identified a calcium carbonate grain from one of the category 3 particles. No fluorine-containing molecular species were detected in fluorine-XANES spectra of the particles. The organic macromolecular features of the category 3 particles were distinct from commercial and/or biological ‘fresh (non-degraded)’ polymers, but the category 3 molecular features could possibly reflect degradation of contaminant polymer materials or polymer materials used on the Hayabusa spacecraft. However, an extraterrestrial origin for these materials cannot currently be ruled out.

Asteroides↗
NASA NTRS2018

Detection Opportunity for Aromatic Signature in Titan's Aerosols in the 4.1-5.3 μm Range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100's of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In this Letter we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan's aerosol analogs. We introduce initial gas mixtures of (i) N2–C5H5N (100%/250 ppm), (ii) N2–CH4–C5H5N (99%/1%/250 ppm), and (iii) N2–CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1–5.3 μm (1850–2450 cm−1) spectral region, attributed to overtones of aromatic C–H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/Visual and Infrared Mapping Spectrometer (VIMS) instrument in the 1–5 μm infrared window.

Mathé, Christophe↗
NASA NTRS2022

The Titan Haze Simulation (THS) Experiment on COSmIC. Part III. XANES Study of Laboratory Analogs of Titan Tholins

We have used the Titan Haze Simulation (THS) experimental set-up at NASA Ames’ COSmIC 19 facility to produce four laboratory analogs of Titan’s aerosols, or tholins. These tholin samples 20 were produced from four gas mixtures, representative of Titan’s atmosphere, of initial 21 compositions N2:CH4 (90:10 and 95:5) and N2:CH4:C2H2 (89.5:10:0.5 and 94.5:5:0.5) at 150 K, 22 using a plasma discharge in the stream of a jet-cooled gas expansion. Here we present an ex-situ 23 X-ray absorption near-edge structure (XANES) spectroscopy analysis of these four tholin 24 samples. The C- and N-XANES spectra show the presence of various functional groups 25 (aromatic carbon, imines, nitriles, etc.) whose abundances are correlated with (i) the relative 26 proportions between N2 and CH4, and (ii) the presence or absence of C2H2 in the initial mixtures. 27 In particular, mixtures containing C2H2 result in the formation of tholins consisting of more 28 aromatic structures and displaying larger relative amounts of imines and nitriles, but lower 29 overall nitrogen content. XANES spectroscopy also allowed for the determination of the 30 elemental C/N ratios for the four tholins, which were all found to be low (< 2.5) and consistent 31 with those measured for tholins produced in other, independent experimental set-ups. The C/N 32 ratios of tholins produced from gas mixtures that contained C2H2 (2.2–2.4) were found to be 33 about twice as large as those of tholins produced from gas mixtures that did not contain C2H234 (0.9–1.3). These new experimental results from the COSmIC/THS experiment demonstrate the 35 impact initial precursors have on the nitrogen chemistry during the formation of tholins, which 36 may help in the interpretation of observations and the development of models of Titan’s 37 atmosphere.

Titan↗
DOE OSTI2025

Preliminary Kinetic Analysis of Non-Equilibrium Plasma- Assisted Methanol Pyrolysis and Oxidation Experiments

Efforts to enhance power generation efficiency and reduce emissions have driven interest in novel combustion techniques, including non-equilibrium plasma (NEP) ignitors. NEP ignitors show promise in improving energy conversion efficiency, fuel reforming, emission control, and lean-flammability limits. However, their adoption is hindered by a limited understanding of the interplay between plasma-enhanced combustion and thermal chemistry, particularly for complex fuels under engine-relevant conditions. Developing experimentally validated kinetic mechanisms is therefore critical. Additionally, the increasing interest in renewable biofuels like ethanol and methanol, coupled with the desirable qualities of NEP ignitors, presents a compelling opportunity for study. Therefore, this work acts as an extension of a previous work (Bopaiah et al., 2023) pertaining to the experimental results of NEP-assisted methanol pyrolysis and oxidation. Experiments were performed with a custom-built plasma flow reactor at 0.5 atm and temperatures from 523-1203 K. All reactive mixtures are extremely diluted to minimize exothermicity due to reactivity, allowing isothermal assumptions and the isolation of plasma chemistry from thermal chemistry. A dielectric barrier discharge plasma, at 14 kV and 15 ns full-width half maximum, was applied to the reactive mixture at varying frequencies to maintain the number of pulses with increasing temperature. Steady-state product speciation was performed downstream of the reactor with ex-situ GC/MS diagnostics. The attained experimental results were examined through in-depth analysis performed by means of an in-development plasma-coupled kinetic mechanism. As discussed in the previous work, the plasma significantly accelerates methanol pyrolysis, increasing stable intermediate production, including oxygenated and nitrile species. Plasma-assisted oxidation shows even faster fuel consumption compared to pyrolysis and a 200 K ignition shift compared to thermal oxidation. For plasma-assisted pyrolysis, the model demonstrates that accelerated fuel consumption stems from dissociative quenching of excited N2 states with fuel and H2, generating H radicals that react to rapidly form CH3 and CH2OH radicals. At low temperatures, these radicals recombine to produce oxygenates, while CH3 drives nitrile and hydrocarbon formation at higher temperatures. While the model captures pyrolysis trends well, discrepancies in methane, ethylene, and ethanol predictions are present. Similarly, the model faces challenges in accurately representing plasma-assisted oxidation, predicting a much steeper fuel gradient and ignition 100 K earlier than the experiment. While a similar scheme to pyrolysis is nested in the reaction pathway, the enhancement of the O and H radical fluxes and their initiation of the OH and HO2 radical pools dominate fuel and intermediate oxidation. The overestimation of these processes is shown to be responsible for the divergence of model from experiment. While the modelling predictions of this preliminary mechanism are not perfect, they serve as a valuable starting point. Primarily, they elicited new reaction pathways that are not otherwise possible in thermal chemistry induced reaction kinetics. The results also provide a basis for the future work that should be performed. For example, theoretical and experimental studies on excited nitrogen species and fuel/fuel radical interactions, quantification of the NOx production, and the kinetics behind the slow ignition observed in oxidation should be emphasized.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Sustainable Shape Memory Elastomers with Reduced Melt Viscosity and Enhanced Stiffness

Melt reactive processing of lignin with nitrile rubber is a promising approach to synthesizing shape memory materials. The strong intramolecular interactions in lignin macromolecular structures, caused by π–π stacking in aromatic rings and hydrogen bonding, often result in large phase separation or low miscibility with rubbers. In this study, we investigated the chemical and molecular characteristics, as well as the stiffness and complex viscosity, of modified kraft lignin melt-reacted with an acrylonitrile/butadiene copolymer containing 41% acrylonitrile (NBR41). To enhance the macromolecular compatibility of kraft lignin with NBR41, kraft lignin was cross-linked with poly(propylene glycol) diglycidyl ether (PPDE) and trimethylolpropane triglycidyl ether (TTE), both rich in epoxy reactive groups capable of forming chemical bonds with hydroxyl and carboxyl groups. Here, our findings demonstrate that the modification of kraft lignin with PPDE and TTE resulted in significantly increased stiffness of the composites. The elastic modulus of NBR41-Kraft lignin-PPDE and NBR41-Kraft lignin-TTE increased by 82 and 162%, respectively. Both the yield strength and Young’s modulus of these two samples showed dramatic improvements. Specifically, the yield strength and Young’s modulus of NBR41-Kraft lignin-TTE increased nearly 4 and 3-fold, respectively, compared to the control sample. Interestingly, despite significant improvements in mechanical properties, the viscosity of NBR41-Kraft lignin-PPDE was substantially lower than that of the control sample. At 210 °C and an angular frequency of 1 rad/s, the complex viscosity of NBR41-Kraft lignin was approximately 100.25 ± 4.77 kPa·s, while that of NBR41-Kraft lignin-PPDE was significantly lower at 56 ± 0.93 kPa·s. These findings were validated through Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic mechanical analysis, thermal characterization, rheological tests, and quasi-elastic neutron scattering techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Intensive Titan exploration begins

The Cassini Orbiter spacecraft first skimmed through the tenuous upper atmosphere of Titan on 26 October 2004. This moon of Saturn is unique in our solar system, with a dense nitrogen atmosphere that is cold enough in places to rain methane, the feedstock for the atmospheric chemistry that produces hydrocarbons, nitrile compounds, and Titan's orange haze. The data returned from this flyby supply new information on the magnetic field and plasma environment around Titan, expose new facets of the dynamics and chemistry of Titan's atmosphere, and provide the first glimpses of what appears to be a complex, fluid-processed, geologically young Titan surface.

Spacecraft↗
DOE OSTI2020

In Situ Construction of Uniform and Robust Cathode–Electrolyte Interphase for Li-Rich Layered Oxides

The high-energy-density Li-rich layered oxides (LLOs) as promising cathodes for Li-ion batteries suffer from the dissolution of transition metals (especially manganese) and severe side reactions in conventional electrolytes, which greatly deteriorate their electrochemical performance. Herein, an in situ “anchoring + pouring” synergistic cathode-electrolyte interphase (CEI) construction is realized by using 1,3,6-hexanetricarbonitrile (HTCN) and tris(trimethylsilyl) phosphate (TMSP) electrolyte additives to alleviate the challenges of an LLO (Li 1.13 Mn 0.517 Ni 0.256 Co 0.097 O 2 ). HTCN with three nitrile groups can tightly anchor transition metals by coordinative interaction to form the CEI framework, and TMSP will electrochemically decompose to reshape the CEI layer. The uniform and robust in situ constructed CEI layer can suppress the transition metal dissolution, shield the cathode against diverse side reactions, and significantly improve the overall electrochemical performance of the cathode with a discharge voltage decay of only 0.5 mV/cycle -1 . Further investigations based on a series of experimental techniques and theoretical calculations have revealed the composition of in situ constructed CEI layers and their distribution, including the enhanced HTCN anchoring effect after lattice densification of LLOs. Finally, this study provides insights into the in situ CEI construction for enhancing the performance of high-energy and high-voltage cathode materials through effective, convenient and economical electrolyte approaches.

25 ENERGY STORAGE↗
DOE OSTI2024

Actuating Liquid Crystals Rapidly and Reversibly by Using Chemical Catalysis

Abstract Microtubules and catalytic motor proteins underlie the microscale actuation of living materials, and they have been used in reconstituted systems to harness chemical energy to drive new states of organization of soft matter (e.g., liquid crystals (LCs)). Such materials, however, are fragile and challenging to translate to technological contexts. Rapid (sub‐second) and reversible changes in the orientations of LCs at room temperature using reactions between gaseous hydrogen and oxygen that are catalyzed by Pd/Au surfaces are reported. Surface chemical analysis and computational chemistry studies confirm that dissociative adsorption of H 2 on the Pd/Au films reduces preadsorbed O and generates 1 ML of adsorbed H, driving nitrile‐containing LCs from a perpendicular to a planar orientation. Subsequent exposure to O 2 leads to oxidation of the adsorbed H, reformation of adsorbed O on the Pd/Au surface, and a return of the LC to its initial orientation. The roles of surface composition and reaction kinetics in determining the LC dynamics are described along with a proof‐of‐concept demonstration of microactuation of beads. These results provide fresh ideas for utilizing chemical energy and catalysis to reversibly actuate functional LCs on the microscale.

Chemistry↗
DOE OSTI2021

Preparation of Potassium Acyltrifluoroborates (KATs) from Carboxylic Acids by Copper‐Catalyzed Borylation of Mixed Anhydrides**

Abstract We report the preparation of potassium acyltrifluoroborates (KATs) from widely available carboxylic acids. Mixed anhydrides of carboxylic acids were prepared using isobutyl chloroformate and transformed to the corresponding KATs using a commercial copper catalyst, B 2 (pin) 2 , and aqueous KHF 2 . This method allows for the facile preparation of aliphatic, aromatic, and amino acid‐derived KATs and is compatible with a variety of functional groups including alkenes, esters, halides, nitriles, and protected amines.

Tung, Pinku↗
DOE OSTI2021

Preparation of Potassium Acyltrifluoroborates (KATs) from Carboxylic Acids by Copper-Catalyzed Borylation of Mixed Anhydrides**

Here we report the preparation of potassium acyltrifluoroborates (KATs) from widely available carboxylic acids. Mixed anhydrides of carboxylic acids were prepared using isobutyl chloroformate and transformed to the corresponding KATs using a commercial copper catalyst, B 2 (pin) 2 , and aqueous KHF 2 . This method allows for the facile preparation of aliphatic, aromatic, and amino acid-derived KATs and is compatible with a variety of functional groups including alkenes, esters, halides, nitriles, and protected amines.

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

Fully Conjugated Poly(phthalocyanine) Scaffolds Derived from a Mechanochemical Approach Towards Enhanced Energy Storage

Phthalocyanines (Pc)-derived materials represent an attractive category of porous organic scaffolds featured by extensive π-conjugated networks, but their construction is still limited to the solution-based pathways, producing materials with inferior conductivity and porosity. Herein, a mechanochemistry-driven approach was developed leveraging the on-surface polymerization of aromatic nitrile monomers with ortho-positioned dicyano groups in the presence of metal catalysts (magnesium, zinc, or aluminum) under neat and ambient conditions. Diverse Pc-functionalized conjugated porous networks (Pc-CPNs) were obtained featured by extensively and fully π-conjugated skeletons, high surface areas, and hierarchical porosities. The monomers in this mechanochemical approach could be extended to those difficult to be handled in solution-based procedures. In this work, the Pc-CPNs displayed attractive electrochemical performance as supercapacitor and anodes in batteries, together with superb long-term stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗