Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “AMINES”

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 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The mechanism of carboxylative cyclization of propargylamine by N-heterocyclic carbene complexes of Au(I)

Here, the complex [Au(IPr)(2-oxazolidinone)] (1 = IKa) was prepared from reaction of [Au(IPr)Cl] (2), K 2 CO 3 , and propargyl amine (PPA). Kinetic studies have been performed for acid cleavage of 1 to yield the oxazolidinone product and an [Au(IPr)(X)] adduct. The fastest rates of cleavage were found to occur for the hydrogen chloride salt of PPA (PPA-HCl) and for the CO 2 adduct of PPA, PPA-CO 2 = the carbamic acid (CA). This transformation was studied as a function of [CA], pressure of CO 2 as well as temperature. Detailed computational studies support the formation of a key intermediate and are also in agreement with a rapid carbonylation/decarbonylation reaction. The computed reactions mechanisms for addition of PPA-HCl and CA are also presented as well as the crystal structure of 1.

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

Tailoring electric dipole of hole-transporting material p-dopants for perovskite solar cells

We report Li-TFSI/t-BP are the most widely employed p-dopants for hole-transporting materials (HTMs) within the state-of-the-art perovskite solar cells (PSCs). The hygroscopicity and migration of these dopants, however, lead to devices with limited stability. To solve this problem, we report here on a diphenyl iodide cation and pentafluorophenyl boric acid anion-based dopant (DIC-PBA) with an oriented interfacial dipole moment as an alternative to Li-TFSI/t-BP. Theoretical and experimental data reveal that DIC-PBA exhibits deep doping of poly[bis(4-phenyl)(2,4,6-triMethylphenyl)aMine] (PTAA) and also creates p-doping of perovskite surface, which originates from ionic interactions-derived dipole arrangement that yields fast interfacial charge transport. The improved intrinsic stability of PSCs originates from the inhibition of dipole moment degeneration on the perovskite surface. Devices prepared with DIC-PBA yielded high efficiency of 22.86%, and the modules (aperture area: 33.2 cm 2 ) efficiency reached 19.13%. Importantly, the storage stability also significantly improved exceeding to 90% after aging 1,200 h under air ambient.

14 SOLAR ENERGY↗
DOE OSTI2016

Heat transfer enhancement in a lithium-ion cell through improved material-level thermal transport

We report that while Li-ion cells offer excellent electrochemical performance for several applications including electric vehicles, they also exhibit poor thermal transport characteristics, resulting in reduced performance, overheating and thermal runaway. Inadequate heat removal from Li-ion cells originates from poor thermal conductivity within the cell. This paper identifies the rate-limiting material-level process that dominates overall thermal conduction in a Li-ion cell. Results indicate that thermal characteristics of a Li-ion cell are largely dominated by heat transfer across the cathode-separator interface rather than heat transfer through the materials themselves. This interfacial thermal resistance contributes around 88% of total thermal resistance in the cell. Measured value of interfacial resistance is close to that obtained from theoretical models that account for weak adhesion and large acoustic mismatch between cathode and separator. Further, to address this problem, an amine-based chemical bridging of the interface is carried out. This is shown to result in in four-times lower interfacial thermal resistance without deterioration in electrochemical performance, thereby increasing effective thermal conductivity by three-fold. This improvement is expected to reduce peak temperature rise during operation by 60%. Finally, by identifying and addressing the material-level root cause of poor thermal transport in Li-ion cells, this work may contribute towards improved thermal performance of Li-ion cells.

36 MATERIALS SCIENCE↗
DOE OSTI2012

The thioantimonate anion SbS{sub 3}{sup 3-} acting as ligand: Syntheses, crystal structures and selected properties of [Mn(1,2-chxn){sub 2}SbS{sub 3}H] and [Cr(1,3-dap){sub 2}SbS{sub 3}]

Two new isolated thioantimonates [Mn(1,2-chxn){sub 2}SbS{sub 3}H] (1) (1,2-chxn=1,2-diaminocyclohexane) and [Cr(1,3-dap){sub 2}SbS{sub 3}] (2) (1,3-dap=1,3-diaminopropane) were synthesized under solvothermal conditions. The crystal structures of 1 and 2 consist of neutral Mn{sup 2+} or Cr{sup 3+} complexes with the transition metal cations being in a distorted octahedral environment of four nitrogen atoms of 1,2-chxn resp. 1,3-dap and two sulphur atoms of the bidentate SbS{sub 3}{sup 3-} unit. Compound 1 is remarkable because charge neutrality is achieved by the presence of Mn{sup 2+} and a SH group which was never observed before. In both compounds intermolecular S Midline-Horizontal-Ellipsis H bonding interactions connect the complexes into higher dimensionality. Compound 1 crystallizes in the monoclinic space group P2{sub 1}/c with a=21.5440(16) A, b=6.9295(3) A, c=13.9276(10) A and {beta}=102.692(8) Degree-Sign . Compound 2 crystallizes in the orthorhombic space group Pbca with a=8.5999(2), b=15.9741(4) and c=21.6770(7) A. - Graphical Abstract: The two new compounds [Mn(1,2-chxn){sub 2}SbS{sub 3}H] and [Cr(1,3-dap){sub 2}SbS{sub 3}] contain the SbS{sub 3}{sup 3-} anion acting as bidentate ligand. Highlights: Black-Right-Pointing-Pointer New isolated thioantimonates(III) with SbS{sub 3}{sup 3-} anion acting as a bidentate ligand. Black-Right-Pointing-Pointer Charge neutrality through protonated sulphur atom. Black-Right-Pointing-Pointer First neutral Mn{sup 2+} complex chelated by bidentate amines and SbS{sub 3}{sup 3-} pyramid.

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

Syntheses, characterization and magnetic properties of two novel inorganic-organic tungstoferrites, [Fe{sup III}{sub 4}(H{sub 2}O){sub 2}(B-{alpha}-Fe{sup III}W{sub 9}O{sub 34}){sub 2}]{sup 10-}

Interaction of the lacunary [{alpha}-SbW{sub 9}O{sub 33}]{sup 9-} with Fe{sup 3+} in the presence of organic amines under hydrothermal conditions yields two novel inorganic-organic hybrid tungstoferrites [dapH{sub 2}]{sub 3}[enH{sub 2}][enH]Na[Fe{sub 4}(H{sub 2}O){sub 2}(FeW{sub 9}O{sub 34}){sub 2}]{center_dot}7H{sub 2}O (dap=1,2-diaminopropane, en=ethylenediamine) (1) and [dapH{sub 2}]{sub 5}[Fe{sub 4}(H{sub 2}O){sub 2}(FeW{sub 9}O{sub 34}){sub 2}]{center_dot}11H{sub 2}O (2), which have been characterized by IR, elemental analysis, UV-Vis, TG and single-crystal X-ray diffraction. Both 1 and 2 consist of two [B-{alpha}-Fe{sup III}W{sub 9}O{sub 34}]{sup 11-} units joined by a rhomb-like tetranuclear iron cluster. Interestingly, 1 displays a new example of 1D chain-like architecture, in which adjacent [Fe{sub 4}(FeW{sub 9}O{sub 34}){sub 2}]{sup 10-} anions are interconnected by two unusual W-O-Fe bridges. Meanwhile, the neighboring chains are further assembled by Na{sup +} ions, forming the 2D extended network. 2 exhibits a discrete dimeric TMSP structure constructed from two trivacant [B-{alpha}-Fe{sup III}W{sub 9}O{sub 34}]{sup 11-} subunits encapsulating a rhomb-like tetranuclear iron cluster with five isolated diprotoned dap molecules. Magnetic measurements indicate that antiferromagnetic exchange interactions are dominant in the hexanuclear {l_brace}Fe{sub 6}O{sub 22}{r_brace} clusters in 1 and 2. - Graphical abstract: Two novel inorganic-organic hybrid tungstoferrites were synthesized from the reaction of lacunary [{alpha}-SbW{sub 9}O{sub 33}]{sup 9-} with Fe{sup 3+} under hydrothermal conditions and structurally characterized. The magnetic properties of them were also studied. Highlights: Black-Right-Pointing-Pointer 1 represents the first example of 1D chain-like {l_brace}Fe{sub 4}(FeW{sub 9}){sub 2}{r_brace} tungstoferrite. Black-Right-Pointing-Pointer Two [B-{alpha}-Fe{sup III}W{sub 9}O{sub 34}]{sup 11-} units linked via a rhomb-like tetranuclear iron cluster. Black-Right-Pointing-Pointer Adjacent {l_brace}Fe{sub 4}(FeW{sub 9}){sub 2}{r_brace} are interconnected by unusual W--O--Fe bridges. Black-Right-Pointing-Pointer Antiferromagnetic exchange interactions are dominant in the {l_brace}Fe{sub 6}O{sub 22}{r_brace} cluster.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis of nanostructured AlN by solid state reaction of Al and diaminomaleonitrile

The solid state reaction of diaminomaleonitrile (DAMN) with aluminum via both mechanochemical and thermal treatment routes was studied by X-ray diffraction and Fourier transform infrared spectroscopy. During the milling process, the reaction starts with the deammoniation of the DAMN molecules, followed by the formation of nanostructured AlN powder as the main solid product after milling for 7 h. The reactivity of the mixed powder was also investigated during the conventional thermal treatment process using differential scanning calorimetry, derivative thermogravimetry and thermogravimetric analysis. The results reveal that DAMN starts to polymerize at 192 Degree-Sign C by the elimination of the amine groups. Furthermore, increasing the annealing temperature leads to the formation of a nitrogen-containing carbonaceous material with the structure similar to non-crystalline carbon. However, no evidence for the formation of AlN was observed in the annealed samples even at temperatures as high as the Al melting point. - Graphical abstract: AlN nanoparticles obtained after milling of Al and diaminomaleonitrile (DAMN) for 12 h. Highlights: Black-Right-Pointing-Pointer Solid state reaction of diaminomaleonitrile (DAMN) with Al was studied via mechanochemical and thermal treatment routs. Black-Right-Pointing-Pointer Nanocrystalline AlN was successfully synthesized by the mechanochemical process. Black-Right-Pointing-Pointer The C/N material was formed by polymerization of DAMN during the thermal treatment process. Black-Right-Pointing-Pointer No reaction between DAMN and Al was detected during the thermal treatment method.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Anchoring of Cu(II) onto surface of porous metal-organic framework through post-synthesis modification for the synthesis of benzimidazoles and benzothiazoles

Efficient synthesis of various benzimidazoles and benzothiazoles under mild conditions catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. In this manner, first, the aminated UiO-66 was modified with thiophene-2-carbaldehyde and then the prepared Schiff base was reacted with CuCl{sub 2}. The prepared catalyst was characterized by FT-IR, UV–vis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N{sub 2} adsorption, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and field emission scanning electron microscopy (FE-SEM). The UiO-66–NH{sub 2}–TC–Cu was applied as a highly efficient catalyst for synthesis of benzimidazole and benzothiazole derivatives by the reaction of aldehydes with 1,2-diaminobenzene or 2-aminothiophenol. The Cu(II)-containing MOF was reused several times without any appreciable loss of its efficiency. - Graphical abstract: Efficient synthesis of benzimidazoles and benzothiazoles catalyzed by Cu(II) anchored onto UiO-66–NH{sub 2} metal organic framework is reported. - Highlights: • A copper Schiff base was immobilized on UiO-66 via postsynthetic modification. • The modified MOFs were fully characterized by a variety of methods. • The catalyst was used for the preparation of benzimidazoles and benzothiazoles. • In comparison of other catalysts, our catalyst was more efficient and forceful.

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

The intercalation chemistry of layered iron chalcogenide superconductors

The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichalcogenides, fullerenes, and layered cobalt oxides. From past studies of these intercalated superconductors, we discuss the role of the intercalates in terms of charge doping, structural distortions, and Fermi surface reconstruction. We also briefly review the physical and chemical properties of the host materials—mackinawite-type FeS and β-FeSe. The three types of intercalates for the iron chalcogenides can be placed in three categories: 1.) alkali and alkaline earth cations intercalated through the liquid ammonia technique; 2.) cations intercalated with organic amines such as ethylenediamine; and 3.) layered hydroxides intercalated during hydrothermal conditions. A recurring theme in these studies is the role of the intercalated guest in electron doping the chalcogenide host and in enhancing the two-dimensionality of the electronic structure by spacing the FeSe layers apart. We end this review discussing possible new avenues in the intercalation chemistry of transition metal monochalcogenides, and the promise of these materials as a unique set of new inorganic two-dimensional systems.

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

N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

Two new Co(II) coordination polymers(CPs), namely [Co{sub 2}(bpe){sub 2}(Hbppc)]{sub n} (1) and [Co{sub 3}(μ{sub 3}-OH)(bppc)(bpm)(H{sub 2}O)]·3H{sub 2}O (2) (H{sub 5}bppc=biphenyl-2,4,6,3′,5′-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co{sub 3}(μ{sub 3}-OH)]{sup 5+} units with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system. - Graphical abstract: Two new Co(II) coordination polymers with bi- and trinuclear units have been obtained. 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology and antiferromagnetic interactions between the adjacent Co(II) ions, while 2 is a binodal (5,7)-connected 3D network with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology and a ferromagnetic system. - Highlights: • Two Co(II) coordination polymers with different multimetallic clusters as building units. • A (4,6)-connected fsc net and a (5,7)-connected 3D network. • A antiferromagnetic coupling for 1 and A ferromagnetic coupling for 2.

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

Solvothermal synthesis of a new 3-D mixed-metal sulfide framework, (H{sub 1.33}tren)[In{sub 2.67}Sb{sub 1.33}S{sub 8}]·tren

A new indium(III) antimony(V) sulfide, (H{sub 1.33}tren)[In{sub 2.67}Sb{sub 1.33}S{sub 8}]·tren, has been prepared solvothermally at 433 K. The compound crystallises in the tetragonal space group I-42d (lattice parameters, a=12.6248(5) and c=19.4387(18) Å at 150 K) and contains adamantane-like T2 supertetrahedral units comprised of corner-sharing InS{sub 4}{sup 5−} and SbS{sub 4}{sup 3−} tetrahedra. The adamantane-like units are then linked through sulfur vertices to generate an open, 3-D framework structure containing large pores in which neutral, protonated tren (tris(2-aminoethylene)amine) molecules reside. The presence of the organic components was confirmed by solid-state {sup 13}C NMR (10 kHz), combustion and thermogravimetric analysis. The band gap, obtained from UV–vis diffuse reflectance measurements, is 2.7(2) eV. Stirring with either water or alkali-metal salt solution leads to removal of the neutral tren molecules and an ~9% reduction in unit-cell volume on formation of (H{sub 1.33}tren)[In{sub 2.67}Sb{sub 1.33}S{sub 8}]·(H{sub 2}O){sub 4}. - Graphical abstract: Linking of In(III)-Sb(V)-S adamantane units to form a 3-D open framework. - Highlights: • Preparation and structural characterisation of a new mixed-metal thiometallate. • The first mixed In(III)/Sb(V) supertetrahedron. • Optical band gap of 2.7(2) eV. • Soaking in aqueous alkali-metal solutions leads to removal of ca. 50% of the organic content.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Cu- and Zr-based metal organic frameworks and their composites with graphene oxide for capture of acid gases at ambient temperature

Highlights: • Incorporation of GO in Cu- and Zr-based MOFs resulted in additional porosity at the interstitial MOF/GO spaces. • The UiO-66-NH{sub 2}/GO composite exhibited enhanced CO{sub 2} capacity at higher pressures. • CO{sub 2}/N{sub 2} selectivity of HKUST-1/GO was higher compared to pure HKUST-1. • The HKUST-1 crystallites in the presence of GO exhibited enhanced H{sub 2}S sorption kinetics. • The UiO-66 based adsorbents were more stable in humidity conditions than the HKUST-1 based ones. - Abstract: Capture of acid gases (CO{sub 2} and H{sub 2}S) by liquid solvent absorption is the common industrial practice, yet capture relying on solid adsorbents is increasingly gaining interest as potential alternative towards less energy-demanding operations. Herein, we developed and examined various metal organic frameworks (MOFs) bearing Cu- and Zr- metal clusters and their composites with graphene oxide (GO), and evaluated their performance for CO{sub 2} and H{sub 2}S adsorption. Specifically, UiO-66, UiO-66-NH{sub 2}, HKUST-1, and their GO composites were grown, subjected to structural, morphological, and textural characterization, and subsequently evaluated for their adsorption capacity and selectivity at ambient temperature. The crystallinity of the parent MOFs was preserved upon in-situ growth of the MOF/GO composites, while incorporation of GO yielded uniformly-shaped and well-dispersed MOF crystals resulting in enhanced sorption kinetics, and increased the pore volume compared to pure MOFs due to additional porosity formed in the interstitial spaces between the MOF crystallites and the GO flakes. To this extent, the interplay between additional porosity and pore functionalities in the competitive CO{sub 2} and N{sub 2} adsorption was investigated. UiO-66-NH{sub 2} exhibited enhanced CO{sub 2} capacity (3.07 mmol/g at 25 °C and 4 bar) and the highest CO{sub 2}/N{sub 2} selectivity (167 at 1 bar) among the tested MOFs, due to the presence of the amine functional groups in the organic linker that enhanced affinity with CO{sub 2}. At increased pressures, the UiO-66-NH{sub 2}/GO composite exhibited higher CO{sub 2} capacity compared to pure UiO-66-NH{sub 2}, which is attributed to activation of the additional porosity between the MOF crystallites and the GO layers. HKUST-1/GO selectivity was also enhanced compared to HKUST-1 in all pressures tested. Under humid environment, the UiO-66 based structures were relatively stable in contrast to the HKUST-1 ones that underwent gradual degradation. These composites offer functionalization tunability due to the presence of both MOF and GO counterparts for targeted gas capture applications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

BODIPY modified g-C{sub 3}N{sub 4} as a highly efficient photocatalyst for degradation of Rhodamine B under visible light irradiation

Highlights: • Post modification strategy to reduce the residual amine on the g-C{sub 3}N{sub 4} frameworks through Schiff base reaction using BODIPY derivatives was adopted. • Reinforced visible light absorption and depressed carrier recombination were seen in the post modified photocatalysts. • Photocatalytic performance of modified photocatalysts were strengthened by more than 3.5 times than the pure g-C{sub 3}N{sub 4}. - Abstract: Developing new energy resource as well as efficient treatment strategies to solve the energy crisis and organic pollutants problems is of crucial importance. Due to medium band gap and highly thermal stability, doped or chemically functionallized graphitic carbon nitride (g-C{sub 3}N{sub 4}) has been envisioned as promising photocatalysts in processing organic pollutants. In this work, we use 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) chemically modified g-C{sub 3}N{sub 4} to degrade Rhodamine B (RhB) under visible light irradiation (λ ≥ 420 nm). When the modified weight ratio of BODIPY in g-C{sub 3}N{sub 4} reaches 0.6% (CN-0.6), the photocatalytic performance is nearly 3.5 times fast than that of without modification (CN-0). Enhanced visible light absorption and depressed electron-hole recombination rate may take responsibilities for the enhanced photocalytic performance. A possible mechanism responsible for this photocatalytic process is proposed. Our work might provide a new strategy to develop valid photocatalysts with broad visible light absorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Synthesis, characterization and cation adsorption of p-aminobenzoic acid intercalated on calcium phosphate

Graphical abstract: Scanning electron microscopy photographs of calcium phosphate (a) and intercalated with p-aminobenzoic acid (b). Highlights: ► Calcium phosphate was intercalated with p-aminobenzoic acid. ► Guest molecule contains nitrogen and oxygen atoms from amine and carboxylic groups. ► These basic centers are potentially useful for cation coordination in ethanol solution. ► Crystal morphology of compounds is lamellar, it agrees with expected structural characteristics. -- Abstract: Crystalline lamellar calcium phosphate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1033 and 1010 cm{sup −1} interval confirmed the presence of the phosphonate groups attached to the inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 712 and 1578 pm for the original and the intercalated compounds, respectively. Solid-state {sup 31}P nuclear magnetic resonance spectra presented only one peak for the phosphate groups attached to the main inorganic polymeric structure near −2.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 6.44 and 3.34 mmol g{sup −1} for nickel and cobalt, respectively, which stability constant and distribution coefficient followed Co > Ni.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Characterization and thermal behavior of PrMO{sub 3} (M = Co or Ni) ceramic materials obtained from gelatin

Graphical abstract: The micrograph in figure shows sample calcined at temperature 900 °C. The sample exhibits morphology with considerable porosity and the formation of agglomerated nanometric particles. Gelatin provides the system with a large amount of organic matter, which is then removed during calcinations, favoring the appearance of pores in the material. Highlights: ► Oxides with PrNiO{sub 3} and PrCoO{sub 3} were prepared by new method synthesis. ► The gelatin, through its carboxylate groups and amine, is an efficient director. ► The obtained materials have magnetic properties and application in catalysis. ► The decomposition kinetic study of bonding groups of gelatin with metallic ions that takes part in the synthesis of PrMO{sub 3}. -- Abstract: Metal oxides with perovskite-type structure have attracted considerable interest in recent years due to their magnetic and electrical properties, as well as their catalytic activity. In this study, oxides with PrNiO{sub 3} and PrCoO{sub 3} composition were prepared by using gelatin powder as a precursor agent for its use as a catalyst. The powders obtained were calcined at 700 °C and 900 °C and characterized using the X-ray diffraction, thermal analysis (thermogravimetry and differential thermal analysis), infrared spectroscopy, temperature programed reduction and scanning electron microscopy techniques. Thermogravimetric data using the non-isothermal kinetic models of Flynn and Wall and “Model-free Kinetics” were used to determine the activation energy to study the decomposition kinetics of the ligand groups with system's metallic ions that takes part in the synthesis of PrMO{sub 3} (M = Ni or Co).

36 MATERIALS SCIENCE↗
DOE OSTI2012

Polymer/organosilica nanocomposites based on polyimide with benzimidazole linkages and reactive organoclay containing isoleucine amino acid: Synthesis, characterization and morphology properties

Highlights: ► A reactive organoclay was formed using L-isoleucine amino acid as a swelling agent. ► Polyimide was synthesized from benzimidazole diamine and pyromellitic dianhydride. ► Imide and benzimidazole groups assured the thermal stability of the nanocomposites. ► Nanocomposite films were prepared by an in situ polymerization reaction. ► The TEM micrographs of nanocomposites revealed well-exfoliated structures. -- Abstract: Polyimide–silica nanocomposites are attractive hybrid architectures that possess excellent mechanical, thermal and chemical properties. But, the dispersion of inorganic domains in the polymer matrix and the compatibility between the organic and inorganic phases are critical factors in these hybrid systems. In this investigation, a reactive organoclay was prepared via ion exchange reaction between protonated form of difunctional L-isoleucine amino acid as a swelling agent and Cloisite Na{sup +} montmorillonite. Amine functional groups of this swelling agent formed an ionic bond with the negatively charged silicates, whereas the remaining acid functional groups were available for further interaction with polymer chains. Then organo-soluble polyimide (PI) have been successfully synthesized from the reaction of 2-(3,5-diaminophenyl)-benzimidazole and pyromellitic dianhydride in N,N-dimethylacetamide. Finally, PI/organoclay nanocomposite films enclosing 1%, 3%, 5%, 7% and 10% of synthesized organoclay were successfully prepared by an in situ polymerization reaction through thermal imidization. The synthesized hybrid materials were subsequently characterized by Fourier transform infrared spectroscopy, X-ray diffraction, electron microscopy, and thermogravimetric analysis techniques. The PI/organoclay nanocomposite films have good optical transparencies and the mechanical properties were substantially improved by the incorporation of the reactive organoclay.

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

n-Alkylamine-assisted preparation of a high surface area vanadyl phosphate/tetraethylorthosilicate nanocomposite

Graphical abstract: CuK{sub α} X-ray diffraction patterns of the VP, VPOc, VPOcT, VPOcT200 and VPOcT500. Highlights: ► TEOS and octylamine incorporation into the VP was achieved by expanding the lamellar. ► The specific surface area increased from 15 m{sup 2} g{sup −1} in VP to 237 m{sup 2} g{sup −1} in VPOcT. ► The VPOcT exhibited thermal resistance up to 200 °C in air. ► Upon thermal treatment up to 500 °C, the surface area increased to 838 m{sup 2} g{sup −1}. -- Abstract: We have developed a vanadyl phosphate/tetraethylorthosilicate (VPO/TEOS) nanocomposite comprised of silicate chains interleaved with VPO layers, prepared by using an n-alkylamines such as octylamine as the structure directing agent. The nanocomposites were synthesized by reacting amine-intercalated vanadyl phosphate with tetraethylorthosilicate via the soft chemistry approach. The synthetic procedure encompassed the exfoliation of the layered vanadyl phosphate as well as the reorganization of this exfoliated solid into a mesostructured lamellar phase with the same V–P–O connectivity as in the original matrix. TEOS incorporation into the vanadyl phosphate was achieved by expanding the lamellar structure with n-alkylamine (Δd = 13 Å with n-octylamine). The specific surface area increased from 15 m{sup 2} g{sup −1} in the vanadyl phosphate matrix to 237 m{sup 2} g{sup −1} in VPOcT, and the isotherm curves revealed the characteristic hysteresis of mesoporous materials. Upon thermal treatment up to 500 °C, the surface area increased to 837 m{sup 2} g{sup −1}, which is suitable for catalytic purposes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2013

Facile synthesis of QD-anchored composite particles with magnetite cluster cores ({sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}@QDs)

Highlights: ► Triple layered Fe{sub 3}O{sub 4}/SiO{sub 2}/QDs were designed as fluorescent magnetic nanocomposites. ► Magnetite cluster-embedded silica exhibited strong and controllable magnetism. ► Effective conjugation between QDs and magnetic silica occurred at pH3. - Abstract: Magnetism-controlled fluorescent composite particles ({sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}@QDs) were prepared as QD-anchored silica nanoparticles with magnetite cluster cores. First, citrate-capped magnetites (C-Fe{sub 3}O{sub 4}) were prepared by the co-precipitation method and subsequently complexed with 3-aminopropyl-trimethoxysilane (APTMS) at room temperature, consequently leading to the formation of magnetite clusters (A-{sup n}Fe{sub 3}O{sub 4}) with alkoxy terminated interfaces. The sol–gel reaction between A-{sup n}Fe{sub 3}O{sub 4} and tetraethoxysilane (TEOS) produced the core-shell {sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}. The resulting core-shell particles exhibited superparamagnetic properties and controllable magnetism simply by adjusting the thickness of nonmagnetic silica layer. After then, amine-terminated {sup n}Fe{sub 3}O{sub 4}@SiO{sub 2} (NH{sub 2}–{sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}) was conjugated with carboxy quantum dots (QDs) using an EDC coupling agent. The QD conjugation with NH{sub 2}–{sup n}Fe{sub 3}O{sub 4}@SiO{sub 2} of lower pH exhibited the higher photoluminescence (PL) intensity, and the resulting composite particles ({sup n}Fe{sub 3}O{sub 4}@SiO{sub 2}@QDs) can be a useful biomedical agent. This chemical strategy can be further applied to prepare the core-shell magnetic nanostructure with various oxide layers for specific applications.

36 MATERIALS SCIENCE↗