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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Transformation of thiolated chitosan-templated gold nanoparticles to huge microcubes

Graphical abstract: - Highlights: • Mercapto groups were grafted to chitosan molecule by a reactive amine reduction. • Functional polymer with well-defined monomer units controls AuNPs assembly. • Assembled morphologies depend on the ratio of AuNPs to thiolate groups. • Microcubes with side length of ∼20 μm was synthesized through a dialysis step. • A edge-to-middle growth mechanism of gold microcubes was observed. - Abstract: The L-cysteine molecules were successfully grafted to the 2-amino group of chitosan by a reactive amine reduction, and the as-synthesized thiolated chitosan (TC) molecules were used as the templates to direct the self-assembly of gold nanoparticles and induce the transformation of these assemblies to gold microcubes through a deep-going dialysis. We found that the ratio of gold nanoparticles to TC molecules could greatly affect the shape of the assembled clusters. Different stages of these clusters and microstructures during the dialysis process were characterized by scanning electron microscope (SEM), and the microcubes with average side length of about 20 μm were successfully synthesized. According to the morphology evolution of the assembly, it could be concluded that the microcubes were formed from external to internal. The SERS area mapping images of microcubes and some clusters were also collected to study the formation mechanism of gold microcubes. Our work demonstrates a simple and highly effective way to assemble gold nanoparticles into microcubes with unique properties.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Development of TRPN dendrimer-modified disordered mesoporous silica for CO{sub 2} capture

Highlights: • A novel series of TRPN dendrimers are synthesized. • Structurally disordered mesoporous silica was used to develop the CO{sub 2} adsorbent. • The CO{sub 2} adsorption capacity is relatively high. • The sorbent exhibits a high stability after 12 cycling runs. • The sorbent achieves complete desorption at low temperature (60 °C). - Abstract: A novel series of tri(3-aminopropyl) amine (TRPN) dendrimers were synthesized and impregnated on structurally disordered mesoporous silica (DMS) to generate CO{sub 2} adsorbents (TS). The physicochemical and adsorption properties of the adsorbents before and after dendrimer modification were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and N{sub 2} adsorption–desorption (N{sub 2}-BET) techniques. CO{sub 2} adsorption–desorption tests indicated that the sorbent demonstrates high CO{sub 2} adsorption capacity (138.1 mg g{sup −1} for G1 sample TS-G1-3CN-50 and 91.7 mg g{sup −1} for G2 sample TS-G2-6CN-50), and can completely desorb CO{sub 2} under vacuum at 60 °C. Its CO{sub 2} adsorption capacity at 25 °C increases with the amine loading, achieving the highest adsorption capacity (140.6 mg g{sup −1} for TS-G1-3CN) at 60%. The developed TS materials exhibited excellent cycling stability. After 12 consecutive adsorption–desorption runs, TS-G1-3CN-50 shows an adsorption capacity of 136.0 mg g{sup −1}, retaining 98.5% of its original value.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Folate conjugated Mn{sub 3}O{sub 4}@SiO{sub 2} nanoparticles for targeted magnetic resonance imaging in vivo

Graphical abstract: The Mn{sub 3}O{sub 4}@SiO{sub 2}(PEG)–FA has been used as a T{sub 1}-MRI probe for in vivo. - Highlights: • The PEG and FA modified Mn{sub 3}O{sub 4}@SiO{sub 2} nanoparticles (Mn{sub 3}O{sub 4}@SiO{sub 2}–FA) were prepared. • Mn{sub 3}O{sub 4}@SiO{sub 2}–FA exhibited the good colloidal stability in the simulated biological medium. • Mn{sub 3}O{sub 4}@SiO{sub 2}–FA showed the targeting ability to HeLa cells overexpressed the FA receptor. • The T{sub 1}-weighted magnetic resonance (MR) imaging demonstrated the targeting ability of Mn{sub 3}O{sub 4}@SiO{sub 2}–FA in vivo tumor. - Abstract: The monodisperse silica-coated manganese oxide nanoparticles (Mn{sub 3}O{sub 4}@SiO{sub 2} NPs) were synthesized via the high temperature pyrolysis approach and were aminated through silanization. The amine-functionalized Mn{sub 3}O{sub 4} NPs enabled the covalent conjugation of hydrophilic methoxypoly(ethylene glycol) (PEG) and the targeting ligand of folate (FA) onto their surface. The formed PEG and FA modified Mn{sub 3}O{sub 4} NPs (Mn{sub 3}O{sub 4}@SiO{sub 2}(PEG)–FA) exhibited the good colloidal stability in the simulated biological medium and the targeting ability to HeLa cells overexpressed the FA receptor. The T{sub 1}-weighted magnetic resonance (MR) imaging and inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis of Mn{sub 3}O{sub 4}@SiO{sub 2}(PEG)–FA NPs further demonstrated their targeting ability in tumor.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Hydrothermal synthesis of highly nitrogen-doped few-layer graphene via solid–gas reaction

Highlights: • A novel approach to synthesis of N-doped few-layer graphene has been developed. • The high doping levels of N in products are achieved. • XPS and XANES results reveal a thermal transformation of N bonding configurations. • The developed method is cost-effective and eco-friendly. - Abstract: Nitrogen-doped (N-doped) graphene sheets with high doping concentration were facilely synthesized through solid–gas reaction of graphene oxide (GO) with ammonia vapor in a self-designed hydrothermal system. The morphology, surface chemistry and electronic structure of N-doped graphene sheets were investigated by TEM, AFM, XRD, XPS, XANES and Raman characterizations. Upon hydrothermal treatment, up to 13.22 at% of nitrogen could be introduced into the crumpled few-layer graphene sheets. Both XPS and XANES analysis reveal that the reaction between oxygen functional groups in GO and ammonia vapor produces amide and amine species in hydrothermally treated GO (HTGO). Subsequent thermal annealing of the resultant HTGO introduces a gradual transformation of nitrogen bonding configurations in graphene sheets from amine N to pyridinic and graphitic N with the increase of annealing temperature. This study provides a simple but cost-effective and eco-friendly method to prepare N-doped graphene materials in large-scale for potential applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

New sterically hindered polyvinylamine-containing membranes for CO 2 capture from flue gas

Amine-containing facilitated transport membranes can have both high permeability and selectivity due to the reversible reaction between CO 2 and amino groups for effective carbon capture from flue gas. In this study, we have developed an improved method for the synthesis of high-molecular-weight sterically hindered polyvinylamine (PVAm) as the new fixed-site carrier in thin-film composite membranes for CO 2 capture. Commercially available PVAm was N-monomethylated into poly-N-methyl-N-vinylamine (PVAm-CH 3 ) using the stepwise reductive amination with a highly polar fluorinated alcohol as the solvent to enhance the equilibrium shift to the formation of the imine intermediate. The method prevented over-alkylation, resulting in the increased yield of the target product. PVAm-CH 3 exhibited excellent CO 2 facilitation with a CO 2 permeability of 445.7 Barrer (1 Barrer = 3.349 x 10 –16 mol m m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 70.3, which are above the Robeson 2008 upper bound. The PVAm-CH 3 solution retained a sufficiently high viscosity after incorporating the aminoacid salt, 2-(1-piperazinyl)ethylamine sarcosinate (PZEA-Sar), as the mobile carrier for the membrane coating on nanoporous polyethersulfone (PES) substrates without any penetration issues. The resultant thin-film composite PVAm-CH3/PZEA-Sar membrane with a thickness of approximately 170 nm exhibited a superior CO 2 performance of 1071 GPU (1 GPU = 3.349 x 10 –10 mol m –2 s –1 Pa –1 ) and a CO 2 /N 2 selectivity of 183 at 57°C and a feed gas pressure of 111.64 kPa (1.5 psig). This PVAm-CH 3 /PZEA-Sar membrane surpassed the latest redefined 2019 CO 2 /N 2 upper bound and outperformed other polymer-based membranes. Density functional theory calculations also demonstrated that PVAm-CH 3 showed a stronger preference, relative to PVAm, toward the more efficient bicarbonate pathway. Thus, the steric hindrance effect of PVAm-CH 3 enhanced the solubility of CO 2 in the polymer matrix and resulted in the higher CO 2 permeance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Development of a Simple Field Test for Vehicle Exhaust to Detect Illicit Use of Dyed Diesel Fuel

The use of tax-free dyed fuel on public highways in the United States provides a convenient way of evading taxes. Current enforcement involves visual inspection for the red azo dye added to the fuel to designate its tax-free status. This approach has shortcomings such as the invasive nature of the tests and/or various deceptive tactics applied by tax evaders. A test designed to detect dyed fuel use by analyzing the exhaust would circumvent these shortcomings. This paper describes the development of a simple color spot test designed to detect the use of tax-free (dyed) diesel fuel by analyzing the engine exhaust. Development first investigated the combustion products of C.I. Solvent Red 164 (the azo dye formulation used in the United States to tag tax-free fuel). A variety of aryl amines were identified as characteristic molecular remnants that appear to survive combustion. A number of microanalytical color tests specific for aryl amines were then investigated. One test based on the use of 4-(dimethylamino)benzaldehyde seemed particularly applicable and was used in a proof-of-principle experiment. The 4-(dimethylamino)benzaldehyde color spot test was able to clearly distinguish between engines burning regular and dyed diesel fuel. Further development will refine this color spot test to provide an easy-to-use field test for Internal Revenue Service Field Compliance specialists.

alkyl aryl amines↗
DOE OSTI2025

Evaluating Autoxidation Radical Scavengers and Additives to Enhance Aminopolymer Sorbent Stability

Solid amine sorbents have shown promise in the removal of ultradilute CO 2 from the atmosphere. Despite being a promising candidate material type for this application, these sorbents are prone to degradation during long-term exposure to environmental components such as CO 2 , O 2 , and H 2 O, with amine oxidation being a particularly challenging problem. In this study, we investigate the potency of different radical scavengers and additives in mitigating the degradation of a model poly- (ethylenimine) (PEI)/Al 2 O 3 sorbent under direct air capture (DAC)-relevant conditions. The results reveal that a 4,4′-bis(α,α- dimethylbenzyl)diphenylamine (BDDPA)-incorporated PEI/Al 2 O 3 sorbent showed the most resistance toward oxidative degradation at varying exposure times and BDDPA loadings under CO 2 -free air (21% O 2 /balance N 2 ) at 120 °C. Interestingly, under humid (∼43% relative humidity (RH) at 26 °C) and dry 0.04% CO 2 -air, the BDDPA/PEI/Al 2 O 3 sorbent showed enhanced sorbent stability both at 70 and 120 °C after 4.5 h of exposure. Under humid CO 2 -free air, at 120 °C, the antioxidant performance slightly declined (in comparison to the dry CO 2 -free air condition) but displayed a much higher stability than the pristine sorbent. Overall, the ability of BDDPA to inhibit sorbent degradation under dry and humid, CO 2 -free and CO 2 -containing (0.04%) air at intermediate (70 °C) and elevated (120 °C) temperatures is promising in prolonging sorbent stability and underscores the importance of performing accelerated oxidation studies in the presence of all species that are expected to be present in DAC processes to identify suitable stabilization treatments for sorbent materials.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Coordination of 2,2'-(Trifluoroazanediyl)bis( N , N '-dimethylacetamide) with U(VI), Nd(III), and Np(V): A Thermodynamic and Structural Study

Thermodynamic properties of the complexation of 2,2'-(trifluoroazanediyl)bis(N,N'-dimethylacetamide) (CF 3 ABDMA) with U(VI), Nd(III), and Np(V) have been studied in 1.0 M NaNO 3 at 25 °C. Equilibrium constants of the complexation were determined by potentiometry and spectrophotometry. In comparison with a series of structurally related amine-bridged diacetamide ligands, including 2,2'-(benzylazanediyl)bis(N,N'-dimethylacetamide) (BnABDMA), 2,2'-azanediylbis(N,N'-dimethylacetamide) (ABDMA), and 2,2'-(methylazanediyl)bis(N,N'-dimethylacetamide) (MABDMA), CF 3 ABDMA forms weaker complexes with U(VI), Nd(III), and Np(V) due to the lower basicity of the center N atom in CF 3 ABDMA resulting from the attachment of the strong electron-withdrawing CF 3 - moiety. The complexation strength of CF 3 ABDMA with the three metal ions follows the order: UO 2 2+ > Nd 3+ > NpO 2 + , consistent with the order of the “effective” charges of the metal ions. Structural information on the U(VI)/CF 3 ABDMA complexes in solution and in solid was obtained by theoretical computation, single crystal X-ray diffractometry, 19 F NMR, and electrospray ionization mass spectrometry. Finally, the structural data indicate that, similar to the three previously studied amine-bridged diacetamide ligands (BnABDMA, ABDMA, and MABDMA), the CF 3 ABDMA ligand coordinates to UO 2 2+ in a tridentate mode, through the center nitrogen and the two amide oxygen atoms.

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

Photoreactive Capture and Conversion of Dilute Carbon Dioxide into Synthetic Natural Gas

This study introduces a photoreactive system that integrates the capture of dilute CO 2 streams with their catalytic conversion to synthetic natural gas (CH 4 ), utilizing a Ru nanoparticle (NP)-doped TiO 2 composite loaded with linear polyethylenimine (L-PEI) and enhanced with plasmonic titanium nitride (TiN). This light-driven approach mitigates challenges that have plagued traditional thermal reactive carbon capture (RCC) methods, such as CO 2 slip and amine degradation. We demonstrate that L-PEI enables stable CO 2 capture and conversion, achieving ~70% conversion of captured CO 2 to CH 4 across multiple reaction cycles using nonflammable forming gas (~5% H 2 ) as the reductant. In contrast, branched PEI (B-PEI)-loaded composites exhibited significant catalyst deactivation after several RCC cycles. Scanning transmission electron microscopy (STEM) imaging confirms that significant sintering of the Ru NPs occur in the B-PEI sample under RCC conditions, whereas their size remains stable in more rigid L-PEI composites. Technoeconomic analysis (TEA) estimates that CH 4 production using this system could cost less than $\$$5/kg based on current electrocatalytic H 2 prices. These results represent one of the most promising demonstrations of amine-based RCC employing dilute CO 2 sources to date.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Linkage Transformations in a Three-Dimensional Covalent Organic Framework for High-Capacity Adsorption of Perfluoroalkyl Substances

Despite their many advantages, covalent organic frameworks (COFs) built from three-dimensional monomers are synthetically difficult to functionalize. Herein, we provide a new synthetic approach to the functionalization of a three-dimensional covalent organic framework (COF-300) by using a series of solid-state linkage transformations. By reducing the imine linkages of the framework to amine linkages, we produced a more hydrolytically stable material and liberated a nucleophilic amino group, poised for further functionalization. We then treated the amine-linked COF with diverse electrophiles to generate a library of functionalized materials, which we tested for their ability to adsorb perfluoroalkyl substances (PFAS) from water. The framework functionalized with dimethylammonium groups, COF-300-dimethyl, adsorbed more than 250 mg of perfluorooctanoic acid (PFOA) per 1 g of COF, which represents an approximately 14,500-fold improvement over that of COF-300 and underscores the importance of electrostatic interactions to PFAS adsorption performance. In conclusion, this work provides a conceptually new approach to the design and synthesis of functional three-dimensional COFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemical Kinetics of the Autoxidation of Poly(ethylenimine) in CO 2 Sorbents

The oxidative degradation rates of a CO 2 sorbent composed of a mesoporous alumina impregnated with poly- (ethylenimine) (PEI) are measured under systematically varied conditions and a reaction rate law is created. Good agreement is shown between the rate of oxidation obtained via in situ calorimetric heat measurement during oxidative degradation reactions and the loss of CO 2 capture performance presented as amine efficiency (mol CO 2 /mol amine). PEI mass loss and elemental composition are tracked over the course of the reaction and used in conjunction with the oxidation rate measurements to shed insight into the oxidation reaction(s). These data, in combination with measurements of the heat of reaction, suggest a common reaction set across the range of temperatures, oxygen concentrations, and sorbent compositions tested. The data are consistent with the basic autoxidation scheme (BAS), the accepted mechanism of autoxidation of aliphatic polymers. We propose a lumped kinetic model to describe the oxidation reaction set and estimate an activation energy of 105 kJ/mol and an oxygen reaction order of 0.5–0.7 from the data accordingly. Furthermore, these parameters can be incorporated into process cycle models to estimate the material lifetime, a critical uncertainty in the deployment of DAC technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Mechanistic and Structural Analyses of the Role of His67 in the Yeast Polyamine Oxidase Fms1

The flavoprotein oxidase Fms1 from Saccharomyces cerevisiae catalyzes the oxidation of spermine and N1-acetylspermine to spermidine and 3-aminopropanal or N-acetyl-3-aminopropanal. Within the active site of Fms1, His67 is positioned to form hydrogen bonds with the polyamine substrate. This residue is also conserved in other polyamine oxidases. The catalytic properties of H67Q, H67N, and H67A Fms1 have been characterized to evaluate the role of this residue in catalysis. With both spermine and N1-acetylspermine as the amine substrate, the value of the first-order rate constant for flavin reduction decreases 2-3 orders of magnitude, with the H67Q mutation having the smallest effect and H67N the largest. The k{sub cat}/K{sub O2} value changes very little upon mutation with N{sup 1}-acetylspermine as the amine substrate and decreases only an order of magnitude with spermine. The k{sub cat}/K{sub M}-pH profiles with N{sup 1}-acetylspermine are bell-shaped for all the mutants; the similarity to the profile of the wild-type enzyme rules out His67 as being responsible for either of the pK{sub a} values. The pH profiles for the rate constant for flavin reduction for all the mutant enzymes similarly show the same pK{sub a} as wild-type Fms1, about {approx}7.4; this pK{sub a} is assigned to the substrate N4. The k{sub cat}/K{sub O2}-pH profiles for wild-type Fms1 and the H67A enzyme both show a pK{sub a} of about {approx}6.9; this suggests His67 is not responsible for this pH behavior. With the H67Q, H67N, and H67A enzymes the k{sub cat} value decreases when a single residue is protonated, as is the case with the wild-type enzyme. The structure of H67Q Fms1 has been determined at a resolution of 2.4 {angstrom}. The structure shows that the mutation disrupts a hydrogen bond network in the active site, suggesting that His67 is important both for direct interactions with the substrate and to maintain the overall active site structure.

08 HYDROGEN↗
DOE OSTI2013

Comprehensive Study of the Impact of Steam on Polyethyleneimine on Silica for CO 2 Capture

An amine sorbent, prepared by impregnation of polyethyleneimine on silica, was tested for steam stability. The stability of the sorbent was investigated in a fixed bed reactor using multiple steam cycles of 90 vol % H 2 O/He at 105 °C, and the gas effluent was monitored with a mass spectrometer. CO 2 uptake of sorbent was found to decrease with repeated exposure to steam. Characterization of the spent sorbent using N 2 physisorption, SEM, and thermogravimetric analysis (TGA) showed that the decrease in CO 2 loading can possibly be attributed to a reagglomeration of the amine in the pores of the silica. No support effect was found in this study. The commercial SiO 2 used, Cariact G10, was found to be stable under the conditions used. While it was found that subjecting the sorbent to several steam cycles decreased its CO 2 uptake, a continuous exposure of the sorbent to steam did not have a significant performance impact. Finally, a silanated sorbent, consisting of a mixture of PEI and aminopropyl-triethoxysilane on SiO 2 support, was also investigated for steam stability. Similarly to the nonsilanated sorbent, the CO 2 loading of this sorbent decreased upon steam exposure, although a mechanism for this change has not been postulated at this time.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Understanding the Impacts of Support–Polymer Interactions on the Dynamics of Poly(ethyleneimine) Confined in Mesoporous SBA-15

Supported amines are a promising class of CO 2 sorbents offering large uptake capacities and fast uptake rates. Additionally, among supported amines, poly(ethyleneimine) (PEI) physically impregnated in the mesopores of SBA-15 silica is widely used. Within these composite materials, the chain dynamics and morphologies of PEI strongly influence the CO 2 capture performance, yet little is known about chain and macromolecule mobility in confined pores. Here, we probe the impact of the support–PEI interactions on the dynamics and structures of PEI at the support interface and the corresponding impact on CO 2 uptake performance, which yields critical structure–property relationships. The pore walls of the support are grafted with organosilanes with different chemical end groups to differentiate interaction modes (spanning from strong attraction to repulsion) between the pore surface and PEI. Combinations of techniques, such as quasi-elastic neutron scattering (QENS), 1 H T 1 –T 2 relaxation correlation solid-state NMR, and molecular dynamics (MD) simulations, are used to comprehensively assess the physical properties of confined PEI. We hypothesized that PEI would have faster dynamics when subjected to less attractive or repulsive interactions. However, we discover that complex interfacial interactions resulted in complex structure–property relationships. Indeed, both the chain conformation of the surface-grafted chains and of the PEI around the surface influenced the chain mobility and CO 2 uptake performance. By coupling knowledge of the dynamics and distributions of PEI with CO 2 sorption performance and other characteristics, we determine that the macroscopic structures of the hybrid materials dictate the first rapid CO 2 uptake, and the rate of CO 2 sorption during the subsequent gradual uptake stage is determined by PEI chain motions that promote diffusive jumps of CO 2 through PEI-packed domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Enzymatic Routes to Designer Hemicelluloses for Use in Biobased Materials

Various enzymes can be used to modify the structure of hemicelluloses directly in vivo or following extraction from biomass sources, such as wood and agricultural residues. Generally, these enzymes can contribute to designer hemicelluloses through four main strategies: (1) enzymatic hydrolysis such as selective removal of side groups by glycoside hydrolases (GH) and carbohydrate esterases (CE), (2) enzymatic cross-linking, for instance, the selective addition of side groups by glycosyltransferases (GT) with activated sugars, (3) enzymatic polymerization by glycosynthases (GS) with activated glycosyl donors or transglycosylation, and (4) enzymatic functionalization, particularly via oxidation by carbohydrate oxidoreductases and via amination by amine transaminases. Thus, this Perspective will first highlight enzymes that play a role in regulating the degree of polymerization and side group composition of hemicelluloses, and subsequently, it will explore enzymes that enhance cross-linking capabilities and incorporate novel chemical functionalities into saccharide structures. These enzymatic routes offer a precise way to tailor the properties of hemicelluloses for specific applications in biobased materials, contributing to the development of renewable alternatives to conventional materials derived from fossil fuels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Unique Challenges Accompany Thick-Shell CdSe/nCdS (n > 10) Nanocrystal Synthesis

Thick-shell CdSe/nCdS (n {ge} 10) nanocrystals were recently reported that show remarkably suppressed fluorescence intermittency or 'blinking' at the single-particle level as well as slow rates of Auger decay. Unfortunately, whereas CdSe/nCdS nanocrystal synthesis is well-developed up to n {le} 6 CdS monolayers (MLs), reproducible syntheses for n {ge} 10 MLs are less understood. Known procedures sometimes result in homogeneous CdS nucleation instead of heterogeneous, epitaxial CdS nucleation on CdSe, leading to broad and multimodal particle size distributions. Critically, obtained core/shell sizes are often below those desired. This article describes synthetic conditions specific to thick-shell growth (n {ge} 10 and n {ge} 20 MLs) on both small (sub2 nm) and large (>4.5 nm) CdSe cores. We find added secondary amine and low concentration of CdSe cores and molecular precursors give desired core/shell sizes. Amine-induced, partial etching of CdSe cores results in apparent shell-thicknesses slightly beyond those desired, especially for very-thick shells (n {ge} 20 MLs). Thermal ripening and fast precursor injection lead to undesired homogeneous CdS nucleation and incomplete shell growth. Core/shells derived from small CdSe (1.9 nm) have longer PL lifetimes and more pronounced blinking at single-particle level compared with those derived from large CdSe (4.7 nm). We expect our new synthetic approach will lead to a larger throughput of these materials, increasing their availability for fundamental studies and applications.

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

Layer-by-Layer Templated Assembly of Silica at the Nanoscale

Bioinspired bottom-up assembly and layer-by-layer (LbL) construction of inorganic materials from lithographically defined organic templates enables the fabrication of nanostructured systems under mild temperature and pH conditions. Such processes open the door to low-impact manufacturing and facile recycling of hybrid materials for energy, biology, and information technologies. Here, templated LbL assembly of silica was achieved using a combination of electron beam lithography, chemical lift-off, and aqueous solution chemistry. Nanopatterns of lines, honeycomb-lattices, and dot arrays were defined in polymer resist using electron beam lithography. Following development, exposed areas of silicon were functionalized with a vapor deposited amine-silane monolayer. Silicic acid solutions of varying pH and salt content were reacted with the patterned organic amine-functional templates. Vapor treatment and solution reaction could be repeated, allowing LbL deposition. Conditions for the silicic acid deposition had a strong effect on thickness of each layer, and the morphology of the amorphous silica formed. Defects in the arrays of silica nanostructures were minor and do not affect the overall organization of the layers. In conclusion, the bioinspired method described here facilitates the bottom-up assembly of inorganic nanostructures defined in three dimensions and provides a path, via LbL processing, for the construction of layered hybrid materials under mild conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

A rare terminal dinitrogen complex of chromium

Cis and trans-Cr–N₂ complexes supported by the diphosphine ligand P{sup Ph}₂N{sup Bn}₂ have been prepared. Positioned pendant amines in the second coordination sphere influence the thermodynamically preferred geometric isomer. Electronic structure calculations indicate negligible Cr–N₂ back-bonding; rather, electronic polarization of N₂ ligand is thought to stabilize Cr–N₂ binding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗