Christopher E. Hamilton

High-Yield Organic Dispersions of Unfunctionalized Graphene

We report a simple, high-yield, method of producing homogeneous dispersions of unfunctionalized and nonoxidized graphene nanosheets in ortho-dichlorobenzene (ODCB). Sonication/centrifugation of various graphite materials results in stable homogeneous dispersions. ODCB dispersions of graphene avert the need for harsh oxidation chemistry and allow for chemical functionalization of graphene materials by a range of methods. Additionally, films produced from ODCB-graphene have high conductivity.

Nitrene addition to exfoliated graphene: a one-step route to highly functionalized graphene.

We demonstrate a high yield method of functionalizing graphene nanosheets through nitrene addition of azido-phenylalanine [Phe(N(3))] to exfoliated micro-crystalline graphite (microG). This method provides a direct route to highly functionalized graphene sheets. TEM analysis of the product shows few layer (n < 5) graphene sheets. The product was determined to have 1 phenylalanine substituent per 13 carbons.

Wet Catalyst-Support Films for Production of Vertically Aligned Carbon Nanotubes

A procedure for vertically aligned carbon nanotube (VA-CNT) production has been developed through liquid-phase deposition of alumoxanes (aluminum oxide hydroxides, boehmite) as a catalyst support. Through a simple spin-coating of alumoxane nanoparticles, uniform centimer-square thin film surfaces were coated and used as supports for subsequent deposition of metal catalyst. Uniform VA-CNTs are observed to grow from this film following deposition of both conventional evaporated Fe catalyst, as well as premade Fe nanoparticles drop-dried from the liquid phase. The quality and uniformity of the VA-CNTs are comparable to growth from conventional evaporated layers of Al(2)O(3). The combined use of alumoxane and Fe nanoparticles to coat surfaces represents an inexpensive and scalable approach to large-scale VA-CNT production that makes chemical vapor deposition significantly more competitive when compared to other CNT production techniques.

Synthesis and characterization of aryl substituted bis(2-pyridyl)amines and their copper olefin complexes: Investigation of remote steric control over olefin binding

The aryl-functionalized pyridylamine 2-(i)PrC(6)H(4)N(H)py (1) and bis(2-pyridyl)amines of the type ArN(py)(2) for Ar = Mes (2), 2,6-Et(2)C(6)H(3) (3), 2-(i)PrC(6)H(4) (4), 2,6-(i)Pr(2)C(6)H(3) (5), and 1-naph (6), have been prepared by the palladium-catalyzed cross-coupling of substituted anilines with 2-bromopyridine, and have been characterized by (1)H and (13)C NMR NMR, FTIR, MS, and TGA. Complexes of these new N-aryl bis(2-pyridyl)amines have been prepared for the acid salts [H{ArN(py)(2)}]BF(4) where Ar = Mes (7) and 2-(i)PrC(6)H(4) (8), and the dimeric bridged complexes [Cu{ArN(py)(2)}(μ-X)(Y)](2) where X/Y = Cl(-) and Ar = Ph (9), 2-(i)PrC(6)H(4) (10), and 1-naph (11), in addition to X = OH(-), Y = H(2)O and Ar = Mes (12). The olefin complexes [Cu(Ar-dpa)(styrene)]BF(4) for Ar = Ph (13), Mes (14), 2-(i)PrC(6)H(4) (15), and 1-naph (16), in addition to the norborylene complexes of Ar = Mes (17) and 2-(i)PrC(6)H(4) (18) have been prepared and characterized by (1)H and (13)C NMR, FTIR, and TGA. The crystal structures have been determined for compounds 1-17. Secondary amine 1 crystallizes in hydrogen-bonded head-to-tail dimers, while the N-aryl bis(2-pyridyl)amines 2-6 crystallize in a three-bladed propellar conformation, having nearly planar geometries about the amine nitrogen. The geometry about copper centers in the dimeric complexes 9-12 is distorted trigonal bypyramidal, with the axial positions occupied by one of the two pyridyl nitrogens and one of the bridging ligands (i.e., Cl or OH). The copper atoms in each of the olefin complexes 13-17 are coordinated to the two pyridine nitrogen atoms and the appropriate olefin; consistent with a pseudo three-coordinate Cu(I) cation. Distortion of pyridyl ring geometries about the copper centers, and concomitant bending of the aryl groups away from the CuN(amine) vectors were found to correlate with the steric bulk of the aryl group present in both dimeric and olefin complexes. Such distortion is also observed to a lesser extent in the acid salts as well. The (1)H and (13)C NMR spectra of [Cu(Ar-dpa)(olefin)]BF(4) exhibit an upfield shift in the olefin signal as compared to free olefin. A good correlation exists between the (1)H and (13)C NMR Δδ values and olefin dissociation temperatures, confirming that the shift of the olefin NMR resonances upon coordination is associated with the binding strength of the complex.

Phosphine functionalized single-walled carbon nanotubes

Ultrashort single-walled carbon nanotubes (US-SWNTs) were covalently derivatized with triaryl and trialkyl phosphines. The resulting US-SWNT-phosphine oxide derivatives were then reduced to the US-SWNT-phosphines. In addition, a triarylphosphine sulfide derivative was prepared. The products were characterized by 31P and 13C MAS NMR. The phosphorus NMR indicates a poor correlation between the chemical shifts of molecular phosphines and the chemical shifts of the related US-SWNT-P derivatives.

Matching Solid-State to Solution-Phase Photoluminescence for Near-Unity Down-Conversion Efficiency Using Giant Quantum Dots.

Efficient, stable, and narrowband red-emitting fluorophores are needed as down-conversion materials for next-generation solid-state lighting that is both efficient and of high color quality. Semiconductor quantum dots (QDs) are nearly ideal color-shifting phosphors, but solution-phase efficiencies have not traditionally extended to the solid-state, with losses from both intrinsic and environmental effects. Here, we assess the impacts of temperature and flux on QD phosphor performance. By controlling QD core/shell structure, we realize near-unity down-conversion efficiency and enhanced operational stability. Furthermore, we show that a simple modification of the phosphor-coated light-emitting diode device-incorporation of a thin spacer layer-can afford reduced thermal or photon-flux quenching at high driving currents (>200 mA).