Raid Edward Haddad

Formation mechanism and optimization of highly luminescent N-doped graphene quantum dots

Photoluminescent graphene quantum dots (GQDs) have received enormous attention because of their unique chemical, electronic and optical properties. Here a series of GQDs were synthesized under hydrothermal processes in order to investigate the formation process and optical properties of N-doped GQDs. Citric acid (CA) was used as a carbon precursor and self-assembled into sheet structure in a basic condition and formed N-free GQD graphite framework through intermolecular dehydrolysis reaction. N-doped GQDs were prepared using a series of N-containing bases such as urea. Detailed structural and property studies demonstrated the formation mechanism of N-doped GQDs for tunable optical emissions. Hydrothermal conditions promote formation of amide between –NH2 and –COOH with the presence of amine in the reaction. The intramoleculur dehydrolysis between neighbour amide and COOH groups led to formation of pyrrolic N in the graphene framework. Further, the pyrrolic N transformed to graphite N under hydrothermal conditions. N-doping results in a great improvement of PL quantum yield (QY) of GQDs. By optimized reaction conditions, the highest PL QY (94%) of N-doped GQDs was obtained using CA as a carbon source and ethylene diamine as a N source. The obtained N-doped GQDs exhibit an excitation-independent blue emission with single exponential lifetime decay.

Templated Photocatalytic Synthesis of Well-Defined Platinum Hollow Nanostructures with Enhanced Catalytic Performance for Methanol Oxidation

Hollow metallic nanostructures exhibit important applications in catalysis, sensing, and phototherapy due to their increased surface areas, reduced densities, and unique optical and electronic features. Here we report a facile photocatalytic process to synthesize and tune hollow platinum (Pt) nanostructures. Through hierarchically structured templates, well-defined hollow Pt nanostructures are achieved. These nanostructures possess interconnected nanoporous framework as shell with high surface area for enhanced catalytic performance/mass transport for methanol oxidation.

Interfacial Self-Assembly Driven Formation of Hierarchically Structured Nanocrystals with Photocatalytic Activity

We report the synthesis of hierarchical structured nanocrystals through an interfacial self-assembly driven microemulsion (μ-emulsion) process. An optically active macrocyclic building block Sn (IV) meso-tetraphenylporphine dichloride (tin porphyrin) is used to initiate noncovalent self-assembly confined within μ-emulsion droplets. In-situ studies of dynamic light scattering, UV-vis spectroscopy, and electron microscopy, as well as optical imaging of reaction processes suggest an evaporation-induced nucleation and growth self-assembly mechanism. The resulted nanocrystals exhibit uniform shapes and sizes from ten to a hundred nanometers. Because of the spatial ordering of tin porphyrin, the hierarchical nanocrystals exhibit collective optical properties resulting from the coupling of molecular tin porphyrin and photocatalytic activities in the reduction of platinum nanoparticles and networks and in photodegradation of methyl orange (MO) pollutants.

Nanostructured Gold Architectures Formed through High Pressure-Driven Sintering of Spherical Nanoparticle Arrays

We have demonstrated pressure-directed assembly for preparation of a new class of chemically and mechanically stable gold nanostructures through high pressure-driven sintering of nanoparticle assemblies at room temperature. We show that under a hydrostatic pressure field, the unit cell dimension of a 3D ordered nanoparticle array can be reversibly manipulated allowing fine-tuning of the interparticle separation distance. In addition, 3D nanostructured gold architecture can be formed through high pressure-induced nanoparticle sintering. This work opens a new pathway for engineering and fabrication of different metal nanostructured architectures.

Morphology-Controlled Self-Assembly and Synthesis of Photocatalytic Nanocrystals

Abilities to control the size and shape of nanocrystals in order to tune functional properties are an important grand challenge. Here we report a surfactant self-assembly induced micelle encapsulation method to fabricate porphyrin nanocrystals using the optically active precursor zinc porphyrin (ZnTPP). Through confined noncovalent interactions of ZnTPP within surfactant micelles, nanocrystals with a series of morphologies including nanodisk, tetragonal rod, and hexagonal rod, as well as amorphous spherical particle are synthesized with controlled size and dimension. A phase diagram that describes morphology control is achieved via kinetically controlled nucleation and growth. Because of the spatial ordering of ZnTPP, the hierarchical nanocrystals exhibit both collective optical properties resulted from coupling of molecular ZnTPP and shape dependent photocatalytic activities in photo degradation of methyl orange pollutants. This simple ability to exert rational control over dimension and morphology provides new opportunities for practical applications in photocatalysis, sensing, and nanoelectronics.

Porous one-dimensional nanostructures through confined cooperative self-assembly.

We report a simple confined self-assembly process to synthesize nanoporous one-dimensional photoactive nanostructures. Through surfactant-assisted cooperative interactions (e.g., π-π stacking, ligand coordination, and so forth) of the macrocyclic building block, zinc meso-tetra (4-pyridyl) porphyrin (ZnTPyP), self-assembled ZnTPyP nanowires and nanorods with controlled diameters and aspect ratios are prepared. Electron microscopy characterization in combination with X-ray diffraction and gas sorption experiments indicate that these materials exhibit stable single-crystalline and high surface area nanoporous frameworks with well-defined external morphology. Optical characterizations using UV-vis spectroscopy and fluorescence imaging and spectroscopy show enhanced collective optical properties over the individual chromophores (ZnTPyP), favorable for exciton formation and transport.

Shear-induced mechanochromism in polydiacetylene monolayers

We use atomic force microscopy to actuate and characterize the nanoscale “mechanochromism” of polydiacetylene monolayers on atomically-flat silicon oxide substrates. We find explicit evidence that the irreversible blue-to-red transformation is caused by shear forces exerted normal to the polydiacetylene polymer backbone. The anisotropic probe-induced transformation is characterized by a significant change in the tilt orientation of the side chains with respect to the surface normal. We discuss preliminary molecular dynamics simulations and electronic structure calculations on twelve-unit polydiacetylene oligomers that allow us to correlate the transformation with bond-angle changes in the conjugated polymer backbone.

CORRIGENDUM: Formation mechanism and optimization of highly luminescent N-doped graphene quantum dots

CORRIGENDUM: Formation mechanism and optimization of highly luminescent N-doped graphene quantum dots

Pressure‐Tuned Structure and Property of Optically Active Nanocrystals

Investigations through high-pressure X-ray scattering and spectroscopy in combination with theoretical computations shows that high-pressure compression can systematically tune the optical properties and mechanical stability of the molecular nanocrystals.

Steric bulkiness of pyrrole substituents and the out-of-plane deformations of porphyrins: nickel(II) octaisopropylporphyrin and its meso-nitro derivative

Sterically bulky substituents at the β-carbons of the pyrrole rings of porphyrins are sufficient to cause large out-of-plane porphyrin distortions even in the absence of substituent groups at the meso carbons. It is well established that substituents at the meso-positions only or at both the β-pyrrole and the meso-positions are sufficiently bulky to result in large non-planar distortions of the macrocycle. However, no systematic studies of the effects of bulky β-pyrrole substituents alone have been reported. Herein, molecular simulations and X-ray crystallography of nickel(II) 2,3,7,8,12,13,17,18-octa(isopropyl)porphyrin reveal that large out-of-plane distortions (>1.5 A) are induced by the steric repulsion of the β-isopropyl groups but fail to lead to a single strongly energetically favored conformer. The molecular simulations indicate that multiple conformers differing in the orientation of the isopropyl groups and the macrocycle conformation coexist in solution and this is confirmed by resonance Raman spectroscopy. Large downshifts in the structure-sensitive lines result from the non-planar distortion, and line broadenings result from structural heterogeneity. The heterogeneity originates from tradeoffs between energy contributions from steric repulsion and macrocycle distortion. Simulations for 5-nitro-2,3,7,8,12,13,17,18-octa(isopropyl)porphyrin suggest two possible orientations of the nitro group with respect to the macrocycle mean plane — one nearly vertical (as in the crystal structure) and another that is nearly parallel. INDO/S semiempirical calculations indicate an orbital of the NO2 group resides between the porphyrin frontier orbitals with significant mixing of the nitro and porphyrin orbitals.KEYWORDS: porphyrin, non-planar, resonance Raman, X-ray crystallography, crystal structure, isopropyl, nitro, conformer, molecular mechanics, molecular simulations, density functional theory, steric crowding, conformational heterogeneity.