Suppression Of The Plasmon Resonance In Au/cds Colloidal Nanocomposites

The nature of exciton-plasmon interactions in Au-tipped CdS nanorods has been investigated using femtosecond transient absorption spectroscopy. The study demonstrates that the key optoelectronic properties of composite heterostructures comprising electrically coupled metal and semiconductor domains are substantially different from those observed in systems with weak interdomain coupling. In particular, strongly coupled nanocomposites promote mixing of electronic states at semiconductor-metal domain interfaces, which causes a significant suppression of both plasmon and exciton excitations of carriers

Heteroepitaxial Growth Of Colloidal Nanocrystals Onto Substrate Films Via Hot-injection Routes

Hot-injection synthesis of colloidal nanocrystals (NCs) in a substrate-bound form is demonstrated. We show that polycrystalline films submerged into hot organic solvents can nucleate the heteroepitaxial growth of semiconductor NCs, for which the ensuing lattice quality and size distribution are on the par with those of isolated colloidal nanoparticles. This strategy is demonstrated by growing lead chalcogenide NCs directly onto solvent-submerged TiO(2) substrates. The resulting PbX/VTiO(2) (X = S, Se, Te) nanocomposites exhibit heteroepitaxial interfaces between lead chalcogenide and oxide domains and show an efficient separation of photoinduced charges, deployable for light-harvesting applications. The extendibility of the present method to other material systems was demonstrated through the synthesis of CdS/TiO(2) and Cu(2)S/TiO(2) heterostructures, fabricated from PbS/TiO(2) composites via cation exchange. The photovoltaic performance of nanocrystal/substrate composites comprising PbS NCs was evaluated by incorporating PbS/TiO2 films Into prototype solar cells

Structural Transitions in Nanoparticle Assemblies Governed by Competing Nanoscale Forces

Assembly of nanoscale materials from nanoparticle (NP) building blocks relies on our understanding of multiple nanoscale forces acting between NPs. These forces may compete with each other and yield distinct stimuli-responsive self-assembled nanostructures. Here, we report structural transitions between linear chains and globular assemblies of charged, polymer-stabilized gold NPs, which are governed by the competition of repulsive electrostatic forces and attractive poor solvency/hydrophobic forces. We propose a simple quantitative model and show that these transitions can be controlled by the quality of solvent, addition of a salt, and variation of the molecular weight of the polymer ligands

The Role of Hole Localization in Sacrificial Hydrogen Production by Semiconductor-Metal Heterostructured Nanocrystals

The effect of hole localization on photocatalytic activity of Pt-tipped semiconductor nanocrystals is investigated. By tuning the energy balance at the semiconductor-ligand interface, we demonstrate that hydrogen production on Pt sites is efficient only when electron-donating molecules are used for stabilizing semiconductor surfaces. These surfactants play an important role in enabling an efficient and stable reduction of water by heterostructured nanocrystals as they fill vacancies in the valence band of the semiconductor domain, preventing its degradation. In particular, we show that the energy of oxidizing holes can be efficiently transferred to a ligand moiety, leaving the semiconductor domain intact. This allows reusing the inorganic portion of the degraded nanocrystal-ligand system simply by recharging these nanoparticles with fresh ligands

Surface patterning of nanoparticles with polymer patches

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest1–3. Surface-patterned particles act as colloidal analogues of atoms and molecules4,5, serve as model systems in studies of phase transitions in liquid systems6, behave as ‘colloidal surfactants’7 and function as templates for the synthesis of hybrid particles8. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient9–11, but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties12. At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles13–15, and nanoparticles with surface ripples16 or a ‘raspberry’ surface morphology17. Here we demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. These patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization

Plasmonic and Catalytic Properties of Shape-Controlled Metal Nanoparticles and their Assemblies

This work explores the effect of the shape of metal nanoscale building blocks on the structural, optical, and plasmonic properties of their assemblies, as well as on the catalytic performance and hydrogen interactions of individual nanoparticles with specific shapes. In Chapter 3, I describe the linear self-assembly of bifunctional metal nanoparticles in the presence of monofunctional nanoscale chain stoppers. Chain stoppers with controlled reactivity were synthesized allowing control over the morphology of the self-assembled structures. Analysis of the degree of polymerization of linear nanostructures provided information about self-assembly kinetics, side reactions, and the distribution of species in the reaction. This work facilitated testing of theoretical models developed for molecular polymerization and fabrication of linear nanoparticle assemblies with controllable properties. In Chapter 4, I developed linear solution-based self-assembly of cubic metal nanoparticles, examined the morphology of the nanocube chains and their optical characteristics. In comparison with chains of nanospheres with similar dimensions, compositions, and surface chemistry, predominant face-to-face assembly of nanocubes leads to a larger volume of plasmonic hot spots, uniform electromagnetic field enhancement in the gaps between nanocubes, and a new coupling mode for nanocube chains, associated with Fabry−Perot structure. In Chapter 5, I investigated plasmon-mediated enhancement of the catalysis by palladium-based nanoparticles with different shapes and composition, bearing surface plasmon resonance in visible range. The photocatalytic activity of palladium-based nanoparticles depended more on their shape than internal structure. These findings pave the way for the design of palladium nanocatalysts with enhanced performance acting under visible light illumination. In Chapter 6, I developed a facile scaled-up synthesis of monodisperse palladium nanoparticles with various shapes, stabilized with a mesoporous silica shell. Hydrogen-nanoparticle interactions were studied using temperature programmed desorption. These findings help elucidate the nature of hydrogen interactions with topologically different palladium nanoparticles.Ph.D

Self-assembled plasmonic nanostructures

<p>Self-assembly of plasmonic nanoparticles offers a labour- and cost-efficient strategy for the expansion of the library of plasmonic nanostructures with highly tunable, coupled optical properties. This review covers recent advances in solution-based self-assembly of plasmonic nanoparticles, modelling of the self-assembly process and of the optical properties of the resulting nanostructures, and potential applications of self-assembled plasmonic nanostructures.</p

Mechanism of Ammonia Oxidation to Dinitrogen, Nitrite, and Nitrate on -Ni(OH)2 from First-Principles Simulations

The electrocatalyzed ammonia oxidation reaction (AOR) is a potential pathway toward waste ammonia remediation, energy generation, and the synthesis of value- added products. To date, mechanistic studies have focused on elucidating the progress of AOR on Pt-based catalysts with an established pathway for N2 only. In this work, density functional theory was applied to determine the lowest energy intermediates towards nitrogen gas, nitrite, and nitrate formation on -Ni(OH)2, a promising electrocatalyst material for AOR. It was found that dinitrogen formation progresses via NH-NH coupling while nitrite and nitrate formation occurs via deprotonation to adsorbed N and subsequent hydroxylation to form oxygenated intermediates. This work is the first to report a mechanism for nitrite and nitrate formation and will also serve as a benchmark for future studies on Ni-based materials