A General Approach for Monolayer Adsorption of High Weight Loadings of Uniform Nanocrystals on Oxide Supports.

Monodispersed metal and semiconductor nanocrystals have attracted great attention in fundamental and applied research due to their tunable size, morphology, and well-defined chemical composition. Utilizing these nanocrystals in a controllable way is highly desirable especially when using them as building blocks for the preparation of nanostructured materials. Their deposition onto oxide materials provide them with wide applicability in many areas, including catalysis. However, so far deposition methods are limited and do not provide control to achieve high particle loadings. This study demonstrates a general approach for the deposition of hydrophobic ligand-stabilized nanocrystals on hydrophilic oxide supports without ligand-exchange. Surface functionalization of the supports with primary amine groups either using an organosilane ((3-aminopropyl)trimethoxysilane) or bonding with aminoalcohols (3-amino-1,2-propanediol) were found to significantly improve the interaction between nanocrystals and supports achieving high loadings (>10 wt. %). The bonding method with aminoalcohols guarantees the opportunity to remove the binding molecules thus allowing clean metal/oxide materials to be obtained, which is of great importance in the preparation of supported nanocrystals for heterogeneous catalysis.

Nanoscale Spatial Distribution of Supported Nanoparticles Controls Activity and Stability in Powder Catalysts for CO Oxidation and Photocatalytic H2 Evolution.

Supported metal nanoparticles are essential components of high-performing catalysts, and their structures are intensely researched. In comparison, nanoparticle spatial distribution in powder catalysts is conventionally not quantified, and the influence of this collective property on catalyst performance remains poorly investigated. Here, we demonstrate a general colloidal self-assembly method to control uniformity of nanoparticle spatial distribution on common industrial powder supports. We quantify distributions on the nanoscale using image statistics and show that the type of nanospatial distribution determines not only the stability, but also the activity of heterogeneous catalysts. Widely investigated systems (Au-TiO2 for CO oxidation thermocatalysis and Pd-TiO2 for H2 evolution photocatalysis) were used to showcase the universal importance of nanoparticle spatial organization. Spatially and temporally resolved microkinetic modeling revealed that nonuniformly distributed Au nanoparticles suffer from local depletion of surface oxygen, and therefore lower CO oxidation activity, as compared to uniformly distributed nanoparticles. Nanoparticle spatial distribution also determines the stability of Pd-TiO2 photocatalysts, because nonuniformly distributed nanoparticles sinter while uniformly distributed nanoparticles do not. This work introduces new tools to evaluate and understand catalyst collective (ensemble) properties in powder catalysts, which thereby pave the way to more active and stable heterogeneous catalysts.

General Self-Assembly Method for Deposition of Graphene Oxide into Uniform Close-Packed Monolayer Films.

Depositing a morphologically uniform monolayer film of graphene oxide (GO) single-layer sheets is an important step in the processing of many composites and devices. Conventional Langmuir-Blodgett (LB) deposition is often considered to give the highest degree of morphology control, but film microstructures still vary widely between GO samples. The main challenge is in the sensitive self-assembly of GO samples with different sheet sizes and degrees of oxidation. To overcome this drawback, here, we identify a general method that relies on robust assembly between GO and a cationic surfactant (cationic surfactant-assisted LB). We systematically compared conventional LB and cationic surfactant-assisted LB for three common GO samples of widely different sheet sizes and degrees of oxidation. Although conventional LB may occasionally provide satisfactory film morphology, cationic surfactant-assisted LB is general and allows deposition of films with tunable and uniform morphologies-ranging from close-packed to overlapping single layers-from all three types of GO samples investigated. Because cationic surfactant-assisted LB is robust and general, we expect this method to broaden and facilitate the use of GO in many applications where precise control over film morphology is crucial.

Langmuir-Blodgett Deposition of Graphene Oxide-Identifying Marangoni Flow as a Process that Fundamentally Limits Deposition Control.

Langmuir-Blodgett deposition is a popular route to produce thin films of graphene oxide for applications such as transparent conductors and biosensors. Unfortunately, film morphologies vary from sample to sample, often with undesirable characteristics such as folded sheets and patchwise depositions. In conventional Langmuir-Blodgett deposition of graphene oxide, alcohol (typically methanol) is used to spread the graphene oxide sheets onto an air-water interface before deposition onto substrates. Here we show that methanol gives rise to Marangoni flow, which fundamentally limits control over Langmuir-Blodgett depositions of graphene oxide. We directly identified the presence of Marangoni flow by using photography, and we evaluated depositions with atomic force microscopy and scanning electron microscopy. The disruptive effect of Marangoni flow was demonstrated by comparing conventional Langmuir-Blodgett depositions to depositions where Marangoni flow was suppressed by a surfactant. Because methanol is the standard spreading solvent for conventional Langmuir-Blodgett deposition of graphene oxide, Marangoni flow is a general problem and may partly explain the wide variety of undesirable film morphologies reported in the literature.

Effects of particle size and annealing on plasmon-induced charge separation at self-assembled gold nanoparticle arrays.

Two-dimensional periodic Au nanoparticle arrays were constructed on TiO2 thin films by a micelle lithography method and seed-mediated photoelectrochemical growth. Their adjustable interparticle distance allows investigation of a particle size effect on plasmon-induced charge separation (PICS) efficiencies without interference from particle aggregation or plasmon coupling. External or internal PICS efficiencies were found to increase and decrease, respectively, with an increase in particle diameter from 25 to 38 nm. Improvement of the contact between Au nanoparticles and TiO2 by annealing enhanced the intensity of a plasmonic interface mode and both external and internal PICS efficiencies.

Hydrogen evolution from water based on plasmon-induced charge separation at a TiO2/Au/NiO/Pt system.

Metal-semiconductor plasmonic nanostructures are capable of converting light energy through plasmon-induced charge separation (PICS), providing fruitful new strategies to utilize solar energy in various fields, including photocatalysis. Here, we enhance the PICS efficiencies for hydrogen evolution from water at a Pt cathode coupled with a TiO2/Au photoanode by coating the TiO2/Au with a p-type NiO layer on which a Pt co-catalyst is deposited. PICS occurs at the Au-TiO2 interface under visible light. The electrons injected from the Au nanoparticles into TiO2 are transported to the Pt cathode and cause hydrogen evolution from water, the action spectrum of which matches the plasmonic extinction spectrum of the Au nanoparticles. The NiO layer extracts the separated positive charges from the Au nanoparticles, accumulates the charges and drives methanol oxidation at the Pt co-catalyst on NiO with the positive charges. As a result of the introduction of the Pt-modified NiO layer, the rates of methanol oxidation and accompanying hydrogen evolution at zero bias voltage were improved by ∼3.5 times. The NiO layer may also protect the Au nanoparticles from self-oxidation.

A general method for growing large area mesoporous silica thin films on flat substrates with perpendicular nanochannels.

Here we introduce a new synthetic approach to grow mesoporous silica thin films with vertical mesochannels on centimeter-sized substrates via an oil-induced co-assembly process. Adding an oil, i.e., decane, into a CTAB-EtOH-TEOS ammonia solution leads to thin-film formation of mesoporous silica of controlled thickness between 20 and 100 nm with vertical mesochannels on various surfaces. The vertical mesoporous channels were evidenced by grazing incidence small-angle X-ray scattering (GISAXS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) characterizations. Decane played two roles: (a) as a pore expansion agent (up to 5.7 ± 0.5 nm) and (b) inducing vertically oriented hexagonal mesophases of micelle-silica composite. The production of periodic and vertical nanochannels is very robust, over many different substrate surfaces (from silicon to polystyrene), various silica precursors (TEOS, fumed silica, or zeolite seed), and many oils (decane, petroleum ether, or ethyl acetate). This wide robustness in the formation of vertical nanophases is attributed to a unique mechanism of confined synthesis of surfactant-silicate between two identical thin layers of oils on a substrate.

Collapsed (kippah) hollow silica nanoparticles.

Novel collapsed kippah-like mesoporous silica nanoparticles were synthesized using an O/W microemulsion system. The oil (hexadecane) can escape from the core while water could not enter through the surfactant filled nanopores of the soft shell during synthesis.