Superhydrophobic Silicon Nanocrystal-Silica Aerogel Hybrid Materials: Synthesis, Properties, and Sensing Application.

Silicon nanocrystals (SiNCs) are abundant and exhibit exquisitely tailorable optoelectronic properties. The incorporation of SiNCs into highly porous and lightweight substrates such as aerogels leads to hybrid materials possessing the attractive features of both materials. This study describes the covalent deposition of SiNCs on and intercalation into silica aerogels, explores the properties, and demonstrates a prototype sensing application of the composite material. SiNCs of different sizes were functionalized with triethoxyvinylsilane (TEVS) via a radical grafting approach and subsequently used for the synthesis of photoluminescent silica hybrids. The resulting SiNC-containing aerogels possess high porosities, SiNC-based size-dependent photoluminescence, transparency, and a superhydrophobic macroscopic surface. The materials were used to examine the photoluminescence response toward low concentrations of 3-nitrotoluene (270 µM), demonstrating their potential as a sensing platform for high-energy materials.

Cellulose nanocrystal-derived hollow mesoporous carbon spheres and their application as a metal-free catalyst.

In this contribution, we demonstrate the fabrication of hollow mesoporous carbon spheres (HCSs) derived from cellulose nanocrystals (CNCs). The HCSs were prepared by templating CNCs onto sacrificial silica spheres followed by heat treatment. Mesoporous carbon spheres result from the removal of the silica spheres by etching. The walls of the HCSs are approximately 4 nm thick and are composed of amorphous and graphitic carbon. The catalytic activity of the HCSs was investigated for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) by sodium borohydride (NaBH4). The present investigation reveals the outstanding catalytic activity of these particles. The reaction rate followed pseudo-first order kinetics with k value of 4.72 × 10-3 s-1 and activity parameter of 52.2 s-1 g-1, which showed superior performance compared to that of metal nanoparticle and metal nanoparticle-carbon hybrid based catalysts.

Cooperative Noncovalent Interactions Induce Ion Pair Separation in Diphenylsilanides.

This crystallographic and computational study describes an unusual potassium silanide structure. A contact ion pair is expected in the solid state between potassium and silicon, yet the potassium cation binds an aromatic ring and the anionic silanide interacts with CH bonds on neighboring crown ether molecules. These structure-bonding phenomena are attributed to strong soft-soft interactions.

In situ IR-spectroscopy as a tool for monitoring the radical hydrosilylation process on silicon nanocrystal surfaces.

Among a variety of SiNC functionalization methods, radical initiated grafting is very promising due to its straightforward nature and low propensity to form surface oligomers. In the present study, we employed in situ IR spectroscopy in combination with visible light transmittance measurements to investigate the radical induced grafting process on the well-defined SiNCs. Our findings support the proposed model: unfunctionalized hydride-terminated SiNCs form agglomerates in organic solvents, which break up during the grafting process. However, clearing of the dispersion is not a valid indicator for complete surface functionalization. Furthermore, radical-initiated grafting reactions in which azobisisobutyronitrile (AIBN) is the initiator are strongly influenced by external factors including initiator concentration, grafting temperature, as well as substrate steric demand. The monomer concentration was proven to have a low impact on the grafting process. Based on these new insights an underlying mechanism could be discussed, offering an unprecedented view on the functionalization of SiNC surfaces via radical initiated hydrosilylation.

Phosphorus Pentachloride Initiated Functionalization of Silicon Nanocrystals.

Phosphorus pentachloride (PCl5) has long been used to chlorinate hydrocarbons. It has also been applied in silicon surface chemistry to facilitate alkylation via a two-step halogenation/Grignard route. Here we report a study of the reaction of PCl5 with hydride-terminated silicon nanocrystals (H-SiNCs). An examination of the reaction mechanism has allowed us to establish a functionalization protocol that uses PCl5 as a surface radical initiator to introduce alkyl and alkenyl moieties to the surface of H-SiNCs. The reaction proceeds quickly in a single step, at room temperature and the functionalized silicon nanocrystals retained their morphology and crystallinity. The resulting materials exhibited size-dependent photoluminescence that was approximately 3× as bright as that observed for thermally hydrosilylated SiNCs. Furthermore, the absolute PL quantum yield (AQY) was more than double. The high AQY is expected to enable SiNCs to compete with chalcogenide-based quantum dots in various applications.

Instantaneous Functionalization of Chemically Etched Silicon Nanocrystal Surfaces.

Remarkable advances in surface hydrosilylation reactions of C=C and C=O bonds on hydride-terminated silicon have revolutionized silicon surface functionalization. However, existing methods for functionalizing hydride-terminated Si nanocrystals (H-SiNCs) require long reaction times and elevated temperatures. Herein, we report a room-temperature method for functionalizing H-SiNC surfaces within seconds by stripping outermost atoms on H-SiNC surfaces with xenon difluoride (XeF2 ). Detailed analysis of the reaction byproducts by in situ NMR spectroscopy and GC-MS provided unprecedented insight into NC surface composition and reactivity as well as the complex reaction mechanism of XeF2 activated hydrosilylation.

Alkoxy-Terminated Si Surfaces: A New Reactive Platform for the Functionalization and Derivatization of Silicon Quantum Dots.

Alkoxy-terminated silicon quantum dots (SiQDs) were synthesized via hydrosilylation of aliphatic ketones on hydride-terminated SiQD (H-SiQD) surfaces under microwave-irradiation. Aromatic ketones undergo hydrosilylation on H-SiQD surfaces at room temperature without requiring any catalyst. The alkoxy-terminated SiQDs are soluble in organic solvents, colloidally stable, and show bright and size dependent photoluminescence (PL). The alkoxy-functionalized silicon surfaces were used as reactive platform for further functionalization via unprecedented ligand exchange of the alkoxy-surface groups with alkyl or alkenyl-surface groups in the presence of BH3·THF. Proton nuclear magnetic resonance ((1)H NMR), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS) spectroscopy confirmed alkoxy-terminated surfaces and their ligand exchange reactions in the presence of various alkenes and alkynes.

Grafting Poly(3-hexylthiophene) from Silicon Nanocrystal Surfaces: Synthesis and Properties of a Functional Hybrid Material with Direct Interfacial Contact.

Hybrid functional materials (HFMs) comprised of semiconductor nanoparticles and conjugated polymers offer the potential of synergetic photophysical properties. We have developed HFMs based upon silicon nanocrystals (SiNCs) and the conductive polymer poly(3-hexylthiophene) (SiNC@P3HT) by applying surface-initiated Kumada catalyst transfer polycondensation (SI-KCTP). One unique characteristic of the developed SiNC@P3HT is the formation of a direct covalent bonding between SiNCs and P3HT. The presented method for obtaining direct interfacial attachment, which is not accessible using other methods, may allow for the development of materials with efficient electronic communication at the donor-acceptor interfaces. Systematic characterization provides evidence of a core-shell structure, enhanced interfacial electron and/or energy transfer between the P3HT and SiNC components, as well as formation of a type-II heterostructure.

Application of Engineered Si Nanoparticles in Light-Induced Advanced Oxidation Remediation of a Water-Borne Model Contaminant.

Surface-engineered amphiphilic polymer-coated silicon nanoparticles (SiNPs) were employed as photocatalysts to capture and degrade a model organic contaminant (methanol) in water. This study represents the first time SiNPs have been employed in the initiation of advanced oxidation processes that are commonly used to degrade organic constituents in industrial wastewaters. The quantum yield of photocatalytic methanol oxidation and the corresponding yield factor for the generation of active OH radicals are reported. The size and surface defect dependent photocatalytic activity of SiNPs was investigated. The yield factors (η) decreased with increasing particle size and reached impressive values that exceeded that of equivalent TiO2 nanoparticle systems by 3-4 times and are comparable to the robust UV/Cl2 and UV/H2O2 systems. The higher photocatalytic efficiency of SiNPs is attributed to the combined effects of quantum confinement, effective band gap, and surface states, among which surface states play a dominant role. SiNPs provide a potentially tunable, biologically inert, and robust nanoparticle system for photocatalytic oxidation of wastewater contaminants.

Spherical nitrogen-doped hollow mesoporous carbon as an efficient bifunctional electrocatalyst for Zn-air batteries.

Materials based upon porous carbon have gained considerable attention due to their high surface area, electric conductivity, thermal and chemical stability, low density, and availability. These superior properties make them ideal for diverse applications. Doping these carbon nanostructures holds promise of designing the properties of these structures and opening the door to practical applications. Herein, we report the preparation of hollow N-doped mesoporous carbon (HMC) spheres fabricated via polymerization and carbonization of dopamine on a sacrificial spherical SiO(2) template that is removed upon hydrofluoric acid etching. The morphology and structural features of these HMCs were evaluated using scanning electron microscopy and transmission electron microscopy and the N-doping (7.1 at%) was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen reduction/evolution reaction (ORR/OER) performance of N-doped HMC was evaluated using rotating disk electrode (RDE) voltammetry in an alkaline electrolyte. N-doped HMC demonstrated a high ORR onset potential of -0.055 V (vs. Hg/HgO) and excellent stability. The outstanding bifunctional activity was implemented in a practical Zn-air battery (ZAB), which exhibited a small charge-discharge voltage polarization of 0.89 V and high stability over repeated cycling.

Radical Initiated Hydrosilylation on Silicon Nanocrystal Surfaces: An Evaluation of Functional Group Tolerance and Mechanistic Study.

Hydrosilylation is among the most common methods used for modifying silicon surface chemistry. It provides a wide range of surface functionalities and effective passivation of surface sites. Herein, we report a systematic study of radical initiated hydrosilylation of silicon nanocrystal (SiNC) surfaces using two common radical initiators (i.e., 2,2'-azobis(2-methylpropionitrile) and benzoyl peroxide). Compared to other widely applied hydrosilylation methods (e.g., thermal, photochemical, and catalytic), the radical initiator based approach is particle size independent, requires comparatively low reaction temperatures, and yields monolayer surface passivation after short reaction times. The effects of differing functional groups (i.e., alkene, alkyne, carboxylic acid, and ester) on the radical initiated hydrosilylation are also explored. The results indicate functionalization occurs and results in the formation of monolayer passivated surfaces.

Direct Evaluation of the Quantum Confinement Effect in Single Isolated Ge Nanocrystals.

To address the yet open question regarding the nature of quantum confinement in Ge nanocrystals (Ge NCs) we employed scanning tunneling spectroscopy to monitor the electronic structure of individual isolated Ge NCs as a function of their size. The (single-particle) band gaps extracted from the tunneling spectra increase monotonically with decreasing nanocrystal size, irrespective of the capping ligands, manifesting the effect of quantum confinement. Band-gap widening of ∼1 eV with respect to the bulk value was observed for Ge-NCs 3 nm in diameter. The picture emerging from comparison with theoretical calculations and other experimental results is discussed.

One-pot synthesis of functionalized germanium nanocrystals from a single source precursor.

One-pot syntheses of surface functionalized germanium nanocrystals (GeNCs) based upon traditional hot injection and microwave-assisted heating of a Ge(II) dihydride single source precursor have been developed. The reported procedures offer in situ hydrogermylation-based covalent attachment of alkene/alkyne derived surface moieties that give access to hydrophobic or hydrophilic GeNCs.

Photoluminescent silicon nanocrystals with chlorosilane surfaces--synthesis and reactivity.

We present a new efficient two-step method to covalently functionalize hydride terminated silicon nanocrystals with nucleophiles. First a reactive chlorosilane layer was formed via diazonium salt initiated hydrosilylation of chlorodimethyl(vinyl)silane which was then reacted with alcohols, silanols and organolithium reagents. With organolithium compounds a side reaction is observed in which a direct functionalization of the silicon surface takes place.

Borane-catalyzed room-temperature hydrosilylation of alkenes/alkynes on silicon nanocrystal surfaces.

Room-temperature borane-catalyzed functionalization of hydride-terminated silicon nanocrystals (H-SiNCs) with alkenes/alkynes is reported. This new methodology affords formation of alkyl and alkynyl surface monolayers of varied chain lengths (i.e., C5-C12). The present study also indicates alkynes react more readily with H-SiNC surfaces than equivalent alkenes. Unlike other toxic transition-metal catalysts, borane or related byproducts can be readily removed from the functionalized SiNCs. The new method affords stable luminescent alkyl/alkenyl-functionalized SiNCs.

Chloride surface terminated silicon nanocrystal mediated synthesis of poly(3-hexylthiophene).

Abundant and environmentally benign metal-free silicon-based reagents, including chloride surface-terminated silicon nanocrystals (Cl-SiNCs) and silicon wafers as well as molecular chlorosilanes, were explored as catalysts for the synthesis of poly-3-hexylthiophene (P3HT) at room temperature. Cl-SiNC catalysts exhibit the highest activity of those investigated, and systems based upon single-crystal silicon wafers provide convenient, straightforward purification. The as-prepared P3HT exhibits moderate molecular weights and bears H/Br or Br/Br end groups; these properties will allow direct application and also facilitate their use as macroinitiators in the syntheses of block and/or telechelic polymers. The silicon-based systems are expected to provide an efficient metal-free catalytic preparation of functional polymers.

Water-soluble photoluminescent d-mannose and l-alanine functionalized silicon nanocrystals and their application to cancer cell imaging.

Herein, we report the straightforward synthesis, photoluminescent properties, and cell imaging studies of d-mannose and l-alanine functionalized silicon nanocrystals (SiNCs). Tailoring nanocrystal surface functionalization is essential to interfacing SiNCs with their environment and rendering them stable - surface modification also offers the opportunity to target specific cell types for imaging. A simple and versatile surface modification procedure was developed to tether biomolecules onto the SiNC surfaces and render them water-soluble. The presented approach is precious metal-catalyst free, straightforward, and provides carbohydrate and amino acid functionalized SiNCs. The functionalized SiNCs have been investigated by fluorescence microscopy and our results indicate that they can be internalized by MCF-7 human breast cancer cells as shown in the cell imaging studies. The obtained SiNCs were characterized using FTIR, XPS, PL, and TEM.

Low temperature synthesis of silicon carbide nanomaterials using a solid-state method.

Silicon carbide (SiC) nanomaterials have been prepared via the solid-state metathesis reaction of various silica sources, magnesium and carbon. This approach enables synthesis of crystalline ß-SiC nanomaterials of varied morphologies at 600 °C - the lowest temperature reported to date. The resulting materials were characterized using XRD, FTIR, XPS, TEM and SEM techniques.

Cytotoxicity of surface-functionalized silicon and germanium nanoparticles: the dominant role of surface charges.

Although it is frequently hypothesized that surface (like surface charge) and physical characteristics (like particle size) play important roles in cellular interactions of nanoparticles (NPs), a systematic study probing this issue is missing. Hence, a comparative cytotoxicity study, quantifying nine different cellular endpoints, was performed with a broad series of monodisperse, well characterized silicon (Si) and germanium (Ge) NPs with various surface functionalizations. Human colonic adenocarcinoma Caco-2 and rat alveolar macrophage NR8383 cells were used to clarify the toxicity of this series of NPs. The surface coatings on the NPs appeared to dominate the cytotoxicity: the cationic NPs exhibited cytotoxicity, whereas the carboxylic acid-terminated and hydrophilic PEG- or dextran-terminated NPs did not. Within the cationic Si NPs, smaller Si NPs were more toxic than bigger ones. Manganese-doped (1% Mn) Si NPs did not show any added toxicity, which favors their further development for bioimaging. Iron-doped (1% Fe) Si NPs showed some added toxicity, which may be due to the leaching of Fe(3+) ions from the core. A silica coating seemed to impart toxicity, in line with the reported toxicity of silica. Intracellular mitochondria seem to be the target for the toxic NPs since a dose-, surface charge- and size-dependent imbalance of the mitochondrial membrane potential was observed. Such an imbalance led to a series of other cellular events for cationic NPs, like decreased mitochondrial membrane potential (ΔΨm) and ATP production, induction of ROS generation, increased cytoplasmic Ca(2+) content, production of TNF-α and enhanced caspase-3 activity. Taken together, the results explain the toxicity of Si NPs/Ge NPs largely by their surface characteristics, provide insight into the mode of action underlying the observed cytotoxicity, and give directions on synthesizing biocompatible Si and Ge NPs, as this is crucial for bioimaging and other applications in for example the field of medicine.