Nanostructured silicon photocatalysts for solar-driven fuel production.

Solar-driven production of fuels such as hydrogen, hydrocarbons, and ammonia using semiconducting photocatalysts has the potential to be a sustainable alternative to current chemical processes. In recent years, silicon (Si) nanostructures have been recognized as a promising photocatalyst for hydrogen generation and organic oxidation reactions owing to its abundance, biocompatibility, and cost. While bulk Si has been studied extensively, on the nanoscale, plenty of opportunities exist to understand and engineer optimally performing Si photocatalysts. This perspective will highlight key results on the use of Si nanostructures for photocatalytic H2 production, CO2 reduction via light and heat-driven chemical looping, and current challenges in utilizing it for fuel-forming reactions. A brief guide on how these challenges can be addressed in the future and other unexplored questions that remain in the field are also discussed.

Solid-state synthesis of UV-plasmonic Cr2N nanoparticles.

Materials that exhibit plasmonic response in the UV region can be advantageous for many applications, such as biological photodegradation, photocatalysis, disinfection, and bioimaging. Transition metal nitrides have recently emerged as chemically and thermally stable alternatives to metal-based plasmonic materials. However, most free-standing nitride nanostructures explored so far have plasmonic responses in the visible and near-IR regions. Herein, we report the synthesis of UV-plasmonic Cr2N nanoparticles using a solid-state nitridation reaction. The nanoparticles had an average diameter of 9 ± 5 nm and a positively charged surface that yields stable colloidal suspension. The particles were composed of a crystalline nitride core and an amorphous oxide/oxynitride shell whose thickness varied between 1 and 7 nm. Calculations performed using the finite element method predicted the localized surface plasmon resonance (LSPR) for these nanoparticles to be in the UV-C region (100-280 nm). While a distinctive LSPR peak could not be observed using absorbance measurements, low-loss electron energy loss spectroscopy showed the presence of surface plasmons between 80 and 250 nm (or ∼5 to 15 eV) and bulk plasmons centered around 50-62 nm (or ∼20 to 25 eV). Plasmonic coupling was also observed between the nanoparticles, resulting in resonances between 250 and 400 nm (or ∼2.5 to 5 eV).

Photocatalytic hydrogen generation using mesoporous silicon nanoparticles: influence of magnesiothermic reduction conditions and nanoparticle aging on the catalytic activity.

In recent years, mesoporous silicon (mp-Si) nanoparticles (NPs) have been recognized as promising materials for sustainable photocatalytic hydrogen (H2) generation, which is both an important chemical feedstock and potential clean energy vector. These materials are commonly prepared via magnesiothermic reduction of silica precursors due to the ease, scalability, and tunability of this reaction. In this work, we investigate how the conditions of magnesiothermic reduction (i.e. reaction temperature and time) influence the performance of mp-Si for photocatalytic H2 generation. The mp-Si NPs were prepared using either the conventional single temperature heating method (650 °C for 3 or 6 h) or a two-temperature method in which the reaction is initially heated to 650 °C for 0.5 h, followed by a second step heating at 100 (mp-Si100), 200 (mp-Si200), or 300 °C (mp-Si300) for 6 h. Of these, mp-Si300 was the best performing photocatalyst and showed the highest H2 evolution rate (4437 µmol h-1 g-1 Si). Our results suggest that crystallinity has a profound effect on the performance of mp-Si photocatalysts. Additionally, high amounts of oxygen and particle sintering lower H2 evolution rates by introducing defect states or grain boundaries. It was also discovered that aging mp-Si NPs under ambient conditions result in continued surface oxidation which deleteriously affects its photocatalytic performance.

Photothermal Transduction Efficiencies of Plasmonic Group 4 Metal Nitride Nanocrystals.

The photothermal transduction efficiencies of group 4 metal nitrides, TiN, ZrN, and HfN, at λ = 850 nm are reported, and the performance of these materials is compared to an Au nanorod benchmark. Transition metal nitride nanocrystals with an average diameter of ∼15 nm were prepared using a solid-state metathesis reaction. HfN exhibited the highest photothermal transduction efficiency of 65%, followed by ZrN (58%) and TiN (49%), which were all higher than those of the commercially purchased Au nanorods (43%). Computational studies performed using a finite element method showed HfN and Au to have the lowest and highest scattering cross section, respectively, which could be a contributing factor to the efficiency trends observed. Furthermore, the changes in temperature as a function of illumination intensity and solution concentration, as well as the cycling stability of the metal nitride solutions, were studied in detail.

The influence of hydrofluoric acid etching processes on the photocatalytic hydrogen evolution reaction using mesoporous silicon nanoparticles.

H2 has been identified as one of the potential energy vectors that can provide a sustainable energy supply when produced through solar-driven water-splitting reaction. Si is the second most abundant element in the Earth's crust and can absorb a significant fraction of the solar spectrum while presenting little toxicity risk, making it an attractive material for photocatalytic H2 production. Hydrogen-terminated mesoporous Si (mp-Si) nanoparticles can be utilized to effectively drive the hydrogen evolution reaction using UV-to-visible light. In this work, the response of the photocatalytic activity of mp-Si nanoparticles to a series of HF acid treatments was investigated. A two-step magnesiothermic reduction method was used to prepare crystalline mp-Si nanoparticles with a specific surface area of 573 m2 g-1. The HF etching process was optimized as a function of the amount of acid added and the reaction time. The reaction time did not influence the H2 evolution rate substantially. However, the amount of HF used did have a significant effect on the photocatalytic activity. In the presence of ≥1.0 mL HF acid per 0.010 g of Si, morphological damage was observed using electron microscopy. N2 adsorption measurements indicated that the pore size and surface area were also altered. Solution-phase 19F{1H} NMR studies indicated the formation of SiF5- and SiF62- when larger volumes of HF were used. Both factors, morphological damage and the presence of byproducts in the pores, likely result in a lowering of the photocatalytic H2 evolution rate. Under the optimized HF treatment conditions (0.5 mL of HF per 0.010 g of Si), a H2 evolution rate of 1398 ± 30 µmol g-1 h-1 was observed.

Overview of Synthetic Methods to Prepare Plasmonic Transition-Metal Nitride Nanoparticles.

The search for new plasmonic materials that are low-cost, chemically and thermally stable, and exhibit low optical losses has garnered significant attention among researchers. Recently, metal nitrides have emerged as promising alternatives to conventional, noble-metal-based plasmonic materials, such as silver and gold. Many of the initial studies on metal nitrides have focused on computational prediction of the plasmonic properties of these materials. In recent years, several synthetic methods have been developed to enable empirical analysis. This review highlights synthetic techniques for the preparation of plasmonic metal nitride nanoparticles, which are predominantly free-standing, by using solid-state and solid-gas phase reactions, nonthermal and arc plasma methods, and laser ablation. The physical properties of the nanoparticles, such as shape, size, crystallinity, and optical response, obtained with such synthetic methods are also summarized.

Synthesis of Plasmonic Group-4 Nitride Nanocrystals by Solid-State Metathesis.

Ceramic nanoparticles that exhibit a plasmonic response are promising next-generation photonic materials. In this contribution, a solid-state metathesis method has been reported for the synthesis of Group 4 nitride (TiN, ZrN, and HfN) nanocrystals. A high-temperature (1000 °C) reaction between Group 4 metal oxide (TiO2 , ZrO2 , and HfO2 ) nanoparticles and magnesium nitride powder yielded nitride nanocrystals that were dispersible in water. A localized surface plasmonic resonance was observed in the near-infrared region for TiN and in the visible region of light for ZrN and HfN nanocrystals. The frequency of the plasmon resonance was dependent on the refractive index of the solvent and the nanocrystal size.

Metallothermic Reduction of Silica Nanoparticles to Porous Silicon for Drug Delivery Using New and Existing Reductants.

In this study, the influence of metals (Mg, Al, and Ca) and reaction conditions (time, temperature, and metal grain size) on the metallothermic reduction of Stöber silica nanoparticles (NPs) to form porous Si has been explored. Mg metal was found to be an effective reducing agent even at temperatures below its melting point; however, it also induced a high degree of structural damage and morphology change. Al was effective in reducing silica NPs only at its melting point or above, but the resulting particles retained a higher degree of structural morphology as compared to those reduced using Mg. Ca was found to be ineffective in reducing silica. A new reductant, a mixture of 70 % Mg and 30 % Al, was found to induce the least amount of morphology change, and the reactions proceeded at a temperature (450 °C) lower than those required with Mg or Al individually. Furthermore, porous Si NPs obtained using Mg, Al, and the mixture of 70 % Mg and 30 % Al as reductants have been investigated as carriers for ibuprofen loading and release. Porous Si obtained from reductions with Mg and the Mg/Al mixture showed higher drug loading and a sustained drug release profile, whereas porous Si obtained from Al reduction had lower loading and showed a conventional release profile over 24 h.

Profiling Photoinduced Carrier Generation in Semiconductor Microwire Arrays via Photoelectrochemical Metal Deposition.

Au was photoelectrochemically deposited onto cylindrical or tapered p-Si microwires on Si substrates to profile the photoinduced charge-carrier generation in individual wires in a photoactive semiconductor wire array. Similar experiments were repeated for otherwise identical Si microwires doped to be n-type. The metal plating profile was conformal for n-type wires, but for p-type wires was a function of distance from the substrate and was dependent on the illumination wavelength. Spatially resolved charge-carrier generation profiles were computed using full-wave electromagnetic simulations, and the localization of the deposition at the p-type wire surfaces observed experimentally correlated well with the regions of enhanced calculated carrier generation in the volumes of the microwires. This technique could potentially be extended to determine the spatially resolved carrier generation profiles in a variety of mesostructured, photoactive semiconductors.

Silicon Nanocrystals and Silicon-Polymer Hybrids: Synthesis, Surface Engineering, and Applications.

Silicon nanocrystals (Si-NCs) are emerging as an attractive class of quantum dots owing to the natural abundance of silicon in the Earth's crust, their low toxicity compared to many Group II-VI and III-V based quantum dots, compatibility with the existing semiconductor industry infrastructure, and their unique optoelectronic properties. Despite these favorable qualities, Si-NCs have not received the same attention as Group II-VI and III-V quantum dots, because of their lower emission quantum yields, difficulties associated with synthesizing monodisperse particles, and oxidative instability. Recent advancements indicate the surface chemistry of Si-NCs plays a key role in determining many of their properties. This Review summarizes new reports related to engineering Si-NC surfaces, synthesis of Si-NC/polymer hybrids, and their applications in sensing, diodes, catalysis, and batteries.

Charge transfer state emission dynamics in blue-emitting functionalized silicon nanocrystals.

We explore the dynamics of blue emission from dodecylamine and ammonia functionalized silicon nanocrystals (Si NCs) with average diameters of ∼3 and ∼6 nm using time-resolved photoluminescence (TRPL) spectroscopy. The Si NCs exhibit nanosecond PL decay dynamics that is independent of NC size and uniform across the emission spectrum. The TRPL measurements reveal complete quenching of core state emission by a charge transfer state that is responsible for the blue PL with a radiative recombination rate of ∼5 × 10(7) s(-1). A detailed picture of the charge transfer state emission dynamics in these functionalized Si NCs is proposed.

Size vs surface: tuning the photoluminescence of freestanding silicon nanocrystals across the visible spectrum via surface groups.

The syntheses of colloidal silicon nanocrystals (Si-NCs) with dimensions in the 3-4 nm size regime as well as effective methodologies for their functionalization with alkyl, amine, phosphine, and acetal functional groups are reported. Through rational variation in the surface moieties we demonstrate that the photoluminescence of Si-NCs can be effectively tuned across the entire visible spectral region without changing particle size. The surface-state dependent emission exhibited short-lived excited-states and higher relative photoluminescence quantum yields compared to Si-NCs of equivalent size exhibiting emission originating from the band gap transition. The Si-NCs were exhaustively characterized using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transformed infrared spectroscopy (FTIR), and their optical properties were thoroughly investigated using fluorescence spectroscopy, excited-state lifetime measurements, photobleaching experiments, and solvatochromism studies.

Detection of high-energy compounds using photoluminescent silicon nanocrystal paper based sensors.

Luminescent silicon nanocrystals (Si-NCs) surface functionalized with dodecyl groups were exposed to solutions of nitroaromatic compounds including nitrobenzene, nitrotoluene, and dinitrotoluene. It was found that Si-NC luminescence was quenched upon exposure to nitroaromatics via an electron transfer mechanism as indicated by Stern-Volmer analysis. This quenching was exploited and a straightforward paper-based Si-NC sensor was developed. This paper motif was found to be sensitive to solution, vapor, and solid phase nitroaromatics, as well as solution borne RDX and PETN.

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.

Chemical insight into the origin of red and blue photoluminescence arising from freestanding silicon nanocrystals.

Silicon nanocrystals (Si NCs) are attractive functional materials. They are compatible with standard electronics and communications platforms and are biocompatible. Numerous methods have been developed to realize size-controlled Si NC synthesis. While these procedures produce Si NCs that appear identical, their optical responses can differ dramatically. Si NCs prepared using high-temperature methods routinely exhibit photoluminescence agreeing with the effective mass approximation (EMA), while those prepared via solution methods exhibit blue emission that is somewhat independent of particle size. Despite many proposals, a definitive explanation for this difference has been elusive for no less than a decade. This apparent dichotomy brings into question our understanding of Si NC properties and potentially limits the scope of their application. The present contribution takes a substantial step forward toward identifying the origin of the blue emission that is not expected based upon EMA predictions. It describes a detailed comparison of Si NCs obtained from three of the most widely cited procedures as well as the conversion of red-emitting Si NCs to blue emitters upon exposure to nitrogen-containing reagents. Analysis of the evidence is consistent with the hypothesis that the presence of trace nitrogen and oxygen even at the parts per million level in Si NCs gives rise to the blue emission.

Solid-state synthesis of luminescent silicon nitride nanocrystals.

Silicon nitride nanocrystals (NCs) have been prepared via in situ nitridation of magnesium followed by a metathesis reaction with sol-gel derived silica particles. Highly luminescent, freestanding ß-Si(3)N(4) NCs with complex surface chemistry dominated by Si-H and N-H moieties were isolated upon etching with hydrofluoric acid.