Turning Trash to Treasure: The Influence of Carbon Waste Source on the Photothermal Behaviour of Plasmonic Titanium Carbide Interfaces.

Pyrolysis of carbonaceous waste materials has emerged as an effective recycling method to generate value-added products. In addition to producing pyrolytic oil and gas, the thermal degradation process yields solid pyrolytic char, which can be further processed. In this study, local waste materials, birch wood residue, Japanese knotweed stems, spent coffee grounds, tire rubber, and lobster shells were assessed for their potential to form pyrolytic char. After a simple acid treatment, many of these chars were successfully incorporated into solid-state synthesis of plasmonic titanium carbide (TiC) nanoparticles (NPs). Each char exhibited unique physical and chemical properties, which were leveraged to synthesize TiC NPs with distinct characteristics. To evaluate the plasmonic behavior of these TiC samples, solar-driven desalination experiments were performed. Notably, TiC derived from tire rubber demonstrated a high broadband absorbance and achieved a solar-to-vapor generation efficiency of 95%, corresponding to an evaporation rate of 1.40 ± 0.01 kg m-2 h-1 under one-sun illumination. This performance is the highest among all chars tested and ranks among the top reported values in the literature. Additionally, the evaporation interface maintained its performance over multiple cycles and under highly hypersaline conditions.

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).

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.

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.

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.

Key developments in magnesiothermic reduction of silica: insights into reactivity and future prospects.

Porous Si (p-Si) nanomaterials are an exciting class of inexpensive and abundant materials within the field of energy storage. Specifically, p-Si has been explored in battery anodes to improve charge storage capacity, to generate clean fuels through photocatalysis and photoelectrochemical processes, for the stoichiometric conversion of CO2 to value added chemicals, and as a chemical H2 storage material. p-Si can be made from synthetic, natural, and waste SiO2 sources through a facile and inexpensive method called magnesiothermic reduction (MgTR). This yields a material with tunable properties and excellent energy storage capabilities. In order to tune the physical properties that affect performance metrics of p-Si, a deeper understanding of the mechanism of the MgTR and factors affecting it is required. In this perspective, we review the key developments in MgTR and discuss the thermal management strategies used to control the properties of p-Si. Additionally, we explore future research directions and approaches to bridge the gap between laboratory-scale experiments and industrial applications.

Unlocking the secrets of porous silicon formation: insights into magnesiothermic reduction mechanism using in situ powder X-ray diffraction studies.

The magnesiothermic reduction of SiO2 is an important reaction as it is a bulk method that produces porous Si for a wide range of applications directly from SiO2. While its main advantage is potential tunability, the reaction behavior and final product properties are heavily dependent on many parameters including feedstock type. However, a complete understanding of the reaction pathway has not yet been achieved. Here, using in situ X-ray diffraction analysis, for the first time, various pathways through which the magnesiothermic reduction reaction proceeds were mapped. Further, the key parameters and conditions that determine which pathways are favored were determined. It was discovered that the reaction onset temperatures can be as low as 348 ± 7 °C, which is significantly lower when compared to previously reported values. The onset temperature is dependent on the size of Mg particles used in the reaction. Further, Mg2Si was identified as a key intermediate rather than a reaction byproduct during the reduction process. Its rate of consumption is determined by the reaction temperature which needs to be >561 °C. These findings can enable process and product optimization of the magnesiothermic reduction process to manufacture and tune porous Si for a range of applications.

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.

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.

Surface properties of water-soluble glycine-cysteamine-protected gold clusters.

We report the synthesis of water-soluble, nearly monodisperse glycine-cysteamine (Gly-CSA) gold monolayer protected clusters (MPCs) via base deprotection of Fmoc-Gly-CSA MPCs. The resulting Gly-CSA MPCs, which have terminal primary amine groups, are fully characterized by (1)H and (13)C NMR, UV-vis spectroscopy, and TEM, and their surface properties were probed by dynamic light scattering and acid-base titrations. The characterization methods indicate that the as-synthesized particles are nearly monodisperse with an average particle size of 1.8 +/- 0.3 nm, but are only stable to aggregation in water at pHs of 4 and below. Acid-base titrations of the Gly-CSA MPCs show that the primary ammonium groups have a pK(a) of approximately 5.5, which is several orders of magnitude lower than the pK(a2) for the ammonium group of glycine (9.6). Thus, the particles are only partially protonated at intermediate pH's, which then drives the aggregation of the nanoparticles via hydrogen-bond formation. Dynamic light scattering results confirm the pH-driven aggregation of the nanoparticles, and studies with ninhydrin confirm that the primary amine groups are reactive and have potential for further functionalization. These results show that amine-terminated MPCs can be synthesized; however, their aggregation at intermediate pH's can limit their utility as building blocks for multifunctional nanoparticle syntheses.

Probing the relative stability of thiolate- and dithiolate-protected Au monolayer-protected clusters.

Dithiolate ligands based on (+/-)-alpha-lipoic acid derivatives have been investigated as ligands for both Au monolayer-protected clusters (MPCs) and mixed alkanethiol/dithiolate Au MPCs. The oxidative and thermal stability of the MPCs were investigated by a combination of UV-vis spectroscopy, TEM, and (1)H NMR experiments. Results show that the dithiolate-protected MPCs are much more prone to oxidation by oxygen under ambient conditions than their alkanethiolate-protected MPC analogues; in addition, the Au core of the dithiolate-protected Au MPCs could be etched by KCN at much faster rates than both alkanethiolate-protected and mixed monolayer MPCs. These results suggest that strategies to increase ligand-metal interactions by incorporating more thiolate linkers into the ligand must also take into account the packing efficiency and/or stability of such ligands on the metal surface, which can make them much more prone to oxidation under ambient conditions.

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.