Unmasking Fluorinated Moieties on the Surface of Hydride-Terminated Silicon Nanoparticles.

Despite the widespread use of hydrofluoric acid (HF) in the preparation of silicon surfaces, the true nature of fluorinated surface species remains unclear. Here, we employ an array of characterization techniques led by solid-state nuclear magnetic resonance spectroscopy to uncover the nature of fluorinated moieties on the surface of hydride-terminated silicon nanoparticles (H-SiNPs). A structural model that explains the observed trends in 19F and 29Si magnetic shielding is proposed and further supported by quantum chemical computations. Fluorine is incorporated into local oxidation domains on the surface and clustered at the interface of the oxide and surrounding hydride-terminated surface. Silicon sites capped by a single fluorine are also identified by their distinct 19F and 29Si chemical shifts, providing insight into how fluorine termination influences the electronic structure. The extent of fluorine passivation and the effects of fluorine on the optical properties of SiNPs are also discussed. Finally, challenges associated with Teflon contamination are highlighted that future explorations of nanomaterials may have to contend with.

Synthesis of high-entropy germanides and investigation of their formation process.

High-entropy alloys and compounds have emerged as an attractive research area in part because of their distinctive solid-solution structure and multi-element compositions that provide near-limitless tailorability. A diverse array of reports describing high-entropy compounds, including carbides, nitrides, sulfides, oxides, fluorides, silicides, and borides, has resulted. Strikingly, exploration of high-entropy germanides (HEGs) has remained relatively limited. In this study, we present a detailed investigation into the synthesis of HEGs, specifically AuAgCuPdPtGe and FeCoNiCrVGe, via a rapid thermal annealing. The structural, compositional, and morphological characteristics of the synthesized HEGs were assessed using laboratory X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Complementing these post-synthesis analyses, we interrogated the formation and growth mechanisms using in situ heating XRD and TEM and determined that HEG formation involved initial decomposition of germanane (GeNSs) during the annealing, followed by gradual grain growth via atom diffusion at temperatures below 600 °C, and finally a rapid grain growth process at elevated temperatures.

Not all silicon quantum dots are equal: photostability of silicon quantum dots with and without a thick amorphous shell.

Luminescent colloidal silicon quantum dots (SiQDs) are sustainable alternatives to metal-based QDs for various optical applications. While the materials are reliant on their photoluminescence efficiency, the relationship between the structure and photostability of SiQDs is yet to be well studied. An amorphous silicon (a-Si) shell was recently discovered in SiQDs prepared by thermally-processed silicon oxides. As a-Si is known as a source of defects upon UV irradiation, the disordered shell could potentially have an adverse effect on the optical properties of nanoparticles. Herein, the photostability of ∼5 nm diameter SiQDs with an amorphous shell was compared with that of over-etched SiQDs of equivalent dimensions that bore an a-Si shell of negligible thickness. An UV-induced degradation study was conducted by subjecting toluene solutions of SiQDs to 365 nm light-emitting diodes (LEDs) under an inert atmosphere for predetermined times up to 72 hours. The structure, composition, and optical responses of the exposed SiQDs were evaluated.

Spectrotemporal characterization of photoluminescent silicon nanocrystals and their energy transfer to dyes.

Silicon nanocrystals (SiNCs) are a promising material for applications in bioanalysis and imaging. Compared to other types of semiconductor nanocrystals, the development and characterization of energy transfer (ET) configurations with SiNCs has been far more limited, resulting in an equally limited understanding of this process and its SiNC-specific nuances. Here, we present a systematic and detailed study of ET between SiNCs and dyes. A combination of spectroelectrophoresis and time-gated and time-resolved photoluminescence measurements were used to characterize the photophysical properties of ensembles of SiNCs and gain insight into how these properties varied as a function of nanocrystal size. ET between SiNC donors and a series of non-fluorescent Black Hole Quencher (BHQ) dyes and fluorescent sulfo-Cyanine 5.5 dye acceptors was evaluated in terms of spectral properties, wavelength-resolved efficiencies, trends with spectral overlap integral, and differences between two methods of BHQ association with the SiNCs. The overall results were consistent with a Förster resonance energy transfer (FRET) mechanism where the polydispersity of the SiNCs had a significant impact on the observed ET: the choice of wavelength and timing parameters were important, and ensemble measurements represented an average of heterogeneous ET behaviors. Prospective advantages and disadvantages of SiNCs as ET donors are discussed. This study serves as a foundation for the continued and optimized development of ET configurations with SiNCs.

Facile synthesis of high-entropy alloy nanoparticles on germanane, Ge nanoparticles and wafers.

The unique solid-solution structure and multi-element compositions of high-entropy alloy nanoparticles (HEA NPs) have garnered substantial attention. Various methods have been developed to prepare a diverse array of HEA NPs using different substrates for support and stabilization. In this study, we present a facile surface-mediated reduction method to prepare HEA NPs (AuAgCuPdPt) decorated germanane (HEA NPs@GeNSs), and employ X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) to characterize their structure, composition, and morphology. Subsequently, we demonstrate that the HEA NPs can be liberated from the surfaces of GeNSs as freestanding systems via straightforward exposure to UV light. We also explore germanium nanoparticles (GeNPs) as an alternative substrate for HEA NP formation/production, given their similarity to germanane and their Ge-H surface. Finally, we extend our investigation to bulk Ge wafers and demonstrate successful deposition of HEA NPs.

Exploring Structural Nuances in Germanium Halide Perovskites Using Solid-State 73Ge and 133Cs NMR Spectroscopy.

Metal halide perovskites remain top candidates for higher-performance photovoltaic devices, but concerns about leading lead-based materials remain. Ge perovskites remain understudied for use in solar cells compared to their Sn-based counterparts. In this work, we undertake a combined 73Ge and 133Cs solid-state Nuclear Magnetic Resonance (NMR) spectroscopy and density functional theory (DFT) study of the bulk CsGeX3 (X = Cl, Br, or I) series. We show how seemingly small structural variations within germanium halide perovskites have major effects on their 73Ge and 133Cs NMR signatures and reveal a near-cubic phase at room temperature for CsGeCl3 with severe local Ge polyhedral distortion. Quantum chemical computations are effective at predicting the structural impact on NMR parameters for 73Ge and 133Cs. This study demonstrates the value of a combined solid-state NMR and DFT approach for investigating promising materials for energy applications, providing information that is out of reach with conventional characterization methods, and adds the challenging 73Ge nucleus to the NMR toolkit.

Metal nanoparticle-decorated germanane for selective photocatalytic aerobic oxidation of benzyl alcohol.

Two dimensional materials such as germanane have attracted substantial research interest due to their unique chemical, optical, and electronic properties. A variety of methods for introducing diverse functionalities to their surfaces have been reported and these materials have been exploited as photocatalysts. Herein, we report the preparation of metal nanoparticle (Au, Ag, Cu, Pd, Pt) decorated germanane (M@GeNSs) via facile surface-mediated reduction and investigate their structure, composition, as well morphology using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). These functional materials were subsequently explored as photocatalysts for selective visible light-induced oxidation of benzyl alcohol to benzaldehyde as freestanding nanosystems and thin films and a reaction mechanism of the photocatalytic oxidation of benzyl alcohol is proposed.

Synthesis, Properties, and Derivatization of Poly(dihydrogermane): A Germanium-Based Polyethylene Analogue.

Polygermanes are germanium-based analogues of polyolefins and possess polymer backbones made up catenated Ge atoms. In the present contribution we report the preparation of a germanium polyethylene analogue, polydihydrogermane (GeH2)n, via two straightforward approaches that involve topotactic deintercalation of Ca ions from the CaGe Zintl phase. The resulting (GeH2)n possesses morphologically dependent chemical and electronic properties and thermally decomposes to yield amorphous hydrogenated Ge. We also show that the resulting (GeH2)n provides a platform from which functionalized polygermanes can be prepared via thermally induced hydrogermylation-mediated pendant group substitution.

Thiophene Cation Intercalation to Improve Band-Edge Integrity in Reduced-Dimensional Perovskites.

The insertion of large organic cations in metal halide perovskites with reduced-dimensional (RD) crystal structures increases crystal formation energy and regulates the growth orientation of the inorganic domains. However, the power conversion performance is curtailed by the insulating nature of the bulky cations. Now a series of RD perovskites with 2-thiophenmethylammonium (TMA) as the intercalating cation are investigated. Compared with traditional ligands, TMA demonstrates improved electron transfer in the inorganic framework. TMA modifies the near-band-edge integrity of the RD perovskite, improving hole transport. A power conversion efficiency of 19 % is achieved, the highest to date for TMA-based RD perovskite photovoltaics; these TMA devices provide a 12 % relative increase in PCE compared to control RD perovskite devices that use PEA as the intercalating ligand, a result of the improved charge transfer from the inorganic layer to the organic ligands.

Simple fabrication of zirconium and nitrogen co-doped ordered mesoporous carbon for enhanced adsorption performance towards polar pollutants.

Ordered mesoporous carbons (OMCs) are a kind of remarkable adsorbents in environment area due to high surface area, controllable pore size and superior stability. However, the inherent hydrophobicity and strong π-π interaction make OMCs have an advantage for the adsorption of nonpolar pollutants, leading to great demands for the development of new-type OMCs with outstanding adsorption efficiencies towards polar pollutants. The zirconium and nitrogen co-doped ordered mesoporous carbon (Zr/N-OMC) was obtained by directly carbonizing the composites of phenolic resin and UiO-66-NH2, with uniform mesopore structure, large surface area (583 m2 g-1) and widely dispersed heteroatoms. Due to these prominent properties, the Zr/N-OMC was fabricated as high-performance solid phase microextraction coating. The results proved that the doping zirconium and nitrogen could act as active sites to interact with polar pollutants, resulting in fast adsorption rate and enhanced adsorption capacity. Therefore, the high-performance Zr/N-OMC-coated fiber was coupled with gas chromatography-mass spectrometry to establish sensitive analytical method for the detection of trace phenols from real water samples. This work would open up a new avenue for simple and efficient modification of OMC with enhanced adsorption performance to expand applications.

Low-cost Scholl-coupling microporous polymer as an efficient solid-phase microextraction coating for the detection of light aromatic compounds.

A cost-effective microporous polymer was synthesized using cheap monomer and catalyst via one-step Scholl-coupling reaction, and its chemical, morphological characteristics and pore structure were investigated. The as-synthesized polymer with large surface area and narrow pore distribution (centered in 1.2 nm) was prepared as a fiber coating for solid-phase microextraction (SPME). Headspace SPME was used for the extraction of the light aromatic compounds, e.g. benzene, toluene, ethylbenzene, m-xylene, naphthalene and acenaphthene. The parameters influencing the extraction and desorption efficiencies, such as extraction temperature and time, salt concentration, desorption temperature and time were investigated and optimized. The results showed that the home-made fiber had superior extraction efficiencies compared with the commercial PDMS fiber. Under the optimized conditions, low detection limits (0.01-1.3 ng/L), wide linear ranges (from 50 to 20000 ng/L to 1-20000 ng/L), good repeatability (4.2-9.3%, n = 6) and reproducibility (0.30-11%, n = 3) were achieved. Moreover, the practical applicability of the coating and proposed method was evaluated by determining the target light aromatic compounds in environmental water samples with satisfied recoveries (83.2%-116%).

Fabrication of powdery polymer aerogel as the stationary phase for high-resolution gas chromatographic separation.

Novel powdery polymer aerogel (PPA) prepared via the (micro)emulsion polymerization and the following hyper crosslinking reaction was fabricated as stationary phase of capillary column for the first time. Due to its powdery morphology, unique 3D nano-network structure, high surface area and good thermostability, the PPA-coated capillary column demonstrated high-resolution chromatographic separation towards nonpolar and weakly polar organic compounds, including benzene series, n-alkanes, ketone mixtures and trichlorobenzenes. Moreover, the reproducibility, quantitative analysis ability and thermostability of PPA-coated capillary column were also evaluated. The relative standard deviations for three replicate determinations of selected analytes were 0.02-0.11%, 0.12-0.26% and 1.2-3.6% for run-to-run, day-to-day and column-to-column analyses, respectively. The PPA demonstrated good thermostability, and the PPA-coated capillary column was proved to be heat-resistant (270 °C). The results of this study show PPA is an excellent candidate to be employed as stationary phase for gas chromatography capillary.

Hollow carbon nanospheres with high surface areas for fast, broad-spectrum and sensitive adsorption of pollutants.

Hollow carbon nanospheres (HCNs) with numerous nanopores in their ultrathin carbon shells have been prepared and applied as SPME fiber coatings. Benefiting from its ultrahigh surface area, short diffusion distance, and nitrogen doping, the HCNs-coated fiber demonstrates excellent properties of fast mass transfer, broad-spectrum adsorption and high extraction efficiencies. These encouraging results could offer a benchmark for developing advanced SPME in environment analyses requiring high-performance enrichment of abundant analytes, especially for unknown compounds.