Efficient one-pot synthesis of monodisperse alkyl-terminated colloidal germanium nanocrystals

An efficient one-pot method for fabricating alkyl-capped germanium nanocrystals (Ge NCs) is reported. Ge NCs with a size of 3.9 ± 0.5 nm, are formed by co-reduction of germanium tetrachloride in the presence of n-butyltrichlorogermane, producing NCs with butyl-terminated surfaces. The advantage of this method is that it allows rapid synthesis and functionalisation of NCs with minimal post-synthetic purification requirements. TEM imaging showed that the Ge NCs are monodisperse and highly crystalline, while EDX and SAED confirmed the chemical identity and crystal phase of the NCs. FTIR and XPS confirmed that the Ge NCs were well passivated, with some oxidation of the nanocrystal surface. Optical spectroscopy of the NCs showed a strong absorbance in the UV region and an excitation wavelength dependent photoluminescence in the UV/violet. Time resolved photoluminescence measurements showed the presence of two nanosecond lifetime components, consistent with recombination of photogenerated excitons at low lying energy states present at the nanocrystal surface. Photoluminescence quantum yields were determined to be 37 %, one of the highest values reported for organically terminated Ge NCs

Size and emission color tuning in the solution phase synthesis of highly luminescent germanium nanocrystals

Highly luminescent germanium nanocrystals (NCs) are synthesized at room temperature by hydride reduction of germanium tetrachloride (GeCl4) within inverse micelles. Regulation of the Ge NC size is achieved by varying the alkyl chain length of the cationic quaternary ammonium surfactants used to form the inverse micelles. The Ge NCs are chemically passivated with allylamine ligands using a Pt-catalyzed hydrogermylation reaction, minimizing surface oxidation while rendering the NCs dispersible in a range of polar solvents. Transmission electron microscopy shows that the NCs are highly crystalline with well-defined core diameters tuned from 3 to 5 nm. UV-Vis absorbance and photoluminescence (PL) spectroscopy show significant quantum confinement effects, with moderate absorption in the UV spectral range, and a strong, narrow luminescence in the visible with a marked dependency on excitation wavelength. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases to 4.5 nm

Germanium nanocrystals as luminescent probes for rapid, sensitive and label-free detection of Fe3+ ions

Luminescent water-soluble germanium nanocrystals (Ge NCs) have been developed as a fluorescent sensing platform for the highly selective and sensitive detection of Fe3+ via quenching of their strong blue luminescence, without the need for analyte-specific labelling groups. The amine-terminated Ge NCs were separated into two discrete size fractions with average diameters of 3.9 +/- 0.4 nm and 6.8 +/- 1.8 nm using centrifugation. The smaller 3.9 nm NCs possessed a strong blue luminescence, with an average lifetime of 6.1 ns and a quantum yield (QY) of 21.5%, which is strongly influenced by solution pH. In contrast, 6.8 nm NCs exhibited a green luminescence with a longer lifetime of 7.8 ns and lower QY (6.2%) that is insensitive to pH. Sensitive detection of Fe3+ was successfully demonstrated, with a linear relationship between luminescence quenching and Fe3+ concentration observed from 0-800 mu M, with a limit of detection of 0.83 mu M. The Ge NCs show excellent selectivity toward Fe3+ ions, with no quenching of the fluorescence signal induced by the presence of Fe2+ ions, allowing for solution phase discrimination between ions of the same element with different formal charges. The luminescence quenching mechanism was confirmed by static and time-resolved photoluminescence spectroscopies, while the applicability for this assay for detection of Fe3+ in real water samples was successfully demonstrated

Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies

Highly selective optical detection of Fe3+ ions in aqueous solution using label-free silicon nanocrystals

High brightness amine‐terminated silicon nanocrystals (Si NCs) have been utilized in a simple and rapid assay for the highly selective and sensitive detection of Fe3+ via quenching of their strong blue luminescence, without the need for analyte‐specific labeling groups. Sensitive detection of Fe3+ is successfully demonstrated, with a linear relationship observed between luminescence quenching and Fe3+ concentration from 5 × 10−6 to 900 × 10−6m and a limit of detection of 1.3 × 10−6m. The Si NCs show excellent selectivity toward Fe3+ ions, with no quenching of the luminescence signal induced by the presence of Fe2+ ions, allowing for solution phase discrimination between the ionic species in different charge states

Proteomic evaluation of citrate-coated silver nanoparticles toxicity in Daphnia magna

Recent decades have seen a strong increase in the promise and uses of nanotechnology. This is correlated with their growing release in the environment and there is concern that nanomaterials may endanger ecosystems. Silver nanoparticles (AgNPs) have some of the most varied applications, making their release into the environment unavoidable. In order to assess their potential toxicity in aquatic environments, the acute toxicity of citrate-coated AgNPs to Daphnia magna was measured and compared to that of AgNO3. AgNPs were found to be ten times less toxic by mass than silver ions, and most of this toxicity was removed by ultracentrifuging. At the protein level, the two forms of silver had different impacts. Both increased protein thiol content, while only AgNP increased carbonyl levels. In 2DE of samples labelled for carbonyls, no feature was significantly affected by both compounds, indicating different modes of toxicity. Identified proteins showed functional overlap between the two compounds: vitellogenins (vtg) were present in most features identified, indicating their role as a general stress sensor. In addition to vtg, hemoglobin levels were increased by the AgNP exposure while 14-3-3 protein (a regulatory protein) carbonylation levels were reduced by AgNO3. Overall, this study confirms the previously observed lower acute toxicity of AgNPs, while demonstrating that the toxicity of both forms of silver follow somewhat different biologic pathways, potentially leading to different interactions with natural compounds or pollutants in the aquatic environment

Environmentally friendly nitrogen-doped carbon quantum dots for next generation solar cells

Shine on you crazy carbon! In this work, nitrogen-doped carbon quantum dots (N-CQDs) are synthesized using a simple custom atmospheric pressure microplasma. The method is facile, rapid, and environmentally friendly and the N-CQDs can be produced in a few minutes with no need for high temperature, complicated chemical techniques, or surface ligands. The N-CQDs are formed using molecular precursors and can be produced in different solvent mixtures. Material characterization techniques show a high degree of nitrogen doping on the QD surface with the amount of nitrogen depending on initial reaction conditions. The NCQDs show interesting quantum confined optical properties that depend on the amount of nitrogen incorporation. Importantly, the band energy structure of the N-CQDs is elucidated and they are incorporated into a photovoltaic device as the photoactive layer achieving an extraordinary open-circuit voltage of 1.8 V and a power conversion efficiency of 0.8% (champion device), amongst the highest reported to date for group IV and carbon based quantum dots

Ultra‐small CuO nanoparticles with tailored energy‐band diagram synthesized by a hybrid plasma‐liquid process

CuO is a versatile p-type material for energy applications capable of imparting diverse functionalities by manipulating its band-energy diagram. We present ultra-small quantum confined cupric oxide nanoparticles (CuO NPs) synthesized via a simple one-step environmentally friendly atmospheric pressure microplasma synthesis process. The proposed method, based on the use of a hybrid plasma-liquid cell, enables the synthesis of CuO NPs directly from solid metal copper in ethanol with neither surfactants nor reducing agents. CuO NPs films are then used for the first time in all-inorganic third generation solar cell devices demonstrating highly effective functionalities as blocking layer

Activated Functionalized Carbon Nanotubes and 2D Nanostructured MoS2 Hybrid Electrode Material for High‐Performance Supercapacitor Applications

Alkali-activated functionalized carbon nanotubes (AFCNTs) and 2D nanostructured MoS2 are investigated as a novel hybrid material for energy-storage applications. The nanoflower-like 2D MoS2 is grown on the surface of AFCNT using the controlled one-step hydrothermal technique. The activation of functionalized carbon nanotubes results in greater performance due to the improved surface area. The Brunauer–Emmett–Teller (BET) surface area of the AFCNTs is found to be 594.7 m2 g−1 which is almost 30 times of the as-prepared carbon nanotubes (CNTs). The improved surface area with attached hydroxyl and carboxylic functional groups helps in the attachment of MoS2 nanoflowers onto the AFCNT, thus reducing the interfacial resistance and providing an easy path for electron transfer. The electrochemical analysis shows a high specific capacitance of 516 F g−1 at 0.5 A g−1 with a corresponding energy density of 71.76 Wh kg−1, which is an encouraging reported value from AFCNT and MoS2 hybrid material. To the best of our knowledge, herein, the first report on AFCNTs and 2D MoS2 nanostructured hybrid electrode material for supercapacitor applications is provided, and promising results in terms of specific capacitance, energy density, and power density by boosting the properties of individual material are explained

Evolution of Anodic Product from Molybdenum Metal in Absolute Ethanol and Humidity Sensing under Ambient Conditions

Authors would like to thank the support from National Natural Science Foundation of China (NSFC) (Nos. 51702264 and 41371275), Fundamental Research Funds for the Central Universities (No. XDJK2017B033), and Research Funding of Southwest University (No. SWU117019). The funding from the Engineering and Physical Sciences Research Council (EPSRC) (under Grant Nos. EP/K022237/1, EP/K036769/1, and EP/M024938/1) is also acknowledged. We also appreciate the funding from the EU COST Action (No. TD1208) for useful exchanges and discussions.Room-temperature nonaqueous synthetic routes turn out to be particularly competitive among all the available liquid-phase synthetic methods for nanometer-sized metal oxides for multiple applications. Microplasma-assisted anodization is employed to prepare soluble and crystalline Mo species in a water-deficient and extraneous ionic-salt-free ethanol electrolyte. The anodization of Mo in absolute ethanol is found to produce Mo oxyethoxide in the liquid ethanol phase, along with a small montage of mixed hexagonal and orthorhombic MoO3 crystals. The evolution of Mo species in solid and liquid phases is characterized to study the crystallization of MoO3 crystal and the formation of blue spherical Mo polyoxometalates (POMs) after extended aging. The addition of water in the suspension delayed the formation of molybdenum blue while hydrogen peroxide induced the precipitation of a dendritic framework of hexagonal MoO3. A thin MoO3 film was produced from the solution and can be used for humidity sensing by the facile conductivity measurement.PostprintPostprintPeer reviewe