Colloidal Synthesis and Photocatalytic Properties of Cu3NbS4 and Cu3NbSe4 Sulvanite Nanocrystals.

Niobium sulvanites Cu3NbX4 (X = S, Se) have been theoretically predicted as promising candidates for solar photovoltaics and photocatalytic water splitting. This report outlines the first synthesis of Cu3NbS4 and Cu3NbSe4 in a nanocrystalline form. The crystal structures were investigated by X-ray diffraction, identity was confirmed by Raman spectroscopy, and the optoelectronic properties and morphology of Cu3NbS4 and Cu3NbSe4 nanocrystals were examined by UV-vis spectroscopy and transmission electron microscopy, respectively. To gain insight into the Cu3NbX4 formation, a mechanistic study was conducted for Cu3NbSe4 monitoring the nanoparticles' formation as a function of reaction time. Methylene blue photodegradation tests were conducted to evaluate the photoactivity of Cu3NbS4 and Cu3NbSe4. The degradation rates, 2.81 × 10-2 min-1 and 1.22 × 10-2 min-1 proved the photocatalysts' potential of nanoscale Cu3NbX4.

Photocatalytic Deposition of Nanostructured CsPbBr3 Perovskite Quantum Dot Films on Mesoporous TiO2 and Their Enhanced Visible-Light Photodegradation Properties.

Herein, we report the in situ photocatalytic deposition of cesium lead bromide (CsPbBr3) perovskite quantum dots on mesoporous TiO2-coated fluorine-doped tin oxide (FTO/TiO2) electrodes. The mesoporous TiO2 layer is used as a photocatalyst to promote the following: (1) the Pb deposition from a Pb2+ aqueous solution and (2) the in situ Pb conversion into CsPbBr3 perovskite in the presence of a CsBr methanolic solution without any organic capping agent. Both steps are carried out under ultraviolet light irradiation under ambient conditions without any post-treatment. The obtained FTO/TiO2/CsPbBr3 film was characterized by UV-vis diffuse reflectance spectroscopy, X-ray diffraction, photoluminescence spectroscopy, scanning electron microscopy, and transmission electron microscopy. The FTO/TiO2/CsPbBr3 heterojunction exhibited enhanced visible-light photodegradation activity demonstrated for the oxidation of curcumin organic dye as a model system. The novel and simple approach to fabricating a supported photocatalyst represents a scalable general method to use semiconductors as a platform to incorporate different perovskites, either all-inorganic or hybrid, for optoelectronic applications. The perovskite deposition method mediated by the UV light at room temperature could be further applied to flexible and wearable solar power electronics.

Stand-Alone CuFeSe2 (Eskebornite) Nanosheets for Photothermal Cancer Therapy.

Two-dimensional CuFeSe2 nanosheets have been successfully obtained via solution-phase synthesis using a sacrificial template method. The high purity was confirmed by X-ray diffraction and the two-dimensional morphology was validated by transmission electron microscopy. The intense absorption in the 400-1400 nm region has been the basis for the CuFeSe2 nanosheets' photothermal capabilities testing. The colloidal CuFeSe2 (CFS) nanosheets capped with S2- short ligands (CFS-S) exhibit excellent biocompatibility in cell culture studies and strong photothermal effects upon 808 nm laser irradiation. The nanosheets were further loaded with the cancer drug doxorubicin and exposed to laser irradiation, which accelerated the release of doxorubicin, achieving synergy in the therapeutic effect.

Sulvanites: The Promise at the Nanoscale.

The class of ternary copper chalcogenides Cu3MX4 (M = V, Nb, Ta; X = S, Se, Te), also known as the sulvanite family, has attracted attention in the past decade as featuring promising materials for optoelectronic devices, including solar photovoltaics. Experimental and theoretical studies of these semiconductors have provided much insight into their properties, both in bulk and at the nanoscale. The recent realization of sulvanites at the nanoscale opens new avenues for the compounds toward printable electronics. This review is aimed at the consideration of synthesis methods, relevant properties and the recent developments of the most important sulvanites.

Cascade synthesis and optoelectronic applications of intermediate bandgap Cu3VSe4 nanosheets.

Two-dimensional (2D) ternary materials recently generated interest in optoelectronics and energy-related applications, alongside their binary counterparts. To date, only a few naturally occurring layered 2D ternary materials have been explored. The plethora of benefits owed to reduced dimensionality prompted exploration of expanding non-layered ternary chalcogenides into the 2D realm. This work presents a templating method that uses 2D transition metal dichalcogenides as initiators to be converted into the corresponding ternary chalcogenide upon addition of copper, via a solution-phase synthesis, conducted in high boiling point solvents. The process starts with preparation of VSe2 nanosheets, which are next converted into Cu3VSe4 sulvanite nanosheets (NSs) which retain the 2D geometry while presenting an X-ray diffraction pattern identical with the one for the bulk Cu3VSe4. Both the scanning electron microscopy and transmission microscopy electron microscopy show the presence of quasi-2D morphology. Recent studies of the sulfur-containing sulvanite Cu3VS4 highlight the presence of an intermediate bandgap, associated with enhanced photovoltaic (PV) performance. The Cu3VSe4 nanosheets reported herein exhibit multiple UV-Vis absorption peaks, related to the intermediate bandgaps similar to Cu3VS4 and Cu3VSe4 nanocrystals. To test the potential of Cu3VSe4 NSs as an absorber for solar photovoltaic devices, Cu3VSe4 NSs thin-films deposited on FTO were subjected to photoelectrochemical testing, showing p-type behavior and stable photocurrents of up to ~ 0.036 mA/cm2. The photocurrent shows a ninefold increase in comparison to reported performance of Cu3VSe4 nanocrystals. This proves that quasi-2D sulvanite nanosheets are amenable to thin-film deposition and could show superior PV performance in comparison to nanocrystal thin-films. The obtained electrical impedance spectroscopy signal of the Cu3VSe4 NSs-FTO based electrochemical cell fits an equivalent circuit with the circuit elements of solution resistance (Rs), charge-transfer resistance (Rct), double-layer capacitance (Cdl), and Warburg impedance (W). The estimated charge transfer resistance value of 300 Ω cm2 obtained from the Nyquist plot provides an insight into the rate of charge transfer on the electrode/electrolyte interface.

Synthesis and optoelectronic properties of Cu3VSe4 nanocrystals.

The ternary chalcogenide Cu3VSe4 (CVSe) with sulvanite structure has been theoretically predicted to be a promising candidate for photovoltaic applications due to its suitable bandgap for solar absorption and the relatively earth-abundant elements in its composition. To realize the absorber layer via an inexpensive route, printed thin-films could be fabricated from dispersions of nano-sized Cu3VSe4 precursors. Herein, cubic Cu3VSe4 nanocrystals were successfully synthesized via a hot-injection method. Similar with reported Cu3VS4 nanocrystals, Cu3VSe4 nanocrystals with cubic structure exhibit three absorption bands in the UV-Visible range indicative of a potential intermediate bandgap existence. A thin film fabricated by depositing the nanoparticles Cu3VSe4 on FTO coated glass substrate, exhibited a p-type behavior and a photocurrent of ~ 4 µA/cm2 when measured in an electrochemical cell setting. This first demonstration of photocurrent exhibited by a CVSe nanocrystals thin film signifies a promising potential in photovoltaic applications.

Real-time imaging of tunable adenosine 5-triphosphate release from an MCM-41-type mesoporous silica nanosphere-based delivery system.

We studied a mesoporous silica nanosphere (MSN) material with tunable release capability for drug delivery applications. We employed luciferase chemiluminescence imaging to investigate the kinetics and mechanism of the adenosine 5-triphosphate (ATP) release with various disulfide-reducing agents as uncapping triggers. ATP molecules were encapsulated within the MSNs by immersing dry nanospheres in aqueous solutions of ATP followed by capping of the mesopores with chemically removable caps, such as cadmium sulfide (CdS) nanoparticles and poly(amido amine) dendrimers (PAMAM), via a disulfide linkage. By varying the chemical nature of the ''cap'' and ''trigger'' molecules in our MSN system, we discovered that the release profiles could indeed be regulated in a controllable fashion.

Fine-tuning the degree of organic functionalization of mesoporous silica nanosphere materials via an interfacially designed co-condensation method.

A synthetic method that can fine tune the amount of chemically accessible organic functional groups on the pore surface of MCM-41 type mesoporous silica nanosphere (MSN) materials has been developed by electrostatically matching various anionic organoalkoxysilanes with the cationic cetyltrimethylammonium bromide micelles in a base-catalyzed condensation reaction of tetraethoxysilane.

A polyamidoamine dendrimer-capped mesoporous silica nanosphere-based gene transfection reagent.

We synthesized a MCM-41-type mesoporous silica nanosphere (MSN)-based gene transfection system, where second generation (G2) polyamidoamines (PAMAMs) were covalently attached to the surface of MSN. The G2-PAMAM-capped MSN material (G2-MSN) was used to complex with a plasmid DNA (pEGFP-C1) that encodes for an enhanced green fluorescence protein. The gene transfection efficacy, uptake mechanism, and biocompatibility of the G2-MSN system with various cell types, such as neural glia (astrocytes), human cervical cancer (HeLa), and Chinese hamster ovarian (CHO) cells, were investigated. The mesoporous structure of the MSN material allows membrane-impermeable molecules, such as pharmaceutical drugs and fluorescent dyes, to be encapsulated inside the MSN channels. The system renders the possibility to serve as a universal transmembrane carrier for intracellular drug delivery and imaging applications.

Gatekeeping layer effect: a poly(lactic acid)-coated mesoporous silica nanosphere-based fluorescence probe for detection of amino-containing neurotransmitters.

We have synthesized a poly(lactic acid) coated MCM-41-type mesoporous silica nanosphere (PLA-MSN) material can serve as a fluorescence sensor system for detection of amino-containing neurotransmitters in neutral aqueous buffer. Utilizing the PLA layer as a gatekeeper, we investigated the molecular recognition events between several structurally simple neurotransmitters, i.e., dopamine, tyrosine, and glutamic acid and a pore surface-anchored o-phthalic hemithioacetal (OPTA) group, which functions as a fluorescence-sensing group that can react with the neurotransmitters with primary amine groups and form the corresponding fluorescent isoindole products. The poly(lactic acid) layer of the PLA-MSN sensor showed a unique "sieving" effect that regulates the rates of diffusion of the amino acid-based neurotransmitters into the sensor mesopores of the material.

Oxidative polymerization of 1,4-diethynylbenzene into highly conjugated poly(phenylene butadiynylene) within the channels of surface-functionalized mesoporous silica and alumina materials.

A polyalkynylene-based conducting polymer (molecular wire) has been synthesized within the Cu-functionalized mesoporous MCM-41 silica catalyst. Fluorescence and 13C solid-state NMR provided spectroscopic evidence that the synthesis of extended polymeric chains with a high degree of alignment requires homogeneously distributed catalytic sites throughout the entire MCM matrix. This type of homogeneity has been achieved via co-condensation of the catalytic groups in narrow pores. In addition, our results indicated that proper adjustment of the pore diameter is vital to prevent clogging of the pores with aggregated or cross-linked polymers or both.