Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu3P@NC) as an Electrode for Enhanced Supercapacitor Performance.

A highly conductive and rationally constructed metal-organic framework (MOF)-derived metal phosphide with a carbonaceous nanostructure is a meticulous architecture toward the development of electrode materials for energy storage devices. Herein, we report a facile strategy to design and construct a new three-dimensional (3D) Cu-MOF via a solvent diffusion method at ambient temperature, which was authenticated by a single-crystal X-ray diffraction study, revealing a novel topology of (2,4,7)-connected three-nodal net named smm4. Nevertheless, the poor conductivity of pristine MOFs is a major bottleneck hindering their capacitance. To overcome this, we demonstrated an MOF-derived Cu3P/Cu@NC heterostructure via low-temperature phosphorization of Cu-MOF. The electronic and ionic diffusion kinetics in Cu3P/Cu@NC were improved due to the synergistic effects of the heterostructure. The as-prepared Cu3P/Cu@NC heterostructure electrode delivers a specific capacity of 540 C g-1 at 1 A g-1 with outstanding rate performance (190 C g-1 at 20 A g-1) and cycle stability (91% capacity retention after 10,000 cycles). Moreover, the assembled asymmetric solid-state supercapacitor (ASC) achieved a high energy density/power density of 45.5 Wh kg-1/7.98 kW kg-1 with a wide operating voltage (1.6 V). Long-term stable capacity retention (87.2%) was accomplished after 5000 cycles. These robust electrochemical performances suggest that the Cu3P/Cu@NC heterostructure is a suitable electrode material for supercapacitor applications.

Mechanistic Study of Amphiphilic-Assisted Self-Assembled Cadmium Sulfide Quantum Dots into 3D Superstructures.

Self-assembling of nanoparticles into complex superstructures is very challenging, which usually depends on postorganizing techniques or pre-existing templates such as polypeptide chains or DNA or external stimulus. Such self-assembled processes typically lead to close-packed structures. Here, it has been demonstrated that under carefully template-free reaction conditions CdS quantum dots (QDs) could be synthesized and simultaneously self-assembled into complex superstructures without compromising individual QD properties. The superstructures of CdS QDs attained by the chemical-based method demonstrate Stokes-shifted photoluminescence (PL) from trap states. Remarkably, the PL decay of superstructures exhibits a single-exponential feature. This behavior is unusual for the synthesized superstructures, indicating that the trap states are restricted to a narrow range. The growth mechanism of these superstructures is explained through the formation of liquid crystal phases (LCPs) with the help of a small-angle X-ray scattering (SAXS) analysis.

Molecular Precursor-Driven Synthesis of Copper Telluride Nanostructures for LIB Anode Application.

Copper tellurides have garnered substantial interest for their applicability as an electrocatalyst for water splitting, battery anodes and photodetectors, etc. Moreover, synthesis of phase pure metal tellurides using the multi-source precursor method is challenging. Therefore, a facile synthesis protocol for copper tellurides is anticipated. The current study involves a simplistic single source molecular precursor pathway for the synthesis of orthorhombic-Cu2.86Te2 nano blocks and -Cu31Te24 faceted nanocrystals employing the [Cu{TeC5H3(Me-5)N}]4 cluster in thermolysis and pyrolysis, respectively. The pristine nanostructures were carefully characterized by powder X-ray diffraction, energy-dispersive X-ray spectroscopy, electron microscopic techniques (scanning electron microscopy and transmission electron microscopy), and diffuse reflectance spectroscopy to know the crystal structure, phase purity, elemental composition, distribution of elements, morphology, and optical band gap. These measurements suggests that the reaction conditions fetch nanostructures of different sizes, crystal structures, morphologies, and band gaps. As prepared nanostructures were evaluated for lithium-ion batteries (LIBs) anode material. The cells fabricated with orthorhombic Cu2.86Te2 and orthorhombic Cu31Te24 nanostructures deliver capacities of 68 and 118 mA h/g after 100 cycles. The LIB anode made up of Cu31Te24 faceted nanocrystals exhibited good cyclability and mechanical stability.

Spherical Silver Nanocrystals Arranged in a Metastable Square Pattern.

The present article demonstrates the development of two-dimensional (2D) assembly of spherical nanocrystals (NCs) in the square arrangement through the delicate balance between repulsive ligand interactions and attractive van der Waals interactions of NCs, respectively, instead of the otherwise stable hexagonal arrangement. The experimental packing efficiency values matched quite well with the theoretically calculated square arrangement patterns. The above fact indicates that the formation of the 2D square arrangement of silver NCs can be explained by introducing the concept of softness to NCs in the hard sphere model.

Synthesis of undoped and manganese-doped hgte nanoparticles using [Hg(TeCH2CH2NMe2)2] as a single source precursor.

The Reaction of [HgCl2(tmeda)] with NaTeCH2CH2NMe2 gave a mercury tellurolate, [Hg(TeCH2CH2. NMe2)2] (1) as a yellow crystalline solid, which was characterized by elemental analysis, UV-vis, mass and NMR (1H, 13C, 125Te, 199Hg) spectroscopy. Thermolysis of 1 in hexadecylamine (HDA) at 90 degrees C in the absence and presence of Mn(OAc)2.4H2O gave undoped and Mn-doped HgTe nanoparticles which were characterized by XRD, EDAX, TEM, EPR and magnetic measurements. These particles could be synthesized with mean particle size of 6-7 nm (from TEM). Manganese substitution at Hg site in HgTe lead to a linear decrease in lattice parameter with increasing concentration of Mn. Magnetization measurements showed ferromagnetic ordering at room temperature with very small coercive field (Hc, 50 Oe) for Hg0.973 Mn0.027 Te sample. This sample also exhibited distinct ferromagnetic resonance (FMR) in the EPR spectrum.

Group 12 metal monoselenocarboxylates: synthesis, characterization, structure and their transformation to metal selenide (MSe; M = Zn, Cd, Hg) nanoparticles.

Reactions of [MCl2(tmeda)] with potassium salts of monoselenocarboxylic acids gave complexes of the general formula [M(SeCOR)2(tmeda)] (M = Zn, Cd; R = Ph, Tol; Tol = C6H4-p-CH3; tmeda = Me2NCH2CH2NMe2). The analogous mercury complexes were unstable at room temperature and afforded HgSe nanoparticles during the course of reaction. All the complexes were characterized by elemental analysis, IR, UV-vis, NMR (1H, 13C, 77Se, 113Cd) data. The X-ray structural analysis of [Cd(SeCOPh)2(tmeda)] revealed that the complex is a discrete monomer having an approximate tetrahedral coordination environment around the central metal atom with monodentate (Se-bonded) selenocarboxylates. Thermal behavior of these complexes was studied by TG analysis. Pyrolysis in a furnace or in HDA (hexadecylamine) gave MSe nanoparticles, which were characterized by XRD, EDAX, SEM and absorption spectroscopy.