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1.
IUCrJ ; 11(Pt 1): 109-119, 2024 Jan 01.
Article in English | MEDLINE | ID: mdl-38099813

ABSTRACT

The orientation ordering and assembly behavior of silica-nickel Janus particles in a static external magnetic field were probed by ultra small-angle X-ray scattering (USAXS). Even in a weak applied field, the net magnetic moments of the individual particles aligned in the direction of the field, as indicated by the anisotropy in the recorded USAXS patterns. X-ray photon correlation spectroscopy (XPCS) measurements on these suspensions revealed that the corresponding particle dynamics are primarily Brownian diffusion [Zinn, Sharpnack & Narayanan (2023). Soft Matter, 19, 2311-2318]. At higher fields, the magnetic forces led to chain-like configurations of particles, as indicated by an additional feature in the USAXS pattern. A theoretical framework is provided for the quantitative interpretation of the observed anisotropic scattering diagrams and the corresponding degree of orientation. No anisotropy was detected when the magnetic field was applied along the beam direction, which is also replicated by the model. The method presented here could be useful for the interpretation of oriented scattering patterns from a wide variety of particulate systems. The combination of USAXS and XPCS is a powerful approach for investigating asymmetric colloidal particles in external fields.

2.
J Phys Chem Lett ; 13(32): 7380-7385, 2022 Aug 18.
Article in English | MEDLINE | ID: mdl-35925676

ABSTRACT

We systematically diagnose here the various phases formed at the electrodes in a Li-CO2 battery. The CO2 cathode comprises a mixture of two-dimensional electrocatalysts, MXene and graphene oxide (MXene/GO), configured on Ni foam. The observed overpotential for MXene/GO (2.4 V) is lower than that for GO (2.8 V). MXene/GO also outperforms GO in terms of battery stability and performance. The overall battery reaction (Li2CO3 ↔ Li + CO2) is more efficient in the case of MXene/GO than in the case of GO. This is convincingly demonstrated using ex situ high-resolution synchrotron X-ray diffraction and Raman scattering spectroscopy, which strongly indicates that the MXene/GO composite is more capable than GO in converting Li2CO3 to Li and CO2. When the Li anode is probed, CO2 crossover is evident via the observation of the formation of LiOH/Li2CO3 phases, the proportions of which change during successive cycles.

3.
Small ; 17(51): e2103212, 2021 12.
Article in English | MEDLINE | ID: mdl-34622549

ABSTRACT

Luminescence enhancement in 2D molecular crystals (2D crystals) is promising for a variety of optical applications, yet the availability is limited because of unclear mechanism and inefficient design strategy of luminescence control. Herein, the room temperature phosphorescence from micron long molecular thin free-standing 2D crystals of a mono-cyclometalated Ir(III) complex designed at the water surface is reported. A large luminescence enhancement is observed from the 2D crystals at 300 K, which is comparable with the rigidified solution at 77 K suggesting room temperature phosphorescence origin of the luminescence. In situ synchrotron grazing incidence X-ray diffraction measurements determine the constituent centered rectangular unit cells with precise molecular conformation that promotes the formation of 2D crystals. The molecular crystal design leads to a reduced singlet-triplet energy gap (ΔEST ) and mixing of singlet-triplet states by spin-orbit coupling (SOC) for efficient intersystem crossing, which explains the phosphorescence origin at room temperature and luminescence enhancement. The supramolecular assembly process provides an elegant design strategy to realize room temperature phosphorescence from 2D crystals by rigid intermolecular interactions.


Subject(s)
Luminescence , Molecular Conformation , Temperature
4.
RSC Adv ; 9(55): 31900-31910, 2019 Oct 07.
Article in English | MEDLINE | ID: mdl-35530788

ABSTRACT

Copper thiourea complexes are an important material class for application as a precursor of copper sulfide nanocrystals with potential use in solar cells, optoelectronics, medicine, etc. They represent a type of single source precursor, comprising both copper and sulfur in one chemical compound, whose tunable stoichiometry and morphology enable control of the quality and properties of the synthesized copper sulfide nanocrystals. Here, we present a template free electrochemical route to prepare nanowires of copper thiourea (tu) chloride hemihydrate ([Cu(tu)]Cl·½H2O) by pulse deposition. We proposed the model of the growth of nanowires. We also demonstrate complete transformation from the precursor to copper sulfide nanowire by heating it to 180 °C that involves 20% volume loss due to the decomposition of organic constituents; the obtained nanowires have around 38% covellite (CuS) and 62% digenite (Cu1.8S) phases. Electrochemistry offers the advantage of spatially selected deposition e.g. in the active regions of a device.

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