A one-pot-one-reactant synthesis of platinum compounds at the nanoscale

Abstract

The preparation of inorganic nanomaterials with a desired structure and specific properties requires the ability to strictly control their size, shape and composition. A series of chemical reactions with platinum compounds carried out within the 1.5 nm wide channel of single-walled carbon nanotubes (SWNTs) have demonstrated the ability of SWNTs to act as both a very effective reaction vessel and a template for the formation of nanocrystals of platinum di-iodide and platinum di-sulphide, materials that are difficult to synthesise in the form of nanoparticles by traditional synthetic methods. The stepwise synthesis inside nanotubes has enabled the formation of Pt compounds to be monitored at each step of the reaction by aberration-corrected high resolution transmission electron microscopy (AC-HRTEM), verifying the atomic structures of the products, and by an innovative combination of fluorescence-detected X-ray absorption spectroscopy (FD-XAS) and Raman spectroscopy, monitoring the oxidation states of the platinum guest-compounds within the nanotube and the vibrational properties of the host-SWNT, respectively. This coupling of complementary spectroscopies reveals that electron transfer between the guest-compound and the host-SWNT can occur in either direction depending on the composition and structure of the guest. A new approach for nanoscale synthesis in nanotubes developed in this study utilises the versatile coordination chemistry of Pt which has enabled the insertion of the required chemical elements (e.g. metal and halogens or chalcogens) into the nanoreactor in the correct proportions for the controlled formation of PtI and PtS with the correct stoichiometry.

Selective Laser-Assisted Synthesis of Tubular van der Waals Heterostructures of Single-Layered PbI2 within Carbon Nanotubes Exhibiting Carrier Photogeneration

“…[27][28][29][30] Alternatively, solution filling can be employed but lower filling yields are generally reported and further processing is required to eliminate the solvent, unless the solvent itself is the chosen material. [31][32][33][34] The controlled synthesis of materials within the cavities of CNTs is getting an increased attention, [35][36][37] and for instance MoS 2 and WS 2 nanoribbons have been prepared in this manner. 27, Laser irradiation of materials can lead to a fast and local increase of the temperature and arises as a promising alternative to the conventional annealing using furnaces that have been widely employed to achieve molten phase capillary filling.…”

Three dimensional nanoscale analysis reveals aperiodic mesopores in a covalent organic framework and conjugated microporous polymer

“…Our hypothesis also explains the presence of the oxygen observed in the elemental analysis, as incomplete condensation has occurred due to the steric interference from the solvent cluster and hence the edges of the defects will be terminated with carbonyl groups of incompletely reacted hexaketocyclohexane. A quantitative EDX analysis can be utilised to estimate the atomic percentage of particular elements within nanomaterials, 31 which can give a reasonable estimation to the amount of ketone groups remaining within the CMP particle (ESI †). Therefore, the atomic percent of oxygen can be used as a measure of completeness of polycondensation, which is expected to be zero for a perfect Aza-CMP ( Fig.…”

Direct Synthesis of Multiplexed Metal‐Nanowire‐Based Devices by Using Carbon Nanotubes as Vector Templates

“…For our studies we employed (7,6) enriched semiconducting SWNTs dispersed in water with sodium dodecyl sulfate (SDS). The nanotubes were initially filled with a copper‐containing metal complex precursor by a universal sublimation method as previously reported for Pt(acac) 2 and 13 other transition‐metal complexes . The dimensions of the internal cavity of the SWNTs enables effective encapsulation (see Figure SI‐1 in the Supporting Information).…”