An official website of the United States government
We report on the synthesis of self-intercalated Nb1+xSe2 thin films by molecular beam epitaxy. Nb1+xSe2 is a metal-rich phase of NbSe2 where additional Nb atoms populate the van der Waals gap. The grown thin films are studied as a function of the Se to Nb beam equivalence pressure ratio (BEPR). X-ray photoelectron spectroscopy and x-ray diffraction indicate that BEPRs of 5:1 and greater result in the growth of the Nb1+xSe2 phase and that the amount of intercalation is inversely proportional to the Se to Nb BEPR. Electrical resistivity measurements also show an inverse relationship between BEPR and resistivity in the grown Nb1+xSe2 thin films. A second Nb-Se compound with a stoichiometry of ∼1:1 was synthesized using a Se to Nb BEPR of 2:1; in contrast to the Nb1+xSe2 thin films, this compound did not show evidence of a layered structure.
more »
« less
Copper Selenophosphate, Cu 3 PSe 4 , Nanoparticle Synthesis: Octadecane Is the Key to a Simplified, Atom-Economical Reaction
Nanoparticle syntheses are designed to produce thedesired product in high yield but traditionally neglect atom economy. Here we report that the simple, but significant, change of the solvent from 1-octadecene (1-ODE) to the operationally inert octadecane (ODA) permits an atom-economical synthesis of copper selenophosphate (Cu3PSe4) nanoparticles. This change eliminates the competing selenium (Se) delivery pathways from our first report that required an excess of Se. Instead Se0 powder is dispersed in ODA, which promotes a formal eight-electron transfer between Cu3−xP and Se0. Powder X-ray diffraction and transmission electron microscopy confirm the purity of the Cu3PSe4, while 1H and 13C NMR indicate the absence of oxidized ODA or Se species. We utilize the direct pathway to gain insights into stoichiometry and ligand identity using thermogravimetric analysis and X-ray photoelectron spectroscopy. Given the prevalence of 1- ODE in nanoparticle synthesis, this approach could be applied to other chalcogenide reaction pathways to improve stoichiometry and atom-economy.
more »
« less
- Award ID(s):
- 2109141
- PAR ID:
- 10530628
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Nano Letters
- Volume:
- 23
- Issue:
- 24
- ISSN:
- 1530-6984
- Page Range / eLocation ID:
- 11430 to 11437
- Subject(s) / Keyword(s):
- 1-octadecene octadecane atom-economical nanoparticle reaction pathway copper selenophosphate
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract To advance the MXene field, it is crucial to optimize each step of the synthesis process and create a detailed, systematic guide for synthesizing high‐quality MXene that can be consistently reproduced. In this study, a detailed guide is provided for an optimized synthesis of titanium carbide (Ti3C2Tx) MXene using a mixture of hydrofluoric and hydrochloric acids for the selective etching of the stoichimetric‐Ti3AlC2MAX phase and delamination of the etched multilayered Ti3C2TxMXene using lithium chloride at 65 °C for 1 h with argon bubbling. The effect of different synthesis variables is investigated, including the stoichiometry of the mixed powders to synthesize Ti3AlC2, pre‐etch impurity removal conditions, selective etching, storage, and drying of MXene multilayer powder, and the subsequent delamination conditions. The synthesis yield and the MXene film electrical conductivity are used as the two parameters to evaluate the MXene quality. Also the MXenes are characterized with scanning electron microscopy, x‐ray diffraction, atomic force microscopy, and ellipsometry. The Ti3C2Txfilm made via the optimized method shows electrical conductivity as high as ≈21,000 S/cm with a synthesis yield of up to 38 %. A detailed protocol is also provided for the Ti3C2TxMXene synthesis as the supporting information for this study.more » « less
-
null (Ed.)A free-standing film composed of bilayered vanadium oxide nanoflakes is for the first time synthesized using a new low-energy process. The precursor powder, δ-Li x V 2 O 5 · n H 2 O, was prepared using a simple sol–gel based chemical preintercalation synthesis procedure. δ-Li x V 2 O 5 · n H 2 O was dispersed and probe sonicated in N -methyl pyrrolidone to exfoliate the bilayers followed by vacuum filtration resulting in the formation of a free-standing film with obsidian color. X-ray diffraction showed lamellar ordering of a single-phase material with a decreased interlayer distance compared to that of the precursor powder. Scanning electron microscopy images demonstrated stacking of the individual nanoflakes. This morphology was further confirmed with scanning transmission electron microscopy that showed highly malleable nanoflakes consisting of ∼10–100 vanadium oxide bilayers. One of the most important consequences of this morphological rearrangement is that the electronic conductivity of the free-standing film, measured by the four-probe method, increased by an order of magnitude compared to conductivity of the pressed pellet made of precursor powder. X-ray photoelectron spectroscopy measurements showed the coexistence of both V 5+ and V 4+ oxidation states in the exfoliated sample, possibly contributing to the change in electronic conductivity. The developed approach provides the ability to maintain the phase purity and crystallographic order during the exfoliation process, coupled with the formation of a free-standing film of enhanced conductivity. The produced bilayered vanadium oxide nanoflakes can be used as the building blocks for the synthesis of versatile two-dimensional heterostructures to create innovative electrodes for electrochemical energy storage applications.more » « less
-
Abstract The compositional screening of K‐Zn‐Sb ternary system aided by machine learning, rapid exploratory synthesis using KH salt‐like precursor and in situ powder X‐ray diffraction yielded a novel clathrate type XI K58Zn122Sb207. This clathrate consists of a 3D Zn‐Sb framework hosting K+ions inside polyhedral cages, some of which are reminiscent of known clathrate types while others are unique to this structure type. The complex non‐centrosymmetric structure in the tetragonal space groupwas solved by means of single crystal X‐ray diffraction as a 6‐component twin due to pseudocubic symmetry and further confirmed by high‐resolution synchrotron powder X‐ray diffraction and state‐of‐the‐art scanning transmission electron microscopy. The electron‐precise composition of this clathrate yields narrow‐gapp‐type semiconductor with extraordinarily low thermal conductivity due to displacement or “rattling” of K cations inside oversized cages and as well as to twinning, stacking faults and antiphase boundary defects.more » « less
-
Atomically precise thiolate-protected gold nanomolecules have attracted interest due to their distinct electronic and chemical properties. The structure of these nanomolecules is important for understanding their peculiar properties. Here, we report the X-ray crystal structure of a 24-atom gold nanomolecule protected by 16 tert -butylthiolate ligands. The composition of Au 24 (S-C 4 H 9 ) 16 {poly[hexadecakis(μ- tert -butylthiolato)tetracosagold]} was confirmed by X-ray crystallography and electrospray ionization mass spectrometry (ESI–MS). The nanomolecule was synthesized in a one-phase synthesis and crystallized from a hexane–ethanol layered solution. The X-ray structure confirms the 16-atom core protected by two monomeric and two trimeric staples with four bridging ligands. The Au 24 (S-C 4 H 9 ) 16 cluster follows the shell-closing magic number of 8.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.nanolett.3c02620
