Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Phase control during the synthesis of nickel sulfide nanoparticles from dithiocarbamate precursors

Roffey, Anna, Hollingsworth, Nathan, Islam, Husn-Ubayda, Mercy, Maxime, Sankar, Gopinathan, Catlow, Charles Richard, Hogarth, Graeme and de Leeuw, Nora 2016. Phase control during the synthesis of nickel sulfide nanoparticles from dithiocarbamate precursors. Nanoscale 8 (21) , pp. 11067-11075. 10.1039/C6NR00053C

[img]
Preview
PDF - Published Version
Available under License Creative Commons Attribution.

Download (1MB) | Preview

Abstract

Square-planar nickel bis(dithiocarbamate) complexes, [Ni(S2CNR2)2], have been prepared and utilised as single source precursors to nanoparticulate nickel sulfides. While they are stable in the solid-state to around 300 °C, heating in oleylamine at 230 °C, 5 mM solutions afford pure α-NiS, where the outcome is independent of the substituents. DFT calculations show an electronic effect rather than steric hindrance influences the resulting particle size. Decomposition of the iso-butyl derivative, [Ni(S2CNiBu2)2], has been studied in detail. There is a temperature-dependence of the phase of the nickel sulfide formed. At low temperatures (150 °C), pure α-NiS is formed. Upon raising the temperature, increasing amounts of β-NiS are produced and at 280 °C this is formed in pure form. A range of concentrations (from 5–50 mM) was also investigated at 180 °C and while in all cases pure α-NiS was formed, particle sizes varied significantly. Thus at low concentrations average particle sizes were ca. 100 nm, but at higher concentrations they increased to ca. 150 nm. The addition of two equivalents of tetra-iso-butyl thiuram disulfide, (iBu2NCS2)2, to the decomposition mixture was found to influence the material formed. At 230 °C and above, α-NiS was generated, in contrast to the results found without added thiuram disulfide, suggesting that addition of (iBu2NCS2)2 stabilises the metastable α-NiS phase. At low temperatures (150–180 °C) and concentrations (5 mM), mixtures of α-NiS and Ni3S4, result. A growing proportion of Ni3S4 is noted upon increasing precursor concentration to 10 mM. At 20 mM a metastable phase of nickel sulfide, NiS2 is formed and as the concentration is increased, α-NiS appears alongside NiS2. Reasons for these variations are discussed.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Cardiff Catalysis Institute (CCI)
Chemistry
Subjects: Q Science > QD Chemistry
Publisher: RSC Publishing
ISSN: 2040-3364
Funders: EPSRC
Date of First Compliant Deposit: 14 June 2016
Date of Acceptance: 26 April 2016
Last Modified: 04 Jun 2017 09:12
URI: http://orca-mwe.cf.ac.uk/id/eprint/91846

Citation Data

Cited 18 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item

Downloads

Downloads per month over past year

View more statistics