Title: Phase control in the colloidal synthesis of well-defined nickel sulfide nanocrystals

Abstract

In this work, morphologically well-defined colloidal nanocrystals of Ni₃S₄, NiS, Ni₉S₈, and Ni₃S₂ were independently prepared through a solution-phase synthesis using N,N'-disubstituted thioureas as the sulfur precursor. Synthetic control over phase and composition of the resulting colloidal nickel sulfide nanocrystals was achieved by primarily adjusting the reactivity of substituted thioureas as well as tuning the key reaction parameters of temperature and precursor ratio. In general, the more reactive N,N'-diphenyl thiourea yields more sulfur-rich phases (Ni₃S₄ and NiS) while less reactive N,N'-dibutyl thiourea yields sulfur-poor phases (Ni₉S₈ and Ni₃S₂). This phase control can be further tuned through the use of 1-dodecanethiol as an important secondary reactivity-directing agent. In the presence of 1-dodecanethiol, nanocrystals of more sulfur-deficient phases are prepared, while in the absence of 1-dodecanethiol, more sulfur-rich phases are prepared. Under the most sulfur-rich synthetic conditions (i.e., with N,N'-diphenyl thiourea and no thiol) a phase progression from Ni₃S₄ to the α-NiS and β-NiS phases was observed upon an increase in reaction temperature and sulfur-to-nickel precursor ratio. In conclusion, this study establishes, for the first time, a systematic evaluation of factors that simultaneously control the phase and yield well-defined nickel sulfide nanocrystals.

Authors:

Barim, Gözde  ^[1];

• Search DOE PAGES for author "Barim, Gözde"
• Search DOE PAGES for ORCID "0000-0001-8139-925X"

Smock, Sara R. ^[1]; Antunez, Priscilla D. ^[1]; Glaser, Daniela ^[1]; Brutchey, Richard L.  ^[1]

• Search DOE PAGES for author "Brutchey, Richard L."
• Search DOE PAGES for ORCID "0000-0002-7781-5596"

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+ Show Author Affiliations

1. Univ. of Southern California, Los Angeles, CA (United States)

Publication Date:

Thu Aug 16 00:00:00 EDT 2018

Research Org.:

Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1582647

Alternate Identifier(s):

OSTI ID: 1465600

Grant/Contract Number:  

SC0006812; FG02-11ER46826

Resource Type:

Accepted Manuscript

Journal Name:

Nanoscale

Additional Journal Information:

Journal Volume: 10; Journal Issue: 34; Journal ID: ISSN 2040-3364

Publisher:

Royal Society of Chemistry

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY