Mechanism of sulfidation of small zinc oxide nanoparticles

Progna Banerjee, Prashant Jain

Research output: Contribution to journalArticle

Abstract

ZnO has industrial utility as a solid sorbent for the removal of polluting sulfur compounds from petroleum-based fuels. Small ZnO nanoparticles may be more effective in terms of sorption capacity and ease of sulfidation as compared to bulk ZnO. Motivated by this promise, here, we study the sulfidation of ZnO NPs and uncover the solid-state mechanism of the process by crystallographic and optical absorbance characterization. The wurtzite-structure ZnO NPs undergo complete sulfidation to yield ZnS NPs with a drastically different zincblende structure. However, in the early stages, the ZnO NP lattice undergoes only substitutional doping by sulfur, while retaining its wurtzite structure. Above a threshold sulfur-doping level of 30 mol%, separate zincblende ZnS grains nucleate, which grow at the expense of the ZnO NPs, finally yielding ZnS NPs. Thus, the full oxide to sulfide transformation cannot be viewed simply as a topotactic place-exchange of anions. The product ZnS NPs formed by nucleation-growth share neither the crystallographic structure nor the size of the initial ZnO NPs. The reaction mechanism may inform the future design of nanostructured ZnO sorbents.

Original languageEnglish (US)
Pages (from-to)34476-34482
Number of pages7
JournalRSC Advances
Volume8
Issue number60
DOIs
StatePublished - Jan 1 2018

Fingerprint

Zinc Oxide
Sorbents
Zinc oxide
Sulfur
Doping (additives)
Nanoparticles
Sulfur Compounds
Sulfur compounds
Petroleum
Sulfides
Oxides
Anions
Sorption
Ion exchange
Nucleation
Negative ions
Crude oil

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Mechanism of sulfidation of small zinc oxide nanoparticles. / Banerjee, Progna; Jain, Prashant.

In: RSC Advances, Vol. 8, No. 60, 01.01.2018, p. 34476-34482.

Research output: Contribution to journalArticle

Banerjee, Progna ; Jain, Prashant. / Mechanism of sulfidation of small zinc oxide nanoparticles. In: RSC Advances. 2018 ; Vol. 8, No. 60. pp. 34476-34482.
@article{042b73520dbd4ccc9f166400dae782cf,
title = "Mechanism of sulfidation of small zinc oxide nanoparticles",
abstract = "ZnO has industrial utility as a solid sorbent for the removal of polluting sulfur compounds from petroleum-based fuels. Small ZnO nanoparticles may be more effective in terms of sorption capacity and ease of sulfidation as compared to bulk ZnO. Motivated by this promise, here, we study the sulfidation of ZnO NPs and uncover the solid-state mechanism of the process by crystallographic and optical absorbance characterization. The wurtzite-structure ZnO NPs undergo complete sulfidation to yield ZnS NPs with a drastically different zincblende structure. However, in the early stages, the ZnO NP lattice undergoes only substitutional doping by sulfur, while retaining its wurtzite structure. Above a threshold sulfur-doping level of 30 mol{\%}, separate zincblende ZnS grains nucleate, which grow at the expense of the ZnO NPs, finally yielding ZnS NPs. Thus, the full oxide to sulfide transformation cannot be viewed simply as a topotactic place-exchange of anions. The product ZnS NPs formed by nucleation-growth share neither the crystallographic structure nor the size of the initial ZnO NPs. The reaction mechanism may inform the future design of nanostructured ZnO sorbents.",
author = "Progna Banerjee and Prashant Jain",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/c8ra06949b",
language = "English (US)",
volume = "8",
pages = "34476--34482",
journal = "RSC Advances",
issn = "2046-2069",
publisher = "Royal Society of Chemistry",
number = "60",

}

TY - JOUR

T1 - Mechanism of sulfidation of small zinc oxide nanoparticles

AU - Banerjee, Progna

AU - Jain, Prashant

PY - 2018/1/1

Y1 - 2018/1/1

N2 - ZnO has industrial utility as a solid sorbent for the removal of polluting sulfur compounds from petroleum-based fuels. Small ZnO nanoparticles may be more effective in terms of sorption capacity and ease of sulfidation as compared to bulk ZnO. Motivated by this promise, here, we study the sulfidation of ZnO NPs and uncover the solid-state mechanism of the process by crystallographic and optical absorbance characterization. The wurtzite-structure ZnO NPs undergo complete sulfidation to yield ZnS NPs with a drastically different zincblende structure. However, in the early stages, the ZnO NP lattice undergoes only substitutional doping by sulfur, while retaining its wurtzite structure. Above a threshold sulfur-doping level of 30 mol%, separate zincblende ZnS grains nucleate, which grow at the expense of the ZnO NPs, finally yielding ZnS NPs. Thus, the full oxide to sulfide transformation cannot be viewed simply as a topotactic place-exchange of anions. The product ZnS NPs formed by nucleation-growth share neither the crystallographic structure nor the size of the initial ZnO NPs. The reaction mechanism may inform the future design of nanostructured ZnO sorbents.

AB - ZnO has industrial utility as a solid sorbent for the removal of polluting sulfur compounds from petroleum-based fuels. Small ZnO nanoparticles may be more effective in terms of sorption capacity and ease of sulfidation as compared to bulk ZnO. Motivated by this promise, here, we study the sulfidation of ZnO NPs and uncover the solid-state mechanism of the process by crystallographic and optical absorbance characterization. The wurtzite-structure ZnO NPs undergo complete sulfidation to yield ZnS NPs with a drastically different zincblende structure. However, in the early stages, the ZnO NP lattice undergoes only substitutional doping by sulfur, while retaining its wurtzite structure. Above a threshold sulfur-doping level of 30 mol%, separate zincblende ZnS grains nucleate, which grow at the expense of the ZnO NPs, finally yielding ZnS NPs. Thus, the full oxide to sulfide transformation cannot be viewed simply as a topotactic place-exchange of anions. The product ZnS NPs formed by nucleation-growth share neither the crystallographic structure nor the size of the initial ZnO NPs. The reaction mechanism may inform the future design of nanostructured ZnO sorbents.

UR - http://www.scopus.com/inward/record.url?scp=85055046716&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85055046716&partnerID=8YFLogxK

U2 - 10.1039/c8ra06949b

DO - 10.1039/c8ra06949b

M3 - Article

AN - SCOPUS:85055046716

VL - 8

SP - 34476

EP - 34482

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 60

ER -