Received: 11 July 2020 | Revised: 5 September 2020 | Accepted: 16 September 2020

DOI: 10.1002/cey2.83

RESEARCH ARTICLE

Sulfidation and selenidation of nickel nanoparticles

Brian B. Lynch | Andrew P. Kelliher | Bryan D. Anderson | Alexander Japit |

Michael A. Spencer | Mehedi H. Rizvi | Mehmet F. Sarac |
Veronica Augustyn | Joseph B. Tracy

Department of Materials Science and

Engineering, North Carolina State
University, Raleigh, North Carolina, USA
Correspondence
Joseph B. Tracy, Department of Materials
Science and Engineering, North Carolina
State University, Raleigh, NC 27695, USA.
Email: jbtracy@ncsu.edu
Present address
Mehmet F. Sarac, Department of
Mechanical Engineering, Suleyman
Demirel University (West Campus),
Isparta, Turkey
Funding information
Basic Energy Sciences,
Grant/Award Number: DE‐SC0020234;
Division of Chemical, Bioengineering,
Environmental, and Transport Systems,
Grant/Award Number: 1605699; Division
of Materials Research,
Grant/Award Number: 1056653; Division
of Electrical, Communications and Cyber
Systems, Grant/Award Number: 1542015;
the National Science foundation,
Grant/Award Numbers: DMR‐1056653,
CBET‐1605699 and CMMI‐1763025
Abstract
Transition metal chalcogenide nanoparticles (NPs) are of interest for energy
applications, including batteries, supercapacitors, and electrocatalysis. Many
methods have been established for synthesizing Ni NPs, and conversion chem-
istry to form Ni oxide and phosphides from template Ni NPs is well‐understood.
Sulfidation and selenidation of Ni NPs have been much less explored, however.
We report a method for the conversion of Ni template NPs into sulfide and
selenide product NPs using elemental sulfur, 1‐hexadecanthiol, thiourea, trioc-
tylphosphine sulfide, elemental selenium, and selenourea. While maintaining
mole ratios of 2 mmol sulfur/selenium precursor: mmol Ni in the Ni NPs, pro-
ducts with phases of Ni3S2, Ni9S8, NiS, NiSO4·6H2O, Ni3S4, Ni3Se2, and NiSe have
been obtained. The products have voids that form through the Kirkendall effect
during interdiffusion. Trends relating the chemical properties of the precursors
to the phases of the products have been identified. While some precursors
contained phosphorus, there was no significant incorporation of phosphorus in
any of the products. An increase of the NP size during sulfidation and seleni-
dation is consistent with ripening. The application of Ni sulfide and selenide NPs
as electrocatalysts for the hydrogen evolution reaction is also demonstrated.
KEYWORDS
conversion chemistry, electrocatalysis, nanoparticles, nickel, selenide, sulfide

1 | INTRODUCTION compound product. Upon accumulation of vacancies in the

core of the NPs, a void or multiple voids form within the
Conversion chemistry refers to performing chemical reac- core of the NP.1–3 The Kirkendall effect has been demon-
tions on presynthesized nanoparticles (NPs), which is often strated for the reactions of many different types of NPs,
accompanied by morphological changes, such as void for- with early work on Co and Cd.4–7 The conversion chemistry
mation. The Kirkendall effect describes a mechanism for of Ni NPs is generally well‐established for oxidation and
void formation in metal NPs, when a chemical reaction phosphidation reactions,8–18 but less is known about sulfi-
causes faster outward diffusion of metal atoms from the dation and selenidation reactions.19–21 Nickel sulfide and
core than inward diffusion of reactive species to form a selenide NPs are of growing interest for a range of energy
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2020 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd

Carbon Energy. 2020;1–8. wileyonlinelibrary.com/journal/cey2 | 1

2 |
applications, including batteries, supercapacitors, and
electrocatalysis.22–32 In this study, we have investigated
sulfidation and selenidation of Ni NPs using several com-
mon precursors and characterized their performance as
electrocatalysts for the hydrogen evolution reaction (HER).
Because sulfur and selenium are both chalcogens, there
are several similarities in sulfidation and selenidation reac-
tions of metal NPs.4,33–45 For example, the solution‐phase
conversion of Co, Cd, and Pb into sulfides has been
reported.4,35,36,39,43,44 As sulfur precursors, these studies
employed elemental S in dichlorobenze,4,43 S in trioctyl-
phosphine (TOP:S),35,39 S in oleylamine (S(OLA)),36,46
1‐octadecanethiol,45 thiourea,33,38 and 1‐hexadecanethiol
(HDT).34 As selenium precursors, selenourea in oleyla-
mine (SeU(OLA))40,42 and elemental selenium in TOP37,41,47
have been investigated. In all of these studies, the sulfur or
selenium precursor was usually added to the reaction mix-
ture at an elevated temperature toward the end of the initial
NP synthesis.
Here, we report the Kirkendall effect during sulfida-
tion and selenidation of Ni NPs. A hypothesis under-
pinning this study is that heating Ni NPs with
hydrocarbon precursors at high temperatures will liber-
ate atomic S and Se and drive sulfidation and selenida-
tion reactions. This hypothesis is based on results from a
previous study on the carburization of Ni NPs in different
organic solvents, where Ni NPs have a catalytic role in
decomposing hydrocarbons.48 This catalytic property of
Ni NPs may make them especially versatile for conver-
sion chemistry using different precursors. The effects of
four different sulfur precursors, HDT, elemental TOP:S,
elemental S(OLA), thiourea in oleylamine (TU(OLA)),
and two different selenium precursors, selenourea in
oleylamine (SeU(OLA)) and elemental Se in TOP
(TOP:Se), on the conversion chemistry of Ni NPs were
investigated. The chemical properties of the precursors
can affect the composition, size, and morphology of the
products of conversion chemical reactions.49–51 The
composition and morphology of the products were in-
vestigated, and trends in the results for different pre-
cursors are established.
2 | EX PERIMEN TA L SECT ION
All sulfur/selenium precursors were handled under an
inert atmosphere in an N2 glove box. For sulfidation re-
actions, HDT (Alfa Aesar; 97%) was used as received. For
the preparation of all other precursors that required
dissolving a solid within a liquid, the mixtures were
stirred for at least 8–24 h to ensure complete dissolution.
TOP:S was prepared by mixing 0.480 g (15.0 mmol) of
elemental S (Alfa Aesar; 99.999%) and 7.2 ml (16.1 mmol)
LYNCH ET AL.
of trioctylphosphine (TOP, Strem; 97%). S(OLA) was
prepared by mixing 0.128 g (3.99 mmol) of elemental S in
2 ml (6.08 mmol) of oleylamine (Acros; 97% primary
amine). TU(OLA) was prepared by mixing 0.608 g
(7.99 mmol) of thiourea (Aesar; 99%) in 8 ml (24.3 mmol)
of oleylamine. TOP:Se was prepared by dissolving 1.32 g
(16.7 mmol) of elemental Se (Alfa Aesar; 99.999%) in 7.2 ml
(16.1 mmol) of TOP. SeU(OLA) was prepared by dissolving
0.393 g (3.2 mmol) of selenourea (Sigma‐Aldrich; 98%) in
3.18 ml (9.67 mmol) of oleylamine.
Dendritic 100 nm Ni NPs were synthesized as re-
ported previously by degassing 0.5 g (1.73 mmol) of
nickel acetylacetonate (Ni(acac)2·xH2O, where x is as-
sumed to be 2), 5 ml (15.2 mmol) of oleylamine, and 4.4 g
(11.4 mmol) of trioctylphosphine oxide (TOPO) under
vacuum on a Schlenk line in a three‐necked, round‐
bottomed flask at 80°C for 2 h.48 The flask was then
backfilled with N2 and heated to 230°C for 30 min. A
1‐ml aliquot of the template NPs was removed from each
sample as a control sample for verifying the NP size and
composition, since these NPs served as templates for the
conversion reactions into sulfides and selenides. The
aliquots were imaged by transmission electron micro-
scopy (TEM) to confirm the dendritic Ni structure, which
was observed for every sample (Figure S1). Sulfidation
and selenidation were initiated by injecting one of the
following precursors, which contained 3 mmol of S or Se
into the flask of Ni NPs and heating to 300°C for 30 min:
0.95 ml of HDT, 1.47 ml of TOP:S, 1.54 ml of S(OLA),
3.07 ml of TU(OLA), 1.38 ml of TOP:Se, or 3.07 ml of SeU
(OLA). In all syntheses, a molar ratio of 2S/Se:Ni was
used. The reaction products were purified by five cycles
of centrifugation after adding excess methanol and re-
dispersing in hexanes.
Samples for TEM were prepared by dropcasting NPs
dispersed in hexanes onto Cu TEM grids with ultrathin
carbon support films and imaged in a JEOL 2000FX
TEM. Samples for X‐ray diffraction (XRD) were prepared
by dropcasting highly concentrated NPs in di-
chloromethane onto an amorphous silica glass slide.
XRD was performed using a Rigaku SmartLab X‐Ray
diffractometer with Bragg–Brentano geometry. Rietveld
refinement tools in HighScore Plus software were used
for refining the XRD data. Before refinement, the amor-
phous silica background signal was subtracted from each
dataset. The data were then fit with the matching com-
positions. The Ni, S, Se, and P content of all samples was
quantified by inductively coupled plasma optical emis-
sion spectroscopy (ICP‐OES) using a PerkinElmer ICP‐
OES 2000 DV instrument.
The catalytic activity of NiSe (TOP:Se) and NiS
(TOP:S) for the HER was studied in a three‐electrode cell
equipped with a rotating disk electrode (RDE) as the
LYNCH ET AL.
working electrode. The Teflon cell was cleaned with 1 M
NaOH, aqua regia (3:1 HCl:HNO3), and deionized water
that was heated to approximately 80°C. The electrolyte
was 0.5 M H2SO4 (TraceMetal Grade; Thermo Fisher
Scientific) purged with hydrogen gas. The reference
electrode was Hg/Hg2SO4 in K2SO4(sat'd; Pine Research),
and the counter electrode was a graphite rod (Pine
Research). The working electrode was a 5‐mm diameter
glassy carbon RDE tip (Pine Research) that was polished
with a 0.05‐μm alumina slurry and subsequently soni-
cated for 10 min in deionized water. Two 5‐μl droplets of
dispersions of NiSe and NiS in THF were deposited on
the polished glassy carbon RDE and dried at 70°C for
15 min. A potentiostat (VMP3; BioLogic) was used to
perform cyclic voltammetry at a sweep rate of 10 mV/s
and an RDE rotation rate of 1800 rpm. The potential
measured with respect to the Hg/Hg2SO4 in K2SO4(sat'd)
was converted to the potential of the reversible hydrogen
electrode (RHE) at pH 0, where the potential of Hg/Hg2SO4
is 0.64 V versus RHE.52
3 | RESULTS A ND DISCUSSION
3.1 | Template nickel NPs
In our previous study, heating Ni(acac)2 and oleyla-
mine in TOPO yielded dendritic Ni NPs.48 Here, an
aliquot was taken before each sulfidation and seleni-
dation reaction to confirm the size and shape of the Ni
NPs by TEM and the face‐centered cubic crystal
structure by XRD (Figures 1 and S1). The broad peak
at approximately 25° is from the glass slide used as a
substrate for XRD.
F I G U R E 1 Transmission electron microscopy (TEM) and
X‐ray diffraction of Ni nanoparticles (NPs) before injection of HDT,
confirming their branched shape and face‐centered cubic crystal
structure. TEM images of the Ni NPs used as starting materials for
the reactions employing different sulfur and selenium precursors
are presented in Figure S1. Reference data for Ni
(PDF 00‐004‐0850)
| 3
3.2 | General observations
We begin with some general observations from structural
and compositional analysis (Table 1) and the following
figures with TEM and XRD results. All sulfidation and
selenidation products had broad size distributions, voids,
and irregular shapes. The nonuniform contrast across in-
dividual NPs from the sulfidation and selenidation pro-
ducts indicates that they are polycrystalline, which is also
consistent with the presence of multiple phases within
each sample. In addition to void formation, the branching
of the initial dendritic Ni NPs is suppressed, and there is a
broadening of the size distribution toward larger sizes,
which is suggestive of Ostwald ripening. Void formation is
consistent with the Kirkendall effect. When each sulfur/
selenium precursor is catalytically decomposed into ele-
mental S/Se, a thin shell of the product phase forms, and a
diffusion couple is established, in which S/Se diffuses in-
ward and Ni atoms diffuse outward. Faster outward dif-
fusion of Ni than inward diffusion of S/Se is expected to
result in the accumulation of vacancies in the core of the
NP that coalesce into a void or voids.
Rietveld refinement was performed on XRD measure-
ments for each sample to identify the phases present and
their proportion, from which an average Ni:S or Ni:Se
composition was calculated and compared with elemental
analysis by ICP‐OES (Table 1). The average composition of
the sulfide products is approximately equimolar in Ni and
S, and the selenide products are enriched in Ni, indicating
less efficient incorporation of selenium. This observation is
consistent with the generally greater reactivity of sulfur
than selenium. There is good agreement between the
compositions measured by XRD and ICP‐OES, but the
ICP‐OES results generally show slight enrichment in Ni in
comparison with the XRD. This minor difference might be
explained by the presence of Ni‐rich amorphous phases
detected by ICP‐OES, but that are not accounted for by
XRD. The sulfide and selenide phases identified by XRD
are next to each other on phase diagrams. The extent of
sulfidation or selenidation should be limited by thermo-
chemistry and the availability of atomic S or Se or time.
Further investigation will be needed to decipher whether
the final products form directly from the starting materials,
or if sulfidation/selenidation reactions occur by repeatedly
progressing through successive phases as the composition
is enriched in S/Se.
Remarkably, all samples have minimal P content,
below 1 mol%. In our previous work, the abstraction of P
from TOPO was not observed, but TOP is commonly
used for phosphidation of Ni NPs.48 Even though sub-
stantial amounts of TOP are present in the TOP:S and
TOP:Se precursors, S and Se were preferentially in-
corporated, and there was minimal incorporation of
4 | LYNCH ET AL.

T A B L E 1 X‐ray diffraction (XRD) refinements, elemental analysis of Ni and S/Se from XRD and inductively coupled plasma optical
emission spectroscopy (ICP‐OES), and determination of P impurities
Average Average composition mol% P
Precursor XRD refinement phase (wt%) composition XRD ICP‐OES ICP‐OESa
HDT Ni9S8 (66%), Ni3S2 (34%) Ni55S45 Ni55S45 0.06
TOP:S Ni3S2 (59%), NiS (41%) Ni56S44 Ni62S38 0.77
S(OLA) Ni3S4 (43%), NiS (31%), Ni46S54 Ni52S48 0.01
NiSO4·6(H2O) (26%)
TU(OLA) NiS (47%), Ni3S4 (25%), Ni48S52 Ni51S49 0.03
NiSO4·6(H2O) (29%)
TOP:Se Ni3Se2 (97%), NiSe (3%) Ni60Se40 Ni69Se31 0.16
SeU(OLA) Ni3Se2 (50%), NiSe (10%), Ni (40%) Ni76Se24 Ni85Se15 0.00
a
The mol% P was calculated with respect to the Ni and S/Se content of the sample and omitted organic content.

P. Incorporation of S/Se is more strongly favored and
suppresses incorporation of P in comparison to similar
experiments conducted in the absence of S/Se.48 Further
experiments will be needed to understand the origin of
the suppressed incorporation of P, but we speculate that
it might be related to the immediate availability of atomic
S/Se in these precursors, while TOP must first undergo
decomposition before atomic P is released. There has
been a report, however, of the conversion of NiO NPs
into both phosphides and sulfides.53
Each precursor may liberate atomic S at different rates,
giving different concentrations, and the chemical en-
vironment can also affect its reactivity. HDT and TOP:S
yielded similar products, and S(OLA) and TU(OLA)
yielded similar products. Differences in the behaviors of
these pairs of precursors might arise from a common
effect when oleylamine is present.54 For example, oley-
lamine is known to serve as a reducing agent in the in-
itial synthesis of Ni NPs.48 Here, oleylamine appears to
have a role in the formation of sulfate.

3.3 | Nickel sulfide NPs 3.4 | Nickel selenide NPs

TEM images of the sulfidation products from HDT and
TOP:S show similar structures (Figure 2). In both sam-
ples, the size distribution was approximately
100–250 nm, and most of the products had large pro-
nounced voids. The voids formed using TOP:S were
somewhat larger than those formed using HDT. Similar
XRD results were obtained for syntheses using HDT and
TOP:S for sulfidation. HDT yields Ni9S8 and Ni3S2, while
TOP:S gives Ni3S2 and NiS.
The sulfidation products from S(OLA) and TU(OLA)
precursors are quite similar (Figure 3). In both samples,
the NPs have sizes of approximately 100–300 nm and
contain small voids. S(OLA) and TU(OLA) yield products
with identical phases, mixtures of Ni3S4, NiS, and
NiSO4·6(H2O). We attribute the formation of a hydrated
salt to the hydrated Ni precursor, Ni(acac)2·xH2O, which
could be the source of water for NiSO4·6(H2O). Sulfate
could also form when oxygen from the waters of hydra-
tion reacts with sulfur in the S(OLA) and TU(OLA)
precursors. The precursors with oleylamine give products
that are slightly richer in sulfur than HDT and TOP:S.
The range of compositions for sulfidation products
using different precursors suggests a causal link.
Selenidation reactions were conducted following the
same protocol as sulfidation and replacing the sulfur
precursor with a selenium precursor (Figure 4).
TOP:Se gave NPs with smaller sizes of approximately
50–150 nm than approximately 100–200 nm for
SeU(OLA). Voids were observed in both products, and
TOP:Se gives a broader range of void sizes. TOP:Se
yielded Ni3Se2 with an impurity of NiSe, while
SeU(OLA) results in a mixture of Ni3Se2, NiSe, and a
substantial amount of unreacted Ni. TOP:Se thus gives
a purer selenide sample with higher selenium content
than SeU(OLA). In contrast, for the sulfides, TU(OLA)
results in higher sulfur content than TOP:S. The dif-
ference in these trends might be explained by the
significant amount of sulfate formation when using
TU(OLA), but there was no comparable formation of
selenoates from SeU(OLA).
3.5 | Electrocatalysis
To determine the potential of these NPs as electro-
catalysts for the HER, cyclic voltammetry was
LYNCH ET AL.
(A) (B)
(C)
(D)
F I G U R E 2 (A,B) Transmission electron microscopy and
(C,D) X‐ray diffraction of nickel sulfide nanoparticles synthesized
using HDT and TOP:S precursors. Reference data for Ni3S2 (PDF
04‐007‐5742), Ni9S8 (PDF 04‐007‐0778), and NiS (PDF 04‐007‐0707)
performed on NiS and NiSe NPs synthesized using
TOP:S and TOP:Se. Cyclic voltammograms were ac-
quired at 10 mV/s for the glassy carbon substrate, NiS,
and NiSe NPs with current normalized to the electrode
geometric area (Figure 5). The glassy carbon shows only
a small, capacitive current and minimal activity for the
HER. On the other hand, both NPs are capable of cat-
alyzing the HER. Furthermore, in the case of NiS, fea-
tures in the cyclic voltammogram before the onset of the
HER current suggest the presence of specific adsorption
and desorption of protons on the surface of the NPs. NiS
outperformed NiSe, reaching a geometric areal current
density of 10 mA/cm2 at −0.31 V versus RHE, as
| 5
(A) (B)
(C)
(D)
F I G U R E 3 (A,B) Transmission electron microscopy and
(C,D) X‐ray diffraction of nickel sulfide nanoparticles synthesized
using S(OLA) and TU(OLA) precursors. Reference data for NiS
(PDF 04‐007‐0707), NiSO4·(H2O)6 (PDF 04‐009‐4339), and Ni3S4
(PDF 04‐006‐5369)
opposed to −0.34 V versus RHE for NiSe. The over-
potential of these NPs for the HER is comparable with
those reported for other sulfide and selenide NPs.55–57
The electrocatalytic performance cannot be assigned to
a specific phase or feature of the NPs, because the
samples have mixed phases, and the surfaces and de-
fects in these NPs have not been characterized. The
ability of these NPs to catalyze the HER raises a ques-
tion about the fate and potential role of the ligands
coating NPs in the electrochemical environment. Fur-
ther studies are necessary to elucidate the effects of the
ligands, including blocking charge transfer at the sur-
face of the NPs, dissociation from the NPs, and dissol-
ving in the electrolyte.
6 |
(A) (B)
(C)
(D)
F I G U R E 4 (A,B) Transmission electron microscopy and
(C,D) X‐ray diffraction of nickel selenide nanoparticles synthesized
using TOP:Se and SeU(OLA) precursors. Reference data for Ni
(PDF 04‐002‐7521), NiSe (PDF 04‐003‐7226), and Ni3Se2
(PDF 04‐007‐3698)
4 | CONCLUSIONS
The rich conversion chemistry of Ni NPs includes sulfi-
dation and selenidation reactions, and all precursors
yielded hollow structures through the Kirkendall effect.
The selection of the sulfur/selenium precursor gives
control over the product phases obtained. The purity of
the desired phase could likely be improved by optimizing
LYNCH ET AL.
F I G U R E 5 Cyclic voltammetry of the glassy carbon substrate,
NiSe, and NiS nanoparticles (NPs) at 10 mV/s and 1800 rpm in
0.5 M H2SO4 electrolyte, showing the catalytic activity of the NPs
for the hydrogen evolution reaction
the stoichiometry and the reaction temperature and time.
We further hypothesize that the ability of Ni NPs to de-
grade hydrocarbon precursors could enable the in-
corporation of other elements. In future work, the
conversion chemistry of the same set of precursors could
be extended to competitive reactions with multi‐metal
NPs. The generalizability of the result that sulfidation/
selenidation suppress phosphidation could also be in-
vestigated for other compositions of NPs. Combining the
Kirkendall effect with subsequent cation or anion ex-
change may also be a useful method for obtaining
structures and compositions of NPs that cannot be syn-
thesized through direct nucleation and growth. NiS and
NiSe NPs showed electrocatalytic activity for the HER in
acidic electrolyte. The role of ligands on NPs during the
electrochemical reaction could provide mechanistic in-
sights into charge transfer at these complex electro-
chemical interfaces.
AC KNOW LEDGM ENTS
The authors acknowledge Ching‐Chang Chung for training
on XRD and assistance with refinement and Kim Hutch-
ison for performing ICP‐OES. This study was supported by
the National Science Foundation (DMR‐1056653, CBET‐
1605699, and CMMI‐1763025) and performed in part at the
Analytical Instrumentation Facility (AIF) at North Carolina
State University, which is supported by the State of
North Carolina and the National Science Foundation
(ECCS‐1542015). The AIF is a member of the North Car-
olina Research Triangle Nanotechnology Network (RTNN),
a site in the National Nanotechnology Coordinated Infra-
structure (NNCI). Part of this material is based upon work
LYNCH ET AL.
supported by the U.S. Department of Energy, Office of
Science, Office of Basic Energy Sciences under Award
Number DE‐SC0020234.
ORCID
Veronica Augustyn https://orcid.org/0000-0001-
9885-2882
Joseph B. Tracy https://orcid.org/0000-0002-3358-3703
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SU PPOR T ING INF OR MATI ON
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How to cite this article: Lynch BB, Kelliher AP,
Anderson BD, et al. Sulfidation and selenidation of
nickel nanoparticles. Carbon Energy. 2020;1–8.
https://doi.org/10.1002/cey2.83