ELSEVIER

Applied Catalysis B: Environmental

7 ( 1996) 225-235

Catalytic oxidation of sulfide ions over nickel

hydroxides
A. Andreev a,*, P. Khristov a, A. Losev b
Institute of Catalysis, Bulgarian Academy of Sciences. 1 I13 Sojia, Bulgaria
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, I1 I3 Sofia, Bulgaria
Received 17 February

1995; revised 10 August 1995; accepted

14 August 1995

Abstract
The catalytic sulfide ion oxidation by oxygen to elemental sulfur over P-Ni( OH), and LiNiOZ has
been studied. As a result of experimental investigation performed, a reaction mechanism is suggested
which involves heterogeneous and homogeneous processes. Dioxygen activation in the heterogeneous
process proceeds via a redox Ni2+ @ Ni+ transition and participation of OH- groups. The active
HO; species thus formed carries on the reaction in homogeneous phase. Nickel hydroxides are
promising catalysts for practical application.
Keywords:

Oxidation;

Nickel hydroxide; S- oxidation

1. Introduction
The process of sulfide ion catalytic oxidation to elemental sulfur by oxygen from
air is important for environmental protection. Due to the high toxicity of sulfide
ions, water containing these ions is hardly purified through biological treatment.
However, elemental sulfur is readily removed from waste and natural water by
biological treatment. Sulfide ion oxidation in aqueous medium can be successfully
used to manufacture colloidal sulfur on a large scale.
The oxidation process in alkali medium can be represented by the following
equations:
S*- + ;O,+H,O

-+ S+20H-

or
* Corresponding author. Tel. ( + 35-92) 724901, fax. ( + 35-92) 756116, e-mail andreev@bgearn.bitnet.
0926-3373/96/$15.00 0 1996 Elsevier Science B.V. All rights reserved
.SSOIO926-3373(95)00045-3

(1)

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HS- + $0, -+ S+OH-

Catalysis B: Environmental

7 (1996) 225-235

(2)

Transition metal complexes and some inorganic salts [ l] and transition metal
oxides [ 2,3] have been reported to manifest catalytic activity for that process. A
high catalytic activity for this reaction was found for NiP& and a reaction mechanism has been proposed [ 41. Catalysts based on iron chelate compounds [ 5,6] and
cobalt phthalocyanines [ 7-101 have found practical application.
This work presents results of a study of sulfide ion oxidation to elemental sulfur
in aqueous alkali solution by using a novel type of heterogeneous catalysts: nickel
hydroxides. By means of a set of experimental methods we aimed at gaining
information about the catalytic reaction mechanism and the possibilities for application.

2. Experimental
2. I. Sample preparation
A sample denoted as NH was prepared by precipitation of nickel from an aqueous
solution of Ni( N03)* * 6H20 (p.a. grade, 450 g/l) and NaOH (250 g/l), aqueous
solution at 80C and pH = 9. After aging for 1 h the slurry was filtered and washed
until the NO, ions were absent and dried at 110C. The dried sample contained
77.68 wt.-% nickel as NiO and had a BET area of ca. 110 m2/g. The X-ray
diffraction pattern of that sample indicated reflections at 0.46, 0.271, 0.233 and
0.156 nm, specific of /3-Ni( 0H)2, as well as the two most intense reflections at
0.175 and 0.148 nm for NiO [ 111. The NiO content in the sample could be evaluated
at no more than 20%.
Sample NH/C was prepared by impregnation of activated charcoal (CECAACLH, BET area = 750 m2/g) with an aqueous solution of Ni( N03) 2. 6H2O, p.a.
grade. Further, NaOH (aqueous solution, 250 g/l) was added at 80C to attain
pH = 9. After aging for 1 h at the same temperature the product was washed with
distilled water and dried at 110C. The dried sample contained 3 1.23 wt.-% nickel
as NiO. Weak and very broad reflections for /3-Ni( OH), were observed in the
diffraction pattern which are consistent with a high dispersion of the deposited
phase.
Samples NH and NH/C were calcined at 400C for 2 h under inert atmosphere.
They are denoted as NH and NH/C, respectively. The BET surface area of NH
was 87 m2/g.
A sample denoted as LN was LiNi02 prepared by calcination of a mixture of
Li20 and NiO and had a BET area of about 2 m2/g. The procedure is described in
detail elsewhere [ 121. The phase identity was verified by means of X-ray diffraction
(reflection at 0.467,0.245,0.235,0.203
and 0.144 nm) [ 131.

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2.2. Catalytic activity measurements

The catalytic activity in S2- oxidation by oxygen was measured in a static system
under continuous stirring by monitoring the volume of oxygen consumed at 20C.
Results were checked with a chemical method by determining the sulfide ion
concentration. For this purpose EDTA titration of excess Cu2+ ions with respect
to the amount of S2- ions was carried out, the Cu2+ ions being added as Cu( Clod) 2
aqueous solution. A Na,S aqueous solution of 19.47 g/l concentration, 10 ml for
each run, was used. The amount of catalyst (very fine powder) was 0.06 g for NH
and NH/C and 0.1 g for LN.
Catalyst activity was expressed as mol S*- converted per gram atom of nickel
(mol S2- /g,, Ni) on comparing supported with unsupported samples. Comparison
between unsupported samples was made by the productivity per 1 m*( mol S2- /
m2). On deducing the temperature dependence of the reaction rate, rate values were
determined as the first derivative of the time dependence of productivity in the
linear part of the curve.
2.3. X-ray diffraction
X-ray diffraction measurements were carried out by means of a conventional
powder diffractometer using Cu Ka radiation.
2.4. X-ray photoelectron

spectroscopy

(XPS)

X-ray photoelectron spectra were recorded on an ESCALAB MK II instrument

using Al Ka excitation source. Corrections related to a charge on the samples were
made with respect to the position of the C 1s peak at 284.6 eV.
2.5. Electrochemical

measurements

A nickel hydroxide (NH) containing electrode was prepared by pressing the

powdered material in an insulated platinum holder. The potential difference
between the NH electrode and a calomel electrode was measured. A special glass
cell was used to conduct the measurements in which a 10% NaOH aqueous solution
was introduced. The cell could be purged with both argon and air.

3. Results
3. I. Catalytic activity
Fig. 1 shows data on the catalytic activity of the NH and LN samples. Both
samples exhibit high catalytic activity in reaction ( 1) . The activity of sample LN
was one order of magnitude higher than that of sample NH.

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7 (1996) 225-235

100

10

\
T
0

0.01

Fig.

~II:IlIl1!111,11,ij
0
10
time

20

30

[min]

1.Catalytic activity of samples NH and LN. (Final conversions: NH-38.5% and LN-16.6%).

These results were confirmed by studies of the temperature dependence of the

reaction rate. The following values were obtained: 8200, 10700 and 3600 cal/mol
for NH, NH/C and LN, respectively.
Experimental results presented in Fig. 2 shows that calcination of the samples at
400C caused a considerable decrease in catalytic activity.
A study of the effect of catalyst amount on the productivity demonstrated a
striking dependence. Samples NH and NH/C manifested decreased amounts of
converted S2- ions as the amount of catalyst was increased (Fig. 3a and Fig. 3b).
3.2. X-ray photoelectron

spectroscopy

XPS spectra of the investigated samples are described by stable charging which
allowed the acquisition of narrow and well resolved peaks. Three ranges were
scanned: 0 1s (520-550 eV), Ni 2p (830-880 eV) and S 2p (140-190 eV).
Fig. 4 and Fig. 5 present the 0 1s peaks of fresh and used NH sample after
operation under the working conditions of reaction ( 1) . Substantial changes in the
spectrum of the fresh sample are observed after the treatment under the working
conditions, namely, considerable peak broadening and clearly resolved asymmetry.
These findings are good grounds to suggest the occurrence of several surface species
10.0

0.0
time

[min]

Fig. 2. Effect of calcination on the catalytic activity of samples NH and NH/C. Catalyst productivity
at 50C. (Final conversions: NH 38.5%, NH4.5%, NH/C 31.9% and NH/C 6.4%).

was measured

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229

6.0

N$ 4.0
:
0

;;

2.0

m
s
E

0.0

15.0
z
s

10.0

\
A
2

5.0

z
0.0
0
Fig. 3. Dependence

10
time

20

30

[min]

of the catalytic activity on the catalyst amount with samples NH (a) and NH/C

(b) at 50C.

530.00
binding

540.00
energy
[eV]

Fig. 4. 0 Is X-ray photoelectron

524.20
Fig. 5.0

1s X-ray photoelectron

529.20
binding

55i.00

spectra of fresh NH sample.

534.20
539.:
energy
[eV]

spectra of the NH sample after the operation under reaction conditions

from oxygen. By means of computer simulation the experimental curve was presented as a sum of three components. The first peak, having 530.0 eV binding
energy, can be interpreted as due to nickel oxide admixtures [ 14,151 formed on
drying the sample. The second peak with 532.3 eV binding energy is determined
by the basic phase, P-Ni( OH), [ 14,161. This result is in agreement with X-ray

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Catalysis B: Environmental

II

840.00
Fig. 6. Ni 2p,,,
conditions.

X-ray photoelectron

I,,

7 (1996) 225-23.5

1/,,,/,,,,,,,,,,,

850.00
860.00
870.00
binding
energy
[eV]

880.00

spectra of sample NH: (a) fresh; (b) after the operation

under reaction

diffraction data. The third peak, 535.0 eV binding energy, can be attributed to the
presence of oxygen-containing compound of trivalent nickel [ 171. Most likely, this
is a surface species with NiOOH like structure. Similar binding energies have been
found in the spectra of the active phase in nickel batteries where redox transitions
are realized, conditionally, between Ni( OH), and NiOOH [ 181. The quantitative
ratio between the three components can be evaluated as 30:60: 10.
Arguments in favour of Ni could be found on recording spectra in the 830-880
eV range. Fig. 6 shows spectra of sample NH in the region of Ni 2p. The relative
decrease in intensity of the satellite peak and its broadening are consistent with the
presence of Ni [ 191.
The XPS spectra of the used LN sample are compatible with considerable
amounts of Ni.
Fig. 7 shows experimental data in the S 2p region ( 140-190 eV) on a NH sample
treated under working conditions and washed with distilled water. The observed
peak at 163.5 eV is assigned to elemental sulfur, S8 [20], which is a reaction
product. Another peak at 168.9 eV is due to the surface SOi- groups [ 211. Small
amounts of sulfates, being also the product of the oxidation, are strongly adsorbed
onto the catalyst surface. It is interesting to note that no emission of sulfide ion
from a surface metal sulfide was observed at around 162.0 eV [ 191. Weak emission
in that region could not be registered because of the strong peak of elemental sulfur.

150.00
Fig. 7. S 2p,,, X-ray photoelectron

160.00
binding

170.00
energy
[ eV]

spectra of the NH sample after operation under reaction conditions.

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3.3. Electrochemical

231

measurements

The potential difference between a nickel hydroxide containing electrode and a

calomel electrode was measured under controlled atmosphere. Upon purging the
electrochemical cell with argon, a potential difference of about 63 mV was attained.
Admission of air caused a shift of the potential to more negative values. The airargon cycles were reversible. They are related to interaction between oxygen and
the nickel hydroxide surface and the occurrence of electron transition.

4. Discussion
Results of the catalytic activity measurements (Fig. 1 and Fig. 2) indicate that
the three samples studied (NH, NH/C and LN) exhibited high catalytic activity in
the oxidation of sulfide ions. The higher activity of sample NH/C, compared to
that of NH, is explained by the higher dispersion of the deposited active component
which was verified by X-ray diffraction.
As was shown by X-ray diffraction phase analysis, P-Ni(OH),
was the basic
component in the NH and NH/C samples. The presence of NiO admixtures did not
substantially affect the catalytic activity. Results in Fig. 2 show that thermal treatment of samples NH and NH/C, causing the formation of nickel oxide phase, is
accompanied by a drastic fall in the catalytic activity. The low activity exhibited
by the nickel oxide samples can be interpreted in terms of a partial hydroxylation
of their surface at high alkalinity (pH = 14) of the working medium. This alkalinity
originates from a strong hydrolysis of the sodium sulfide and accumulation of OHions, being the product of reaction ( 1) .
It is worth noting that according to the XPS study under the reaction conditions
no significant amount of sulfide phase is formed on the catalyst surface. Most
probably, this is due to a shifted equilibrium to the hydroxide of the surface sulfide
hydrolysis in a strong alkali solution. In this connection an active nickel hydroxide
phase occurs on the surface under reaction conditions, despite the presence of sulfide
ions in the solution.
Based on the above mentioned, one can arrive at the conclusion that the nickel
hydroxide manifests high and stable catalytic activity in sulfide ion oxidation by
oxygen in aqueous solution.
Detailed notion about the active nickel hydroxide phase can be obtained from
XPS data. It is essential that, along with nickel hydroxide, NiOOH like structures
also occur in the working catalyst. This allows to model the catalytic redox process
with a reversible redox transfer between the active species, Ni t) Ni, like in the
anode phase of nickel batteries [ 221.
The higher catalytic activity of sample LN, compared to that of NH, can be
explained in the following way. Prior to any contact with the reaction medium,
only trivalent nickel occurs on the surface of that sample. Under the influence of

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180
Fig. 8. Absorption spectrum
catalyst bed at 25C.

Catalysis B: Environmental

240
300
Wavelength

360
[nm]

7 (1996) 225-235

420

in the 200-400 nm range of Na,S solution after passing it with air through a NH

the reaction medium, however, the surface undergoes reduction hydrolysis with the
formation of NiOOH and Ni( OH), like structures [ 231. An optimum ratio between
Ni and Ni creates favourable conditions for the participation of high amount of
surface nickel ions in the redox transition Ni ti Ni. A detailed study of LN
samples related to the promising prospect of practical application is now in progress.
The XPS study is consistent with the conclusion that redox Ni ++ Ni transitions
proceed on the catalyst surface which are associated with hydroxide, Ni*+ (OH)*,
and oxyhydroxide, Ni3+OOH, structures.
Electrochemical
studies indicated that the catalyst electrode was sensitive to
oxygen from the air. Summarizing these studies one can draw the conclusion that
a reversible interaction between oxygen and the surface of the nickel hydroxide
electrode in an alkali solution was found which is related to the electron transfer
between oxygen and the catalyst.
Special attention should be given to the observed experimental finding of the fall
of the reaction rate on increasing the catalyst amount. It is assumed that sulfide ion
oxidation by oxygen from the air in aqueous solution [ 241 as well as in the presence
of homogeneous catalyst [ 251 proceeds via a chain-radical mechanism. A similar
mechanism can operate in the oxidation of sulfide ions in aqueous solution in the
presence of heterogeneous catalysts. If the oxidation reaction proceeds both over
the catalyst surface and with the participation of active species from the solution,
the decrease in the reaction rate upon increasing catalyst amount should be consistent with the destruction of the active sites on the solid catalyst [ 261.
For that reason an attempt was made to determine the active species in the liquid
medium under the conditions of reaction ( 1) . A solution of sodium sulfide was
circulated with air through a specially designed cell containing the NH sample.
Fig. 8 shows the absorbency in the range 200-400 nm. The observed maximum
around 290 nm can be ascribed to the HO; ion radical. This species has been
identified upon H202 dissociation in alkali solution [ 271.
Thus the observed antibate dependence of the catalytic activity in reaction ( 1)
on the amount of heterogeneous catalyst is a good reason to propose that the reaction
proceeds both on the surface and with the participation of active species in the

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HETEROGENEOUS
(HS-

+ 02 -

s + IiO2_)

HOMOGENEOUS
KS-

PROCESS

+ H02-

PROCESS

S + 20H-

Scheme 1.

solution. Most likely, the HO; ion radical is the active species for that reaction.
Based on the experimental results and the conclusions made, a reaction mechanism of sulfide ion oxidation over nickel hydroxide catalysts can be proposed
( Scheme 1) .
According to the experimental data, a steady state of the Ni hydroxide catalyst
is assumed, containing certain amount of Nirn ions bonded to NiOOH-like structures. The mechanism involves two processes: heterogeneous and homogeneous.
Considering the heterogeneous process, along with elemental sulfur active HO,
species are formed which carries on the reaction in homogeneous phase. Interaction
between the acid HS and the base O*- of the catalyst leads to an initially reduced
state of the active site.
The heterogeneous mechanism envisages dioxygen activation through electron
transfer onto the oxygen species via the Ni*+ ++ Ni3+ transition.
Of essential importance is the formation of intermediate species from oxygen, a
hydroxyl group and the metal ion (Scheme 2). Such a type of dioxygen activation
with the participation of hydroxyl group has been described for oxidation processes
in aqueous solution with transition metal complex catalysts [ 241.
The Ni( OH), catalyst considered has a layered structure and can be represented
no.
HO\
as a package of lamellas ( - Ni,) n. Trivalent nickel ions ( . . .Ni.&. ) are
OH

build in the plane of divalent nickel as defects. In this case Na+ ions and water
molecules can intercalate into the interlamellar space thus increasing the interla-

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Catalysis B: Environmental

7 (1996) 225-235

Scheme 2.

mellar distance and promoting a highly defective structure. The nickel ions which
participate in catalysis are probably located on edge sites at the end of the lamellae
(Scheme 2). Water intercalation increases the number of defects and edge sites.
The presence of intercalated Na + ions into the interlamellar space is substantial.
Its considerable potential facilitates the formation of HO; ions.
Recently, a high catalytic activity of the nickel hydroxide catalysts, discussed in
the present work, has been reported in the water-gas shift reaction [ 281. Due to
their specific structure, the nickel hydroxides are potential catalysts for a wide range
of oxidative and other processes.

Acknowledgements
The authors are grateful to the Bulgarian National Scientific Research Foundation
for financial support.

References
[ 11 T. Sakano and K. Miyata, Chinetsu Gijutsu, 3 (1978) 35.
[2] C.H. Knight, J.W. Smith and R.A. Barton, Can. Pat. 1 212 819 Al.
[ 31 A. Andreev, K. Kirilov, V. Ivanova, L. Prahov and E. Manova, in Y.E. Fisher (Editor), NATO AS1 Chemical
Physics of Intercalation II, Series B, Vol. 305, Plenum, New York, 1993, p. 375.
[4] A. Andreev, V. Ivanova, K. Kirilov and G. Passage, Appl. Catal. A, 107 (1994) 189.
[5] H.F. Fang, D.S. Kushner and R.T. Scott, Oil Gas J., 54 March (1982) 169.
[6] Y. Yamamoto, D. Terasaki, H. Uchiola, T. Kojima and W. Izutsu, Aromatikkusu, 34 ( 1982) 152.
[7] K. Chen and J. Morris, Environ. Sci. Technol., 6 (1972) 529.
[ 81 M. Hoffman and B. Lim, Environ. Sci. Technol., 13 ( 1979) 1406.
[9] A. Simonov, N. Kundo, E. Mamaeva and L. Akimova, Zh. Prakt. Khim., 50 ( 1977) 307.
[lo] M. Vassileva, A. Andreev, G. Schulz-Ekloff and D. Woherle, React. Kinet. Catal. Lett., 50 ( 1993) 139.
[ 111 H. Bode, K. Dehmeelt and J. Witte, Electrochim. Acta, 11 ( 1966) 1079.
[ 121 A. Lecerf, M. Broussely and J.P. Gabano, EP 0 345 707, US 4 980 080.
[ 131 T. Ohzuku, A. Veda, M. Nogayama, Y. Iwakoshi and H. Komori, Electrochim. Acta, 38 ( 1993) 1159.
[ 141 T.L. Barr, J. Phys. Chem., 82 (1978) 1801.

A. Andrew

et al. /Applied

Catalysis B: Environmental

7 (1996) 225-235

235

[ 151 G. Tynliev, P. Stefanov and M. Atanasov, J. Electron Spectrosc. Relat. Phenom., 63 ( 1993) 267.
[ 161 KS. Kim and N. Winograd, Surf. Sci., 43 (1974) 625.
[ 171 J. Jindra, I. Kreici, J. Mrha, B. Foekesson, L.Y. Johansson and R. Larsson, J. Power Sources, 13 (1984)
123.
[ 181 H. Bode, K. Dehmelt and J. Witte, Electrochim. Acta, 11 (1966) 1079.
[ 191 B. Nefedov, XPS Spectroscopy of the Chemical Compounds, Chemistry, Moscow, 1984.
[20] H. Rapp and U. Weser, Bioinorg. Chem., 5 ( 1975) 21.
1211 B.J. Lindberg e.a., J. Phys. Scripta, 1 (1975) 286.
1221 P. Oliva, J. Leonard and J.F. Laurent, J. Power Sources, 8 ( 1982) 229.
[ 23 1 J.J. Braconnier, C. Delmas, F. Fouassier, M. Figlarz, B. Beaudonin and P. Hagenmuller, Rev. Chim. Minerale,
21 (1984) 496.
[24] K.B. Yatsimirskii, Pure. Appl. Chem., 6 ( 1963) 117.
[25] N.N. Kundo and N.P. Keijer, Kinet. Katal., 9 (1970) 91.
[26] P.G. Ashmore, Catalysis and Inhibition of Chemical Reactions, Buttetworths, London, 1963.
[27] G. Bredig, H.L. Lehmann and W. Kuhn, Z. Anorg. Allgem. Chemie, 218 ( 1934) 16.
[28] A. Andreev, V. Idakiev, K. Kostov and M. Gabrovska, Catal. Lett., 31 ( 1995) 245.