9194 J. Phys. Chem.

1995, 99, 9194-9200

Structure of Amorphous M0S3

Th. Weber, J. C. Muijsers, and J. W. Niemantsverdriet*
Schuit Institute of Catalysis, Eindhoven University
of Technology, P.O. Box 513,
5600 MB Eindhoven, The Netherlands
Received: January 4, 1995; In Final Form; March 23, 1995®

The amorphous compound M0S3 has been investigated by monochromatic X-ray photoemission (XPS) and
vibrational spectroscopy, as well as by chemical extrusion aimed at identifying structural units inside M0S3.
XPS shows that all molybdenum in M0S3 occurs in the 4+ oxidation state, while sulfur is present in at least
two states, including S2- and S22' ligands in different types of coordination. This composition corresponds
to a formal charge state of MoIV(S2-)(S22-). The emission infrared spectrum of M0S3 exhibits characteristic
vibrations that are also encountered in the spectra of triangular Mo^S* cluster compounds. Three of such
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cluster compounds, i.e. (NFLMMo^S 13] 20, Ks [ 384( )9]·2 2 , and (NEtiMMo'^SvCle] can be extruded
from M0S3 by reactions that are essentially destructive. On the basis of these results it is proposed that
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M0S3 is essentially an aggregation of Mo(IV)3—sulfur cluster types.

Introduction sulfidation of molybdenum oxides. The well-defined structure

of the (NH4)2MoS4 complex and the fact that only sulfur ligands
Molybdenum sulfides are widely used as catalysts for are involved lead to a reduction of complexity and make this
hydrotreating, where hydrodesulfurization (HDS), the removal
reaction suitable for a structural chemical study.
of sulfur from crude oil, is one of the most important examples.1
The structure of M0S3 has been the subject of several studies.
HDS catalysts are prepared as highly dispersed molybdenum
The earliest results suggested that M0S3 was not an individual
oxides (M0O3 type structures) on a high surface area carrier
and subsequently converted into the catalytically active molyb- compound but a mixture of M0S2 and noncrystalline sulfur.14-16
denum sulfides (M0S2 type structures) via sulfidation, typically Analysis of X-ray radial distribution functions (RDF) indicated
that M0S3 may be considered as a genuine compound and a
in H2S/H2 atmospheres at temperatures between 300 and 400
structure with a metal—sulfur short-range order similar to the
°C.2,3 During the sulfidation, sulfur rich phases with stoichi-
ometries of nearly 1 Mo:3 S have been observed, and conse- W3S92- anion was proposed.17 Later, a new structural model
for M0S3 was proposed by Liang et al.,18·19 based on extended
quently, M0S3 has been assumed to be a relevant intermediate4-7
in sulfidation reaction: X-ray absorption fine structure (EXAFS), high-resolution RDF,
X-ray photoelectron spectroscopy (XPS), vibrational spectros-
— —
(1) copy, and magnetic susceptibility measurements. These data
Mo03 MoS3 MoS2
were interpreted in terms of the structures of the crystalline

At present, the knowledge about the reaction steps involved trichalcogenides of the group IVB and VB elements, and a
similar structure was proposed for M0S3 (structure 1). This
in the oxide—sulfide phase conversion is fragmentary, and also
model includes a chainlike arrangement of molybdenum atoms,
the structures of the oxidic precursor and the active sulfide are
which have a trigonal prismatic coordination of six sulfur atoms.
not precisely known.8 While crystalline Mo(VI) oxides9·10 and
MoIVS2U provide convenient references for the determination
Adjacent molybdenum atoms are bridged by three sulfur atoms
of structural features of the oxidic and sulfided states, respec- along the chain. Every two metal atoms in the chain are paired
up with a shorter metal—metal distance and one S—S bond in
tively, of the supported catalyst, a well-structured analogue for
the M0S3 intermediate is not readily available, as M0S3 can every other triangle. The proposed arrangement of M0S3
corresponds to a formal charge state of Mov(S22-)i/2(S2-)2-
only be prepared in the amorphous form. Further studies from these authors appeared in agreement with
M0S3 is typically prepared from (NH4)2MoVIS4, either by
this structure, in particular with the presence of two different
acidification of an aqueous solution or by thermal decomposition
Mo—Mo distances.20
in an inert gas atmosphere at temperatures between 260 and
300 °C.12 Above 310 °C, M0S3 decomposes to microcrystalline
M0S2,13 which is the thermodynamically most stable Mo(IV)—
sulfur solid-state compound. The final product of the decom-
position reaction

— —
(NH4)2MoVIS4 MoS3 MoIVS2 (2)

is essentially the same as that of the sulfidation of molybdenum

oxides (reaction 1), while the reduction of MoVI —1- MoIV is a
common feature in both reactions. The formation of amorphous
M0S3 and its further reaction to microcrystalline M0S2 as given
in (2) thus mimicks to some extent the chemistry of the
*
Corresponding author.
Whereas diffraction and spectroscopy provide direct structural
probes, important information on the nature of structural units
® Abstract published in Advance ACS Abstracts, May 1, 1995.

0022-3654/95/2099-9194$09.00/0 © 1995 American Chemical Society

Structure of Amorphous M0S3 J. Phys. Chem., Vol. 99, No. 22, 1995 9195

can also be obtained chemically by cluster extrusion. Two of hydrochloric acid. The reaction mixture was boiled for 1 h
such extrusion experiments, in which M0S3 was treated with under argon and filtered while hot. After adding 0.5 g of NEL-
aqueous solutions of NH3 and KCN, yielded the (NFL^- Cl, an orange solid precipitated from the yellow-green solution
[MoIV3S,3]-H2021 and the K5[MoIV3S4(CN)9]-2H2022 cluster within 2 days with a yield of 90 mg (i.e. 9.3% related to the
compounds, respectively. As both compounds contain MoIV amount of Mo in M0S3). Characterization was done by
comparing the infrared spectrum of the extrusion product with
that of (NEt4)2[Mo3S7Cl6]*H20 as prepared from (NILOr
[Mo3S13]-H20.29
Techniques. XPS spectra were obtained with a VG Escalab
200 spectrometer equipped with a monochromated Al Ka source
(1486.3 eV) and a hemispherical analyzer connected to a five-
channel detector. Measurements were done at 20 eV pass
energy. Charging was corrected for by using the C Is peak at
284.6 eV as a reference. The spectra of M0S3 were measured
[Mo3S4(CN)9]5· after pressing the compound in indium foil, while (NILt)2-
[Mo3S13]-H20 was deposited on the surface of a stainless steel
in a triangular geometry, their formation from M0S3 under
sample holder from a solution in MJV-dimethylformamide
essentially destructive reaction conditions is impossible to (DMF) and subsequent evaporation of the solvent. All steps
explain on the basis of the Mov chainlike structure M0S3 of the XPS sample preparation were done under inert conditions
proposed by Liang et al.18·19 (structure 1). Reinvestigation of
using a glovebox and a special transport vessel for introducing
the M0S3 structure therefore becomes necessary.
the samples into the UHV chamber of the spectrometer.
In this paper we report on the formation and the structure of
Raman spectra were obtained with a Spex Ramalog V (triple
amorphous M0S3, as investigated with three spectroscopic
monochromator) and a Coherent Innova 70/4 Ar+ laser. The
techniques, monochromatic XPS and in situ Raman and infrared 514.5 nm line was employed at 100 mW incident power. Before
emission spectroscopy (IRES). We refer to the literature for
measurement, (NH4)2MoS4 was pressed into a wafer with a KBr
further information on these methods.23-25 A new extrusion
back, which was mounted in the in situ cell.30 The latter was
experiment yields the (NEt4)2[MoIV3S7Cl6] (Et = C2H5) cluster
purged with argon. To study the thermal decomposition product
of (NH4)2MoS4, the cell was heated to 260 °C for 5 min. The
spectra were measured at room temperature in Ar with a spectral
resolution of 8 cm-1.
Infrared spectra were obtained with a Bruker IFS 113v
spectrometer equipped with a pyroelectric DTGS detector, and
with different beam splitters for the far and mid infrared region.
Infrared spectra of (NH4)2MoS4, (NH4)2[Mo3Si3],H20, and of
our extrusion product were measured in Csl in the absorption
[Mo3S7CI6]2-
mode. The spectra of M0S3 and of the thermal decomposition
intermediate of (NH4)2MoS4 were measured in the emission
compound and gives valuable information regarding the quan-
tification of structural units within the M0S3 solid. This mode in a cell that is very similar to the one described by
extrusion experiment, as well as the ones mentioned above, Diemann et al.,31 but was modified to fit in the Bruker
suggests a close relationship between the structure of amorphous spectrometer. Emission infrared spectroscopy was chosen
M0S3 and the structures of Mo(IV)3—sulfur cluster compounds. because M0S3 samples can conveniently be prepared and spectra
Therefore, we also studied the extrusion products, in particular of superior quality are obtained. M0S3 and (NH4)2MoS4 were
(NH4)2[Mo3S 13] 20, as reference compounds. We propose a applied as thin layers on the furnace of the cell as follows.
new structural model for M0S3 which explains the results Approximately 2 mg of the sample and 5 mL of 2-propanol
were shaken in a vibrating mill. The resulting suspension was
reported here and is also compatible with spectroscopic data
from the literature. spread on the surface of the sample deposition area, and the
liquid was slowly evaporated. The emission cell was purged
Experimental Section with argon and heated up to 260 °C. The spectmm of M0S3
and of the thermal decomposition intermediate of (NH4)2MoS4
Sample Preparation and Cluster Extrusion. (NH4)2MoS426 were measured with a spectral resolution of 8 cm-1 after a period
and (NH4)2[Mo3S 13]· 2027 were prepared as described in the
of 15 min to achieve thermal equilibration. Each spectrum is
literature. M0S3 was prepared according to ref 21 from a the sum of 500 scans, while the emission of the empty sample
solution of 1.0 g of freshly made (NH4)2MoS4 in 30 mL of holder served as a background spectrum.
degassed water, which was treated with 2 mL of concentrated
HC1 under stirring. The precipitated dark brown product was
Results
filtered and washed several times with H20, CH3OH, CS2, and
diethyl ether, respectively, dried in an argon stream, and finally We start with a discussion of the photoemission results.
stored under argon to prevent oxidation. Since the preparation Figure 1 shows the monochromatic Mo 3d XPS spectra of
of M0S3 by thermal decomposition of (NH4)2MoS4 depends (NH4)2[Mo3S 13]· 20 (Figure la) and of M0S3 (Figure lb). The
critically on the temperature and only in a narrow interval, Mo 3ds/2 binding energy (see Table 1) of the cluster compound
between 280 and 300 °C, is a phase with the correct stoichi- (229.0 eV) corresponds to the expected value for Mo(IV)—sulfur
ometry obtained,28 we used this type of reaction only for the compounds, i.e. (NH4)2[Mo3Si3],H2032 and MoS2.33 Note that
spectroscopic characterization of decomposition intermediates. the sulfur ligands in both compounds differ, but do not affect
This was done in situ in the respective measuring cells. the Mo 3ds/2 binding energy. The Mo 3d XPS spectrum of
For the extrusion of the (NEt4)2[Mo3S7Cl6] cluster compound, M0S3 (Figure lb) shows, in principle, the same binding energy
0.65 g of M0S3 was suspended in 35 mL of concentrated (229.1 eV). We therefore assign molybdenum in M0S3 the same
9196 J. Phys. Chem., Vol. 99, No. 22, 1995 Weber et al.

>x

\n
c
CD
(b)

(a) (a)

167 166 165 164 163 162 161 160

Binding energy [eV]

Figure 1. Mo 3d XPS spectra of (NH4)2[Mo3Si3]*H20 (a) and M0S3 Figure 2. S 2p XPS spectra of (NH4MM03S13] 20 (a) and M0S3
(b). (b).

formal oxidation state as in (NHak [ 38] 2 and M0S2,

namely, 4+. This assignment is also reasonable in view of our
discussion of the extrusion experiments (vide infra). As will
be discussed in detail elsewhere,34 the S 2p spectrum of (NHO2-
[Mo3Si3]-H20, as shown in Figure 2a, contains three doublets
corresponding to the bridging and terminal S22- ligands and to
the µ3 (apical) S2- ligand of the cluster anion. The S 2p3/2
binding energies are given in Table 1, along with the value for
M0S2. Note that the basal plane S2- ligands of M0S2 have the
same binding energy as the terminal disulfide ones. The S 2p
spectrum of MoS3 (Figure 2b) consists of at least two doublets
at 162.9 and 161.6 eV with an intensity ratio of 5:4. The doublet
with the higher binding energy is consistent with the presence
of bridging S32~ and/or apical S2~ ligands and the other with
either terminal S22-, S2-, or both. The fact that different kinds
of sulfur ligands have the same binding energy in XPS makes
an accurate relative quantification impossible. We will return
to this point later.
The XPS spectra of MoS3 and (NH4MM03S13]· 2 strongly
resemble each other and point to certain similarities in the
structure of the two compounds. We conclude that M0S3
contains molybdenum in the 4+ oxidation state, which implies
that the formation of MoIVS3 from (NH4kMoVIS4 is ac-
companied by molybdenum-sulfur redox processes, which lead v [cm ']
to reduction of molybdenum, MoVI —*
MoIV, and consequently Figure 3. Absorption infrared spectrum of ( 4)2[ 38 3]· 20 (a)
to oxidation of S2~ ligands of the M0S42- anion. and emission infrared spectrum of M0S3 measured at 260 °C in argon
The infrared spectra of (NH4)2[MoS13> 20 and M0S3 are (b).
shown in Figure 3. The spectrum of (NH4MM03S13] 20
(Figure 3a) shows the characteristic bands of the [M03S13]2- due to the v(S—S) vibrations, i.e. the r(S—S)t,r vibration at 544
cluster anion. The bands with the highest intensity are those cm-1 and the v(S—S), vibration at 510 cm-1. A characteristic

TABLE 1: XPS Data of Molybdenum Compounds

compound Mo 3d3/2 (eV) assignment S 2p3/2 (eV) assignment
(NH4MM03S13] 229.0 ± 0.2 Mo4+ 163.1 ±0.2 S22- bridging
161.7 ±0.2 S22- terminal
163.0 ± 0.5 S2_ apical
M0S3 229.1 ±0.2 Mo4+ 162.9 ±0.2 S22™ bridging
161.6 ±0.2 S22- terminal and/or S2-
M0S233 229.0 ± 0.2 Mo4+ 161.8 ±0.2 basal plane S2~
Structure of Amorphous M0S3 J. Phys. Chem., Vol. 99, No. 22, 1995 9197

[cm"']
Figure 4. Raman spectra of (NHO2M0S4 (a) and of a decomposition v [cm-’]
intermediate after 5 min at 260 °C in argon (b). Figure 5. Absorption infrared spectrum of (NHOzMoSí (a) and
emission infrared spectrum of a decomposition intermediate after 15
min at 260 °C in argon (b).
feature of this compound is the v(Mo—S) vibration of the apical
sulfur at 459 cm-1. The bands below 400 cm-1 are due to
due to a very weak shoulder around 550 cm-'. The band at
coupled v(Mo-S) vibrations.35
The infrared emission spectrum of M0S3 (Figure 3b) shows 525 cm-1 and the shoulder at 550 cm-1 are characteristic of
features very similar to those of the IR absorption spectrum of v(S—S) vibrations of terminal and bridging S22- ligands,
(NH4MM03S13] 2<3, although the bands of the former are respectively, which are observed at 522 cm-' (terminal) and
553 cm-1 (bridging) in the Raman spectrum of (NHak-
considerably broader and less well resolved. We assign the
bands at 545, 520, and 470 cm-1 to v(S-S)t,r, v(S-S)t, and [ 38 3] 2 .35 The broad band with a maximum around 350
cm-1 must be due to v(Mo—S) vibrations and corresponds to
v(Mo—Sap) vibrations, respectively. The band corresponding
to the r(S—S)t vibration is shifted by 10 cm-1 to higher the presence of bridging S22- ligands. Although this Raman
wavenumbers as compared to that of (NH4)2[Mo3Si3]*H20. Due spectrum is of modest quality, it nevertheless unequivocally
to coupling of v(Mo-S) and v(S—S) vibrations, the actual band confirms the presence of S2 groups in thermally decomposed
(NH4)2MoS4.
position of the latter depends in part on the structural environ-
ment of the disulfide ligands. A stronger coupling leads to Figure 5 shows the infrared spectra of (NH4)2MoS4 and of a
higher values for the v(S—S) vibrations.36 The bands at 285, thermal decomposition intermediate. The absorption IR spec-
330, and 380 cm-1, which also have corresponding features in trum of (NH4)2MoS4 (Figure 5a) contains two sharp bands at
the spectrum of (NH4MM03S1 sFFhO, can be assigned to coupled 456 and at 478 cm-1 corresponding to the symmetric and
v(Mo-S) vibrations containing v(Mo—St), v(Mo—Sbr), and antisymmetric v(Mo—S) vibrations of the M0S42- anion (see
v(Mo-Sap) contributions. The important point to note is that above). The emission spectrum of the decomposition interme-
virtually all the characteristic vibrational features of the diate (Figure 5b), measured at 260 °C in argon directly after
[M03S13]2- cluster anion appear to be present in the spectrum thermal equilibration (15 min), resembles that of M0S3, as
of M0S3 as well. shown in Figure 3b. Its major features are broad bands around
The results described thus far concern M0S3 prepared in 325 and 525 cm-1 and smaller but clearly visible contributions
solution. The following experiments pertain to thermally around 385 and 445 cm-'. We attribute the broad band around
decomposed (NIit)2MoS4 and serve to demonstrate that part of 525 cm-' to the unresolved contributions of terminal and
the terminal S2- ligands as present in the M0S42- anion indeed bridging disulfide ligands and the two bands at 325 and 385
undergo oxidation to disulfide ligands. cm-1 to coupled v(Mo-S) vibrations, as discussed above. The
Figure 4 displays the Raman spectra of (NH4)2MoS4 and of 445 cm-' band with shoulders at 430 and 470 cm-’ is probably
a decomposition intermediate after 5 min at 260 °C. The a superposition of v(Mo—S) vibrations of Mo=St fragments (see

spectrum of (NH4)2MoS4 (Figure 4a) contains two sharp bands above) and of the v(Mo—S) vibration of apical S2- ligands. The
at 455 and 476 cm-’ corresponding to the symmetric (vi(Ai)) emission infrared spectrum thus indicates that the thermal
and antisymmetric (V3(p2)) v(Mo-S) vibrations of the M0S42- decomposition product obtained after heating ( 4)2 $4 for
anion,37 respectively. The spectrum of the decomposition 15 min at 260 °C possesses disulfide as well as apical sulfur
intermediate (Figure 4b) also shows a band around 455 cm-1, ligands and is almost similar to that of amorphous M0S3.
which we assign to the v(Mo-S) vibration of Mo=St fragments If M0S3 is treated with boiling concentrated HC1, an extrusion
in an environment of lower symmetry compared with the product can be isolated from the reaction mixture by adding
M0S42- anion. However, two new, rather broad bands appear, NEt4Cl. The infrared spectrum of this extrusion product is
one with a maximum around 350 cm-1 and the other around shown in Figure 6. This spectrum is virtually equivalent to the
525 cm-'. The shape of the latter one is slightly asymmetric one published for the (NEtiMMosSyClej'^O cluster compound
9198 J. Phys. Chem., Vol. 99, No. 22, 1995 Weber et al.

destructive reaction conditions. This particular interpretation

of the extrusion experiments (an extrusion of preformed
structures instead of a synthesis in the reaction mixture) is
supported by a FAB-MS study of K2[Mo3Si3]‘ziH20, which has
been extruded from a physical mixture of 92MoS3/100MoS3.38 The
mass spectrum of the extrusion product shows mainly signals
due to pure 92Mo3— and l00Mo3—sulfur fragments.
The M0S3 structure as built up from Mo3S., units possesses
locally a relatively high degree of internal organization. How
reasonable is it to assume that this kind of structure forms in a
thermal decomposition of a rather simple compound as (NH4)2-
M0S4?
The thermal decomposition of (NFLO2M0S4 according to

(NH4)2MoVIS4
—
2 NH3 + H2S + MoIVS3 (3)

is accompanied by molybdenum—sulfur redox processes, namely,

oxidation of S2_ ligands of the M0S42- anion (2S2_ —
S22- +
2e) and reduction of the metal (Movl + 2e —
MoIV). The first
elementary step in (3) may be described as a proton transfer
from the two NH4+ cations to an S2_ ligand of the M0S42-
anion, leading to NH3 and a neutral {S3Mo(SH2)} intermediate,
which immediately decomposes to gaseous H2S and {M0S3}.
Simultaneous with the release of H2S, the molybdenum—sulfur
v [cm '] redox process takes place where the ligand oxidation reaction
Figure 6. Absorption infrared spectrum of the extrusion product leads to the formation of disulfide groups and provides the
obtained by treating M0S3 in boiling hydrochloric acid. The spectrum electrons for the reduction of the metal. This is recognized in
is virtually identical to that of the triangular (NEtihtMosSrCyTIjO the Raman spectrum of Figure 4b: Treating (NFLO2M0S4 at 260
cluster compound. °C for 5 min forms mainly terminal disulfide ligands, suggesting
that a resulting “mononuclear” {M0S3} intermediate may
as prepared from (NFL02[Mo3S 3] 20,29 where also a vibra-
formally be described as {(S2-)—MoIV—(S22-)}. The latter is
1

tional analysis is given. The bands at 559 and 570 cm-1 are not expected to be stable due to the low coordination number
due to v(S—S) vibrations, and the band at 461 cm-1 corresponds
of the metal. Stabilization is achieved by aggregation of these
to the v(Mo-S) vibration of the apical sulfur. The bands
{S—Mo—S2} fragments (indicated by the band corresponding
between 350 and 250 cm-1 are due to coupled v(Mo-S) + to bridging S22~ ligands in the Raman spectrum), where the
v(Mo-Cl) vibrations; those between 250 and 200 cm-1 mainly formation of Mo3—sulfur substructures is thermodynamically
correspond to deformation modes mixed with external, i.e. favored.
translational and rotational, modes. The bands at low wave- The aggregation of the {S—Mo—S2} units is a random
numbers, i.e. at 166 and 177 cm-1, contain significant metal-
process. The positions of all molybdenum and sulfur atoms at
metal stretching contributions. Although the band at 528 cm-1
the beginning of the decomposition reaction is determined by
has the highest intensity, it is not discussed in ref 29; we
the crystal structure of (NH4)2MoS4·39 Directly after the loss
tentatively assign this band to coupled v(S—S) + r(Mo—Cl) of NH3 and H2S, the packing of the system is loose. This, in
vibrations. The fact that (NEt4)2[Mo3S7Cl6] can be prepared
combination with the temperature of 260 °C, causes the mobility
from both M0S3 and (NELth [Mo3S 13] 2 under comparable to be higher, as is usually the case within solid-state reactions,
reaction conditions again points to similarities in the structures and the {S—Mo—S2} fragments aggregate mainly within one
of M0S3 and the triangular Mo3—S.r compounds.
plane (the aft-plane of (NH4)2MoS4).17 This can be seen in the
Discussion powder diffraction pattern of M0S3 (cf. ref 4), which shows a
reflection at 2 = 14.5°. This reflection corresponds to a lattice
The following results are essential in considering a structure plane distance of 0.63 nm and points to a “layered structure”
for amorphous M0S3. for M0S3. During the aggregation of the {S—Mo—S2} frag-
(i) The XPS Mo 3ds/2 binding energy of 229.1 eV indicates ments four different types of triangle structures (Mo—S short-
that M0S3 contains molybdenum in a formal 4+ oxidation state. range order) can be formed. There are triangles in which the
(ii) The XPS S 2p spectrum of M0S3 shows the presence of three metal atoms are bonded together with only bridging S22-
different types of sulfur ligands, which may include bridging and those which also include S2_ ligands between two metal
and terminal S22- and bridging S2_ ones. atoms. Both types of triangle structures can occur with and
(iii) The emission infrared spectrum of M0S3 contains all the without an apical sulfur atom. These four possibilities are
characteristic vibrations that are encountered in the infrared depicted in structures I—IV of Figure 7. Note that these
spectrum of the triangular cluster compound (NH4)2[Mo3S 13] 20. structures do not represent compounds in their own right, but
(iv) Three triangular cluster compounds, (NFLi)2[M03S13] 20,21 the building blocks within the M0S3 solid, which, however, all
Ks [Mo3S4(CN)9>2H20,22 and (NEt4)2[M03S7CI6], can be ex- satisfy the requirements of stoichiometry and electroneutrality.
truded from M0S3 using chemical reactions that are essentially The M0S3 structure (long-range order) is essentially an
destructive. interconnection of the structure types I—IV by means of sulfur
On the basis of these results, we propose that M0S3 is ligands. There are two possibilities for interconnections. If both
essentially an aggregation of Mo(IY)3—sulfur cluster types, from molybdenum atoms of two adjacent triangles have an S2~ ligand,
which the {M03S7}44" and {M03S4}4"1" cores—the central parts such as the Mo atoms at the top of structures I and II, the
of the extrusion products—can be readily abstracted under triangles connect via the two S2~ ligands in an {Mo—(S)2—Mo}
Structure of Amorphous M0S3 J. Phys. Chem., Vol. 99, No. 22, 1995 9199

Figure 7. Structures of the {MoIV3—S9} cluster types within M0S3 and a representative part of the M0S3 structure.

bridge. If only one S2_ ligand is available, as when the Mo Treatment of M0S3 with an aqueous solution of KCN
atoms at the top of structures I and III combine, the triangles produces K5[Mo3S4(CN)9]'2H20 with a yield of ca. 35%. The
connect via an {Mo—S—Mo} bridge. Figure 7 shows a reactions involved in its formation are
representative part of the M0S3 structure. Note that the
interconnection of the structures I—IV preclude the presence
of Mo—St fragments and also of coordinatively unsaturated + CM" —-
Mo^-S-Mo™ + NCS" (4)
{ Mo1)^ |
} { }
molybdenum atoms as structures I—IV might imply. It is
conceivable that Mo atoms at the boundaries of a M0S3 particle
are terminated by S2 groups (see the arrows in Figure 7), which —

| + 3CN--- MoIV(CN)3 + S22- (5)

are required for the coordinative saturation of edge metal centers,
where they impede further aggregation. This effect leads to a
slightly higher stoichiometry, namely, M0S3.1—M0S3.2, which in which the { 3$4}4+ core is formed by subsequent sulfur

in fact was found by elemental analysis,13·17 in agreement with redox (4) and the metal—ligand substitution (5) reactions from
the surplus of sulfur found in the XPS spectrum. As the the {M03S7}44 (structure HI) and the {MojSe}44 core (structure
oxidation state of sulfur in the {S—Mo—S2} fragments does IV), which means that the portion of structure IV in M0S3 is
not change during the aggregation process, the charge state of about 25%. The cyanolysis of M0S3 is often accompanied by
M0S3 can formally be written as MoIV(S2~)(S22“). This charge the formation of Ks[Monl4S4(CN)8]'4H20 in varying low
stoichiometry itself cannot be obtained from the S 2p spectrum percentages (<3%).22 Since the Mo 3d XPS spectrum of M0S3
(Figure 2b) without additional structural information (vide (Figure lb) does not indicate a second molybdenum state beside
supra). However, our structural model is in full agreement with Mo4+, we argue here that the {MoIH4S4}4+ core is not a relevant
the S 2p spectrum of M0S3, i.e. (S2t2- + S2_):(S2br2_ + Sap2-) local structure within the M0S3 solid.
=
4:5. The remaining part of the M0S3 solid (65%) can obviously
The M0S3 structure model (Figure 7) readily accounts for not be extruded in the form of stable clusters, probably due to
the fact that the extrusion experiments yield triangular M03 the absence of apical sulfur atoms (structures I and ). We
cluster compounds. The [M03S7CI6]2- cluster anion forms from therefore conclude that structures I and together contribute
{M03S7}44 fragments as present in structure (cf. dashed box) to the structure of M0S3 with ca. 65% and structures HI and IV
by substitution of all interconnecting sulfur ligands outside the with ca. 25 and 10%, respectively. Such a composition favors
triangle by chlorine. We correlate the yield of this reaction the interconnection of triangles by Mo—(8)2—Mo bridges over
(ca. 10% related to the amount of Mo) with the portion of that by Mo—S—Mo ones.
structure III in M0S3. EXAFS measurements by Cramer et al.20 have indicated that
The extrusion of (NFL^ [M03S13] 2 (ca. 20% on the basis the spectrum of M0S3 possesses scattering contributions from
of Mo) cannot straightforwardly be correlated with the portion two Mo—Mo distances, 0.274 and 0.314 nm, and mainly one
of a substructure in M0S3. In this experiment M0S3 was treated Mo—S distance of 0.241 nm. Metal—metal and metal—sulfur
with a solution of NH3 in H2O for several days. From the distances in our structural model can be estimated using the
chemistry in solution it is known that (NH4MM03S13] 2 can X-ray structure data of relevant molybdenum—sulfur cluster
only be synthesized in a large excess of polysulfide.21·27 We compounds. The Mo—Mo distance in structure HI should be
therefore argue that M0S3 decomposes in the reaction mixture close to that in the [M03S13]2- anion,32 namely, 0.272—0.275
under formation of (NFL^S*. This would then enable the nm, and should be slightly longer in structure I. The distance
extrusion of (NH4MM03S13> 2 , in agreement with its higher between molybdenum atoms bonded via an S2_ ligand within
relative sulfur content than M0S3. structures II and IV is expected to be around 0.3 nm40 due to
9200 J. Phys. Chem., Vol. 99, No. 22, 1995 Weber et al.

the symmetry of the triangle structure. The distances of Mo References and Notes
atoms of different triangles interconnected with S2~ ligands are
(1) Gates, B. C.; Katzer, J. R.; Schuit, G. C. A. Chemistry of Catalytic
expected to be longer than 0.3 nm, because here an enlargement Processes; McGraw-Hill: New York, 1979.
of Mo—S—Mo bonding angles must be involved for a minimi- (2) Prins, R.; De Beer, V. H. J.; Somorjai, G. A. Catal. Rev.-Sci. Eng.
zation of the sterical interaction with the atoms of neighbored 1989, 31, 1.
(3) De Jong, A. M.; Borg, H. J.; van IJzendoom, L. J.; Soudant, V. G.
triangles (cf. also the discussion in ref 21). F. M.; de Beer, V. H. J.; van Veen, J. A. R.; Niemantsverdriet, J. W. J.
Metal—sulfur distances in M0S3 should fall between 0.236 Phys. Chem. 1993, 97, 6477.
and 0.248 nm according to the X-ray data of the [M03S13]2- (4) Chang, C. H.; Chan, S. S. J. Catal. 1981, 72, 139.
(5) Payen, E.; Kasztelan, S.; Houssenbay, S.; Szymanski, R.; Grimblot,
and the [MoaSaCCNM5- cluster anions,32·33 which are ¿(Mo- J. J. Phys. Chem. 1989, 93, 6501.
Sap)
=
0.236 nm, ¿(Mo—St) = 0.245 nm, and ¿(Mo—Sbr) = (6) De Boer, M.; van Dillen, A. J.; Koningsberger, D. C.; Geus, J. W.
0.248 nm, while the distance between molybdenum and a J. Phys. Chem. 1994, 98, 7862.
(7) Amoldy, P.; van der Heijkant, J. A. M.; de Bok, G. D.; Moulijn,
bridging S2_ ligand is expected between 0.238 and 0.240 nm. J. A. /. Catal. 1985, 92, 35.
These small differences in distance would be hard to resolve in (8) Knozinger, H. In Proc. 9th Int. Congr. Catal. Calgary 1988;
EXAFS, and an average metal—sulfur distance of 0.24 ± 0.01 Phillips, M. J., Teman, Eds.; The Chemical Institute of Canada: Ottawa,
nm is expected. 1989; p 20.
(9) Gmelin Handbook of Inorganic Chemistry, 8 th ed.; Molybdenum
We thus expect two metal—metal distances in the M0S3 solid,
Supplement Vol. Bl; Springer-Verlag: Berlin, 1975; p 88.
a shorter one around 0.275 nm and a longer one of about 0.31 (10) Gmelin Handbook of Inorganic Chemistry, 8th ed.; Molybdenum
nm, and an average metal—sulfur distance between 0.236 and Supplement Vol. B3a; Springer-Verlag: Berlin, 1986; p 23.
(11) Dickinson, R. G.; Pauling, L. J. Am. Chem. Soc. 1923, 45, 1466.
0.248 nm, in good agreement with the EXAFS results of Cramer
(12) Diemann, E.; Müller, A. Coord. Chem. Rev. 1973, 10, 79.
et al.20 Also the magnetic measurements given in ref 18 can (13) Wildervanck, J. C.; Jellinek, F. Z. Anorg. Allg. Chem. 1964, 328,
easily be explained, as the diamagnetic properties of M0S3 are 309.
due to the electronic structure of MoIv. The fact that two types (14) Voorhoeve, R. J. H.; Wolters, . B. . Z. Anorg. Allg. Chem. 1970,
376, 309.
of Mo—Mo distances are observed in M0S3 with EXAFS has (15) Ratnasami, P.; Rodrique, L.; Leonard, A. J. Phys. Chem. 1973,
implications for the identification of intermediate phases formed 77, 2242.
(16) Stevens, G. C.; Edmonds, T. J. Catal. 1975, 37, 544.
during the sulfidation of molybdenum oxides. De Boer et al.6
(17) Diemann, E. Z. Anorg. Allg. Chem. 1977, 432, 127.
encountered an M0S3 type intermediate phase but observed only
(18) Liang, K. S.; DeNeufville, J. P.; Jacobson, A. J.; Chianelli, R. R.
one Mo—Mo distance of 0.276 nm with EXAFS. Although J. Non-Cryst. Solids 1980, 35&36, 1249.
this intermediate phase has the correct stoichiometry, the absence (19) Liang, K. S.; Cramer, S. P.; Johnston, D. C.; Chang, C. H.;
of the longer Mo—Mo distance (0.31 nm) indicates that this Jacobson, A. J.; DeNeufville, J. P.; Chianelli, R. R. J. Non-Cryst. Solids
1980, 42, 345.
phase does not have the characteristic M0S3 structure as (20) Cramer, S. P.; Liang, K. S.; Jacobson, A. J.; Chang, C. H.; Chianelli,
discussed above. R. R. Inorg. Chem. 1984, 23, 1215.
(21) Müller, A.; Diemann, E.; Krickemeyer, E.; Walberg, H.-J.; Bogge,
Finally, any structural model for M0S3 must be able to H.; Armatage, A. Eur. J. Solid State Inorg. Chem. 1993, 30, 565.
account for its decomposition into microcrystalline M0S2 at (22) Müller, A.; Jostes, R.; Eltzner, W.; Nie, C.-S.; Diemann, E.; Bogge,
elevated temperatures: H.; Zimmermann, M.; Dartmann, M.; Reinsch-Vogell, U.; Che, S.; Cyvin,
S. J.; Cyvin, B. N. Inorg. Chem. 1985, 24, 2872.
(23) Niemantsverdriet, J. W. Spectroscopy in Catalysis, an Introduction;
MoS2 + S° (6)
-*
MoS3 VCH: Weinheim, 1993.
(24) Bates, J. B. In Fourier Transform Infrared Spectroscopy—Applica-
tion To Chemical Systems; Ferraro, J. R., Basile, L. J., Eds.; Academic
This reaction, which takes place in inert gas at temperatures Press: New York, 1978; Vol. 1, p 99.
above 310 °C, involves the reduction of bridging disulfide (25) Barr, J. K. Infrared Phys. 1969, 9, 97.
ligands due to reductive elimination of S2_ and terminal S22- (26) McDonald, J. W.; Delbert Friesen, G.; Rosenhein, L. D.; Newton,
W. E. Inorg. Chim. Acta 1983, 72, 205.
ligands30·31 formally according to (27) Müller, A.; Krickemeyer, E. Inorg. Synth. 1990, 27, 47.
(28) Prasad, T. P.; Diemann, E.; Müller, A. J. Inorg. Nucí. Chem. 1973,
35, 1895.
+ S2° (7) (29) Fedin, V. P.; Sokolov, . N.; Mironov, Yu. V.; Kolesov, B. A.;
{ Mol^ j Tkachev, S. V.; Fedorov, V. Ye. Inorg. Chim. Acta 1990, 167, 39.
(30) Müller, A.; Weber, Th. Appl. Catal. 1991, 77, 243.
(31) Diemann, E.; Weber, Th.; Müller, A. J. Catal. 1994, 148, 288.
During decomposition the preformed M03 units are preserved, (32) Müller, A.; Wittneben, V.; Krickemeyer, E.; Bógge, H.; Lemke,
and after the loss of one sulfur per molybdenum center, reactive . Z. Anorg. Allg. Chem. 1991, 605, 175.
{M03S6} units may remain, similarly as has been shown for (33) Patterson, T. A.; Carver, J. C.; Leyden, D. E.; Hercules, D. M. J.
the thermal decomposition of (NFLth[M03S1j^FUG.41 These Phys. Chem. 1976, 80, 1702.
(34) Muijsers, J. C.; Weber, Th.; van Hardeveld, R. M.; Zandbergen,
{M03S6} units are formed in every “layer” and aggregate to H. W.; Niemantsverdriet, J. W. J. Catal., to be published.
build up the M0S2 lattice. (35) Fedin, V. P.; Kolesov, B. A.; Mironov, Yu. V.; Fedorov, V. Ye.
Polyhedron 1989, 8, 2419.
(36) Müller, A.; Jaegermann, W.; Enemark, J. H. Coord. Chem. Rev.
Acknowledgment. We thank J. . M. C. van Wolput for 1982, 46, 245.
assisting with the infrared measurements. Valuable discussions (37) Nakamoto, K. Infrared and Raman Spectra of Inorganic and
with Dr. E. Diemann (Bielefeld), Prof. Dr. J. A. R. van Veen, Coordination Compounds, 3rd. ed.; Wiley: New York, 1978; p 142.
and Dr. V. H. J. de Beer (Eindhoven) are gratefully acknowl- (38) Müller, A.; Fedin, V.; Hegetschweiler, K.; Amrein, W. J. Chem.
Soc., Chem. Commun. 1992, 1795.
edged. We are indebted to Prof. Dr. A. Müller, University of (39) Schafer, H.; Schafer, G.; Weiss, A. Z. Naturforsch. 1969, B19, 76.
Bielefeld, for his kind permission to do Raman measurements (40) Pan, W.-H.; Leonowicz, . E.; Siefel, E. I. Inorg. Chem. 1993,
in his laboratory. This work was supported by Pionier Grant 22, 672.
70—154 from the Netherlands Organization for Scientific (41) Müller, A.; Diemann, E. Chimia 1985, 39, 312.
Research (NWO). JP950037J