SURFACE AND INTERFACE ANALYSIS, VOL.

23, 204-212 (1995)

Study of the Reduction Behavior of W/Ti02

Catalysts by XPS using Curve Fitting,
Deconvolution and Factor Analysis

Joseph N. Fiedor, Andrew Proctor, Marwan Houalla and David M. Hercules*

Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA

X-ray photoelectron spectroscopy (XPS,ESCA) was used to determine the tungsten oxidation states in a 5 wt.%
WO,/l%O, catalyst reduced in hydrogen in the temperature range 400-700 "C.Because, in the region of interest,
W 4f overlaps with the Ti 3p energy level, a multiple analysis procedure including deconvolution, non-linear least-
squares curve fitting and factor analysis was used to analyze the data. Deconvolution was better able to resolve the
peaks in the W 4f region and thus elucidate the positions of the tungsten components for each reduction tem-
perature. It was shown that there is a maximum of three W 4f doublets. The W 4f,,, peaks of these components
were located at 35.5,33.3 and 31.1 eV and they were assigned to W+6, W+4 and W", respectively. Factor analysis
verified the presence of three spectral tungsten components. X-ray ditaction verified the presence of W" on
reduction at 675OC. Non-linear least-squares curve fitting, using the positions from deconvolution, was able to
determine the distribution of tungsten oxidation states as a function of reduction temperature: W+6 steadily
decreased with increasing reduction temperature, W" initially appears at 408OC and goes through a maximum
around 58OOC; W" was first detected following reduction at 550OC and was the only species present for reduction
temperatures higher than 665 OC. From the distribution, it is proposed that, unlike the molybdenum systems,
tungsten undergoes a more simplified reduction process in which only one intermediate oxidation state (presumably
W+4) is detected.

INTRODUCTION The present study will expand on the use of various

data analysis methods to define the reduction pathway
of a 5 wt.% W03/Ti02 catalyst reduced in hydrogen in
Tungsten-supported catalysts are active for reactions the temperature range 400-700 "C.
such as hydrogenation, metathesis and isomer- The XPS tungsten energy level investigated in the
i2ati0n.l~~ Activation of these catalysts often requires present study is the W 4f region. The W 4d region
reduction pretreatment. The reduction step can produce proved to be too broad to be unambiguously useful.
a surface containing a mixture of tungsten oxidation Analysis of the W 4f region is complicated by inter-
states of varying relevance to the catalytic activity. ference from the Ti 3p level of the support and other
Therefore, understanding the reduction of supported less-intense tungsten core levels. In an attempt to solve
tungsten catalysts is essential for any attempt to estab- this problem, an extensive analysis procedure is under-
lish surface structure/activity relationships. taken so that the distribution of tungsten oxidation
The reduction of W/TiO, catalysts has been studied states in reduced 5 wt.% WO,/TiO2 catalysts can be
previously by Bond et ~ 1 and . ~Vermaire et ~ 1 using
. ~ determined with confidence. The use of multiple com-
temperature-programmed reduction (TPR). Bond et al. plementary analysis techniques avoids the ambiguity
suggested that W + 6 reduces directly to W metal, while that often results from using a single technique. First, a
Vermaire et al. concluded that W undergoes a two-step deconvolution algorithm' was employed to resolve
reduction (i.e. W + 6+ W + 4+ WO). However, TPR better the peaks and thus elucidate the number and
studies, as well as gravimetric and volumetric analyses, positions of the W and Ti components for each
are ambiguous because they measure only an average reduction temperature. Such a procedure has been used
oxidation state. Clearly, there is a need for a more direct previously in the analysis of XPS envelopes,'*' where it
method of examining the reduction process and the was shown to enhance the resolution threefold. Next, a
surface of reduced W/Ti02 catalysts. NLLSCF routine used the information provided by the
Recent work has shown that x-ray photoelectron deconvolution procedure concerning the number and
spectroscopy (XPS, ESCA) can be used in conjunction positions of the peaks to provide a firmer base for curve
with various data analysis techniques, such as non- fitting the individual W 4f envelope. From NLLSCF
linear least squares curve fitting (NLLSCF) and factor results the distribution of W oxidation states in each W
analysis (FA), to determine the distribution of Mo oxi- 4f envelope was measured. Finally, FA was used to
dation states in reduced Mo-supported determine the number of tungsten components in the
reduction series; the results were compared with those
* Author to whom correspondence should be addressed. obtained by deconvolution and the NLLSCF routine.
CCC 0142-242 1/95/040204-09 Receiued 21 July 1994
0 1995 by John Wiley & Sons, Ltd Accepted 15 November 1994
 REDUCTION BEHAVIOR OF W/TiO, CATALYSTS BY XPS 205

EXPERIMENTAL AND METHODOLOGY data analysis. Binding energy values for the 5 wt.%
W03/Ti0, catalysts were referenced to the Ti 2p3,, line
of TiO, (458.7 eV',).
For reduction experiments, the catalysts were pressed
Catalyst preparation (2000 psi) into pellets and mounted on a sealable
probe.', The sample was heated to the desired tem-
Degussa P-25 TiO, (84/16 anatase/rutile, pore perature (400-700 "C)by ramping the temperature at a
volume = 0.5 cm3 g-' and BET surface area = 50 5 rate of 2" min-' in flowing H, at a flow rate of 100 cm3
m2 g-') was first mixed with deionized water, dried min-'. The catalysts were reduced for 12 h at the
(110°C) and calcined (400°C) in air for 12 h. It was desired reduction temperature and then cooled to room
ground and sieved to 100 mesh, then tungsten (5 wt.% temperature under H, flow. The sealable probe was
WO,) was deposited by incipient wetness impregnation pressurized to 20 psi, sealed and transferred to the
using an ammonium metatungstate (Cerac) spectrometer.
[(NH4)6H2W12040* 4H20] solution. The resulting
catalyst was dried at 110°C for 16 h followed by calcin-
ation for 16 h in air at 500 "C.
Deconvolution

Deconvolution was accomplished by using the point

Raman simultaneous over-relaxation Jansson a l g ~ r i t h m . ~ . ' ~
Deconvolution is the removal of broadening effects
Raman spectra were recorded on a Spex Ramalog from a spectrum. An XPS spectrum is broadened by
spectrometer equipped with holographic gratings. The convolution of the intrinsic signal with several broaden-
5145 A line from a Spectra-Physics Model 165 argon ing functions that are either Gaussian or Lorentzian in
ion laser was adjusted so that 50 mW of power was nature. Examples of these broadening functions include
measured at the sample. The spectral slit width was 4 the natural linewidth (due to the lifetime of the core-
cm-' and the scan rate was 0.4 cm-' s-'. A Spex data- hole state), the exciting x-ray lineshape, the detection
mate computer was used for each data analysis. The system and any broadening due to charging. In order to
peak areas were calculated assuming a linear back- achieve a successful deconvolution, each spectrum must
ground. be pretreated. Pretreatment includes background
The 5 wt.% W03/Ti02 catalyst and the TiO, removal and spectral smoothing. The backgrounds were
support were pressed into 13 mm KBr-backed pellets removed using a Shirley-type integral14 and spectral
and scanned under ambient conditions. The samples smoothing was carried out using a cubic All
were rotated to minimize local heating. Raman was data analysis programs (GOOGLY Software) were
used to determine if the 5 wt.% W03/Ti02 catalyst written in house by A.P. The Jansson algorithm imple-
contained any bulk tungsten compounds (e.g. WO,). ments an iterative type of procedure that can be con-
trolled interactively by a visual evaluation or by
monitoring the residual variance between the original
X-ray difiaction data and the reconstructed data (i.e. the convolution of
the broadening function and the current deconvoluted
A Diano Model 700 diffractometer using Ni-filtered Cu spectrum).
Kcr radiation (A = 1.540 456 A) equipped with a graphite The most important variable in any deconvolution is
monochromator was used to obtain x-ray diffraction the broadening function. In the present case the
(XRD) data. The copper x-ray tube was operated at 50 broadening function was chosen to be a symmetric
kV and 25 mA, and the spectrum was scanned at a rate Voigt function" with 20% Lorentzian character. The
of 0.4" min-' (in 28). The pressed catalysts used in the width chosen happened to be slightly narrower than
reduction treatment for XPS analysis (see XPS section those used in curve fitting (see below) the spectrum of
for reduction procedure) were mounted on a glass slide interest. In our case the width was selected to be 1.9 eV.
for XRD analysis. The peak areas of anatase (101) and This allows for maximal deconvolution while not losing
rutile (110) with reflections at 48.1" and 41.2" (in 28), components because of 'over deconvoluting'.
respectively, were measured to determine the anatase/ The deconvolution procedure is also able to provide
rutile composition of the reduced catalysts. An equation information about the peak positions of the Ti and W
relating the intensity ratio for these reflections to per components as well as the number of spectral com-
cent anatase was obtained from Ref. 11. ponents for each reduction temperature. Thus, it can
give an indication when each new tungsten component
begins to emerge in the reduction series.
X-ray photoelectron spectroscopy

The XPS spectra were obtained with a modified AEI Non-linear least-squares curve fitting
ES2OOA photoelectron spectrometer equipped with an
A1 anode (hv = 1486.6 ev) at a power of 240 W (12 kV, The methodology used to fit the individual Ti 3 p W 4f
20 mA). The instrument was operated in the fixed retar- envelopes was slightly different than that adopted in
dation ratio (FRR) mode and the analysis pressure was previous work',' because of the Ti 3p interference.
< 5 x lo-' Torr. The instrument was interfaced to an Information about the Ti 3p region for the W/Ti02
IBM PC compatible for data collection and subsequent catalysts, such as peak width and peak position, was
206 J. N. FIEDOR ET AL.

obtained by curve fitting the Ti 3p region of TiO, alone. A A- r”\ REX%=6.0

Once the Ti 3p envelope was fitted, the peak position
and peak width were kept relatively constant (i.e. 50.2
eV) when fitting the envelopes of the reduced catalysts.
This can be done because there is no evidence from
XPS for any significant change of the Ti 2p envelope as
a function of reduction temperature. Therefore, it is safe
to assume that the Ti 3p envelope will not change
either.
Curve fitting of the W 4f envelopes was accomplished
by using the Levenberg-Marquardt damping method.”
All peaks were fitted using a Voigt function’* with 20%
Lorentzian character. The background was assumed to
be integral and it was applied individually to each peak.
The W 4f5,,/W 4f7/2 area ratio for the spin-orbit “satellite” i
doublet was fixed at 0.78.20The separation between the
W 4f7/2 and W 4f5,, was set at 2.1 eV and the width
ratio was assumed to be unity.
Figure 1 shows the W 4f region for WO,. It can be
seen that a small high-binding-energy peak (indicated
by an arrow) appears at - 6 eV higher than the main W
4f,/, peak. A similar high-binding-energy peak was Binding Energy I eV
reported earlier” for W metal and tentatively assigned
Figure 2. Curve-fitted spectra of WO,
to the W 5p3/2 level. To verify this hypothesis a high-
binding-energy window was selected to include both W
5p components. The small broad peak centered around envelopes of the reduced catalysts. As the high-binding-
50 eV corresponds to the W 5p,/, energy level. The W energy peak and the W 5p3/, peak contribute only mar-
5p3/2 peak should be located at -12 eV from the W ginally to the Ti 3 p W 4f envelope, any errors associ-
5p,,, energy and it should exhibit a similar full ated with it will not affect the overall results.
width at half-maximum (FWHM = 4.5 eV). This would The next step was to fit the envelopes of the reduced
put it more or less into the spectral background of W 4f. catalysts. The tungsten parameters used for these
As the additional high-binding-energy peak in the W 4f envelopes were the same as those established for WO, .
region is clearly narrower and its position does not As mentioned previously, the Ti 3p peak width and
coincide with the theoretical value, it cannot be attrib- peak position were kept relatively constant throughout
uted to the W 5p3/, peak. the reduction series. The initial peak positions of the
In our fitting procedure the small high-energy peak tungsten components were those obtained by deconvol-
was designated as a ‘satellite’ and fitted as a single peak. ution. However, when performing NLLSCF these tung-
Figure 2 shows the fit for W 0 3 . The position of the sten positions were allowed to float until they relaxed
‘satellite’ peak relaxed to 41.8 eV. An effort was made to into their local minimum.
fit the W peak but its area completely disappeared
when it was allowed to float. Therefore, it was assumed
that the W 5p,,, area is contained within the individual Spectral subtraction
integral background. The area ratio and the binding A difference procedure was implemented to remove the
energy difference between the ‘satellite’ peak and the Ti 3p contribution from the Ti 3 p W 4f envelope so
main W 4f peak were kept constant when fitting the that subsequent FA could be performed. When per-
forming a difference procedure one must ensure that the
two spectra are correctly aligned and n o r m a l i ~ e d In
.~~
our case the two spectra used in the analysis are the Ti
3p envelope of the TiO, support and the Ti 3 p W 4f
envelopes of the reduction series (see Fig. 6). To begin
the alignment and/or calibration procedure, each spec-
trum must undergo interpolation. A detailed description
of the interpolation procedure can be found in Ref. 23.
Once each spectrum is interpolated, the two spectra are
calibrated by referencing each spectrum to the Ti 2p,,,
line of TiO, (458.7 eVI2). On that basis, the Ti 3p peaks
for both the support and 5 wt.% W03/Ti0, catalysts
are positioned at 37.3 eV.
Next, one must carry out a normalization process. In
the present case normalization consisted of determining
the Ti 3p area to be removed from the Ti 3 p W 4f
.
L L- ~ p _ _ L- -A -- I
I ~
\--
envelope. The normalization constant ( N C ) for each
60 50 40 30 reduction temperature is simply
Binding Energy I eV
Figure 1. Spectrum of WO,
 REDUCTION BEHAVIOR OF W/TiO, CATALYSTS BY XPS 207

where (Ti 2p),,, and (Ti 2p),,, are the Ti 2p areas for the
catalysts and the TiO, support alone. The Ti 3p peak of
.= .
the TiO, support was then multiplied by the normal-
ization constant and the subsequent subtraction was
carried out.
. I
Factor analysis

The requirements for FA and a detailed description of

the technique have been given earlier.6924In this study,
F A comprised only principal component analysis
(PCA), which involves the decomposition of a data
matrix consisting of c spectra into c abstract (non-spec-
troscopic) components by single value decomposition
(SVD).I9 Through PCA it is possible to determine
Reduction Temperature (/OC)
which abstract components account for signal (1 . .. n)
and which account for noise (n + 1 .. . c). This study Figure 3. Anatase/rutile ratio of the TiO, support as a function of
will focus on the weight of evidence of several statistical reduction temperature.
methods, such as the F indicator function
IND24 and the reduced eigenvalue (REV) ratio,24 as An in situ XRD experiment was carried out to verify
well as other non-statistical methods, to determine n. A the presence of W metal for catalysts reduced at
more detailed explanation for the determination of n by -700°C. For this experiment a lo00 mg catalyst was
these various techniques can be found in Refs 24 and 27. packed against a quartz wool plug in a quartz reactor
None of the criteria chosen for this work require prior tube. The heating, reduction and cooling procedures
knowledge of the noise content in the original data were the same as those used in the XPS reduction
matrix.24 experiments. After the reactor was cooled it was sealed
and the samples were transferred to a glove box con-
taining ultrahigh purity Ar. In the glove box the
RESULTS samples were packed into a 2 x 2 x 0.2 cm hollowed-
out plastic slide and covered with Kapton tape so that
Raman the XRD measurements could be taken with minimal
exposure of the reduced catalysts to air. Figure 4 shows
Raman spectroscopy was used to determine if the 5 the XRD reflections in the region of 30-50" in 26 for the
wt.% W03/Ti02 catalyst contained any bulk tungsten TiO, support (a), the support reduced at 675°C (b), W
compounds (e.g. W03). The Raman spectrum (not
shown) of the 5 wt.% WO,/TiO, catalyst showed no
peaks characteristic of W 0 3 . A broad band at -960
-
metal (c) and a 5 wt.% WO,/TiO, catalyst reduced at
675 "C (d). The oxidic TiO, support [Fig. qa)] shows
XRD reflections characteristic of anatase and rutile. The
cm-' was observed and is attributed to the W=O reflections characteristic of anatase are located in 28 at
stretching band of the tungsten interaction species.,* 36.9", 37.8", 38.5" and 48.07", while those characteristic
These Raman results indicate that the tungsten phase in of rutile are found at 36.05", 39.2", 41.2" and 44.05" in
the 5 wt.% WO,/TiO, catalyst is exclusively present as 26. It is evident from the relative intensity of these
a surface tungsten species. reflections that anatase is the dominant form present in
the oxidic T i 0 2 support. Upon reduction to 675 "C the
reflections characteristic of anatase disappear and only
X-ray difiaction those of rutile remain [Fig. 4(b)]. The XRD pattern of
W metal exhibits an intense reflection at 40.2" in 28
X-ray diffraction analysis of the reduced 5 wt.% [Fig. 4(c)]. Figure 4(d) displays the XRD spectrum of
W03/Ti02 catalysts was performed to monitor any the 5 wt.% W03/Ti02 catalyst reduced at 677°C. In
changes in the anatase/rutile composition and the for- addition to the lines characteristic of rutile, the XRD
mation of any new tungsten phases. Figure 3 plots the
anatase/rutile ratio as a function of reduction tem-
perature for the 5 wt.% W0,/Ti02 catalyst. Samples
-
pattern of the reduced catalyst shows a broad shoulder
at 40.2" which can be attributed to W metal.
-=
reduced at temperatures 600 "C exhibit a constant
anatase/rutile composition that is approximately equal X-ray photoelectron spectroscopy
to that of the oxidic catalyst. A sharp decline in the
anatase/rutile ratio occurs for the samples reduced X-ray photoelectron spectroscopy was used to provide
between 600 and 712°C. This type of behavior was also information about the tungsten dispersion and distribu-
observed for the Mo/TiO, system.' The same study also tion of tungsten oxidation states of the 5 wt.%
found that the TiO, support alone undergoes the W03/Ti02 catalyst as a function of reduction tem-
change from anatase to rutile at a much lower tem- perature. Because of the overlap between W 4f and Ti
perature, indicating that Mo inhibits the transformation 3p, the W 4d region was used for monitoring tungsten
of anatase to rutile upon reduction (7). Our data shown dispersion. Figure 5 shows the variation in the W 4d/Ti
in Fig. 3 indicate that the W/TiO, system behaves in a 2p XPS intensity ratio as a function of reduction tem-
similar manner. These results agree with those postu- perature. The oxidic catalysts and the catalysts reduced
lated by Ramis et al.29 between 400 "C and 500 "C exhibit similar intensity
208 J. N. FIEDOR ET AL.

Reduction Temp ( P C )

oxidic

408

503

529

549

582

604

629

650

662

712
I I I
32 36 40 44 40 36 32
2 theta Binding Energy I eV
Figure 4. X-ray diffraction reflections for: (a) TiO,; (b) TiO,
reduced at 675°C; (c) W metal powder; (d) a 5 wt.% WO,/riO, Figure 6. The Ti 3p-W 4f spectra for re1 iced 5 wt. WOfliO,
catalyst reduced at 677 "C. catalysts.

a
r\l
0.4 I

0.3 1 9 .
(indicated by arrows) emerge. However, because the Ti
3p energy level is a major contributor to these XPS
envelopes it is difficult to determine the exact nature of
the tungsten components as a function of reduction
temperature. Therefore, there is a need to improve the
resolution in a manner that will help to define the posi-
tions of all the tungsten components. Thus, a deconvol-
ution procedure was carried out on each individual Ti
3 p W 4f envelope in an attempt to resolve the com-
ponents. Figure 7 displays the series of deconvoluted Ti
3 p W 4f envelopes. A decrease in peak width by about
O ~ ' " " ' " " ' " ' ' I a factor of 3 can be seen. The peak (A) at 37.5 eV attrib-
400 500 600 700
Reduction Temperature ( P C )
Figure 5. Variation of ESCA W 4d/Ti 3p intensity ratio as a func- Reduction Temp. ( P C )
tion of reduction temperature.
oxidic

408
ratios. A considerable decrease in the intensity ratio is
observed for reduction temperatures between 500 "C 503
and 600 "C. This can be attributed to particle growth of
the tungsten surface species and/or a change in the mor- 529
phology of the surface tungstates upon
Note the increase in the intensity ratio from 650°C to 549
700 "C. This behavior has been observed previously for
the Mo/TiO, system and it can be attributed to the col- 582
lapse of the TiO, surface area, which occurs on trans- 604
formation from anatase to rutile.
629

DATA ANALYSIS 650

662
Deconvolution
712
I I I I
Figure 6 shows the series of W 4f-Ti 3p envelopes 40 36 32
obtained from a set of reduced 5 wt.% WOJTiO, cata- Binding Energy I eV
lysts. It is clear that as the reduction temperature Figure 7. Deconvoluted Ti 3p-W 4f envelopes for reduced 5
increases from 400 to 700°C new tungsten components wt.% WO,/TiO, catalysts.
 REDUCTION BEHAVIOR OF W/TiO, CATALYSTS BY XPS 209

uted to Ti 3p is constant throughout the series. As the cedure on the original experimental data the positions
reduction temperature is increased it is evident that new were allowed to relax slightly into their local minima.
tungsten components appear. These new components Typical examples of curve-fitted Ti 3 p W 4f
are indicated by arrows. The four positions appearing in envelopes of the catalyst are shown in Fig. 9. Figure 9
the reduction series are 37.5 eV (A), 35.5 eV (B), 33.3 eV shows the Ti 3 p W 4f envelopes (*) for the 5 wt.%
(C) and 31.1 eV (D), respectively. The peaks at 35.5 eV W03/Ti02 catalyst reduced at 529 "C and at 582 "C.
and 31.1 eV are assigned to the W 4f,/2 positions for The residuals indicate that the overall fits (-) for
W+6 and W", respectively, based on model compounds. both envelopes agreed well with the experimental data.
W 4f7/2 binding energy values ranging from 34.5 eV to Statistically, the goodness of fit was measured by the
32.7 eV have been assigned to W+4.30-35On this basis residual excursion (REX%) value.6 The lower the
the peak at 33.3 eV can be assigned tentatively to the W REX% values the better the fit. The REX% values are
4f7/2 position of W+4. noted on the figure. Figure 9(a) has a REX% of 4.1
Close examination of the individual deconvoluted while the value for Fig. 9(b) is 3.8. Both values indicate
spectra (Fig. 8) reveals that the peak assigned to W+4 relatively good fits.
appears at 503 "C and that the peak assigned to Wo first Because the fitting procedure used in this study is
appears at 549°C. From Fig. 7 one can see that as the complicated, it is important to show that the fits are
reduction temperature is increased the peak assigned to legitimate. To verify the legitimacy of the fits certain
W 4f7/2 of W + 6 disappears (-650°C) and the peak experimental criteria were used. First, results from the
assigned to W 4f7/2 of W" increases. The behavior of the fits show that the Ti 3p fitted area was found to be
W + 4 species is not quite as straightforward. This is within f 7 % of the calculated Ti 3p area. The calcu-
partly due to the fact that the doublet separation (2.1 lated Ti 3p peak area was determined by multiplying
ev) of a particular tungsten oxidation state coincides the measured Ti 3p/Ti 2p ratio for TiO, alone by the
with the separation between the W 4f7,, peaks of W f 6 measured area of the Ti 2p region for the catalysts.
and W + 4 (i.e. 2.2 eV) and that of W'4 and W" (i.e. 2.2 Another way to check the consistency of the fits was to
eV). compare the variation of W 4f/Ti 2p intensity ratios
with those of W 4d/Ti 2p (see Fig. 5) as a function of
reduction temperature. The W 4f area was found by
Non-linear least-squares curve fitting summing the fitted area of the W 4f doublets for each
A NLLSCF routine was used to determine the dis-
tribution of tungsten species as a function of reduction
temperature. Deconvolution has provided a logical
starting point for the NLLSCF routine. It was able to
give positional information for all the components and
V
REX% - 4.1
to provide an indication of the reduction temperatures
at which new components appear. Thus, the initial
guesses used in the NLLSCF routine are more accurate,
which inherently makes the curve fitting procedure a
more efficient process. In performing the NLLSCF pro-
W4f-Ti3p

A
I I I
40 36 32
Binding Energy I eV

REX% = 3.8

I I I
44 40 36 32 40 36 32
Binding Energy I eV Binding Energy I eV
Figure 8. Deconvoluted spectra for 5 wt.% WO,piO, catalysts Figure 9. Curve fits for 5 wt.% WO,/TiO, catalysts reduced at (a)
reduced at 503 "C and at 549 "C. 529°C and (b) 582°C.
210 J. N. FIEDOR ET AL.

that the analysis will provide information about only

the spectral tungsten components. The envelopes of the
reduced catalysts were used as the original data matrix
for PCA. The W 4f envelope of the oxidic catalyst was
not included in the analysis because this sample
exhibited significant charging and therefore will prob-
ably experience charge broadening compared to the
others. This may cause PCA to overestimate the
number of components and/or factors in the original
data matrix.
As the reduction temperature is increased one can
readily observe that the envelope broadens owing to the
appearance of other tungsten oxidation states. Principal
component analysis was performed on this series of
envelopes to determine the number of tungsten oxida-
Reduction Temp. (PC) tion states or components in the original overall data
matrix (Fig. 11). Data pretreatment included removal of
Figure 10. Distribution of tungsten oxidation states in 5 wt.% the background from each spectrum by using a Shirley-
WO,/TiO, catalysts as a function of reduction temperature. type integral,I4 subtracting the minimum from each
spectrum and scaling the area of each to a constant
oxidation state at each reduction temperature. The W 4f value. Initial PCA results are given in Table 1. All cri-
energy level gave a similar trend (not shown) to that teria indicate the presence of three factors. The IND
observed in Fig. 5. function minimizes at the third factor, the REV ratio
Figure 10 shows the distribution of tungsten oxida- rises from 1.47 to 7.40 on moving from factor 4 to factor
tion states as a function of reduction temperature: W + 6 3, and the Q% value falls below 10 from factor 4 to
decreases steadily until it disappears at 650 "C; W + 4 factor 3. Therefore, all the statistical criteria quite con-
increases steadily with increasing reduction tem- vincingly point to the fact that the original data matrix
perature, reaches a maximum at -529"C, stays con- is comprised of three factors. This result is consistent
stant until 629 "C and then decreases for higher with those obtained by deconvolution and NLLSCF. It
reduction temperatures; and Wo first appears at 549 "C, should also be pointed out that if the Ti 3p peak is
which is in agreement with the deconvolution results, included, then the rank of the data matrix merely
and rapidly increases until 712°C where it is the only increases by one. This is to be expected.
species detected.

DISCUSSION
Factor analysis

Figure 11 shows the W 4f envelopes from the series of As mentioned previously, few studies have focused on
reduced 5 wt.% W0,/Ti02 catalysts following subtrac- the reduction of W/Ti02 catalysts. Temperature-
tion of the Ti 3p envelope. The Ti 3p was removed so programmed reduction experiments conducted by Bond
et al. showed that a monolayer W/Ti02 catalyst pre-
Reduction Temp. (/OC) pared by incipient wetness impregnation reduces
directly and completely to Wo between the tem-
408 peratures of 730 and 770"C.4 They also pointed out that
above monolayer coverage (4.8 wt.% WO,) the presence
503 of bulk WO, suppresses the reduction to Wo. These
results were at variance with those reported by Ver-
529 maire and van Berge5 which suggest that a monolayer
WO,/TiO, catalyst prepared by equilibrium adsorption
549 undergoes a two-step reduction (W+6+ W t 4 + WO).
582

604 Table 1. Principal component analysis results for the

data matrix shown in Fig. 11
629 Factor % Eigenvalue REV ratio IND 0%

1 79.467 3.62 4.1 1 E-04 0.24

650 2 19.683 33.73 1.00E-04 0.48
3 0.517 7.1 0 6.69E-05 1.12
662 4 0.063 1.47 7.53E-05 19.78
5 0.037 1.35 9.14E-05 24.76
712 6 0.022 1.39 1.21E-04 29.45
I I I
40 35 30 7 0.013 1.19 1.89E-04 37.57
Binding Energy / eV 8 0.008 0.92 3.86E-04 45.96
9 0.006 0.73 1.39E-04 54.84
Figure 11. Original data matrix for reduced 5 wt.% WO,/TiO, 10 0.004 1.o 0.00 40.45
catalyst from which the Ti 3p peak has been removed.
 REDUCTION BEHAVIOR OF W/TiO, CATALYSTS BY XPS 211

energy value very close to that of W + 4 or tungsten

-
The TPR peak associated with the formation of W + 4
occurs at 744 "C; that corresponding to W" formation
occurs around 975°C. They also stated that the tung-
metal cannot be completely ruled out. Non-linear least-
squares curve fitting could conceivably miss the contri-
sten surface species did not reduce completely to tung- bution from a minor component if its presence does not
sten metal. Their TPR results indicated that 32% of the better the overall fit. Factor analysis can also miss
tungsten remained as W+4 at 1227°C. This was attrib- minor constituents of the overall data matrix. This
uted to stabilization of the W-0 bond of WO, by the should not significantly affect the main conclusion of
rutile structure of TiO, . this study; namely, that unlike the Mo system only one
In a sense, our results agree with some part of both important intermediate tungsten oxidation state can be
works. For instance, XPS results suggest that the tung- detected on the reduction of monolayer-like W/Ti02
sten surface phase of a 5 wt.% W03/Ti02 catalyst catalysts.
reduces completely to Wo at 712°C. The in situ XRD
results verify the presence of Wo (i.e. reflection at 40.2')
following reduction at 677°C. The in situ XRD results
also showed that there were no reflections characteristic CONCLUSION
of WO, at this reduction temperature. This finding is
more consistent with that of Bond et al. However, it is
clear from the present work that there are three tung- A detailed analysis procedure, which included deconvol-
sten components, assigned to W f 6 , W f 4 and W", ution, NLLSCF and FA, of XPS data from a series of
present in the reduction temperature range of 400- reduced 5 wt.% W03/Ti02 catalysts has indicated that
700 "C. This is consistent with the results found by Ver- three tungsten components are needed to describe the
maire and van Berge.5 data. These tungsten components have been assigned to
It is interesting to compare the reduction results of W+6,W + 4and W". X-ray diffraction verified that tung-
the W/TiO, system with those reported for supported sten reduces to W" at 675 "C. It was shown that W + 6
N

Mo catalysts. Previous XPS studies of Mo/TiOZ7 and decreases with increasing reduction temperature; W + 4
Mo/Al,O,* indicated that Mo forms a wide range of first appears around 400 "C, goes through a maximum
, o + ~M
stable oxidation states (i.e. M o + ~M , o + ~M, o+~, around 580 "C and then decreases as the reduction tem-
Mo" and Moo) upon reduction with H, . Fiedor et aL6 perature is increased further, W" first appears around
also showed that three Mo oxidation states (i.e. M o + ~ , 550 "C then maximizes at -675 "C at 100%. It is con-
M o + ~and M o + ~ )were present on a 5 wt.% cluded that, unlike the Mo/TiO, system, the tungsten in
MoO,/TiO, catalyst after reduction at relatively low a monolayer-like W/TiO, catalyst undergoes a more
temperatures (< 300 "C). The results of the present study simplified reduction process in which only one interme-
for a monolayer-like W/TiO, system indicate that, diate oxidation state was detected.
unlike the Mo systems, tungsten undergoes a more sim-
plified reduction process in which only one intermediate
oxidation state was detected. Acknowledgement
It should be noted, however, that the presence of an
intermediate tungsten oxidation state, such as W +,,in The authors acknowledge financial support for this work from the US
relatively low concentrations or having a binding Department of Energy, Grant DE-FG02-87ER13781.

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