Applied Catalysis A: General 259 (2004) 269–279

Butan-1-ol and butan-2-ol dehydration on nitrided aluminophosphates:

influence of nitridation on reaction pathways夽
Stéphanie Delsarte∗ , Paul Grange1
Unité de Catalyse et Chimie des Matériaux Divisés, Université Catholique de Louvain, 2/17 Croix du Sud, 1348 Louvain-la-Neuve, Belgium
Received in revised form 22 September 2003; accepted 25 September 2003

Abstract

The dehydration of butan-2-ol and butan-1-ol was studied at atmospheric pressure using an AlPO4 amorphous sample and two nitrided
phosphates AlPON (11 and 20 wt.% N), at 200 and 275 ◦ C, respectively. The acid–base properties of AlPON can be tailored by adjusting their
nitrogen content, as proved by NH3 chemisorption and SO2 microcalorimetry experiments. In the present work, butan-2-ol and butan-1-ol
dehydration reactions were used to characterise the changes induced by nitridation on the acid–base properties of AlPON. The dehydration
of butan-2-ol and butan-1-ol over AlPON was studied, because the reactivities of those linear alcohols are not similar. As the basicity of
butan-2-ol is higher than that of butan-1-ol it can give olefins as the major product, through an E1 mechanism even on AlPO(N) weak acid
sites. Product distribution of 1-butanol dehydration over AlPO(N) rather suggests a bifunctional acid–base E2 mechanism.
On AlPON, the rate of butan-2-ol dehydration is proportional to the total number of acid sites detected by measuring the volume of ammonia
chemisorbed on the catalyst at 35 ◦ C.
On the other hand, the activity of butan-1-ol dehydration passes by a maximum for an intermediate nitrogen content. This indicates that the
density of bifunctional acid–base sites is increased at the beginning of nitridation, and there is an optimum for intermediate nitrogen contents.
The changes in the nature and the density of surface NHx species during time on stream were also evaluated using DRIFTS and X-ray
photoelectron spectroscopy (XPS) spectroscopies.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Nitrided phosphates; Oxynitrides; Butanol dehydration; Stability; Basic catalysis; AlPON

1. Introduction
AlPON, nitrided aluminophosphates, appear as promising
acid–base catalysts [1,2]. They are obtained by heating an
amorphous, reactive AlPO4 precursor under ammonia flow
up to 800 ◦ C. This allows to substitute part of the oxygen
atoms by nitrogen atoms. The degree of O/N substitution
depends on the nitridation conditions [3].
As was published for the first time in 1994 [1], the AlPON
catalysts are active for the Knoevenagel condensation be-
• The decrease in the number of acid sites is due to the si-
tween benzaldehyde and malononitrile, a reaction known to
be catalysed by bases, while under similar conditions, the
AlPO4 precursor is practically inactive. A year later, it was
shown [2], by ammonia thermoprogrammed desorption ex-
periments, that nitridation also reduced in an important way
夽
doi of original article 10.1016/S0926-860X(02)00092-3.
∗ Corresponding author. Tel.: +32-10-47-87-26; fax: +32-10-47-36-49.
E-mail address: delsarte@cata.ucl.ac.be (S. Delsarte).
1 Deceased 11th July 2003.
the number of surface acid sites. Our findings were later
confirmed by other groups [4].
Afterward, the changes induced by nitridation on the
acid–base properties of a mixed gallium–aluminum phos-
phate were also investigated [5], and the same conclusions
were reached: as nitrogen is introduced in the phosphate
network, acidity decreases, while basicity increases [6–8].
The changes induced by nitridation can be summarised as
follows:
multaneous decrease of the number of Brönsted and Lewis
acid sites. (i) The replacement of the acid P–OH groups
by P–NHx species during nitridation induces an important
decrease in the number of Brönsted acid sites. (ii) The
decrease in the number of Lewis acid sites induced by ni-
tridation is due to the neutralisation of the coordinatively
unsaturated ions by NHx species and/or to the substitution
of oxygen atoms by nitrogen atoms around the coordi-
natively unsaturated cations, which reduces their positive
charge, and hence, their tendency to attract electrons.

0926-860X/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2003.09.030
270 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279
• The increase in the number of basic sites is due to the
generation of hydrogenated nitrogen species (NHx , 1 ≤
x ≤ 4) on the surface, their superficial concentration in-
creasing with the nitrogen enrichment [9]. Those species
are more responsible for the basic properties of the ni-
trided samples than the stable nitrogen or oxygen frame-
work atoms.
The use of AlPON and AlGaPON oxynitrides as sup-
port for platinum for the dehydrogenation of isobutane to
isobutene was proposed because the dehydrogenation cat-
alytic activity of platinum-supported catalysts can be in-
creased by modifying the acidity/alkalinity of the support.
The Pt/AlPON and Pt/AlGaPON proved to be very active
and stable for this reaction [10,11]. One of the hypotheses
advanced to explain their good performance was the exis-
tence, on the oxynitrides surface, of acid–base site pairs of
intermediate strength able to form, stabilise, and discard ad-
sorbed intermediates during a catalytic turn-over [12].
In order to confirm the existence of acid–base site pairs
able to interact simultaneously with reactant molecules, and
to examine the evolution of the number of these sites with
nitrogen enrichment, the study of the activity and selectivity
of AlPON catalysts for the dehydration of linear alcohols
(butan-1-ol and butan-2-ol) was proposed, because the intra-
and intermolecular dehydration of those alcohols can occur
through concerted acid–base mechanisms.
The catalytic properties of the samples for butan-1-ol and
butan-2-ol dehydration were studied in parallel because the
reactivities of those linear alcohols are not similar: the ease
of removal of the –OH groups indeed depends on whether
it is attached to a primary or a secondary carbon atom. The
dehydration of a primary alcohol is less favourable than the
dehydration of a secondary alcohol through an acid mecha-
nism [13]. Hence, one could expect that on AlPON the re-
action would take place on different sites for butan-1-ol and
butan-2-ol and that the activity of the catalysts could reflect
the density of different catalytic sites.
The surface NHx species responsible for the basic prop-
erties of AlPON are prone to hydrolysis [14]. Since water
is produced during alcohol dehydration, it was important to
study the stability of the AlPON samples under our operat-
ing conditions. To evaluate changes in the nature and den-
sity of surface NHx species during time on stream, DRIFTS
and X-ray photoelectron spectroscopy (XPS) analysis prior
to and after reaction were also performed.
Table 1
AlPO4 and AlPON characteristics [18]
Name Composition Nitridation time (h) Nitrogen content (wt.%)
AlPO AlPO4 – 0
AlPON1 AlPO2.67 N0.89 64 11.0
AlPON2 AlPO1.71 N1.53 ≈250 20.0
a Determined by measuring the total amount of ammonia molecules chemisorbed on the surface at 35 ◦ C, according to the procedure described in [6].
b Determined by measuring the total amount of sulphur dioxide molecules adsorbed at 80 ◦ C on the surface, according the procedure described in [7].
2. Methods
2.1. Materials
The citric acid complexation method [15] was used to
prepare an amorphous aluminophosphate precursor AlPO4 ,
with a high surface area. In order to have Al/P = 1, equimo-
lar amounts of Al(NO3 )3 ·9H2 O (Merck) and (NH4 )H2 PO4
(Merck) were dissolved in distilled water. Both solutions
were mixed at room temperature. After 1 h of stirring, an
excess of citric acid (Merck) was added. The resulting aque-
ous solution was further stirred overnight. Water was then
evaporated under reduced pressure in a rotavapour and the
resulting gel was dried for 10 h at 105 ◦ C in a vacuum oven.
The gel swelled and took a meringe-like appearance. The
sample was then calcined for 16 h at 550 ◦ C.
In order to analyse the relationship between the nitro-
gen content and the catalytic properties of the solids, two
“AlPONs” with intermediate and high nitrogen contents
were prepared from nitridation of this sole precursor. The
AlPO4 precursor was placed in the isothermal region of a
tubular furnace, and heated under ammonia flow (30 l/h) to
800 ◦ C. The variation of the nitrogen content was obtained
by modifying the nitridation time (Table 1). At the end of the
activation process, the samples were cooled down to room
temperature under pure and dry nitrogen flow.
The total nitrogen content of the AlPON samples was
determined by titration with a sulphuric acid solution of
the ammonia liberated in alkaline digestion at 400 ◦ C with
melted KOH [16]. The specific surface area was measured
by the single-point BET method after 20 min degassification
at 250 ◦ C. Values reported in Table 1 are lower than those
reported for the same samples in [17], because of sample
ageing during stocking time.
Reference oxide catalysts were also prepared and tested.
Their main characteristics are reported in Table 2.
2.2. X-ray photoelectron spectroscopy
A Fisons SSI SSX-100/206 spectrometer was used for
the XPS experiments. This spectrometer consists of a
monochromatised microfocus Al X-ray source operated at
10 kV, an electron collection lens, a hemispherical analyser
and a microchannel plate as detector. Details concerning
this spectrometer have been given previously [21]. The
sample powders were pressed in stainless steel troughs
SBET (m2 /g) Aciditya (␮mol/m2 ) Basicityb (␮mol/m2 )
118 7.38 0.04
54 3.36 0.15
49 1.68 0.61
 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279
Table 2
Reference oxide catalysts characteristics
Catalyst SBET (m2 /g)
SiO2 –Al2 O3 (6.38 wt.% Al) 370
Al2 O3 339
ZrO2 88
MgO 63
(4 mm diameter) and placed on an aluminium carrousel. The
samples were heated by a quartz lamp (maximum 120 ◦ C)
three times during 15 min under vacuum. The heating pe-
riods were separated by 30 min pauses for outgassing. The
samples were then outgassed overnight under vacuum and
introduced in the analysis chamber. The residual pressure
during the analysis remained between 1 and 7 × 10−7 Pa.
A low energy flood gun (6 eV) with a Ni grid placed 3 mm
above the samples was used to compensate for charging
during measurements. For each sample, a survey spectrum
was recorded, followed by detailed scans of C1s , O1s , N1s ,
P2p , Al2p and finally, C1s again. The spectra were decom-
posed with the least-squares fitting routine with a Gaus-
sian/Lorentzian ratio of 85/15 and after subtraction of a
non-linear baseline. The atomic ratios were calculated from
relative intensities corrected by the elemental sensitivity fac-
tors provided by the manufacturer. In the calculation of those
factors, Scofield’s photoionisation cross-section was used.
2.3. DRIFTS measurements
In situ DRIFTS spectra were collected using a spectrom-
eter equipped with KBr optics and a pyroelectric DTGS
(deuterated triglycine sulphate) detector. Pure samples were
placed inside a commercial controlled environmental cham-
ber equipped with SeZn windows, attached to a diffuse re-
flectance accessory. The samples were heated from room
temperature to 300 ◦ C under a 30 ml/min inert gas flow (He,
99.999%).The temperature was increased manually at ap-
proximately 5 ◦ C/min. Spectra were recorded (200 scans,
4 cm−1 resolution) after 30 min of stabilisation. The spec-
trum of an aluminium mirror was used as background.
2.4. Catalytic tests
The dehydration reactions were carried out at atmo-
spheric pressure, in a quartz fixed bed microreactor (10 mm
i.d.), in up flow mode. The reactor was placed in a vertical
furnace with temperature control. The real reaction tem-
perature was measured by a thermocouple situated in the
middle part of the reactor near the catalyst. Before reaction,
the catalysts were sieved, and the particle size fraction of
100–200 ␮m was used. The catalyst mass was 100 mg, and
the corresponding bed height was adjusted to 13 mm, by
adding 200–500 ␮m glass balls.
Catalyst activation was performed in helium flow
(30 ml/min) (Indugas 4.5), at reaction temperature for 2 h.
271
Structure Synthesis procedure Reference
Amorphous Co-gel
Amorphous Sol–gel [19]
Baddeleyite Microwave-assisted synthesis [20]
Periclase Citrate complexation [15]
In order to remove H2 O and CO2 , known to be strongly ad-
sorbed on the basic sites, the MgO and ZrO2 catalysts were
heated at higher temperature (550 ◦ C) prior to the reaction.
Helium was then saturated with butan-1-ol (p.a., ACROS
organics) or butan-2-ol (p.a., Janssen Chimica) vapour by
contact in a saturator. The butanol partial pressure was
2.6 kPa in both cases. This helium/butanol gas reaction mix-
ture supplies the reactor at a rate of 30 ml/min (WHSV =
1.3 h−1 ). To prevent the condensation of butanol or reaction
products, all lines from the saturator to the chromatograph
were heated above 100 ◦ C.
Unconverted butanol and the dehydration products
were analysed by gas chromatography, using a Shimadzu
Chrompac C-R3A chromatograph, equipped with a flame
ionisation detector. A 50m × 0.32 mm (RSL-160) capillary
column was used for the separation of the various com-
pounds. Water was not considered in the characterisation of
the composition of the reaction mixture.
The reaction rate, r, was defined as the number of butanol
moles transformed in one second per square meter of spe-
cific surface area of the catalyst. The conversion (%), was
defined as the ratio of the amount of converted butanol to
the amount of butanol supplied at the reactor inlet. The se-
lectivity for each product (mol%) was defined as the molar
ratio of each of them to all the detected products. We verified
that the carbon balance was reached without significant er-
ror. For quantitative comparison between the catalysts, care
was taken that the data were controlled neither by external
nor internal diffusion.
3. Results
3.1. Fresh catalysts characterisation
The physico-chemical properties of the fresh catalysts are
presented in Table 1. As can be seen in this table, adsorption
of probe molecules indicates that the acidity of the AlPO4
sample decreases with nitrogen enrichment, while the basic-
ity increases. Those results have been thoroughly discussed
in [1,2,17,18].
3.2. Butan-2-ol dehydration
3.2.1. Butan-2-ol dehydration on the AlPO4 precursor
The effect of temperature on the initial conversion and se-
lectivity of butan-2-ol dehydration was studied on the AlPO4
272 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279

100 100 100 50

90 90 80 40

Selectivities (%)
Conversion (%)
Initial conversion (%)

80 80
Selectivities (%)

70 70 60 30
60 60
40 20
50 50
40 40 20 10
30 30
0 0
20 20
0 5 10 15 20
10 10
0 0 Time (hr)

145 195 245
Temperature (°C)
Fig. 1. Conversion and selectivity of butan-2-ol dehydration over AlPO4
precursor as a function of temperature: (䊐) conversion; ( ) selectivity of
1-butene; (䊏) selectivity of trans-2-butene; (䉱) selectivity of cis-2-butene.
precursor. The sample was progressively heated from 175
to 250 ◦ C, and the catalytic activity was measured every 25
or 50 ◦ C, after 15 min of stabilisation (Fig. 1).
Under our operating conditions, conversion reaches 50%
around 190 ◦ C, and 100% around 250 ◦ C. In the range of the
studied temperatures, only three reaction products were de-
tected: 1-butene, trans-2-butene and cis-2-butene. All three
are elimination products. No cracking or squelettal isomeri-
sation products were detected.
At 200 ◦ C, our ‘standard’ reaction temperature, selectiv-
ities measured after 15 min of stabilisation for 1-butene,
trans-2-butene and cis-2-butene are 17, 45 and 38%, respec-
tively. Selectivities are not much affected by the reaction
temperature.
The evolution of the conversions and selectivities with
time on stream, at 200 ◦ C, is shown in Fig. 2. The initial
conversion, at 72%, reaches 65% after 17 h on stream.
This small decrease could be linked either to the de-
crease of specific surface area (SBET after 17 h on stream:
61 m2 /g), or to the formation of carbonaceous deposits
on the sample. We noticed indeed, that the initially white
catalyst exhibited a slight colour change (yellowish) after
test.
Fig. 2. Evolution of the activity and selectivity of butan-2-ol dehydration
over AlPO4 precursor as a function of time, at 200 ◦ C: (䊐) conversion; ( )
selectivity of 1-butene; (䊏) selectivity of trans-2-butene; (䉱) selectivity
of cis-2-butene.
Conversions and selectivities obtained with the reference
catalysts, tested at the same WHSV are presented in Table 3.
Because they are less active, ZrO2 and MgO were treated at
300 ◦ C rather than 200 ◦ C.
3.2.2. Butan-2-ol dehydration on AlPON oxynitrides
The evolution of the conversion with time on stream on
the AlPON1 oxynitride is shown in Fig. 3. At initial condi-
tions, the nitrided catalyst converts 15% of butanol, while
the AlPO4 precursor converted 72% of butanol under the
same conditions. The only detected products were 1-butene,
trans-2-butene, cis-2-butene, with initial selectivities of 20,
41 and 39%, respectively. With time on stream, the con-
version progressively increases, to reach 24% after 17 h on
stream, while selectivities for 1-butene and cis/trans ratio
decreases. No changes were observed, at the end of the test,
in the catalyst colour or its specific surface area.
Fig. 4 presents the evolution of the selectivities on the
AlPON series of samples, as a function of the nitrogen con-
tent. The activity of the catalyst is represented by r, the
reaction rate, in order to take into account the differences
in specific surface areas between the oxide precursor and
the oxynitrides. The activity decreases with nitrogen enrich-
ment. A slight increase of the 1-butene production, as well
as an increase of the cis/trans-2-butene ratio as the nitrogen
content increases, is observed.

Table 3
Conversions and selectivities of butan-2-ol dehydration over AlPO4 precursor and reference oxides, during reaction at 200 ◦ C (except if stated otherwise)
Catalyst Conversion (%) Selectivity (%) Mechanism of olefin formation

1-Butene trans-2-Butene cis-2-Butene Methyl ethyl ketone

AlPO4 72 17 45 38 0 E2 with strong E1 character

SiO2 -Al2 O3 40 16 40 44 0 E2 with strong E1 character
Al2 O3 12 27 14 59 0 E2
ZrO2 (tested at 300 ◦ C) 40 57 14 22 7 E1cB
MgO (tested at 300 ◦ C) 3 0 0 0 100
Reaction mechanisms deduced from the product distribution are also shown.
 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279 273

100 50 100 100

90 45 90 90
80 40
Initial conversion (%)

80 80
Selectivities (%)
Conversion (%)

Selectivities (%)
70 35 70 70
60 30 60 60
50 25 50 50
40 20 40 40
30 15 30 30
20 10 20 20
10 5 10 10
0 0 0 0
0 5 10 15 20 175 225 275 325
Time (hr) Temperature (˚C)
Fig. 3. Evolution of the activity and selectivity of butan-2-ol dehydra- Fig. 5. Conversion and selectivity of butan-1-ol dehydration over AlPO4
tion over AlPON1 oxynitride for as a function of time, at 200 ◦ C: (䊐) precursor as a function of temperature: (䊐) conversion; ( ) selectivity of
conversion; ( ) selectivity of 1-butene; (䊏) selectivity of trans-2-butene; 1-butene; (䊏) selectivity of trans-2-butene; (䉱) selectivity of cis-2-butene;
(䉱) selectivity of cis-2-butene. (䊉) selectivity of dibutylether.

3.3. Butan-1-ol dehydration

main reaction product; above this temperature, dibutylether
formation decreases and tends towards zero at temperature
3.3.1. Butan-1-ol dehydration on the AlPO4 precursor
approaching 350 ◦ C. 1-Butene formation increases with
Fig. 5 presents the evolution of the butan-1-ol conver-
temperature, becoming the main product above 275 ◦ C. In
sion as a function of temperature, on the AlPO4 precursor.
parallel, production of cis-2-butene and trans-2-butene in-
The sample was progressively heated from 175 to 350 ◦ C,
creases, the cis/trans ratio being close to 1 in the studied
and the conversion was measured every 25 or 50 ◦ C, af-
temperature range.
ter 15 min of stabilisation. Under our operating conditions,
At 275 ◦ C, our ‘standard’ reaction temperature (Fig. 6),
conversion reached 50% at a temperature of 245 ◦ C, and
initial selectivities are equal to 34% for 1-butene, 7%
100% at 350 ◦ C. Those temperatures are higher than those
for trans-2-butene, 7% for cis-2-butene and 53% for
necessary to dehydrate the more reactive secondary alco-
dibutylether, for a conversion of 74%. With time on stream,
hol. For the all range of studied temperatures, the only de-
the conversion decreases, particularly in the first 2 h of
tected products were 1-butene, trans-2-butene, cis-2-butene
reaction. A very small increase in dibutylether selectivity
and dibutylether.
is observed, with a simultaneous decrease of 1-butene se-
1-Butene is the intramolecular dehydration product
lectivity. As was already mentioned for the dehydration of
(elimination reaction); dibutylether is the intermolecular
butan-2-ol, the activity decrease could be explained either
dehydration product (substitution reaction). Trans-2-butene
by a reduction of specific surface area (SBET after 12 h on
and cis-2-butene are secondary reaction products, formed
stream: 68 m2 /g) or formation of carbonaceous deposits on
by isomerisation of 1-butene. Selectivities are strongly af-
fected by the temperature: below 275 ◦ C, dibutylether is the
80 100
3,5E-08 50 70 90
45 80
3,0E-08 60
consumed/m2.sec)

Selectivities (%)
Conversion (%)
r (mol of 2-butanol

40 70
Selectivities (%)

2,5E-08 35 50 60
2,0E-08 30
40 50
25
1,5E-08 30 40
20
15 30
1,0E-08 20
10 20
5,0E-09 5 10 10
0,0E+00 0 0 0
0 5 10 15 20 25 0 5 10 15
Nitrogen content (wt.%) Time (hr)

Fig. 4. Evolution of the reaction rates r, and of the selectivities as Fig. 6. Evolution of the activity and selectivity of butan-1-ol dehydration
a function of the nitrogen content of AlPON for the dehydration of over AlPO4 precursor as a function of time, at 275 ◦ C: (䊐) conversion; ( )
butan-2-ol at 200 ◦ C: (䊐) reaction rate r; ( ) selectivity of 1-butene; (䊏) selectivity of 1-butene; (䊏) selectivity of trans-2-butene; (䉱) selectivity
selectivity of trans-2-butene; (䉱) selectivity of cis-2-butene. of cis-2-butene; (䊉) selectivity of dibutylether.
274 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279

Table 4
Conversions and selectivities of butan-1-ol dehydration over AlPO4 precursor and reference oxides during reaction at 275 ◦ C (except if stated otherwise)
Catalyst Conversion (%) Selectivity (%) Mechanism of olefin formation

1-Butene trans-2-Butene cis-2-Butene Dibutylether Butyraldehyde

AlPO4 74 34 7 7 53 0 E2
SiO2 –Al2 O3 100 43 28 29 0 0 E1
MgO (tested at 400 ◦ C) 35 33 6 14 0 47 E1cB
Reaction mechanisms, deduced from the product distribution, are also shown.

the surface. The recovered catalyst presents a grey colour 5,0E-08 80

after test. 4,5E-08 70
Conversions and selectivities obtained with the reference 4,0E-08
consumed/m2.sec)
r (mol of 1-butanol

60
catalysts, tested at the same WHSV are presented in Table 4. 3,5E-08 Selectivities (%)
Because it is less active, MgO was treated at 400 ◦ C rather 3,0E-08 50
than 275 ◦ C. 2,5E-08 40
2,0E-08 30
3.3.2. Butan-1-ol dehydration on AlPON oxynitrides 1,5E-08
20
1,0E-08
Fig. 7 shows the evolution with time on stream, of the 10
5,0E-09
catalytic activity of the AlPON1 catalyst. At initial condi-
0,0E+00 0
tions, the catalyst converts 48% of butan-1-ol with a selec-
0 5 10 15 20 25
tivity of 29% for 1-butene, 7% for trans-2-butene, 7% for
cis-2-butene and 57% for dibutylether. Neither the conver- Nitrogen content (wt.%)
sion, nor the selectivities are significantly modified with time Fig. 8. Evolution of the reaction rates, and of the selectivities as a func-
on stream. tion of the nitrogen content of AlPON for the dehydration of butan-1-ol
Fig. 8 presents the evolution of the reaction rates and of at 275 ◦ C: (䊐) reaction rate r; ( ) selectivity of 1-butene; (䊏) selectiv-
ity of trans-2-butene; (䉱) selectivity of cis-2-butene; (䊉) selectivity of
the selectivities, as a function of the nitrogen content. The
dibutylether.
evolution of the dibutylether yield (mol dibutylether/(m2 s))
as a function of the nitrogen content is also reported (Fig. 9). 2,0E-08
1,8E-08
mol of dibutylether

1,6E-08
produced/m2.sec

3.4. Physico-chemical characterisation of the tested 1,4E-08

1,2E-08
catalysts 1,0E-08
8,0E-09
6,0E-09
3.4.1. XPS results 4,0E-09
Table 5 presents the surface atomic compositions evalu- 2,0E-09
0,0E+00
ated by XPS before and after butan-1-ol dehydration tests 0 5 10 15 20 25
performed on the AlPON2 sample. After 10 h on stream at Nitrogen content (wt.%)

Fig. 9. Evolution of the dibutylether yield as a function of nitrogen content

of AlPON during dehydration of butan-1-ol at 275 ◦ C.
100 100
90 90
80 80 275 ◦ C, the catalyst has lost a significant amount of its sur-
Selectivities (%)
Conversion (%)

70 70 face nitrogenous species.

60 60
50 50 3.4.2. DRIFTS results
40 40 Fig. 10 presents the DRIFTS spectra recorded at 300 ◦ C
30 30 on the AlPON2 sample before and after test. The assign-
20 20
10 10 Table 5
0 0 AlPON2 surface atomic compositions evaluated by XPS prior to and after
0 5 10 butan-1-ol dehydration tests
Time (hr) Surface atomic compositions (%)

Fig. 7. Evolution of the activity and selectivity of butan-1-ol dehydration Al 2p P 2p O 1s N 1s

over AlPON1 oxynitride as a function of time, at 275 ◦ C: (䊐) conver-
Fresh catalyst 14.7 17.6 44.8 22.9
sion; ( ) selectivity of 1-butene; (䊏) selectivity of trans-2-butene; (䉱)
Used catalyst 15.1 16.5 61.6 6.7
selectivity of cis-2-butene; (䊉) selectivity of dibutylether.
 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279
Absorbance (a.u.)
4000
(a)
Fig. 10. In situ DRIFTS spectra of the AlPON2 sample recorded at 300 ◦ C prior to and after the butan-1-ol dehydration tests. Spectra are displayed in
two regions: (a) 4000–2500 cm−1 ; (b) 2000–500 cm−1 .
Table 6
Position (cm−1 ) and assignments of the DRIFTS bands observed in the
spectra of the AlPON2 oxynitride, according to [9]
Wavenumbers Assignments
(cm−1 )
3779 ␯(OH) in tetrahedral Al–OH
3670 ␯(OH) in tetrahedral P–OH
3432 ␯(NH) in M–NH2
3340 ␯(NH) in M–NH–M
1560 ␦(HNH) in free M–NH2
1337, 1295 P=O, P–O2 , stretching vibrations and/or ␯as (P=N–P)
ments of the bands appearing in the spectra are shown in
Table 6.
Comparison of the spectra before and after the catalytic
test, shows that the superficial concentration of M–NH2
species (␦(HNH) in free M–NH2 ) decreases, while the su-
perficial concentration of M–OH species (␯(OH) in tetra-
hedral Al–OH and P–OH) increases after test. The intense
and broad band that appears at 1295 cm−1 in the DRIFTS
spectra of the fresh AlPON2 sample has been decomposed
in three bands by Centeno et al. [14]: two bands were as-
signed to P=O groups with a different environment associ-
ated with the presence or not of aluminium atoms in the
second co-ordination sphere of phosphorus, and a third one,
at lower wavenumbers, was assigned to P=N stretching vi-
brations. This broad band undergoes on a apparent shift to
1337 cm−1 after test.
4. Discussion
In this study, we used butan-1-ol and butan-2-ol to char-
acterise the changes induced by nitridation on the acid–base
properties of ‘AlPON’. This probe reaction is interesting
because the acid–base properties are studied in conditions
very close to those applied in catalysis, as compared to other
physico-chemical techniques that require anhydrous condi-
tions. Comparing the activities of AlPON to those measured
under the same reaction conditions on a series of oxides with
275
1295
3340
3670
3432
1560
Absorbance (a.u.)
3779
Fresh Fresh
Used
Used
1337
3500 3000 2500 2000 1500 1000
-1 -1
Wavenumbers (cm ) (b) Wavenumbers (cm )
very well known and contrasted acid (silica–alumina), basic
(magnesium oxide) or amphoteric (alumina and zirconium
oxides) character also allows to situate this new family of
catalysts in the scale of already available materials.
We will first discuss how the product distribution for
dehydration reactions is affected by small changes in the
acid–base properties of catalysts. Then, we will discuss the
mechanisms prevailing on the AlPO4 precursor, and the in-
fluence of nitridation on the catalytic results, in order to
gather information on the acid–base properties of those sam-
ples under catalytic conditions.
4.1. Butan-2-ol dehydration
Butan-2-ol dehydration to olefins is an elimination reac-
tion. To link the activity and the distribution of 1-butene,
trans-2-butene and cis-2-butene to the acid–base properties
of the catalysts, it is necessary to differentiate between E1,
E2 and E1cB eliminations. The possibilities are shown in
Scheme 1 (text and scheme adapted from [13]).
• In the E1 mechanism, the action begins with the abstrac-
tion of the OH− group by an acid site and the formation of
a carbocation, that loses a proton in the second step. Al-
though all possible alkenes are formed from the carboca-
tion, Saytzeff orientation (i.e. formation of 2-olefins) is
favoured with this mechanism.
• The E1cB mechanism can be related to the amount
of basic centres, and leads mainly to the formation of
1-olefins (Hoffmann orientation). ZrO2 is a good example
of a catalyst allowing alcohol dehydration through this
mechanism. It catalyses the dehydration of butan-2-ol to
1-butene with high selectivity (see Table 3 and [22,23]),
suggesting the involvement of anionic carbon species.
The high selectivities observed for 1-butene are due to
the fact that ZrO2 possesses not only basic sites strong
enough to activate the C–H bond through proton abstrac-
tion, but also acid sites capable of stabilising the anionic
product of the C–H bond activation step [22]. A strongly
basic oxide, as MgO, with weaker conjugated acid sites
276 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279
Scheme 1. Butan-2-ol dehydration.
is unable to dehydrate butan-2-ol under our experimental
conditions (Table 3).
• The E2 mechanism (bimolecular elimination) consists in
a one-step concerted reaction that proceeds through the
intervention of both acid and basic sites: the alcoholic hy-
droxyl groups are removed by an acid site, and the proton
by a basic site. However, the process will be truly syn-
chronous in exceptional cases, and the concerted reaction
thus covers a broad range of possibilities with tendencies
towards E1 or E1cB mechanisms.
The above categories are rarely clear-cut and quite often
an intermediate situation occurs, particularly with E1 and E2
pathways [24]. Summarising, it appears that the proportion
of 1-butene among all butenes increases, as a function of the
number of basic sites on the surface.
On very strong basic sites, dehydrogenation of butan-2-ol
to methyl ethyl ketone can become the most important reac-
tion. It is, for instance, the case on the tested MgO (Table 3).
High selectivities of butan-2-ol dehydrogenation to methyl
ethyl ketone over MgO have also been reported by others and
attributed to the strong basicity of MgO (see [25]). However,
we must note that a redox mechanism can also be envisaged
to explain ketone formation from alcohol dehydrogenation
on other families of catalysts [26]. Methyl ethyl ketone was
never observed on AlPON.
The above discussion allows us to discriminate between
the mechanisms dominating the product distribution when
performing butan-2-ol dehydration on our reference cata-
lysts (see Table 3). There is a good agreement between the
mechanisms proposed and the known acid–base properties
of the reference catalysts.
Product distribution obtained on the AlPO4 precursor is
very close to that observed for silica–alumina, and hence we
concluded that E2 elimination reaction with a strong amount
of E1 character occurs on the AlPO4 used in this study.
Nitridation has only a small influence on the butenes dis-
tribution: 1-butene selectivity increases very slightly with
nitrogen introduction and does not reach the values obtained
on alumina; the cis/trans-2-butene ratio also increases, al-
though in very small proportions. In fact, selectivities ob-
tained on AlPON remain typical of an E1 mechanism. The
decrease in activity following nitridation shows that there is
a decrease in the number of acid sites capable to catalyse the
dehydration of butan-2-ol through an E1 mechanism. It also
shows the absence, on AlPON, of basic sites strong enough
to allow a significant dehydration through E2 or E1cB mech-
anisms, or the dehydrogenation of butan-2-ol to methyl ethyl
ketone.
4.2. Butan-1-ol dehydration
Butan-1-ol dehydration was extensively studied in our lab-
oratory, as probe of the acid–base properties of pure [24] and
modified aluminas [27], silica–aluminas [27], SiO2 –Ta2 O3
mixed oxides [28] and aluminophosphates [29]. Those stud-
ies showed that the various reactions that take place on the
surface can give valuable information on the acid–base prop-
erties of oxide catalysts.
Those reactions are the following (Scheme 2, adapted
from [30]):
• The intramolecular dehydration of butan-1-ol to 1-butene,
which occurs through the E1, E2 or E1cB mechanisms,
as discussed in Section 4.1.
• The consecutive isomerisation of 1-butene to cis/trans-2
butene, a reaction often used to test the acid or basic char-
acter of catalysts. It occurs either through an acid catalysis,
or through a basic catalysis, a high cis/trans ratio being
observed for the base-catalysed isomerisation, in contrast
to the value close to 1 for an acid-catalysed isomerisa-
tion. An example can be found in Table 4, presenting the
results obtained on our reference catalysts. On the acid
silica–alumina, more than 50% of 1-butene isomerises to
2-butene, the cis/trans ratio being close to 1, while on
the basic MgO, the cis/trans ratio is higher than 2. On
 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279
Scheme 2. Butan-1-ol dehydration.
AlPO4 , a smaller fraction of 1-butene isomerises (30%),
the cis/trans ratio being 1.
To evaluate which mechanism is effective during the
intramolecular dehydration of butan-1-ol to 1-butene
(E1, E2 or E1cB), Noller et al. [31] suggest to study
the 1-butene and 2-butene distributions among reaction
products:
◦ On a strong acid, catalysing the intramolecular dehydra-
tion of 1-butanol through an E1 mechanism, 1-butene
isomerises rapidly to 2-butene (the cis/trans ratio be-
ing close to 1) and 2-butene will be the major reaction
product.
◦ On amphoteric or basic catalysts, catalysing the in-
tramolecular dehydration through an E2 or E1cB mech-
anism, 1-butene will be the major reaction product.
Hence, from the distribution of butenes (1-butene and
2-butene proportions, cis/trans-2-butene ratios), one can
deduce the mechanisms dominating the reaction. The
mechanism for AlPO4 and reference catalysts is pre-
sented in Table 4. On AlPO4 , it is most probable that the
direct transformation of butan-1-ol to 1-butene occurs
through a bifunctional E2 mechanism.
• The intermolecular dehydration of two molecules of
butan-1-ol to dibutylether. The mechanisms of ether for-
mation by intermolecular dehydration of alcohols have
been extensively studied on alumina. The various mech-
anisms proposed in the literature were briefly reviewed
in [24]. What is of interest to us is that the reaction
necessitates the co-operation of acid and basic surface
sites. This was clearly established by Jain and Pillai [32]
by selective poisoning of catalysts by acid (phenol) and
basic (pyridine) molecules. Our tests on reference cata-
lysts (Table 4) clearly confirm their findings: dibutylether
is not formed either on the very acidic silica–alumina,
nor on the very basic MgO. On this second sample, de-
hydrogenation to butyraldehyde occurs, because of the
existence of very strong basic sites on this oxide. On the
AlPO4 phosphate, however, intermolecular dehydration
to dibutylether is the main reaction.
277
All the parallel-consecutive reactions that occur using
butan-1-ol can take place simultaneously, making the inter-
pretation of the results somewhat difficult. Indeed, product
composition is depends on the acid–base properties of the
catalysts, as well as on the reaction parameters such as
temperature and contact time [24]. The effect of temper-
ature on the product distribution for the AlPO4 precursor
is illustrated in Fig. 5. At low temperatures, selectivities
for dibutylether are very high, indicating the prevalence of
bifunctional acid–base sites capable of catalysing the inter-
molecular dehydration of butan-1-ol on the precursor. When
the temperature increases, 1-butene selectivity increases,
possibly via a stage in which ether is produced (consecutive
pathways). Increasing the temperature not only increases
dibutylether decomposition, but also favours the intramolec-
ular dehydration, as the occupancy of catalytic sites by the
alcohol is less pronounced at high temperature [33]. At high
temperature, a non-negligible part of 1-butene is isomerised
to cis-2-butene and trans-2-butene with a cis/trans ratio
close to 1, indicating an acid-catalysed isomerisation.
The above considerations lead us to conclude that, under
our ‘standard reaction conditions’, primary alcohol dehy-
dration (intra- and intermolecular reactions) on the AlPO4
precursor, as well as dehydration on AlPON, requires the
co-operation of both acid and basic sites (see Fig. 8).
Hence, reaction rates obtained under our standard re-
action conditions must be proportional to the density of
bifunctional acid–base sites on the tested series. Observa-
tion of Fig. 8, where the dependence of the catalytic activity
on the nitrogen content can be seen, shows that the density
of bifunctional acid–base sites able to catalyse butan-1-ol
dehydration is increased by nitridation, but that an opti-
mum is found for intermediate nitrogen contents. The low
activity obtained for the most nitrided sample (AlPON2)
could be due to the very strong decrease in the number of
acid sites induced by nitridation. This strong decrease is
attested by ammonia chemisorption experiments (Table 1)
and also explains the absence of isomerisation of 1-butene
to cis-2-butene or trans-2-butene on the most nitrided
278 S. Delsarte, P. Grange / Applied Catalysis A: General 259 (2004) 269–279
sample (Fig. 8). Evolution of the dibutylether yield (mol
produced/(m2 s)) with the nitrogen content follows the same
trend (Fig. 9). It is also important to note that nitridation
does not allow the creation of basic sites strong enough to
dehydrogenate butan-1-ol to butyraldehyde.
4.3. Stability of the AlPON samples under reaction test
conditions
The sensitivity of AlPON to the presence of water in
the atmosphere was previously mentioned [14]. In situ
DRIFTS experiments showed that they undergo hydrolysis
even when the water in the gas flow is as low as 3 ppm
(parts per million). Hence, it was important to characterise
the nitrogen loss in the catalysts after test. The superficial
loss undergone by the AlPON2 catalyst after 10 h of test
at 275 ◦ C (during butan-1-ol dehydration experiments) is
very high, as attested by XPS results presented in Table 5.
DRIFTS was used to determine the nature of the species
most sensitive to hydrolysis. The hydrolysis of M–NH2
species (M = Al and/or P) by gaseous water during time on
stream explains the decrease in the concentration of M–NH2
groups and the increase of the M–OH groups observed by
DRIFTS:
M–NH2 + H2 O → M–OH + NH3
Substitution of basic –NH2 species by more acid –OH
species explains the slight selectivity changes, as well as the
increase in activity (from 15 to 24% conversion after 17 h
on stream) observed during the butan-2-ol dehydration tests
(Fig. 3). Indeed, we concluded from the product distribution
that butan-2-ol dehydration on AlPO(N) presented a strong
E1 character, and hence, that the activity was proportional
to the number of acid sites. On the opposite, substitution of
basic –NH2 species by –OH species does not have a notice-
able influence on butan-1-ol dehydration tests (Fig. 7). This
may be an indication that the superficial species involved
in butan-1-ol and butan-2-ol dehydration are not the same.
Although previous experiments showed that –NH–
species can also be subject to hydrolysis, it is not observed
under our experimental conditions. The apparent shift of
the main structural band from 1295 to 1337 cm−1 observed
in the DRIFTS spectra after test can be explained by the
increase of the intensity of the band components assigned
to P=O bonds, and the decrease of the band components
assigned to P=N bonds, at lower wavenumbers. Those struc-
tural changes indicate that, not only superficial NH2 species
are removed from the surface by hydrolysis, but also some
P=N bonds are replaced by P=O bonds during the tests.
While that information helps to understand, from a fun-
damental point of view, the nature of the species involved
in the reactions, the sensitivity of AlPON to hydrolysis is a
drawback in their use as catalysts under conditions where
water is present. An option would be to search for oxynitride
compositions less prone to hydrolysis.
5. Conclusions
We used butan-2-ol and butan-1-ol dehydration reactions
to characterise the changes induced by nitridation on the
acid–base properties of “AlPON”:
• The reaction rate for butan-2-ol dehydration is propor-
tional to the total number of acid sites detected by measur-
ing the volume of ammonia chemisorbed on the catalyst
at 35 ◦ C.
• Using butan-1-ol, intermolecular dehydration to dibutyl-
ether is favoured. Literature indicates that the formation
of dibutylether requires the activation of two alcohol
molecules on adjacent basic and acid sites. From that,
we suppose that the reaction rate can be used as an indi-
cator of the density of acid–base conjugated sites on our
samples.
Contrarily to what was observed for butan-2-ol, the activity
for butan-1-ol dehydration passes by a maximum for an
intermediate nitrogen content. This indicates that the density
of bifunctional acid–base sites is increased at the beginning
of nitridation, but that an optimum is found for intermediate
nitrogen contents.
Acknowledgements
The authors thank Pierre Eloy (Unité de Catalyse et
Chimie des Matériaux Divisés, Université Catholique de
Louvain, Belgium) for the help provided in the recording
and processing of XPS spectra. They are grateful to Roland
Conanec and Anne Massinon for synthesising and charac-
terising the AlPON samples tested in this publication, in the
course of a joint project involving among others the Unité
de Catalyse et Chimie des Matériaux Divisés (Université
Catholique de Louvain, Belgium) and the Laboratoire de
Verres et Céramiques (Université de Rennes 1, France).
They would also like to thank the Fonds National de la
Recherche Scientifique (FNRS) for the fellowship awarded
to Stéphanie Delsarte.
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