Hydrodechlorination of (CH3)3SiCHCl2 over Pd, Ni, Co and Fe supported on AlF3

Article abstract of DOI:10.1007/s12039-017-1234-1

Gas phase hydrodechlorination (HDC) process of Me₃SiCHCl ₂ was studied in a flow reactor at 200 ^°C using a 2% metal loading (w/w) of four different monometallic catalysts (Pd/AlF ₃, Ni/AlF ₃,Co/AlF ₃ and Fe/AlF ₃). The catalysts were prepared by sol-gel method and structurally examined by BET method, FT-IR and XPS techniques. The XPS technique showed that Ni ^II, Fe ^III and Co ^III exist as oxides. The major products in the HDC process of Me ₃SiCHCl ₂ were identified by GC and GC-MS and found to include Me ₃SiCH ₂Cl, Me ₃SiCl, and Me ₄Si. The effect of these catalysts on the quantitative conversion, selectivity and conversion rates are reported. [Figure not available: see fulltext.]

Full text of DOI:10.1007/s12039-017-1234-1

c
J. Chem. Sci. ꢀ Indian Academy of Sciences.
DOI 10.1007/s12039-017-1234-1
REGULAR ARTICLE
Hydrodechlorination of (CH3)3SiCHCl2 over Pd, Ni, Co and Fe
supported on AlF3
RATEB HINA∗, ISAM ARAFA and OMAR ENNAB
Department of Chemistry, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110, Jordan
Email: rhhina@just.edu.jo
MS received 9 December 2016; revised 18 December 2016; accepted 7 January 2017
Abstract. Gas phase hydrodechlorination (HDC) process of Me3SiCHCl2 was studied in a flow reactor at
200◦C using a 2% metal loading (w/w) of four different monometallic catalysts (Pd/AlF3, Ni/AlF3,Co/AlF3
and Fe/AlF3). The catalysts were prepared by sol-gel method and structurally examined by BET method, FT-IR
and XPS techniques. The XPS technique showed that NiII, FeIII and CoIII exist as oxides. The major products
in the HDC process of Me3SiCHCl2 were identified by GC and GC-MS and found to include Me3SiCH2Cl,
Me3SiCl, and Me4Si. The effect of these catalysts on the quantitative conversion, selectivity and conversion
rates are reported.
Keywords. Hydrodechlorination; chloroorganosilane; Aluminium Fluoride; dichloromethyl trimethylsilane.
1. Introduction
chemistry, surface modification of commodity poly-
mers, and chemical vapor deposition (CVD) in thin-film
industry.16 24
Catalytic hydrodechlorination process (HDC) of chlo-
rinated organic compounds over monometallic (Pd, Pt,
Fe, Ni, Zn, etc.) and bimetallic (Pd-Fe, Pt-Au, Pd-Ag
and Pd-Au, etc.) supported catalysts is well documented
in the literature.1 7 This process is widely employed
in the elimination of alkyl and aryl chlorides such
as CCl4, CH3Cl, CH2Cl2, CH3Cl and C6HxCl6−x from
organic waste. This reductive de-chlorination process
was shown to proceed through a dissociative adsorption
mechanism of the chlorinated organic substrates form-
ing different intermediate species and consequently
leading to the formation of C1, C2-C5 coupled products
and coke.2 6,8,9
The present work describes the HDC process of
Me3SiCHCl2 precursor over 2% loading of monometal-
lic Pd/AlF3, Ni/AlF3, Co/AlF3 and Fe/AlF3 catalysts in
a flow reactor. The catalysts were prepared using sol-gel
method and characterized by BET, infrared (FT-IR) and
X-ray photoelectron spectroscopy (XPS). Gas-phase
reaction of H2/Me3SiCHCl2 mixture at constant temper-
ature (200◦C) was chosen as a model reaction to study
the activity and selectivity of the obtained catalytic sys-
tems, as depicted below (Scheme 1). The products were
identified using GC and GC-MS techniques.
Although, catalytic HDC process of chlorinated
organic compounds was widely investigated, it is
scarcely reported for chlorinated organosilane com-
pounds such as RxSiCl4−x and R3SiCH2Cl.10 15 In this
respect, these chlorinated organosilanes belong to two
different classes of organosilanes where, in the first
class (≡Si-Cl) the -Cl is directly bonded to the silicon
whereas in the second class (≡Si-CH2-Cl), the -Cl is
bonded to the carbon. Consequently, the Cl in ≡Si-Cl is
readily hydrolysable whereas in the ≡Si-CH2-Cl com-
pounds it is stable towards hydrolysis and other chemi-
cal reagents. The first class of chlorinated organosilanes
plays a key role in silicone polymer and silicon aero-
gel industries, while the second class provide essential
precursors in electronic silicon industry, organosilicon
2. Experimental
2.1 Materials and methods
All chemicals were of reagent grade and used as received
without further purification. The hydrogen (99%) was pur-
chased from International Industrial and Medical Liquid-
Gas Co., Jordan. The reagents ((CH3)3SiCHCl2, 96%;
HFaq, 48%; PdCl2, 99%; NiCl2·6H2O; FeCl2·6H2O and
CoCl2·6H2O) were obtained from Sigma-Aldrich Co. Abso-
lute ethanol was supplied by Baker (BDH) and AlF3 was
obtained from Riedel-deHaen. All supported catalysts of 2%
(w/w) metal loading used in this study Pd/AlF3, Ni/AlF3,
Co/AlF3 and Fe/AlF3 were prepared by sol-gel method.
The internal surface area of the supported catalysts
was measured by BET method using surface area ana-
lyzer (Quanta Chrom, Nova 2000 series, USA). All samples
were degassed at 200◦C for 16 h. The surface area (m2/g)
∗For correspondence

Rateb Hina et al.
CH3
Si
CH3
CH3
CH3
H-H
+
+
H3C
+
+
HCl
CH4
Si
Si
Si
CH2Cl
CH3
CHCl2
CH3
CH3
CH3
Cl
CH3
H3C
H3C
H3C
M/AlF3
Scheme 1. Products of gas-phase catalytic reaction of H2/Me3SiCHCl2 mixture at constant temperature (200◦C).
was determined from the obtained isotherms of adsorption- both a temperature controller (Antiness controls TCE) and
desorption of nitrogen at 77 K. The FT-IR spectra of samples AC transformer power supply. A suitable condenser was con-
were recorded on Nicolet Impact 410-FT-IR spectrometer as nected to the outlet of the reactor tube to condense the prod-
KBr pellets. The samples were dried and placed in a des- ucts of the reaction at −10◦C. Each fresh catalyst (∼0.50 g)
iccator at 20◦C prior to the pellet preparation. Analysis of sample was activated immediately before the reaction by
the prepared catalysts was also performed using X-Ray Pho- flowing hydrogen gas at 450◦C for 1 h, then cooling the cat-
toelectron Spectroscopy (XPS). The samples were degassed alyst to room temperature under helium gas flow. The vapor-
prior to data collection on a Kratos Axis 165-X-Ray photo- phase HDC reaction was performed in a glass fixed-bed
electron spectrometer (monochromatic Al Kα radiation, 260 reactor in a flow system under a total pressure of 1 atm.
W; the samples were fixed to the sample holder using double-
The composition of the reaction mixture was analyzed by
sided conductive copper tape, and charge neutralization was GC (Shimadzu 2010) equipped with FID detector and DB-
required to minimize charge build up on the surface; pressure 1701 capillary column (30 m length; 0.32 mm internal diam-
of the system was below 5 × 10−8 torr. throughout the data eter; 0.25 μm film thickness, mid-polar stationary phase of
collection).
14% cyanopropyl-phenyl-86% polydimethylsiloxane). The
flow rate of helium carrier gas was 1.78 mL/min. The detector
and injector temperature was 200◦C, while the temperature
of the oven was controlled through the computer program
of the GC. GC-MS instrument was used for further qualita-
tive identification of products using Varian 450–GC, DB wax
column (30 m length; 0.25 mm internal diameter; 0.25 μm
film thickness; polar stationary phase polyethylene glycol)
and mass spectrum (Varian 320-MSTQ). The flow rate of
the carrier gas (helium) was 1 mL/min. The temperature of
the detector, injector and oven were as mentioned above
in the GC.
2.2 Preparation of Pd/AlF3 catalyst by sol-gel method
A calculated mass of anhydrous aluminum chloride salt
(AlCl3) was dissolved in ∼40 mL of absolute ethanol in a
plastic container. Immediately, the ethoxy derivative of alu-
minum, Al(OEt)3 was observed to form accompanied by HCl
evolution. The pH of the solution was adjusted to 1.0 by
addition of HCl solution, then the required weight of PdCl2
needed to prepare 2% (w/w) was suspended in a minimum
amount of aqueous ethanol and added to the solution. The
mixture was stirred and heated in a water bath to 60◦C for
20 min. Excess volume of HF (∼10 mL) solution was added
slowly in a dropwise manner to the solution over a period of
30 min where a gel formed. The reaction was further heated
(70◦C, 3–4 h) to finally get a homogeneous gel. The ethanol
was removed at ∼80◦C and the gel was dried overnight
(100◦C). The resulting dried gel was subjected to calcination
in airflow (1 h, 100 mL/min, 200◦C) followed by hydrogena-
tion (4 h, 25 mL/min, 450◦C). This procedure finally yielded
2% Pd/AlF3 catalyst.
3. Results and Discussion
3.1 Preparation of Catalysts and Characterization
The investigated catalysts of 2% Pd, Ni, Fe, Co sup-
ported on AlF3 were prepared by a standard sol-gel
procedure and characterized by BET surface area,
FT-IR and XPS techniques (Table 1). It is clear from
the BET surface area that the 2% metal loaded catalysts
exhibit smaller surface area (20–29 m2/g) than that of
the unloaded AlF3 support (72 m2/g).
Similar procedure was adopted for the preparation of 2%
Ni/AlF3, Co/ AlF3 and Fe/ AlF3.
2.3 HDC reaction
The prepared catalytic systems were further exam-
ined by XPS spectroscopy, which is a powerful surface
analytical technique.25 27 Two important information
can be gathered from this technique, namely, the actual
loading percentage of the catalytic metals (Pd, Ni, Co,
Fe) on the surface of the AlF3 support and their oxi-
dation states (Table 1). The XPS spectrum of the AlF3
support displays one signal at 76.1 eV due to the Al (2p)
and at 686.3 eV corresponding to the F (1s) (Table 1).
These XPS peaks of the support were observed to
shift to higher values of (76.6–76.9 eV) and (686.4–
The catalyst was placed on a glass fixed-bed reactor in which
the catalyst was immobilized between two disks of glass
wool. A mixture of H2 and Me3SiCHCl2 vapor was intro-
duced into the reactor tube at constant temperature by bub-
bling the H2 gas through Me3SiCHCl2 liquid. The pressure
ratio of Me3SiCHCl2:H2 of ≤0.05 (atm) in the feed stream
was controlled by adjusting the temperature of Me3SiCHCl2.
The gas flow was controlled by using a mass flow controller
(Cole Parmer) and manual flow meter controller (Gilmon,
model 150 MM). The temperature of the reactor oven was
measured by a thermocouple, and controlled ( 1◦C) using 688.2 eV), respectively, for the metal loaded catalysts.

Hydrodechlorination of Methylchlorosilane
Table 1. BET surface area and XPS data for the prepared Pd, Ni, Fe and Co catalysts
supported on AlF3.
SBET
Catalytic
site
Catalyst (m2/g)
Binding Energy (eV)a
M%b
AlF3
72 Al 2p (76.1); F 1s (686.3)
–
1.9
–
Pd/AlF3 27 Al 2p (76.9); F 1s (687.1); Pd 3d(334.6, 339.7)
Pd0
Ni/AlF3 29 Al 2p (76.8); F 1s (688.2); Ni 2p(857.6, 862.0c, 874.2); 1.9 Ni(OH)2
O 1s (533.2)
Fe/AlF3 26 Al 2p (76.6); F 1s (686.4) Fe 2p(711.0-712.9, 717.2c,
722.0, 738.7c); O 1s (530.1, 533.0)
1.5 α−Fe2O3
α−FeOOH
Co/AlF3 20 Al 2p (76.6); F 1s (687.2); Co 2p(780,0, 785.1c, 802.5); 1.3
O 1s (531.9)
Co2O3
aReference, C 1s (284.8 eV).
bThe percentage of the experimentally loaded metal was 2%.
cSatallite peak.
These shifts are attributed to their interaction with the shape due to Ni(2p3/2) and (2p1/2) doublets at 857.6
AlF3 support (Table 1).
and 874.2 eV, respectively, (ꢀ = 16.6 eV), shows that
Analysis of XPS data of the Pd/AlF3 catalyst shows they correspond to Ni(OH)2 rather than NiO. The XPS
that metallic Pd0 is present with a loading percentage of Ni (2p3/2 and 2p1/2) has a typical spin-orbit sepa-
of 1.9% which is slightly less than the experimentally
loaded value of 2%, Pd(3d) exhibits a well-separated
ration of 17.3 eV which is close to the observed value
of 16.6 eV. The FT-IR spectrum of this catalyst con-
tains peaks due to the stretching frequency of hydroxide
(υO−H = 3420 cm−1) in agreement with the formation
spin-orbit doublets at 334.6 (3d5/2) and 339.7 (3d3/2
)
eV (ꢀ = 5.1 eV) which is typical for metallic Pd0,
Figure 1 (See xpssimplified.com/knowledgebase.php, of Ni(OH)2, as observed in the XPS spectrum. Further-
Thermoscientific, 2013). However, the XPS data of the more, the XPS due to the oxygen appears at 533.2 eV
other three catalysts show that they are present in the confirming the presence of hydroxide (OH) species.
form of oxides / hydroxides (Ni(OH)2, Co2O3, Fe2O3). Generally, the XPS of Fe3+ compounds are high spin
The percent loading of Fe- and Co-oxides are lower with multiplet-spin Fe(2p) spectra. The XPS analysis
than 2% while Ni-oxide is close to 2% (Table 1). Close of the Fe(2p) signal of the catalyst shows a broad mul-
examination of the observed XPS peak position and tiplet pattern centered at 711.0–712.9 eV region and a
Figure 1. X-ray photoelectron spectra (XPS) for the prepared monometallic Pd, Fe,
Co and Ni catalysts supported on AlF3.

Rateb Hina et al.
measurements. The reported values in Table 2 are the
broad featureless shoulder at 722.0 eV (ꢀ = 11.0 eV),
which are attributed to the Fe3+(2p3/2) and (2p1/2),
respectively, of α-Fe2O3 and/or α-FeOOH. The com-
monly reported spin-orbit separation in the XPS of
Fe3+ is about 13.0 eV which is close to the obtained
value. However, the corresponding peak of the oxide
appears at 530–533 eV which indicates the presence of
two different type of oxygen due to oxide (530 eV) and
hydroxide (533 eV). This observation suggests that oxy-
gen is present as oxide and hydroxide which fits the
presence of α-FeOOH. Furthermore, the FT-IR spec-
trum of this catalyst contains an unresolved broad peak
average of three trials with deviation of less than 6%.
The Lewis acidity of the AlF3 support plays an impor-
tant role in the desorption process of HCl formed during
the HDC reaction and hence may affect the conversion
rate and distribution of products. The HDC process of
Me3SiCHCl2 over Pd, Ni, Fe, Co supported on AlF3
catalysts yielded CH4, different organosilane prod-
ucts identified as Me3SiCH2Cl, Me3SiCl, Me4Si and
other coupled products (Me3SiCH2-CH2SiMe3 . . ...);
see Table 2. It is clear from the data in Table 2 that the
conversion rate over Pd/AlF3 is much higher than those
catalyzed over other transition metal catalysts, Ni/AlF3,
Fe/AlF3 and Co/AlF3. These metals show lower conver-
sion rate. Inspection of the selectivity data in Table 2
shows that the Pd/AlF3 catalyst exhibits high tendency
due to the stretching frequency of hydroxide (υO−H
=
3549–3350 cm−1) in accordance with the formation of
a hydroxide moiety (α-FeOOH) as deduced from the
XPS spectrum.
Examination of the XPS spectrum of the cobalt for the formation of Me3SiCH2Cl while other transition
catalyst shows a very broad Co(2p) peaks at 780.0 and metals comparably favor the formation of Me3SiCl.
802.5 eV regions, assigned to 2p3/2 and 2p1/2 peaks of
The plot in Figure 2 shows that the HDC rate
Co2O3 (Figure 1). The estimated spin-orbit of the XPS increases linearly with increasing partial pressure of
peaks of ꢀ = 22.5 eV is higher than the commonly Me3SiCHCl2. These results suggest that the Me3
observed value of about 17 eV. This point may be the SiCHCl2 was not adsorbed on the surface of the metal
result of a strong interaction between the catalyst and catalyst and the reaction mechanism can be represented
its support. The appearance of XPS of the oxygen at by Eley-Rideal model28 where the reaction takes place
531.9 eV indicates the presence of oxide (Table 1). This
conclusion is supported by the FT-IR data where no
observable stretching frequency due to hydroxide was
identified.
120
100
80
60
40
20
0
♦ Pd/AlF3 ▲Ni/AlF3
□ Fe/AlF3 + Co/AlF3
3.2 Vapor phase HDC of Me3SiCHCl2 over M/AlF3
catalysts (M = Pd, Ni, Fe, Co)
The reaction rates are expressed as micromoles of reac-
tant Me3SiCHCl2 converted per unit contact time (min)
and mass (g) of the catalyst. Product selectivity is
defined as the percentage ratio of the detected product
Ci to the sum total amount of products: (% S) = 100
(Ci/ꢁ Ci).
0
0.01 0.02 0.03 0.04 0.05 0.06
Pressure ratio (DCMTMS)/H2 atm
All the HDC process rates quoted in this paper
represent the steady-state values with no evidence of
any catalyst deactivation throughout the course of the
Figure 2. Rate of conversion as a function of pressure ratio
of Me3SiCHCl2:H2 over Pd, Ni, Fe and Co supported on
AlF3 at 200◦C.
Table 2. Rate of conversion, percent conversion and percent selectivity for HDC process over
M/AlF3 where M = Pd, Ni, Fe, Co.
Rate
Conversiona
Selectivity (%)a
Catalyst μmol/g min
%
CH4 /CH3Cl Me3SiCH2Cl Me3SiCl Me3SiCH3 Coupledb
Pd/AlF3
Ni/AlF3
Fe/AlF3
Co/AlF3
106
20
11
11.6
5.5
3.5
1.7
10
25
33
34
49
22
18
24
15
34
38
35
10
6
4
16
13
7
12
3
4
aAverage of three trials; P (Me3SiCHCl2) / P(H2) = 0.05 atm; 1 h on stream, 200◦C.
bCoupled products such as Me3SiCH2-CH2SiMe3, . . . . . ...

Hydrodechlorination of Methylchlorosilane
between the adsorbed hydrogen while Me3SiCHCl2 is Furthermore, one can anticipate the formation of dif-
present in the gas phase.
ferent reactive species including Cl∗ (M-Cl) and H∗
(M-H). The formation of Me3SiCH2Cl depends on the
adsorbed reactive species Cl∗ and H∗ where the obser-
vation of high selectivity towards Me3SiCH2Cl on those
catalysts may attributed to the long resident time of Cl∗
and H∗-rich environment on the surfaces of the cata-
lysts. The presence of Cl∗ and H∗ species may result
in breaking of the Me3Si-CH2Cl, yielding Me3SiCl,
CH3Cl, CH4 and other silane derivatives including the
coupled products. The formation of Me3SiMe indicates
the generation of CH∗3 adsorbed species. Different rate
expressions and mechanisms have been proposed in lit-
erature specifically for catalytic HDC.5,29,30 So, based
upon the selectivity data, a proposed 3-step mechanism
can be put forward:
The effect of time–on–stream on the selectivity
towards the formation of Me3SiCH2Cl and Me3SiCl for
all catalysts at 200◦C is shown in Figures 3 and 4.
The selectivity towards formation of both products
showed linear and insignificant variation during the pas-
sivation time of ∼2 h. However, the selectivity towards
Me3SiCl over Ni/AlF3, Fe/AlF3 and Co/AlF3 are com-
parable (34–38%) and higher than Pd/AlF3 catalyst
(16%). Interestingly, Ni/AlF3, Pd/AlF3 catalysts exhibit
higher tendency for the formation of coupled organosi-
lane products than Fe/AlF3 and Co/AlF3.
It is clear from the selectivity data and the plots in
Figures 3 and 4 that the Pd/AlF3 catalyst favors the
selective cleavage of C-Cl while the others, Ni, Fe and
Co supported catalyst favor the cleavage of Si-C bond.
Me3SiCHCl2(g) +M-H → Me3SiCH2Cl(g) +M-Cl (1)
60
♦ Pd/AlF3 ∆ Co/AlF3 ▲ Ni/AlF3
Me3SiCH2Cl(g) + M-H + M-Cl → Me3SiCl(g)
+ Me3SiCH3(g) +CH3Cl(g) +CH4(g)
□ Fe/AlF3
50
+ Coupled Silanes
(2)
(3)
40
30
20
10
M-Cl + H2(g) ꢀ M-H + HCl(g)
Step 1 involves the oxidative addition of Me3SiCHCl2
on the metal surface and its interaction with M-H and
thus eliminating Me3SiCH2Cl into gas phase. Conse-
quently, Me3SiCH2Cl gets adsorbed, undergoes sim-
ilar process leading to the elimination of Me3SiCl,
Me3SiCH3, CH3Cl and rest of the products into gas
phase, as step 2. The surface is reversibly reduced by
H2 in step 3 and re-adsorption of HCl.5,29 Each step 1,
2 and 3 can be described as having rate constants k1, k2
and k3, respectively. The kinetic rate according to the
proposed mechanism is given as follows:
20
40
60
80
100
120
140
Time (minute)
Figure 3. A plot of selectivity the monochloro product
(Me3SiCH2Cl) as a function of time for HDC process of
Me3SiCHCl2 over Pd, Ni, Fe and Co supported on AlF3 at
200◦C.
50
□ Fe/AlF3 ∆ Co/AlF3 ▲ Ni/AlF3
Rate = k1k2 PRPH2/(k1PR + k2PH2 + k3PHCl
)
(4)
♦ Pd/AlF3
40
PR is the partial pressure of Me3SiCHCl2. This expres-
sion predicts a first order dependence with respect to
Me3SiCHCl2. Under the reaction conditions employed
in this study where PMe SiCHCl << PH2 >> PHCl, eq. 4
30
20
10
3
2
can be simplified as
Rate = k1PR
(5)
20
40
60
80
100
120
140
The data presented in Figure 4 and Table 2 reflects
the dependence of reaction rate on partial pres-
sure of Me3SiCHCl2. The experimentally determined
rates increased with increasing partial pressure of
Me3SiCHCl2 within the range of partial pressures used
in this study.
Time (minute)
Figure 4. A plot of selectivity chlorosilane derivative
(Me3SiCl) as a function of time for HDC process of
Me3SiCHCl2 over Pd, Ni, Fe and Co supported on AlF3 at
200◦C.

Rateb Hina et al.
12. Kim B-h and Woo H-G 2004 Dehydrocoupling, redis-
4. Conclusions
tributive coupling, and addition of main group 4
hydrides Adv. Organomet. Chem. 52 143
Our findings show that unlike the HDC process of
organic chlorides where the coupled products (C2-C5)
are the major ones, the examined Me3SiCHCl2 gives
a minor quantity of coupled products (Me3SiCH2-
CH2SiMe3; Me3SiCHCl-CHClSiMe3). The three
major organosilane products are Me3SiCH3,
Me3SiCH2Cl, and Me3SiCl.
13. Colin P, Jacquot R and Morel P 2002 U.S. Patent
No. US 06384257. Washington, D.C.: U.S. Patent and
Trademark Office
14. Drose J, Knott W and Wolfgram D 1999 U.S. Patent
No. 5856548 A. Washington, D.C.: U.S. Patent and
Trademark Office
15. Lee J Y, Lee W H, Park Y-K, Kim H Y, Kang N Y, Yoon
K B, Choi W C and Yang O-B 2012 Catalytic conversion
of silicon tetrachloride to trichlorosilane for a poly-Si
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This work was financially supported by the Deanship of
Research, Jordan University of Science and Technology,
Irbid, Jordan.
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