Journal of Nanomaterials
Volume 2015, Article ID 912104, 8 pages
http://dx.doi.org/10.1155/2015/912104
Research Article
Catalytic Hydrodechlorination of Trichlorobenzenes with
Pd(Phen)Cl2 as Catalyst Precursor
Guanlin Zhang,1 Hu Xu,1 Yuehui Fan,1 Yuhong Wang,1 Lirong Zhang,2 and Guanzhong Lu1
1
Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology,
Shanghai 201418, China
2
School of Perfume and Aroma Technology, Shanghai Institute of Technology, Shanghai 201418, China
Correspondence should be addressed to Hu Xu; xuhu@sit.edu.cn and Yuhong Wang; yuhong wang502@sit.edu.cn
Received 11 November 2014; Revised 30 December 2014; Accepted 31 December 2014
Academic Editor: Guoran Li
Copyright 2015 Guanlin Zhang et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
We reported the catalytic hydrodechlorination (HDC) of trichlorobenzenes by an organometallic compound Pd(Phen)Cl2 as a
catalyst precursor. The catalyst precursor was prepared by chemical coordination reaction and characterized by FTIR and 1 H NMR
techniques. The HDC performance of Pd(Phen)Cl2 as catalyst precursor was evaluated on 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzenes
(TCBs). All TCBs could be converted to dechlorination products with high conversion. Products distribution was closely related
with the substrate structures and C-Cl bond energies. A reasonable reaction mechanism was also proposed.
1. Introduction
Aryl chlorides are considered the persistent toxic pollutants
because the environment does not possess a comparatively
assimilative ability [1]. The dechlorination of aryl chlorides is
becoming a global issue [2]. With the ever increasing concerns for environmental protection and human health, the
safe disposal of aryl chlorides has attracted much attention [2,
3]. Various methods like incineration and thermal oxidation
do degrade aryl chlorides, but incomplete oxidation usually
leads to the formation of more toxic species such as dioxins
and chlorine [4]. In contrast, catalytic hydrodechlorination (HDC) may become a promising treatment for these
chlorinated compounds by means of an environmentally
friendly way [5]. Although HDC process does not usually
cause the complete destruction of pollutants, it can result
in the convenient transformation to less toxic compounds.
Other advantages of HDC reflect in high conversion levels,
conducting at low temperature and pressure, and so forth [6].
Catalytic HDC can be usually effectively performed in
both liquid and vapor phases using the supported noble
metal (Pd [2, 4, 68], Pt [9], and Ru [10]) or nonnoble
metal (Ni [4, 11, 12] and Ni-Mo [11]) as catalysts, among
which Pd-based catalysts are considered the most suitable
2
could smoothly promote the HDC reactions of several TCBs
to occur and different dechlorination products were detected.
Products distribution was closely related with the substrate
structures and C-Cl bond energies. The possible reaction
pathway was also discussed.
2. Experimental
2.1. General. PdCl2 , phenanthroline, and other chemicals
were purchased from Sinopharm Chemical Reagent Company. 1 H NMR spectra were acquired on a Bruker Avance III
spectrometer (500 MHz). Transmission electron microscopy
(TEM) investigations were performed with an FEI Tecnai
G2 20 microscope operated at 200 kV. Before the detection,
the catalyst was dispersed in ethanol and reduced by NaBH4
for 10 min until the color of the catalyst became black. To
confirm that the catalyst distributed uniformly, the sample
should be put into the ultrasonic vibration meter for another
30 min. Catalytic HDC activity of Pd catalysts was evaluated
by gas chromatograph (GC-9790, Fuli, MD) equipped with
a flame ionization detector (FID), a PEG-20 M capillary
column (30 m 0.25 mm 0.5 m), and N2 as carrier gas.
The initial oven temperature was set at 50 C for 3 min and
was then raised with a gradient of 10 C/min until 200 C and
held for 5 min. The temperature of the FID and injection was
settled at 250 C. The FTIR analysis was performed on Nicolet
380 spectrometer with a KBr tablet.
2.2. The Preparation of Catalyst Precursor Pd(Phen)Cl2 . Typically, a solution of PdCl2 (0.355 g, 2 mmol) in acetonitrile
(50 mL) was heated to 70 C under stirring and maintained at
this temperature for 2 h. During this process a clear solution
appeared, which indicated the formation of Pd(CH3 CN)2 Cl2 .
Then the solvent was removed at reduced pressure and a pale
yellow solid was obtained. The yellow solid was dissolved
in 25 mL EtOH, to which a solution of 1,10-phenanthroline
(0.396 g, 2 mmol) was dropwise added. With the addition
of phenanthroline, the color of solution became gradually
violent. Two hours of reaction resulted in the formation of a
substantial white precipitate, which was collected by filtration
and washed by EtOH (3 5 mL). The product was dried
in vacuum drying oven at 50 C for 12 h to give the catalyst
precursor Pd(Phen)Cl2 (0.580 g, 81.23%).
2.3. The Hydrodechlorination of Aryl Chlorides. Typically,
hydrodechlorination reaction was carried out in a 150 mL
three-necked, round-bottomed reactor equipped with a balloon for hydrogen supply (1 atm) at a temperature of 333 K.
0.25 mmol catalyst precursor was dispersed in 25 mL of
MeOH by means of ultrasonation. To this dispersion the acidbinding agent triethylamine (15 mmol) and NaBH4 (0.02 g)
were added. The reduction process was maintained for 1 h,
after which the aryl chlorides substrates (5 mmol) were added
and the HDC reaction started counting. The aliquots of
reaction solution were taken every 30 min for GC analysis.
Journal of Nanomaterials
Journal of Nanomaterials
Pd(Phen)Cl2
1425
1515
840
707
Phen
1619
1560
1421
1600
Phen
854
1510
1800
Pd(Phen)Cl2
Transmittance
Transmittance
1631 1581
1400
1200
1000
Wavenumber (cm1 )
735
800
10
600
7
6
5
Chemical shift (ppm)
(a)
(b)
35
30
(%)
25
20
15
10
5
5.66
5.25.6
4.85.2
4.44.8
44.4
3.64
3.23.6
2.83.2
2.42.8
22.4
(d)
Figure 1: Comparison of FTIR spectra (a) and 1 H NMR spectra in [D6 ]DMSO (b) of free Phen ligand and Pd(Phen)Cl2 . (Asterisks in 1 H
NMR spectra denote the residual solvents signals.) The TEM of the reduzate of Pd(phen)Cl2 (c). Particle size was calculated to analyse the
distribution (d).
Journal of Nanomaterials
80
100
60
60
Yields (%)
Conversion (%)
80
40
40
20
20
0
2
6
8
Time (h)
10
12
1,3-DCB
CB
10
12
2
0.9937
0.9928
0.9904
0.9915
40
30
Conversion (%)
(h1 )
0.4497
0.5382
0.9283
1.6570
Benzene
Time (h)
323 K
333 K
303 K
313 K
Temperature (K)
303
313
323
333
20
10
0
0
6
Time (h)
10
12
Journal of Nanomaterials
100
Conversion (%)
80
60
40
20
0
0
6
Time (h)
10
12
1,2,4-TCB
1,3,5-TCB
1,2,3-TCB
(a)
80
60
40
Yields (%)
Yields (%)
60
40
20
20
0
0
6
Time (h)
1,2-DCB
CB
10
12
Benzene
(b)
6
Time (h)
1,3-DCB
1,4-DCB
10
12
CB
Benzene
(c)
Figure 5: Temporal conversion profiles of 1,2,3-, 1,2,4-, and 1,3,5-TCB (a) and product yields of 1,2,3-TCB (b) and 1,2,4-TCB (c) as a function
of time at 323 K using Pd(Phen)Cl2 as catalyst precursor.
Journal of Nanomaterials
100
100
80
60
Yields (%)
Conversion (%)
80
40
20
60
40
20
0
0
6
Time (h)
10
12
1,4-DCB
1,2-DCB
1,3-DCB
(a)
6
Time (h)
10
12
CB
Benzene
(b)
Figure 6: Temporal conversion profiles of 1,2-, 1,3-, and 1,4-DCB (a) and product yields of 1,3-DCB (b) as a function of time using Pd(Phen)Cl2
as catalyst precursor at 323 K. Only the product yields of 1,3-DCB were depicted as atypical since the similar results were observed in the cases
of 1,2- and 1,4-DCB.
Journal of Nanomaterials
Pd2+ (Phen)Cl2
Acknowledgments
Step 1
NaBH4
Pd0 (Phen)
1
HAr
H2
References
Step 2
Step 5
H
Pd0 (Phen) 2
2+
4 HPd (Phen)Ar
H
Step 3
Step 4
HCl
ArCl
Pd2+ (Phen)Cl
Ar
H
4. Conclusions
In this work, we investigated the HDC performance of
Pd(Phen)Cl2 as catalyst precursor using TCBs as substrates.
All TCBs could be fully converted under the described
conditions, but they could not be degraded completely to
produce the final dechlorination product benzene, which was
ascribed to the deactivation of catalyst. Products distribution
was closely related to the substrate structures and C-Cl bond
energies. The possible reaction pathway was also discussed.
Conflict of Interests
The authors declare that there is no conflict of interests
regarding the publication of this paper.
8
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