A highly active Pd on Ni-B bimetallic catalyst for liquid-phase hydrodechlorination of 4-chlorophenol under mild conditions

Article abstract of DOI:10.1007/s10562-011-0567-5

A Pd on Ni-B (Pd/Ni-B) bimetallic catalyst was prepared and tested in the hydrodechlorination (HDC) of 4-chlorophenol (4-CP). The catalysts were synthesized by replacement method and treated at different temperatures (298-673 K). The results showed that the one treated at 473 K could achieve complete dechlorination of 200 ppm 4-CP under the pH = 8 within 30 min and keep the high activity in the first four recycles. The introducing of Pd greatly promoted the catalytic HDC efficiency of Ni-B, and the high dispersion of Pd species ensured the high activity of Pd/Ni-B catalysts. The catalytic HDC reaction of 4-CP followed the pseudo-first-order dynamics and the kinetic data was obtained. Graphical Abstract: A series of Pd/Ni-B catalysts were prepared by replacement method and treated at different temperatures. These catalysts were characterized and applied to the hydrodechlorination reaction of 4-chlorophenol, and complete degradation of chlorophenols could be realized in a few minutes.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-011-0567-5

Catal Lett (2011) 141:792–798
DOI 10.1007/s10562-011-0567-5
A Highly Active Pd on Ni–B Bimetallic Catalyst for Liquid-Phase
Hydrodechlorination of 4-Chlorophenol Under Mild Conditions
•
Chongxia Sun Zhijie Wu Yuzhen Mao
•
•
•
•
•
Xiaoqian Yin Liyuan Ma Danhong Wang
Minghui Zhang
Received: 17 November 2010 / Accepted: 19 February 2011 / Published online: 17 March 2011
Ó Springer Science+Business Media, LLC 2011
Abstract A Pd on Ni–B (Pd/Ni–B) bimetallic catalyst
was prepared and tested in the hydrodechlorination (HDC)
of 4-chlorophenol (4-CP). The catalysts were synthesized
by replacement method and treated at different tempera-
tures (298–673 K). The results showed that the one treated
at 473 K could achieve complete dechlorination of
200 ppm 4-CP under the pH = 8 within 30 min and keep
the high activity in the first four recycles. The introducing
of Pd greatly promoted the catalytic HDC efficiency of
Ni–B, and the high dispersion of Pd species ensured the
high activity of Pd/Ni–B catalysts. The catalytic HDC
reaction of 4-CP followed the pseudo-first-order dynamics
and the kinetic data was obtained.
environment [1–3]. Some chlorinated solvents such as tri-
chloroethylene, tetrachloroethylene, and trichloroethane
are widely used in industrial processes, and a large quantity
of reaction intermediates like those that chlorophenols are
generated in the production of pesticides, herbicide, dis-
infector, and dyestuff [3, 4]. These chlorinated organics
have made very severe pollution to the environment.
4-chlorophenol is carcinogenic, teratogenic, and mutagenic
pollutant and is among the 194 priority pollutants put
forward by the US Environmental Protection Agency in
1994.
Plenty of methods have been developed for the elimi-
nation of chlorinated organics: incineration, reduction
dechlorination [5, 6], oxidation dechlorination [7–10],
biodegradation, photochemical catalysis, and catalytic
HDC [4, 11, 12]. From an economical and environmental
point of view, HDC is the most effective and promising
method, which could avoid the formation of more toxic
compounds such as dioxins, phosgene, and chlorine. Hoke
et al. [13] studied that the complete destruction of 4-CP
over Pd/C was possible under mild conditions (307 K,
0.2 MPa) early in 1992. In the last 5 years, it attracted
more attention on the preparation of more effective cata-
lysts, in which Pd/C catalysts were the most commonly
used [12, 14–16]. The catalysts involved are essentially
from the group VIII, such as Pd, Pt, Ru, Rh, and Ni, among
which Pd and Ni are the most widely used.
Keywords Palladium ꢀ Ni–B ꢀ Bimetallic catalysts ꢀ
Hydrodechlorination ꢀ 4-Chlorophenol
1 Introduction
Chlorinated organics are among the most universal and
persistent toxic pollutants in groundwater and soil con-
taminants and have posed a significant burden on the global
C. Sun ꢀ Z. Wu ꢀ Y. Mao ꢀ X. Yin ꢀ D. Wang (&) ꢀ
M. Zhang (&)
Institute of New Catalytic Materials Science, College of
Chemistry, and Key Laboratory of Advanced Energy Materials
Chemistry (MOE), Nankai University, Tianjin 300071, China
e-mail: dhwang@nankai.edu.cn
Active carbon supported Pd (Pd/C) was a typical cata-
lyst in HDC reaction, and on the performance of 5% Pd/C
catalyst, complete dechlorination of 4-chlorophenol could
achieve after 60 min at room temperature and atmosphere
pressure [17, 18]. Catalytic supports in the form of woven
fibrous cloths or faveolate have apparent surface area, large
adsorption capacity and high dispersion of impregnated
metal made them potential alternatives to the properties of
M. Zhang
e-mail: zhangmh@nankai.edu.cn
L. Ma
NanoScience Technology Center, University of Central Florida,
Orlando, FL 32826, USA
123

A Highly Active Pd on Ni–B Bimetallic Catalyst
793
the catalysts. As the HDC reaction of 4-CP was structure
sensitive, so particle diameter, metal loading and disper-
sion had great influence to their activity.
inorganic ion with deionized water and anhydrous ethanol.
Finally, the Pd/Ni–B bimetallic nanoparticles were drying
in a quartz tube at 353 K in a 40 mL/min argon flow for
1 h, and the heating treatment was carried out at different
temperatures from 298 to 673 K for 2.0 h.
In 2005, Pd on Au bimetallic nanoparticles were first
designed [19] and used for the HDC of trichloroethylene,
which exhibited high activity. Following his work,
researchers prepared a series of bimetallic catalysts, such as
Au/Ni catalysts [20, 21], Pd/Fe bimetallic particles [22–
24], Pd/Au bimetallic particles [25, 26] and Pd–Ag bime-
tallic nanoparticles [27], among which Pd/Ni bimetallic
catalysts received most of the attention. Simagina et al.
[28] studied the synergistic effect in Pd–Ni/C bimetallic
catalysts. Such a Pd–Ni/C catalysts were also prepared for
the HDC of 1,2-dichloroethane [29] and the surface char-
acterization of the catalyst was studied by TPR method.
Wang et al. [30] prepared Pd/Ni catalysts for the HDC of
4-CP, and studied the influence conditions of Pd loading
amount, formic acid dosage and solution pH value for the
reaction.
2.2 Activity Testing
The batch experiments for 4-chlorophenol HDC were
performed in a 500 mL three-necked flask at room tem-
perature and atmospheric pressure, to which 1.0 g cata-
lysts, 0.05 g NaOH, deionized water and hydrogen flow
was added. To evaluate the catalyst activity under catalytic
control, reaction conditions were first established. The
effect of increasing H2 flow rate and stirring speed on
hydrodechlorination performance was investigated, and a
hydrogen flow rate of 60 mL/min and a stirring speed of
600 rpm were set to exclude the limit of H2 diffusion. After
stirring for 10 min, a certain amount of 4-chlorophenol was
introduced and the reaction was timed immediately. To
evaluate the conversion of the reaction, the sample was
collected with a glass syringe at an interval of 5 min, and
then passed through a 0.45 lm membrane filter.
In this study, we prepared a highly dispersed Pd/Ni–B
(1.0 wt% Pd) bimetallic catalyst for the HDC of 4-chlo-
rophenol. Proper heating treatment of Ni–B catalysts could
promote the electron transfer from element boron to nickel
and the electron property of Ni strongly affected the
activity of the Ni–B catalysts [31]. Therefore, we studied
the effect of heating treatment on the formation of Pd/Ni
alloying and investigated a proper treatment temperature at
which the Pd/Ni–B nanoparticles have the best activity and
stability in the reaction.
In many cases, the reactions were tested for the repeat-
ability under identical conditions, and the reaction repro-
ducibility was better than 5%. A carbon balance was
performed by comparing the amount of carbon entering per
unit time and the number of products exiting per unit time.
Carbon mass balance was complete to better than 1%.
2.3 Analytical Methods
2 Materials and Methods
The chemical composition of samples was analyzed by
inductively coupled plasma atomic emission spectrometry
(ICP-AES) on an IRIS intrepid spectrometer. Transmission
electron microscopy (TEM) images were acquired using a
FEI Tecnai G2 high-resolution transmission electron
microscopy operating at 200 kV. Powder X-ray diffraction
(XRD) patterns of the catalysts was obtained on a Rigaku
2.1 Catalyst Preparations
Amorphous Ni–B nanoparticles were prepared by the
method of chemical plating. 6.66 mL of ethylenediamine
and 14.46 g NiSO4ꢀ6H2O were dissolved in 900.0 mL of
deionized water under stirring, and then certain amount of
NaOH was added to adjust the pH of the solution to 13.0.
Finally, by the addition of 5.4 g KBH4 the plating solution
was successfully prepared. In order to accelerate the
reaction, 0.1 mL 0.2 wt% AgNO3 aqueous solution was
added. The plating solution was heated to 343 K and stirred
for 0.5 h until no bubbles were observed. The as-prepared
catalyst was washed with deionized water until the pH at
7.0 and with ethanol to make them anhydrous.
˚
D/max 2500 X-ray diffractometer (Cu Ka, k = 1.54178 A)
operated at 40 kV and 40 mA in the 2h range of 10–80° and
with a scanning speed of 4°/min. X-ray photoelectron
spectroscopy (XPS) analysis of the catalysts was carried out
using a Kratos Axis Ultra DLD spectrometer using a
monochromatic Al Ka source, hybrid magnetic/electrostatic
optics, and a multichannel plate and delay line detector.
The concentration of 4-chlorophenol and phenol were
detected by a Shanghai WuFeng HPLC using a C18 col-
umn (150 9 46 mm). The column temperature was con-
trolled at 308 K and the UV–Vis detector was set at the
wavelength of 280 nm. A mixture of methanol and water
(1:1, v/v) was used as mobile phase and the flow rate was
1.0 mL/min. The sample loop was 20 lL.
The Pd/Ni–B bimetallic nanoparticles were prepared by
soaking the freshly prepared Ni–B particles with a
Pd(NH3)4Cl2 solution and stirred for 4 h under the pro-
tection of argon gas atmosphere at 298 K. The Pd loading
was controlled at 1.0 wt% to ensure its high dispersion.
After the reaction, the black catalysts were washed free of
123

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C. Sun et al.
3 Results and Discussion
3.1 Characterization
TEM sample. It may be due to the sintering and phase
transformation of unstable amorphous Ni–B at the
increasing temperature. Pd/Ni–B nanoparticles treated at
373 and 473 K (Fig. 1f, g) show the similar topography
with the Ni–B and the slightly decreasing size of *80 nm
(Fig. 1b, c) due to the replacement reaction on the surface
of Ni–B. For the same property of Ni–B matrix, the
agglomeration of catalysts was also observed when
Pd/Ni–B was treated at 573 and 673 K (Fig. 1h, i).
The composition of the as-prepared Ni–B amorphous cat-
alyst was determined as Ni67.4B32.6 by ICP-AES analysis.
No significant influence of the heating treatment on the
composition was observed. The content of Pd was mea-
sured as 0.96 wt% in fresh Pd/Ni–B catalyst.
Figure 1a shows that freshly prepared spheral Ni–B
nanoparticles with the diameter of *85 nm. After treated
at 373 and 473 K, Ni–B particles almost keep the original
shape and size like the fresh ones (Fig. 1b, c), but the
agglomeration of particles began to occur when treated at
573 K (Fig. 1d). With the increasing treatment temperature
of 673 k, the cross-linking particles formed the bulk
agglomerates as shown in Fig. 1e, which could not be
separated by ultrasonic during the preparation process of
Figure 2 illustrates the XRD patterns of Pd/Ni–B cat-
alysts treated at different temperatures rang from 373 to
673 K. Since XRD patterns of Ni–B catalysts with
heating treatment are the same with those of Pd/Ni–B,
they are not plotted in the figure. A broad diffraction
peak at around 2h = 45° indicating the amorphous
structure of the Pd/Ni–B catalysts treated under the
temperature of 473 K. At higher treatment temperature
(above 473 K), the diffraction of crystalline Ni3B was
Fig. 1 TEM images of Ni–B treated at 298 K (a), 373 K (b), 473 K (c), 573 K (d), and 673 K (e) Pd/Ni–B treated at 373 K (f), 473 K (g),
573 K (h), and 673 K (i)
123

A Highly Active Pd on Ni–B Bimetallic Catalyst
795
hydrogen-splitting and resistance to chlorine deactivation
[32].
3.2 HDC Activity
3.2.1 The Activity of the Catalysts
Firstly, a series of blank experiments were conducted in the
absence of catalyst with the 4-chlorophenol preliminary
concentration (C0) of 200 ppm and hydrogen flow rate of
60 mL/min. The loss of 4-chlorophenol content in the H2
flow was negligible (\0.1%) in 1.0 h. The impacts of
hydrogen flow rate, temperature, stirring speed and initial
pH on the reaction were also studied, and the reaction
conditions were selected to minimize the transport
limitations.
At room temperature and atmosphere pressure, the HDC
of 4-chlorophenol with hydrogen over Pd/Ni–B catalysts
was carried out (Eq. 1). 4-chlorophenol was mainly trans-
formed to phenol, and at the same time HCl was formed,
but quickly reacted with the NaOH in the reaction system.
The formed NaCl would dissolve in water and could
Fig. 2 XRD patterns of Pd/Ni–B catalysts treated at 373–673 K
OH
OH
observed, which demonstrating the transformation of Pd/
Ni–B nanoparticles from amorphous state to crystalline
state. The diffraction peaks of Pd or Pd compounds were
not detected in all Pd/Ni–B catalysts, which illuminated
the high dispersion of the Pd species on the surface of the
Pd/Ni–B catalyst.
298K, 105Pa
cat.
HCl
(1)
H2
Cl
not accumulate at the surface of the catalysts. So, the
addition of excess amount of NaOH against Cl atoms [33]
could get the reaction free of the negative effect of HCl
[34] and effectively prevent the poisoning of the catalysts
[17].
It can be seen from the XPS characterization (as shown
in Table 1) that, the binding energy (BE) of the main and
satellite peak of the Ni spectra was increased on heat
treatment while the Pd and B spectra decreased. In addi-
tion, more excitation peaks occurred at 473 K, demon-
strating that the valence state of Ni and Pd was changed
and electron transfer occurred between Ni, Pd, and B. The
surface content of Pd decreased from 6.2 to 5.1, whereas
the content of B varied from 4.5 to 2.2 with the elevated
temperature of 298–473 K. It shows a decreasing surface
concentration of Pd in the Pd/Ni–B with heating treatment.
According to the peak shifts of XPS spectra and the
changes of surface composition, it suggests that the strong
interaction (surface alloying) among Pd, Ni, and B ele-
ments on the surface of catalyst is formed when Pd/Ni–B is
treated at the temperature of 473 K, which will increase the
The effect of initial solution pH on the HDC reaction
was investigated, and the result was shown in Fig. 3.
Acidic condition (pH = 3) was not conductive to the
reaction equilibrium. The pH 8 was just the condition of
Cl/OH- slightly above one (mol/mol) and was proved the
optimum pH condition for the reaction. NaOH added could
neutralized the HCl generated in the reaction and avoided
the deactivation of the catalysts. Higher pH could cause
structural damage to the catalyst.
It can be seen from Fig. 4 that both Ni–B and Pd/Ni–B
catalysts exhibited high HDC activity, and the complete
Table 1 Binding energy of Pd, Ni, and B analyzed from the XPS characterization in Pd/Ni–B catalysts treated at different temperature
Treatment temperature (K)
Ni 2p (eV)
Pd 3d (eV)
B 1s (eV)
298
473
853.2
855.7
856.5
860.5
335.8
335.6
341.1
334.1
188.4
187.1
853.0a
851.2a
339.6a
340.9a
a
New excitation peak
123

796
C. Sun et al.
Fig. 3 Effect of initial pH on the HDC rate of 4-CP. Conditions:
C0 = 200 ppm; Cat. = 2 g/L, 298 K, 1 atm
Fig. 5 The dynamics of the 4-chlorophenol hydrodechlorination
reaction over the Ni–B catalysts
the addition of a second metal Pd. Interpretation to this
behavior is that Ni assembled high concentration of H2 and
reactants on the surface of the catalyst and Pd could fre-
quently activate H2 molecule to active hydrogen. The
synergistic effect between Pd and Ni facilitated the catalyst
with better activity and resistance to poisoning [37].
The HDC dynamic data over the Ni–B catalysts treated
at different temperatures were shown in Fig. 5. The one
treated at 473 K showed the highest reaction velocity
whereas the one treated at 673 K showed almost no con-
version of the reactant. According to the XRD patterns
(Fig. 2), below the temperature of 473 K, the Ni–B cata-
lysts maintained the amorphous structure. On the study of
the XPS spectra of Ni–B catalysts [38–40], binding energy
of B element was higher than the standard pure B after
heating treatment, indicating that electron transfer from B
to Ni occurred in this course, and the electron-enrichment
of Ni species favored the hydrodechlorination reaction.
Crystallization of the amorphous Ni–B nanoparticles cat-
alysts was observed at higher temperature (573 K). The
crystallization deactivation [38] is the main reason of the
decrease of the activity, which refers to the transportation
of amorphous structure to crystalline structure of Ni–B.
When the treatment temperature increased to 673 K, the
crystalline catalyst grew to larger particles and agglomer-
ation occurred because of strong sintering [32], resulting in
almost absence of HDC activity.
Fig. 4 Hydrodechlorination of 4-chlorophenol over Ni–B and Pd/Ni–
B catalysts ([4-CP]0: 200 mg/L, [cat.]: 2 g/L, 298 K, 105 Pa, H2 flow:
60 mL/min)
dechlorination achieved after 30 min. Amorphous Ni–B
alloy catalysts exhibited high activity in the reaction,
resulting from their specific short-range disordering and
long-range ordering structure. B donated electrons to Ni,
making Ni electron enriched [35, 36]. High concentration
of coordinately unsaturated sites on the catalyst surface
ensured them with higher ability of adsorbing H2 and
activating the reactants, which contributed to their high
reaction ability.
Pd/Ni–B bimetallic catalyst exhibited a higher activity
than Ni–B catalyst at any reaction time. It suggests that the
catalytic ability of Ni–B catalyst was highly promoted by
We also researched the effect of heating treatment on
the Pd/Ni–B catalysts and the results were shown in Fig. 6.
123

A Highly Active Pd on Ni–B Bimetallic Catalyst
797
exhibited much better activity compared with the Ni–B
(673 K) catalyst, showing an improved thermal stability.
3.2.2 The Stability of the Pd/Ni–B (473 K) and Ni–B
(473 K) Catalysts
The activity of a catalyst when recycled is an important
indicator of its catalytic performance. The recycle
activity and stability of the Pd/Ni–B (473 K) catalyst are
shown in Table 2. The Pd/Ni–B catalysts exhibited
preferable stability in the first four recycles from the data
of reaction rate constants (kobs), whereas quick decrease
of kobs over Ni–B catalyst appeared. According to the
previous studies [25, 41–43], catalyst deactivation was
mainly due to the chemisorption of chloride onto the
active sites. In our study, the addition of a small amount
of NaOH can effectively neutralized the HCl formatted in
the reaction and avoided the poisoning of Pd sites.
Moreover, Pd/Ni–B bimetallic catalysts exhibited better
capacity to resist poisoning than Ni–B catalysts, which
could be attributed to the presence of Pd species. In
Pd/Ni–B catalysts, Pd was the main active sites and
activated H2 to active H atoms. Active H combined
quickly with Cl and HCl formatted, then neutralized with
NaOH in the solution and separated from the surface of
the catalyst, which avoided the deactivation of the active
sites. In conclusion, the promoting effect of Pd species
ensured the Pd/Ni–B catalysts with better stability than
Ni–B catalysts.
Fig. 6 The dynamics of the 4-chlorophenol hydrodechlorination
reaction over the Pd/Ni–B catalysts
The Pd/Ni–B catalyst treated at 473 K demonstrated the
highest reaction velocity. Higher treatment temperatures
(573 and 673 K) reduced the reaction activity of catalyst,
which was consistent with the results of Ni–B catalysts.
Researches on the XPS spectra of Ni 2p, Pd 3d, and B 1s
for Pd/Ni–B catalysts [32] demonstrated that there was
electron transfer between Pd, Ni, and B and the content of
Pd and B on the catalyst surface reduced as the treatment
temperature increasing. They confirmed that the decrease
of Pd content was not due to the agglomeration of Pd
species, but because of the Pd species diffused into the
inner surface of Ni–B, then surface alloy occurred. The Pd
species dispersed better, which indicating that proper
heating treatment could promote the interaction between
every component and facilitate the formation of surface
alloy, and the diffusion process promoted the high disper-
sion of external Pd atoms. Pd/Ni–B (673 K) catalysts
3.2.3 The Dynamics of the Reaction
The rate of transformation of 4-chlorophenol is determined
from the pseudo-first-order rate law [44] (Eq. 2), where
C is the concentration of 4-chlorophenol
dC
ꢁ
¼ kobs
C
ð2Þ
dt
(ppm), t is the time (min) and kobs is the reaction rate
constants (/min). Then by the method of linear regression
(as shown in Figs. 5 and 6), kobs was obtained from the
Table 2 Hydrodechlorination stability of Ni–B (473 K) and Pd/Ni–B (473 K)
Samples
Ni–B
Fresh
Recycle 1
Recycle 2
Recycle 3
Recycle 4
Recycle 5
kobs (/min)a
R2
Conversion (%)b
kobs (/min)a
R2
0.2501
0.9968
100
0.1280
0.9955
93.25
0.3074
0.9901
100
0.0369
0.9945
50.47
0.0086
0.9918
15.79
–
–
–
–
–
–
Pd/Ni–B
0.3666
0.9960
100
0.2754
0.9838
95.16
0.1947
0.9811
91.65
0.1515
0.9699
75.84
0.0911
0.9660
63.31
Conversion (%)b
a
The reaction rate constant
b
Conversion after reacting for 30 min
123

798
C. Sun et al.
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slope of the straight line. The first 10 min were the intro-
duction period of the reaction, which included the
adsorption of hydrogen gas and the reactant on the surface
of the catalysts, therefore, the data before 10 min was
neglected (t0 = t - 10).
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to be 0.1089 (298 K), 0.1333 (373 K), 0.3368 (473 K),
0.1968 (573 K), and 0.0015 (673 K)/min, whereas the kobs
of the five Pd/Ni–B catalysts were 0.1463, 0.2383, 0.3666,
0.3335, and 0.1082/min, respectively. It manifested that the
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4 Conclusions
We have prepared a Pd on Ni–B catalyst with the Pd
loading of 0.96 wt% by replacement method, in which the
Pd species were characterized as small size and high dis-
persion. For the series of Pd/Ni–B catalysts with a heating
treatment, the one heated at 473 K could achieve complete
dechlorination of 4-CP within 30 min and exhibit the
highest reaction rate constant (kobs = 0.3666/min) because
of strong surface interaction among Pd, Ni, and B elements.
Such a catalyst also had a high resistance to chlorine
deactivation and could keep stable in the first four recycles.
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A 367:70
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Acknowledgments The present study was partly supported by the
Natural Sciences Foundation of Tianjin (10JCYBJC04400) and MOE
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