Hydrodehalogenation of Polyhalogenated Aromatics Catalyzed by NiPd Nanoparticles Supported on Nitrogen-Doped Graphene

Article abstract of DOI:10.1002/cssc.201800289

Ni₃₀Pd₇₀ nanoparticles supported on nitrogen-doped graphene (NG) acts as a catalyst for the hydrodehalogenation of halogenated aromatics under mild reaction conditions. It reduces mono- or dichloroarenes to the corresponding dehalogenated arenes in >90 % yield in 10 % aqueous isopropanol solvent at or below 50 °C within 5 h. Tests on a variety of substrates containing various functional groups show that the catalyst is selective for reduction of C?Cl and C?Br bonds. In addition, this catalyst completely hydrodehalogenates high-concentration solutions of dioxin, polychlorinated biphenyls, chloroaromatic constituents of the defoliant agent orange, and polybrominated diphenyl ethers in 12 h. The catalyst is reusable and shows no morphological or compositional changes after 5 cycles. This methodology offers a powerful, low-cost, and safe technology for the degradation of polyhalogenated aromatics, and may be useful for preventing proliferation of these toxins in the environment from causing serious health issues.

Full text of DOI:10.1002/cssc.201800289

Accepted Article
Title: Hydrodehalogenation of polyhalogenated aromatics catalyzed by
NiPd nanoparticles supported on nitrogen-doped graphene
Authors: Xuefeng Guo, Chao Yu, Zhouyang Yin, Shouheng Sun, and
Christopher Takakazu Seto
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201800289
Link to VoR: http://dx.doi.org/10.1002/cssc.201800289
A Journal of
www.chemsuschem.org

ChemSusChem
10.1002/cssc.201800289
COMMUNICATION
Hydrodehalogenation of polyhalogenated aromatics catalyzed by
NiPd nanoparticles supported on nitrogen-doped graphene
†
†
Xuefeng Guo , Chao Yu , Zhouyang Yin, Shouheng Sun* and Christopher T. Seto*
Abstract: We report
a
Ni30Pd70/nitrogen-doped graphene (NG)
2
with water to generate H for the subsequent Pd catalyzed-
catalyst that hydrodehalogenates halogenated aromatics under mild
reaction conditions. It reduces mono- or dichloroarenes to the
corresponding dehalogenated arenes in >90% yield in 10% aqueous
isopropanol solvent at or below 50°C within 5 hours. Tests on a
variety of substrates containing various functional groups show that
the catalyst is selective for reduction of C-Cl and C-Br bonds. In
addition, this catalyst completely hydrodehalogenates high
concentration solutions of dioxin, polychlorinated biphenyls (PCBs),
chloroaromatic constituents of the defoliant agent orange, and
polybrominated diphenyl ethers (PBDEs) in 12 hours. The catalyst is
reusable and shows no morphological or compositional changes
after 5 cycles. This methodology offers a powerful, low-cost and safe
technology for the degradation of polyhalogenated aromatics, and
may be useful for preventing proliferation of these toxins in the
environment from causing serious health issues.
hydrodechlorination reaction. In this process, Fe(0) is oxidized
and must be regenerated by a stronger reducing agent such as
sodium borohydride for the catalysis to proceed. Still, the
composite catalyst is not efficient for the dechlorination of high
concentrations of PHAs. Supported transition metal catalysts
have also been developed for hydrodehalogenation reactions.[11]
However, these reactions often use pressured hydrogen gas,
which makes them difficult to apply outside of the lab to
remediate polluted soil or water. As part of the development of
3 3
the hydrogen economy, ammonia borane (AB, H NBH ) has
emerged as an appealing sustainable fuel source because it is a
solid with a high hydrogen storage capacity. In addition, energy-
efficient chemical processes have been developed to regenerate
AB from its dehydrogenation products, making it an attractive
alternative to H
based NPs catalyze the dehydrogenation of AB for subsequent
hydrogenation of nitro compounds (R-NO ) to amines (RNH
).[13]
2
gas for hydrodehalogenation reactions.[12] Pd-
2
2
Polyhalogenated aromatics (PHAs), such as polychlorinated
biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs),
are a class of persistent organic pollutants that adversely affect
human health. Due to the stability of CAr-Cl (97.1 kcal/mol) and
Combining the Pd-catalyzed CAr-X reduction with the AB-initiated
transfer hydrogenation, here we report an efficient NiPd
nanoparticle (NP) catalyst for hydrodehalogenation of high
concentrations of chlorinated and brominated aromatics to the
corresponding aromatics in near quantitative yield. The NP
catalyst is comprised of 3 nm NiPd NPs assembled on nitrogen-
doped graphene (NG). It catalyzes the one-pot dehydrogenation
of AB and subsequent hydrodehalogenation of halogenated
aromatics in 10% aqueous isopropanol at or below 50°C. It is
C
Ar-Br (84.0 kcal/mol) bonds,[1] these PHAs are extremely
difficult to degrade in the natural environment, and can
accumulate and pass from one organism to another through the
food chain.[2] Activation of CAr-X (X = Cl or Br) bonds to achieve
full conversion to CAr-H is the key step in PHA degradation.
Conventional methods to accomplish this transformation rely on
hydrodehalogenation reactions in the presence of a catalyst with
effective for converting
CAr-X to
CAr-H, not only for
monohalogenated aromatics, but also for PHAs, including PCBs
and PBDEs.
2
either isopropanol or pressurized H as the hydrogen source.
Transition metal complexes of Pd,[3] Rh,[4] Ni,[5] Co,[6] or Fe,[7] are
often selected as hydrodehalogenation catalysts under
homogeneous reaction conditions, but these complexes often
show limited stability and re-usability. For example, a Rh[4a]
catalyst requires strong base (tBuOK), high temperature (100
We first tested MPd (M = Ni, Co, Fe) NP catalysts for AB-
initiated CAr-Cl conversion to CAr-H. 3-4 nm MPd NPs were first
prepared as shown in Figure S1.[14] We deposited these NPs
onto the common carbon (C) or graphene (G) supports (Figure
S2) and studied their roles in catalyzing AB-initiated
hydrodechlorination of chlorobenzene. We found NiPd NPs to be
more active than either CoPd or FePd. To further enhance NiPd
catalysis, we deposited these NPs on nitrogen-doped graphene
(NG)[15] for NPs to be better anchored against aggregation via
pyridine-N coordination. In the catalytic reaction, the NG serves
as a NP anchor, while NG and AB neutralize the HCl generated
during the reaction, enhancing catalysis and stabilizing the
catalyst. We assembled 3 nm Ni30Pd70 NPs on NG by mixing
and sonicating a hexane dispersion of NPs and NG. We tested
the assembly conditions and used a 1:1 w/w mixture of NPs/NG
to form a well-dispersed monolayer of NPs on the NG surface
°
C) and a long reaction time (24 h) to dehalogenate
chlorobenzene. Mild biological reagents have also been
developed to degrade halogenated pollutants, but these systems
require extremely long reaction times, and only work with low
concentrations of PHAs. For example, bio-remediation
processes using microalgae[8] or cyanobacteria[9] to dechlorinate
PHAs require weeks to months to achieve only partial
dechlorination of low concentrations of PHAs in soil.
Recently, a nanostructured composite of Fe(0) and Pd(0)
was studied as a catalyst to degrade PHAs in water.[10] Fe reacts
(
Figure 1a). We further prepared Ni30Pd70/C, Ni30Pd70/G,
Ni54Pd46/NG, Ni67Pd33/NG and Pd/NG (Table 1 and Figure 1b-
d). After testing the AB-initiated transfer hydrogenation and
[*]
X. Guo,[†] Dr. C. Yu,[†] Z. Yin, Prof. S. Sun and Prof. C. T. Seto
Department of Chemistry, Brown University
Providence, RI, 02912 (United State)
E-mail: christopher_seto@brown.edu
ssun@brown.edu
1
hydrodechlorination of chlorobenzene and dichlorobenzene, we
found Ni30Pd70/NG to be the most efficient catalyst for the
hydrodechlorination reaction (Table 1).
[†]
These authors contributed equally to this work
Supporting information for this article is given via a link at the end of
the document.
1
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201800289
COMMUNICATION
during the reaction, which is key to maintaining the pH of the
reaction mixture and to stabilizing the NiPd/NG catalyst.
Using Ni30Pd70/NG (abbreviated as NiPd/NG) as the catalyst,
we studied the time-dependent AB initiated hydrodechlorination
of chlorobenzene at 40°C. Figure S4 shows the concentration
changes of chlorobenzene and benzene over time in the
presence of
3
mol% NiPd/NG. The disappearance of
chlorobenzene and growth of benzene follows the exponential
concentration changes of a first order reaction, indicating that
the reaction proceeds without formation of other detectable
intermediates. Using these reaction conditions, we examined a
series of other mono-halogenated aromatic compounds (Table
2
). NiPd/NG is an efficient and selective hydrodechlorination
catalyst for these substrates. Chlorobenzene, 2-
chloronaphthylene and 3-chloropyridine are reduced in greater
than 94% yield (entries 1-3). The reaction is effective for
substrates with either electron-donating (entries 4-9, 13-14) or
electron-withdrawing groups (entries 10-12, 15). The conversion
is not sensitive to the position of the halogen atom relative to
other functional groups (entries 4-12). Hydroxyl, amine, amide,
and carboxylic acid groups are not reduced under the reaction
conditions. Furthermore, the reaction can be extended to
brominated substrates (entries 16-21).
Figure 1. a) TEM image of 3.0 ± 0.1 nm Ni30Pd70/NG, b) TEM image of 3.4 ±
0.3 nm Ni54Pd46/NG, c) TEM image of 3.8 ± 0.2 nm Ni67Pd33/NG, d) TEM
image of 4.0 ± 0.2 nm Pd/NG. These NiPd/NG samples were prepared by
mixing hexane dispersions of NiPd NPs and NG in 1:1 mass ratios. Each TEM
sample was prepared by adding a drop of hexane dispersion of NiPd/NG on
an amorphous carbon coated Cu grid followed by hexane evaporation under
ambient conditions.
Table 2. Hydrodehalogenation of mono-halogen substituted compounds[a]
X
3 mol% NiPd/NG, H3NBH3
H
R
R
1
0% aqueous isopropanol, 40 °C, 3h
Table 1. Hydrodehalogenation of dichlorobenzene catalyzed by Pd-based
Entry
1
Ar-X
Yield[b] (%)
Entry
2
Ar-X
Yield[b] (%) Entry
Ar-X
Yield[b] (%)
98[c]
catalysts on different carbon supports[a]
Cl
Cl
Cl
Cl
99[c]
98[c]
94[c]
99[c]
3
6
3
mol% catalyst, H NBH3
H
H
N
Cl
Cl
3
Cl
Cl
Cl
1
0% aqueous isopropanol, 50 °C, 5h
4
7
5
8
99[c]
93
Yield[b] (%)
Cl
OH
Cl
Entry
Catalyst
91
97
91
97
9
HO
OH
1
2
3
4
5
6
Ni30Pd70/C
Ni30Pd70/G
Ni30Pd70/NG
81
Cl
Cl
Cl
84
99
69
72
44
10
11
14
17
20
12
15
18
21
98
COOH
Cl
HOOC
COOH
Cl
O
Cl
H
N
1
1
3
6
87
90
92
Pd/NG
H2N
O
Ni54Pd46/NG
Br
Br
Br
Br
99[c]
97[c]
99[c]
Ni67Pd33/NG
N
Br
Br
COOH
[a] Reaction conditions: dichlorobenzene (1 mmol), ammonia borane (6 mmol),
19
99[c]
96
97
10% aqueous isopropanol (3.0 mL) and catalyst (3 mol %) for 5 h at 50 °C. [b]
HO
Yields determined by GC-MS.
[a] Reaction conditions: aryl halides (1 mmol), ammonia borane (2 mmol), 10%
To demonstrate that AB is the source of hydrogen in the
reactions, and not isopropanol, we performed the
hydrodechlorination of dichlorobenzene in 10% aqueous
isopropanol without adding AB and found the yield of
dechlorinated products to be less than 3%. We also tested the
reaction in aqueous AB solution without adding isopropanol as a
cosolvent, and obtained a 76% yield of benzene. The reduction
in yield from 99% (10% aqueous isopropanol solvent) to 76%
aqueous isopropanol (3.0 mL) and NiPd/NG (3 mol%) for 3 h at 40 °C. [b]
Isolated yield except where noted otherwise. [c] Yield determined by GC−MS.
Encouraged by the general applicability of NiPd/NG to
mono-halogenated substrates, we extended the study to
substrates containing multiple Cl or Br atoms. Using 1,2-
dicholorobenzene as an example, we examined its time-
dependent hydrodechlorination at 50°C. As shown in Figure S5,
the first hour of the reaction gives exponential decay of
dichlorobenzene accompanied by an increase in both the
chlorobenzene and benzene concentrations. This pattern is
typical of a stepwise process in which the two chlorine atoms are
reduced sequentially. The chlorobenzene concentration reaches
a maximum at two hours, and subsequently decreases with a
corresponding increase in the concentration of the benzene final
product. The reaction is complete after 5 hours. During the
(
pure water as the solvent) is likely caused by the poor solubility
of dichlorobenzene in pure water. When 10% isopropanol was
added to improve the dichlorobenzene solubility, the reaction
was completed within 5 hours and all the dichlorobenzene was
converted to benzene. AB serves as both the hydrogen source,
and as a base to neutralize the hydrochloric acid generated
2
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201800289
COMMUNICATION
course of the reaction we do not detect any other intermediates
by GC-MS. Using these reaction conditions, we examined other
polyhalogenated substrates (Table 3). Dichlorinated substrates
In conclusion, the NiPd/NG catalyst reported here shows
superior performance for the hydrodehalogenation of PHAs
under mild and environmentally friendly reaction conditions.
Dehalogenation reactions often require strong bases, strong
reducing agents and harsh reaction conditions including high
temperatures. In contrast, this NiPd/NG system uses ammonia
borane as the hydrogen source and base, and an aqueous
solvent system. The reaction is compatible with a variety of
functional groups including hydroxyl groups, amines, amides
and carboxylic acids. Under these mild conditions, the NiPd/NG
catalyst promotes the complete dehalogenation of several
severe environmental contaminants including the components of
agent orange, dioxins, PCBs and PBDEs, which are extremely
difficult to decontaminate using conventional methods. This
concept of exploiting nanoparticles for green chemistry
applications may provide a promising avenue for the rational
design and assembly of nanostructured catalysts for solving
long-standing problems in environmental chemistry.
(
entries 1-6) are dehalogenated to their parent compounds in
high yield. The environmental pollutants 2,4-
dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid
and 2,3,7,8-tetrachlorodibenzodioxin (entries 7-9) are all
completely dechlorinated in high yield under the reaction
conditions. We also examined five chlorinated biphenyl
substrates (entries 10-14). Compounds 10-12 that contain
chlorine atoms meta and/or para to the biphenyl bond are fully
reduced under the standard conditions. In contrast, substrates
with chlorine atoms ortho to the biphenyl bond are reduced more
slowly (entries 13 and 14). These are the most sterically
hindered positions in the molecule, and the ortho chlorine
substituents enforce a perpendicular geometry of the two phenyl
rings. These substrates require 12 hours to achieve complete
reduction of all of the C-Cl bonds. In a similar manner, the four
bromine atoms in PBDE (entry 12) that are ortho to the ether
oxygen reside in sterically hindered positions, and PBDE also
requires 12 hours for full dehalogenation.
Experimental Section
General Procedure for the Hydrodehalogenation Reactions: The aryl
halide (1 mmol), NPs/NG (10 mg, 3 mol %), NH3BH3 (3 mmol) and 10%
aqueous isopropanol (3 mL) were stirred in a 10 mL sealed tube at 50 °C
for 5 hours. After the reaction was complete, the catalyst was filtered and
the mixture was extracted with ethyl acetate. The organic phase was
evaporated under vacuum and purified by flash column chromatography
(hexane/ethyl acetate = 8:1) to give the final product.
Table 3. Hydrodehalogenation of multi-halogen substrates[a]
X
X
3
mol% NiPd/NG, H3NBH3
0% aqueous isopropanol, 50 °C, 5h
Yield[b] (%) Entry
H
H
R
R
1
Entry
1
Ar-X
Yield[b] (%) Entry
Ar-X
Ar-X
Yield[b] (%)
98[c]
Cl
Cl
Cl
Cl
Cl
98[c]
2
5
97[c]
3
6
Cl
Cl
Cl
Cl
Cl
Acknowledgements
Cl
Cl
4
7
OH
O
97
90
93
HO
The work was supported by the U.S. Army Research Laboratory
and the U.S. Army Research Office under grant W911NF-15-1-
0147 and by Strem Chemicals.
O
OH
O
Cl
Cl
O
O
Cl
O
Cl
Cl
O
92[c,d]
OH 90
8
OH
Cl
87
9
Cl
Cl
Cl
Cl
Cl
Cl
Keywords: Dehalogenation • Heterogeneous catalyst •
1
1
0
3
Cl
99[c]
11
99[c]
12
98[c]
Cl
Cl
Cl
Cl
Nanoparticles • Hydrogen Transfer • Ammonia Borane •
Br
Br
Cl Cl
Cl Cl
Cl
Cl
Cl Cl
Cl Cl
Cl
Cl
Br
Br
O
Br
97[c,e] 14 Cl
Cl 94[c,e,f] 15
97[c,e]
Br
Br Br
Br
Br
[1]
2]
S. J. Blanksby, G. B. Ellison, Accounts Chem. Res. 2003, 36, 255-263.
a) A. J. Jamieson, T. Malkocs, S. B. Piertney, T. Fujii, Z. Zhang, Nat.
Ecol. Evol. 2017, 1, 51; b) M. Bartrons, J. Catalan, J. Penuelas, Sci.
Rep. 2016, 6, 25446; c) B. C. Kelly, M. G. Ikonomou, J. D. Blair, A. E.
Morin, F. A. P. C. Gobas, Science 2007, 317, 236-239.
[
[a] Reaction conditions: organic halides (1 mmol), ammonia borane (3.0 equiv
with respect to halogen atoms), 10% aqueous isopropanol (3.0 mL) and
NiPd/NG (3 mol%) at 50 °C. [b] Isolated yield except where noted. [c] Yield
determined by GC−MS. [d] 0.003 mmol (1 mg) of dioxin was used in the
reaction. [e] Reaction was run for 12 h. [f] 0.04 mmol of decachlorobiphenyl
was used in the reaction.
[3]
[4]
a) A. Pyo, S. Kim, M. R. Kumar, A. Byeun, M. S. Eom, M. S. Han, S.
Lee, Tetrahedron Lett. 2013, 54, 5207-5210; b) N. Iranpoor, H.
Firouzabadi, R. Azadi, J. Organomet. Chem. 2010, 695, 887-890; c) O.
Navarro, N. Marion, Y. Oonishi, R. A. Kelly, S. P. Nolan, J. Org. Chem.
2006, 71, 685-692.
We have also examined if the NiPd/NG catalyst can be
recycled through several sequential hydrodehalogenation
reactions. We measured the stability of the catalyst by observing
NiPd NP morphology and composition changes before and after
the hydrodechlorination of dichlorobenzene. After the first
reaction was complete, we separated the catalyst from the
reaction solution by filtration, and washed it with water and
isopropanol. We then re-used it in the next hydrodehalogenation
reaction. Our tests showed that after the 5th reaction/separation
cycle, the catalyst had no obvious loss in activity and the product
a) T. J. You, Z. R. Wang, J. J. Chen, Y. Z. Xia, J Org Chem 2017, 82,
1340-1346; b) G. Lazaro, V. Polo, F. J. Fernandez-Alvarez, P. Garcia-
Orduna, F. J. Lahoz, M. Iglesias, J. J. Perez-Torrente, L. A. Oro,
Chemsuschem 2015, 8, 495-503; c) K. Fujita, M. Owaki, R. Yamaguchi,
Chem. Commun. 2002, 2964-2965.
[
5]
6]
K. Mochizuki, M. Suzuki, Inorg. Chem. Commun. 2011, 14, 902-905.
K. S. Chan, C. R. Liu, K. L. Wong, Tetrahedron Lett. 2015, 56, 2728-
2731.
[
[7]
a) W. M. Czaplik, S. Grupe, M. Mayer, A. Jacobi von Wangelin, Chem.
Commun. 2010, 46, 6350-6352; b) H. Q. Guo, K. Kanno, T. Takahashi,
Chem. Lett. 2004, 33, 1356-1357.
yield remained >91% (Table S1). TEM and ICP-AES analyses of
the catalyst after the 5th reaction cycle showed that the NPs
[
8]
9]
a) A. Papazi, K. Kotzabasis, Plos One 2013, 8; b) A. Papazi, E.
Andronis, N. E. Ioannidis, N. Chaniotakis, K. Kotzabasis, Plos One
display no obvious morphology changes or aggregation (Figure
S6), and the NP composition is stabilized at Ni28Pd72. These
results suggest that NG offers the necessary anchoring sites to
stabilize NiPd NPs against aggregation. The combination of NG
and AB neutralizes the hydrochloric acid generated during the
reaction, and prevents Ni from leaching out of the NiPd NPs.
2012, 7; c) M. Cvancarova, Z. Kresinova, A. Filipova, S. Covino, T.
Cajthaml, Chemosphere 2012, 88, 1317-1323.
[
a) H. J. Zhang, X. J. Jiang, L. P. Lu, W. F. Xiao, Plos One 2015, 10; b)
H. J. Zhang, C. M. Hu, X. Y. Jia, Y. Xu, C. J. Wu, L. N. Chen, F. P.
Wang, J. Appl. Phycol. 2012, 24, 221-225.
3
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201800289
COMMUNICATION
[
10] a) F. D. Kopinke, Environ. Sci. Technol. 2012, 46, 11467-11468; b) Y.
Zhuang, S. Ahn, A. L. Seyfferth, Y. Masue-Slowey, S. Fendorf, R. G.
Luthy, Environ. Sci. Technol. 2011, 45, 4896-4903.
[
11] a) A. Goswami, A. K. Rathi, C. Aparicio, O. Tomanec, M. Petr, R.
Pocklanova, M. B. Gawande, R. S. Varma, R. Zboril, Acs Appl. Mater.
Inter. 2017, 9, 2815-2824; b) H. P. Rong, S. F. Cai, Z. Q. Niu, Y. D. Li,
Acs. Catal. 2013, 3, 1560-1563; c) Y. Shiraishi, Y. Takeda, Y. Sugano,
S. Ichikawa, S. Tanaka, T. Hirai, Chem. Commun. 2011, 47, 7863-7865.
12] a) A. D. Sutton, A. K. Burrell, D. A. Dixon, E. B. Garner, J. C. Gordon, T.
Nakagawa, K. C. Ott, P. Robinson, M. Vasiliu, Science 2011, 331,
[
1
426-1429; b) B. L. Davis, D. A. Dixon, E. B. Garner, J. C. Gordon, M.
H. Matus, B. Scott, F. H. Stephens, Angew. Chem. Int. Ed. 2009, 48,
812-6816; c) S. Hausdorf, F. Baitalow, G. Wolf, F. O. Mertens, Int. J.
6
Hydrogen. Energ. 2008, 33, 608-614
[
13] a) C. Yu, J. J. Fu, M. Muzzio, T. L. Shen, D. Su, J. J. Zhu, S. H. Sun,
Chem. Mater. 2017, 29, 1413-1418; b) W. W. Zhan, Q. L. Zhu, Q. Xu,
Acs. Catal. 2016, 6, 6892-6905; c) H. Goksu, S. F. Ho, O. Metin, K.
Korkmaz, A. M. Garcia, M. S. Gultekin, S. H. Sun, Acs. Catal. 2014, 4,
1777-1782. d) C. Yu, X. F. Guo, Z. Xi, M. Muzzio, Z. Y. Yin, B. Shen, J.
R. Li, C. T. Seto, S. H. Sun, J. Am. Chem. Soc. 2017, 139, 5712-5715;
e) C. Yu, X. Guo, M. Shen, B. Shen, M. Muzzio, Z. Yin, Q. Li, Z. Xi, J. Li,
C. T. Seto, S. Sun, Angew. Chem. Int. Ed., 2018, 57, 451-455.
[
14] a) O. Metin, A. Mendoza-Garcia, D. Dalmizrak, M. S. Gultekin, S. H.
Sun, Catal. Sci. Technol. 2016, 6, 6137-6143; b) S. F. Ho, A. Mendoza-
Garcia, S. Guo, K. He, D. Su, S. Liu, Ö. Metin, S. Sun, Nanoscale 2014,
6, 6970-6973.
[
15] a) H. B. Yang, J. W. Miao, S. F. Hung, J. Z. Chen, H. B. Tao, X. Z.
Wang, L. P. Zhang, R. Chen, J. J. Gao, H. M. Chen, L. M. Dai, B. Liu,
Sci. Adv. 2016, 2, e1501122; b) J. L. Shui, M. Wang, F. Du, L. M. Dai,
Sci. Adv. 2015, 1, e1400129.
4
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201800289
COMMUNICATION
COMMUNICATION
†
†
A NiPd/NG catalyst was
developed for the
Xuefeng Guo , Chao Yu ,
Zhouyang Yin, Shouheng Sun*
and Christopher T. Seto*
hydrodehalogenation of
polyhalogenated aromatics
under mild and environmentally
friendly conditions. The catalyst
promotes the complete
Page No. – Page No.
Hydrodehalogenation of
polyhalogenated aromatics
catalyzed by NiPd nanoparticles
supported on nitrogen-doped
graphene
dehalogenation of several
severe environmental
contaminants including the
components of agent orange,
dioxins, PCBs and PBDEs.
5
This article is protected by copyright. All rights reserved.