A fixed-bed photoreactor using conjugated nanoporous polymer-coated glass fibers for visible light-promoted continuous photoredox reactions

Article abstract of DOI:10.1039/c6ta10768k

Here, we report on a fixed-bed photoreactor containing conjugated nanoporous polymer-coated glass fibers for visible light-promoted, heterogeneous photoredox reactions in a continuous flow system. A thin film of nanoporous polybenzothiadiazole with a thickness of ca. 80 nm was fabricated directly on the glass fiber with an effective catalyst content of ca. 3.2 wt%. The photocatalytic dehalogenation reaction of α-bromoacetophenones and the enantioselective α-alkylation of aldehydes were carried out in the fixed-bed photoreactor with comparable efficiencies to the state-of-art transition metal-based photocatalysts.

Full text of DOI:10.1039/c6ta10768k

View Article Online
View Journal
Journal of
M at erials Chemistry A
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: W. Huang, B. C.
Ma, D. Wang, Z. J. Wang, R. li, L. Wang, K. Landfester and K. A. I. Zhang, J. Mater. Chem. A, 2017, DOI:
1
0.1039/C6TA10768K.
Volume
4
Number
1
7
January 2016 Pages 1–330
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Journal of
Materials Chemistry A
Accepted Manuscripts are published online shortly after
Materials for energy and sustainability
www.rsc.org/MaterialsA
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
rsc.li/materials-a

Please do not adjust margins
Journal of Materials Chemistry A
Page 1 of 6
View Article Online
DOI: 10.1039/C6TA10768K
Journal Name
COMMUNICATION
Fixed-bed photoreactor using conjugated nanoporous polymer-
coated glass fibers for visible light-promoted continuous
photoredox reaction
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Wei Huang, Beatriz Chiyin Ma, Di Wang, Zi Jun Wang, Run Li, Lei Wang, Katharina Landfester, and
Kai A. I Zhang*
www.rsc.org/
Here, we report on a fix-bed photoreactor containing conjugated and reuse technique from the liquid reaction media, given the
nanoporous polymers-coated glass fibers for visible light- fact that the post-separation of these micro- or nanoscale-
promoted, heterogeneous photoredox reactions in a continuous sized heterogeneous catalysts is indeed a tedious and costly
2
3, 24
flow system. A thin film of nanoporous polybenzothiadiazole with process.
From this point of view, continuous flow synthesis
a thickness of ca. 80 nm was fabricated directly on the glass fiber using fix-bed catalytic systems could serve as an attractive
with an effective catalyst content of ca. 3.2 wt%. Photocatalytic alternative via efficiently avoiding additional separation
dehalogenation reaction of α-bromoacetophenones and procedures of the catalysts and accelerating further catalytic
enantioselective α-alkylation of aldehydes were carried out in the processes.
Recent reports showed that inorganic
have been immobilized in a
microreactor for photocatalytic alkylation of benzylamine with
fix-bed photoreactor with comparable efficiencies as the state-of- photocatalysts such as TiO
2
art transition metal-based photocatalyts.
2
5
high yield and selectivity, or employment of Ag/AgCl
nanowires-coated polymer sponges for continuous water
Visible light-active, heterogeneous, photocatalysts have been
developed as a powerful tool in organic synthesis due to their
broad absorption in the visible range, efficient recyclability and
2
6
purification under sunlight. As metal-free systems, only few
examples of monolithic conjugated porous polymers for visible
light-promoted photoredox reactions in the continuous flow
1
-4
excellent photostability.
Compared to the noble metal-
1
5, 27
containing catalytic systems, pure organic and metal-free
photocatalysts have gained enormous attention regarding to
their low cost, synthetic diversity and easily tunable
system were reported.
However, due to the usually high
absorption efficiency of the photoactive catalyst material, the
light penetration path is limited within the monolithic
photocatalyst. And a considerable part inside the polymer
materials could not contribute to the photocatalytic reaction.
To fully make use of the photocatalyst and achieve high
materials economy in the continuous flow synthesis, an
enhanced photocatalyst design is strongly needed.
5
-8
photoredox potentials.
Among the recent metal-free
heterogeneous photocatalytic systems, carbon nitrides, a
state-of-art example, have been widely employed as efficient
metal-free photocatalysts with their modifiable electronic and
9
-12
optical properties.
semiconductor-based photocatalysts, conjugated nanoporous
polymers, which combine visible light-active -electron
Another emerging class of organic
Here, we report a facile design of a fix-bed photoreactor
containing conjugated nanoporous polymers-coated glass
fibers for visible light-promoted, heterogeneous photoredox
π
backbone and highly porous interfacial properties, has recently
been introduced as stable heterogeneous photocatalysts for
organic transformation reactions under irradiation of visible
light. Recent research activities showed their use in a vast
number of visible light-promoted photocatalytic reactions such
as oxygen activation, selective oxidation of amine and sulfides
reactions in
a continuous flow system. A conjugated
nanoporous polymer film with a thickness of ca. 80 nm was
fabricated via directly polymerization on the glass fiber, with
an effective catalyst content of ca. 3.2 wt% of the photoactive
hybrid fiber. The design of the photoreactor could not only
effectively avoid the aggregation of the heterogeneous
photocatalysts, but also greatly improve the light penetration
throughout the reaction medium with an efficient catalyst
material economy. The advanced photocatalytic activity and
stability of the photoreactor was demonstrated in the
reductive dehalogenation of haloketones and enantioselective
α-alkylation of aliphatic aldehydes as model reactions.
1
3-22
and hydrogen evolution from water.
Beside the material choice, a more industrially relevant
concept in catalytic processes is the efficient catalyst removal
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 2 of 6
View Article Online
DOI: 10.1039/C6TA10768K
COMMUNICATION
Journal Name
Additionally, the reaction mechanism of both photocatalytic The Fourier transform infrared (FTIR) spectrum of the polymer
redox reactions was also described.
is displayed in Figure 2a. The typical single of internal alkynes (-
C
1
≡C-) and alkenes (-C=C-) were observed at around 2202 and
-
1
30
662 cm , respectively. Signals at 1480 and 1570 cm can be
-1
assigned to the skeleton stretching and vibration modes of the
C=N- and =N-S- groups of the BT units in the polymer
–
backbone. The UV/Vis diffuse reflection (DR) spectrum of the
B-BT-coated glass fibers showed a broad absorption range in
the visible region up to approximately 600 nm with a
maximum at 420 nm (Figure 2b). In comparison, only a weak
absorption at ultraviolet range was observed for bare glass
fibers. From the Kubelka-Munk-transformed reflectance
spectrum, an optical band gap of 2.48 eV could be estimated
(Figure 2c). For organic semiconductor-based phtocatalytic
systems, the energetic band positions represent their light-
induced redox potentials. Cyclic voltrammetry (CV)
measurement was carried out to further reveal the highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) positions of B-BT. As shown in Figure
S4, a reduction onset potential of -1.06 V vs. SCE could be
determined. Correspondingly, the HOMO level was derived to
be +1.42 V (vs. SCE) via extracting the LUMO value from the
optical band gap (Figure 2d). Notably, the derived
oxidation/reduction potentials of B-BT are comparable to
those of well-developed organometal complex-based
Figure 1. a) An illustrated setup of fix-bed photoreactor using
conjugated nanoporous polymer-coated glass fibers. b) Molecular
structure of B-BT. c) Photography of pure glass fibers and d) B-BT-
coated glass fibers. e) SEM images of pure glass fiber and f-h) B-BT-
coated glass fibers.
The design of the fixed-bed photoreactor containing the
conjugated nanoporous polymer-coated glass fibers is
illustrated in Figure 1a
.
Commercially available glass fibers
3+
photocatalysts such as [Ru(bpy)3] (+1.29 V vs. SCE) and
31
with a dimeter of ca. 10 μm were used as the catalyst support.
A conjugated nanoporous poly-benzothiadiazle network (B-
2+
[Rubpy]
(-0.81
V
vs. SCE),
indicating promising
photocatalytic capability of the polymer network. The electron
paramagnetic resonance (EPR) spectra of B-BT showed an
enhanced signal under visible light irradiation (λ>420 nm)
compared to the one taken in the dark, signifying the
generation of photo-induced electron-hole pairs in the
polymer network (Figure 2e).
1
3, 28
BT),
was coated on the surface of glass fiber via direct
polymerization reaction of 1,3,5-triethynylbenzene and 4,7-
dibromo-2,13,-benzothiadiazole using Sonogashira cross-
coupling method. The molecular structure of B-BT is shown in
Figure 1b. The synthetic details are described in the Electronic
Supplementary Information (ESI). As displayed in Figure 1c and
1d, after polymerization, the color of glass fiber changed from
colorless to bright yellow, indicating the successful coating and
uniform distribution of the polymer film on the surface of the
glass fibers. The scanning electron microscopy (SEM) further
verified the successful coating of a dense polymer layer of B-BT
on the glass fiber with a tough surface compared to the rather
smoother surface of the glass fibers (Figure 1e-h). The
thickness of the polymer layer was estimated to be 80 nm
(Figure 1g).The amount of the polymer B-BT on the glass fibers
was estimated to be 3.2 wt% after the calcination at 450 °C in
air.
2
9
13
Similar to our previous reports, the solid state C CP/MAS
NMR spectrum (Figure S1 in ESI) of B-BT showed typical signals
at 80 and 96 ppm, which could be assigned to the sp carbon
atoms in the triple bonds. The chemical shifts between 116
and 154 ppm were attributed to the aromatic carbons in the
BT units along with the central phenyl rings. The Brunauer-
Emment-Teller (BET) surface area of B-BT was measured to be
2
3
Figure 2. a) FT-IR spectrum of B-BT, b) Diffuse reflectance (DR) UV/Vis
spectra of pure and B-BT-coated glass fiber, c) Kubelka-Munk-
transformed reflectance spectra of B-BT, d) HOMO and LUMO
positions of B-BT, and e) EPR spectra of B-BT in dark and under visible
light irradiation.
136 m /g with a pore volume of 0.16 cm /g and a pore
diameter of ca. 1.5 nm, respectively (Figure S2). Thermal
gravimetric analysis (TGA) of pure B-BT showed a high thermal
stability up to ~350 °C under nitrogen atmosphere (Figure S3).
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
Jou Pr nl e aa ls oe fd Mo an to et r ai ad lj su s Ct hm ea mr g ii sn ts ry A
View Article Online
DOI: 10.1039/C6TA10768K
Journal Name
COMMUNICATION
Scheme 1. Photocatalytic reduction dehalogenation of α-
bromoacetophenone derivatives in the fix-bed photorector under
visible light irradiation.
To investigate the feasibility of the photoreactor for
continuous flow photocatalytic reactions, we first investigated
the photoreductive dehalogenation reaction of α-
bromoacetophenones under visible light irradiation (λ>420 Table 1. Enantioseletive α-alkylation reactions in the continuous fix-bed photoreactor.
nm) as shown in Scheme 1. 200 mg of B-BT-coated glass fibers
(
ca. 6.4 mg pure B-BT) were loosely packed into a glass column
r= 0.35 cm, L= 7 cm), which was connected with fluorinated
(
ethylene propylene (FET) tubing (d = 8 nm). The typical setup is
shown in Figure S5. It could be determined that under a
constant flow rate of 0.5 ml/min,
a series of α-
entr
α-
t
conv.
ee
aldehyde
product
bromoacetophenone derivatives could be effectively
dehalogenated in a quantitative manner in all cases within two
hours. The catalytic efficiency of the photoreactor was
comparable with that of state-of-art transition metal-based
a)
b)
c)
y
bromoketone
[h]
[%]
[%]
3
2
1
12
96
83
photocatalysts such as [Ru(bpy) ] Cl , or organocatalysts
3
2
2
3
3
such as eosin Y. The high catalytic efficiency of the
photoreactor could most likely be attributed to the high
reductive potential of the conjugated nanoporous polymer B-
BT (-1.06 V vs. SCE), which was sufficient enough to reduce the
C-Br bond of the α-bromoacetophenone (Ered.= -0.78 V vs.
H
d
O
O
2
12
12
12
12
5
-
-
-
-
O
O
O
3
4
SCE). The mechanism presumably follows the proposed
5-38
3
pathway similar to previous reports,
which involved first
H
O
the mediation of one extracted electron from the sacrificial
agent (DIPEA) by the photogenerated hole and the electron
transfer from conductive band of B-BT to the α-
bromoacetophenone, resulting into the cleavage of C-Br bond
and the generation of phenone radical, which then abstracted
a proton from the Hantzsch ester to form the final product
e
O
O
3
12
19
20
O
O
H
O
f
O
O
4
O
O
(Figure S6).
O
O
We then tested the enantioselective α-alkylation reaction of
3
9
aldehydes developed by MacMillan et al. The results are
listed in Table 1. The model coupling reaction of diethyl-2-
bromomalonate and 3-phenylpropanal was obtained in a high
conversion of 96% and enantioselectivity of 83% (entry 1).
Control experiments conducted in the absence of catalyst fiber
or in dark showed dramatically decreased conversions of 5%
and 12%, respectively (entries 2 and 3), indicating the
indispensable roles of the catalyst and light for the
photocatalytic process. To further study the reaction
mechanism of the α-alkylation reaction and the specific role
played by the photogenerated electron/hole pair inside the B-
BT, several control experiments were conducted. For example,
by adding N,N-diisopropylethylamine as a hole scavenger into
the reaction mixture, the product was obtained with a
conversion of only 19% (entry 4). Similarly, the employment of
H
O
g
O
O
5
6
7
5
7
>99
98
89
93
8
10
15
78
83
93
95
2,6-di-tert-butyl-4-methylphenol as a radical scavenger led to a
reduced conversion of 20 % (entry 5). On the basis of the
above observation and previous reports, we propose a
plausible mechanism as displayed in Figure S7. The first half
reaction should be derived from the photocatalytic
dehalogenation reaction of the aforementioned α-
bromoacetophenones.
9
a)
Reaction conditions: 200 mg catalyst fibers (ca. 6.4 mg B-BT), α-bromo-
carbonyl compound (1.6 mmol), aldehyde (3.2 mmol), 2,6-lutidine (375 μl,
3.2 mmol) and (2R,5S)-2-tertbutyl-3,5-dimethylimidazolidin-4-one×HCl (66
b)
mg, 0.32 mmol), 10 ml DMF, white LED (λ>420 nm); conversion
1
c)
H NMR; enantioselectivity estimated according to
determined by
4
0
d)
e)
no photocatalyst; no light; N,N-diisopropylethylamine as
f)
literature;
hole scavenger; 2,6-di-tertbutyl-4-methylphenol as radical scavenger.
g)
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 4 of 6
View Article Online
DOI: 10.1039/C6TA10768K
COMMUNICATION
Journal Name
dehalogenation reaction of the α-bromoacetophenones, the
Under visible light irradiation, the photogenerated electron photocatalytic efficiency of the α-alkylation reactions in the
transfer from LUMO level of B-BT (Ered. = -1.06 V vs. SCE) to photoreactor with B-BT-coated glass fibers was comparable to
alkyl bromide (E1/2= -0.49 V vs. SCE) resulted into the C-Br those of transition metal-based homogenerous photocatalysts
4
.
4
cleavage and the formation of alkyl radical and bromide anion. such as [Ru(bpy)
3
]
2
Cl
2
We envision that the high
The alkyl radical then reacted with the intermediate enamine photocatalytic efficiency is not only attributed to the favorable
formed by the condensation of MacMillan catalyst and energy levels of the B-BT, but also the nanoscale thickness of
aldehyde in the organocatalytic cycle. The generated amine the catalyst, which is beneficial for light penetration and
radical (Eoxi. = 0.92 V vs. SCE) was oxidized by the efficient utilization of the photocatalyst during the reaction
photogenerated hole of B-BT (Eoxi. = 1.42 vs. SCE), yielding the process.
unstable imine cation that subsequently released the final Additionally, repeating experiments were conducted to
product and regenerated the photocatalyst back to the ground demonstrate the high stability and reusability of the
3
9
state. The formation of initial alkyl radicals could be photoreactors. As shown in Figure S11, The conversion of
determined by the electron paramagnetic resonance (EPR) model reaction could be repeated for five extra reaction cycles
trapping experiment in the presence of N-tert-butyl-α- without significantly suffering the catalytic efficiency. No
4
1
phenylnitrone (PBN) under visible light irradiation (Figure apparent changes of the UV/vis absorption spectra or SEM
S8). images of the B-BT-coated glass fibers could be observed
To further demonstrate the advantage of the photoreactor (Figure S12 and S13), demonstrating that the functionalization
design using B-BT-coated glass fibers, we then synthesized a method of the glass fibers by direct polymerization of the
nanoporous polymer (m-B-BT) containing the same backbone nanoporous polymer was indeed mechanically and chemically
4
2
structure of B-BT in the monolithic shape as comparison stable.
Figure S9). By investigating the α-alkylation reaction of
(
octanal with α-bromomalonate, a much lower catalytic
efficiency could be determined (90.3 % after 24 h), although a
tremendously large amount (100 mg) of the m-B-BT-based
catalyst was used. In comparison, using the B-BT-coated glass
fibers as photocatalyst, which only contain ca. 6.4 mg pure B-
BT, a quantitative conversion of the reaction could be achieved
within 5 h (entry 6 in Table 1). This is likely due to the high
absorption efficiency of the polymer, leading to a short light
penetration path within the polymer monolith, and the
photocatalytic reaction likely only occurred on the surface of
the monolith. A majority part inside the monolith m-B-BT did
not take part of the photocatalytic reaction and can be
considered “wasted” material.
Conclusions
In summary, we present a facile design of a fix-bed
photoreactor using visible light-active, conjugated nanoporous
polymer-coated the glass fibers. This easy immobilization of
the conjugated nanoporous polymer-based photocatalyst
afford an promising prospective to construct continuous flow
photocatalytic systems as an alternative to traditional metal-
based catalysts, which is desirable for industrial applications as
it effectively avoids the tedious and costly separation process
of the catalysts from the reaction mixture. High photocatalytic
efficiency of the fix-bed photoreactor was demonstrated in
visible light-promoted dehalogenation reaction of α-
bromoacetophenones and enantioselective α-alkylation of
aldehydes with comparable catalytic efficiency of that of the
state-of-art transition metal-based photocatalytic systems.
With the facile design and simple preparation principle and
high stability and reusability, we believe the fix-bed
photoreactor using conjugated nanoporous polymers could be
used in a wider range of visible light-promoted photoredox
reactions.
9
, 43
An extra comparison experiment with g-C
3
N
4
,
a state-of-art
metal-free photocatalyst showed that B-BT in the powder
shape could demonstrate a higher catalytic efficiency as shown
in Figure S11. It is worth to note that the photoreactor with B-
BT-coated glass fibers showed similar high catalytic efficiency
in continuous flow. Additionally, by investigating different
reaction temperatures from 0°C to 50°C, no significant
temperature effect could be observed (Table S1).
A modified turnover frequency (TOF) with respect of the
catalyst weight could be calculated, giving a TOF for the
References
-
1
-1
dehalogenation of α-bromoacetophenones as 0.08 mol h g ,
and for the α-alkylation of 3-phenylpropylaldehyde and α- 1.
bromomalonate (Entry 1) as 0.021 mol h g (see ESI).
To demonstrate the general applicability of the fix-bed 2.
X. Lang, X. Chen and J. Zhao, Chem. Soc. Rev., 2014, 43,
473-486.
T. Zhang and W. Lin, Chem. Soc. Rev., 2014, 43, 5982-
-1 -1
photoreactor, a series of α-alkylation reactions between
5993.
3
.
H. Kisch, Angew. Chem. Int. Ed., 2013, 52, 812-847.
X. Lang, W. Ma, C. Chen, H. Ji and J. Zhao, Acc. Chem. Res.,
alkylation bromides and aldehydes were investigated. As listed
in Table 1, all reactions exhibited high yields and
enantioselectivities. In particular, the reaction of aliphatic
aldehydes and α-bromomalonate exhibited higher reaction
rate (entry 6) than those with aromatic aldehydes. This could
be caused by the steric hindrance effect, as the similar
4
5
6
.
.
.
2
013, 47, 355-363.
Z. J. Wang, S. Ghasimi, K. Landfester and K. A. Zhang, Adv.
Mater., 2015, 27, 6265-6270.
S. Dadashi-Silab, H. Bildirir, R. Dawson, A. Thomas and Y.
Yagci, Macromolecules, 2014, 47, 4607-4614.
4
1
observation was reported previously. by Similar to the
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
Jou Pr nl e aa ls oe fd Mo an to et r ai ad lj su s Ct hm ea mr g ii sn ts ry A
View Article Online
DOI: 10.1039/C6TA10768K
Journal Name
COMMUNICATION
7
.
.
V. S. Vyas, F. Haase, L. Stegbauer, G. Savasci, F. Podjaski,
C. Ochsenfeld and B. V. Lotsch, Nat. Commun., 2015, 6.
R. S. Sprick, B. Bonillo, R. Clowes, P. Guiglion, N. J.
Brownbill, B. J. Slater, F. Blanc, M. A. Zwijnenburg, D. J.
Adams and A. I. Cooper, Angew. Chem. Int. Ed., 2015.
X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M.
Carlsson, K. Domen and M. Antonietti, Nature materials,
33.
34.
35.
36.
M. Neumann, S. Füldner, B. König and K. Zeitler, Angew.
Chem. Int. Ed., 2011, 50, 951-954.
D. D. Tanner and H. K. Singh, The Journal of Organic
Chemistry, 1986, 51, 5182-5186.
Z. J. Wang, S. Ghasimi, K. Landfester and K. A. Zhang, J.
Mater. Chem. A, 2014, 2, 18720-18724.
M. Neumann, S. Fuldner, B. Konig and K. Zeitler, Angew.
Chem. Int. Ed., 2011, 50, 951-954.
8
9.
2009, 8, 76-80.
1
1
1
0.
1.
2.
Y. Zheng, J. Liu, J. Liang, M. Jaroniec and S. Z. Qiao, Energy 37.
Environ. Sci., 2012, 5, 6717-6731.
J. Zhang, Y. Chen and X. Wang, Energy Environ. Sci., 2015,
M. Cherevatskaya, M. Neumann, S. Füldner, C. Harlander,
S. Kümmel, S. Dankesreiter, A. Pfitzner, K. Zeitler and B.
König, Angew. Chem. Int. Ed., 2012, 51, 4062-4066.
L. Wang, W. Huang, R. Li, D. Gehrig, P. W. Blom, K.
Landfester and K. A. Zhang, Angew. Chem. Int. Ed., 2016,
55, 9783-9787.
D. A. Nicewicz and D. W. MacMillan, Science, 2008, 322,
77-80.
D. A. Nicewicz and D. W. C. MacMillan, Science, 2008, 322,
77.
8, 3092-3108.
38.
J. Zhang, G. Zhang, X. Chen, S. Lin, L. Möhlmann, G.
Dołęga, G. Lipner, M. Antonietti, S. Blechert and X. Wang,
Angew. Chem., 2012, 124, 3237-3241.
K. Zhang, D. Kopetzki, P. H. Seeberger, M. Antonietti and
F. Vilela, Angew. Chem. Int. Ed., 2013, 52, 1432-1436.
N. Kang, J. H. Park, K. C. Ko, J. Chun, E. Kim, H. W. Shin, S.
39.
40.
1
3.
4.
1
M. Lee, H. J. Kim, T. K. Ahn, J. Y. Lee and S. U. Son, Angew. 41.
Chem. Int. Ed., 2013, 52, 6228-6232.
K. Zhang, Z. Vobecka, K. Tauer, M. Antonietti and F. Vilela,
A. Gualandi, M. Marchini, L. Mengozzi, M. Natali, M.
Lucarini, P. Ceroni and P. G. Cozzi, ACS Catal., 2015, 5,
5927-5931.
15.
16.
17.
18.
Chem. Commun., 2013, 49, 11158-11160.
J. Luo, X. Zhang and J. Zhang, ACS Catal., 2015, 5, 2250-
42.
43.
44.
J. Liu, J. M. Tobin, Z. Xu and F. Vilela, Polym. Chem., 2015,
6, 7251-7255.
2254.
J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang, Y. Lifshitz,
S.-T. Lee, J. Zhong and Z. Kang, Science, 2015, 347, 970.
M. Cherevatskaya, M. Neumann, S. Füldner, C. Harlander,
S. Kümmel, S. Dankesreiter, A. Pfitzner, K. Zeitler and B.
König, Angew. Chem. Int. Ed., 2012, 51, 4062-4066.
Z. J. Wang, S. Ghasimi, K. Landfester and K. A. I. Zhang,
Adv. Mater., 2015, 27, 6265-6270.
R. S. Sprick, J.-X. Jiang, B. Bonillo, S. Ren, T. Ratvijitvech, P.
Guiglion, M. A. Zwijnenburg, D. J. Adams and A. I. Cooper,
J. Am. Chem. Soc., 2015, 137, 3265-3270.
19.
20.
21.
S. Ghasimi, S. Prescher, Z. J. Wang, K. Landfester, J. Yuan
and K. A. I. Zhang, Angew. Chem. Int. Ed., 2015, 54, 14549-
14553.
C. Yang, B. C. Ma, L. Zhang, S. Lin, S. Ghasimi, K.
Landfester, K. A. I. Zhang and X. Wang, Angew. Chem. Int.
Ed., 2016, 55, 9202-9206.
R. S. Sprick, B. Bonillo, R. Clowes, P. Guiglion, N. J.
Brownbill, B. J. Slater, F. Blanc, M. A. Zwijnenburg, D. J.
Adams and A. I. Cooper, Angew. Chem. Int. Ed., 2016, 55,
1
792-1796.
G. Zhang, Z.-A. Lan and X. Wang, Angew. Chem. Int. Ed.,
016, 55, 15712-15727.
22.
2
2
2
3.
4.
C. Wiles and P. Watts, Green Chem., 2014, 16, 55-62.
B. Gutmann, D. Cantillo and C. O. Kappe, Angew. Chem.
Int. Ed., 2015.
25.
26.
27.
28.
29.
30.
Y. Matsushita, N. Ohba, S. Kumada, T. Suzuki and T.
Ichimura, Catal. Commun., 2007, 8, 2194-2197.
J. Ge, X. Wang, H.-B. Yao, H.-W. Zhu, Y.-C. Peng and S.-H.
Yu, Materials Horizons, 2015, 2, 509-513.
Z. J. Wang, S. Ghasimi, K. Landfester and K. A. Zhang,
Chem. Commun., 2014, 50, 8177-8180.
Z. J. Wang, K. Garth, S. Ghasimi, K. Landfester and K. A. I.
Zhang, ChemSusChem, 2015, 3459-3464.
Z. J. Wang, K. Garth, S. Ghasimi, K. Landfester and K. A.
Zhang, ChemSusChem, 2015, 8, 3459-3464.
S. Ren, R. Dawson, A. Laybourn, J.-x. Jiang, Y. Khimyak, D.
J. Adams and A. I. Cooper, Polym. Chem., 2012, 3, 928-
9
34.
J. M. Narayanam and C. R. Stephenson, Chem. Soc. Rev.,
011, 40, 102-113.
J. M. Narayanam, J. W. Tucker and C. R. Stephenson, J.
Am. Chem. Soc., 2009, 131, 8756-8757.
3
1.
2.
2
3
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Journal of Materials Chemistry A
Page 6 of 6
View Article Online
DOI: 10.1039/C6TA10768K