Capillary-Bound Dense Micelle Brush Supports for Continuous Flow Catalysis

Article abstract of DOI:10.1002/anie.202110206

Flow reactors are appealing alternatives to conventional batch reactors for heterogeneous catalysis. However, it remains a key challenge to firmly immobilize the catalysts in a facile and flexible manner and to simultaneously maintain a high catalytic efficiency and throughput. Herein, we introduce a dense cylindrical micelle brush support in glass capillary flow reactors through a living crystallization-driven self-assembly process initiated by pre-immobilized short micelle seeds. The active hairy corona of these micellar brushes allows the flexible decoration of a diverse array of nanocatalysts, either through a direct capture process or an in situ growth method. The resulting flow reactors reveal excellent catalytic efficiency for a broad range of frequently utilized transformations, including organic reductions, Suzuki couplings, photolytic degradations, and multistep cascade reactions, and the system was both recyclable and durable. Significantly, this approach is readily applicable to long capillaries, which enables the construction of flow reactors with remarkably higher throughput.

Full text of DOI:10.1002/anie.202110206

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Accepted Article
Title: Capillary-bound dense micelle brush supports for continuous flow
catalysis
Authors: Geyu Lin, Jiandong Cai, Yan Sun, Yan Cui, Qiuwen Liu, Ian
Manners, and Huibin Qiu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202110206
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Capillary-bound dense micelle brush supports for continuous
flow catalysis
[
a]
[a,b]
[a]
[a]
[a]
[b]
[a]
Geyu Lin, Jiandong Cai,
Yan Sun, Yan Cui, Qiuwen Liu, Ian Manners,* Huibin Qiu*
[
a]
G. Lin, J. Cai, Y. Sun, Y. Cui, Q. Liu, H. Qiu
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, State Key Laboratory of Metal Matrix Composites
Shanghai Jiao Tong University
Shanghai 200240, P. R. China
E-mail: hbqiu@sjtu.edu.cn
J. Cai, I. Manners
[
b]
Department of Chemistry
University of Victoria
Victoria BC, V8P5C2, Canada
E-mail: imanners@uvic.ca
Supporting information for this article is given via a link at the end of the document.
[
3–5]
Abstract: Flow reactors are appealing alternatives to conventional
batch reactors for heterogeneous catalysis. However, it remains a
key challenge to firmly immobilize the catalysts in a facile and
flexible manner and to simultaneously maintain a high catalytic
efficiency and throughput. Herein, we introduce a dense cylindrical
micelle brush support in glass capillary flow reactors through a living
crystallization-driven self-assembly process initiated by pre-
immobilized short micelle seeds. The active hairy corona of these
micellar brushes allows the flexible decoration of a diverse array of
nanocatalysts, either through a direct capture process or an in situ
growth method. The resulting flow reactors reveal excellent catalytic
efficiency for a broad range of frequently utilized transformations,
including organic reductions, Suzuki couplings, photolytic
degradations, and multistep cascade reactions and the system was
both recyclable and durable. Significantly, this approach is readily
applicable to long capillaries, which enables the construction of flow
reactors with remarkably higher throughput.
nanoparticles on a static substrate.
Over the past few
decades series of supports with distinct length scales,
a
morphology and compositions have been developed to anchor
[
6,7]
nano-catalysts in flow reactors (Fig. 1a). These include silica,
[
8,9]
[10]
zeolites,
and polymeric materials such as dendrimers,
[
11]
[12,13]
polymer brushes,
porous organic polymers,
and metal-
[
14]
/covalent organic frameworks.
Nevertheless, it remains a
major challenge to obtain a solid and flexible nanocatalyst
loading while simultaneously balance the flow throughput and
long-term
catalytic
performance.
We
have
recently
[
15]
demonstrated a facile strategy to fabricate micellar brushes on
various material surfaces by using the seeded growth strategy
[
16–19]
termed living crystallization-drive assembly (CDSA)
from
pre-immobilized micelle seeds derived from crystallizable block
copolymers. Micelle elongation via the addition of additional
dissolved polymer (unimer) led to brush layer heights of > 165
[
15]
nm, far exceeding the values accessible using surface-grafted
[
20]
polymers (typically < 10 nm).
Herein, we have used this
platform to facilely grow micellar brushes on the internal wall of
capillaries under ambient conditions. Upon the incorporation of a
rich array of nanocatalysts, the micellar brush functions as a
Nanosized particles exhibit impressive catalytic reactivity
because of their exceptionally large surface area and high
[
1]
surface energy, which makes them promising candidates for
continuous flow heterogeneous catalysis where chemical
highly efficient catalytic platform for
a broad range of
transformations under conditions of continuous flow (Fig. 1b).
[
2]
reactions occur in a relatively confined space. To prevent
aggregation or leaching it is essential to immobilize catalytic
1
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Figure 1. Advantageous features of micellar brush support in flow reactors. a) Traditional supports for nanocatalysts in flow reactors. b) Micellar brush
support used in this work.
Short glass capillaries with diameter of 0.5 mm and length
of 10 cm were selected to construct the flow reactors. Short
S1). Subsequently, the seed-coated glass capillary was soaked
in isopropanol, a selective solvent for P2VP, followed by the
addition of PFS30-b-P2VP226 unimers in tetrahydrofuran (THF, 10
mg/mL), a good solvent for both blocks. Unimer addition led to
growth at the termini of the immobilized micelle seeds and
eventually formed dense, forest-like micellar brushes on the
inner glass wall as revealed by SEM (Figs. 2c,d, S2). The
micelle brush layer was clearly denser and more erect than
those prepared by homogeneous nucleation or direct deposition
of relatively long (ca. 500 nm) pre-prepared cylindrical micelles
which gave rise to sparse surface coverage (Figs. S3, S4). The
length of the micellar brushes increased with the amount of
added unimer and can be increased to several micrometers
(Figs. 2c,d, S2). It should be noted that although the micellar
brushes are in the collapsed state after drying, they become
cylindrical micelle seeds (L
where L and L are the number- and weight-average lengths,
respectively) comprising a diblock copolymer PFS30-b-P2VP226
the subscripts refer to the number-average degree of
polymerization) with a crystallizable polyferrocenyldimethylsilane
PFS) core-forming block and a surface- and nano-particle-
binding poly(2-vinylpyridine) (P2VP) segment. colloidal
n w w n
= 66 nm, L = 68 nm, L /L = 1.03,
n
w
(
(
A
solution of the PFS30-b-P2VP226 seeds in isopropanol (a
selective solvent for P2VP) was syphoned into glass capillaries
by immersing one end of the tube into the solution. The pyridine
groups on the P2VP corona strongly associated with the silanol
groups on the glass wall via hydrogen bonding (H-bonding) and
[
15,21]
(
after proton transfer) electrostatic interactions
leading to
[
15]
immobilization on the internal walls of the capillaries (Figs. 2a,b,
more upright when solvent is present.
2
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Figure 2. Growth of micellar brushes in short glass capillaries. a, Schematic illustration of the fabrication process where the solutions of PFS30-b-P2VP226
micelle seeds and unimers were sequentially added through syphoning and soaking. b, SEM images (after solvent evaporation) of the internal wall of a glass
n w w n
capillary coated with PFS30-b-P2VP226 micelle seeds (L = 66 nm, L = 68 nm, L /L = 1.03, 0.5 mg/mL in isopropanol, fed with 200 µL). The micelle seeds were
immobilized on the glass wall via H-bonding and electrostatic interactions. c,d, SEM images of the internal walls of two glass capillaries after the growth of forest-
like PFS30-b-P2VP226 micellar brushes in the collapsed state after drying. The brushes were prepared by adding (c) 9 µL and (d) 12 µL of solutions of PFS30-b-
P2VP226 unimers (10 mg/mL in THF), respectively. The resulted micellar brushes possessed L
n n
> 300 nm (c) and L > 400 nm (d), respectively. For SEM analysis,
the capillaries were broken into small pieces and then fixed on conductive tape with the internal surfaces facing up.
The pyridine groups on the P2VP corona of the PFS30-b-
assigned to the GOx thiol and disulfide groups (Fig. 3c, Fig. S6c).
[
23]
P2VP226 micellar brushes enable the introduction of a rich variety
The P2VP coronas also provide an efficient environment for
the adsorption of metal ions and the subsequent in situ
[
22]
of nanocatalysts through various bonding interactions.
example, when a solution of gold nanoparticles (Au NPs, Fig.
S5a, number-average diameter, D = 13.3 nm) in water was
For
[
24]
generation of nanoparticles (Figs. S7–S9).
aqueous solutions of NaPdCl Na PtCl
precursors were syphoned into the glass capillaries before the
addition of NaBH , a typical reductant. This immediately led to
the in situ formation of palladium (Pd) NPs (D = 7.3 nm),
platinum (Pt) NPs (D = 8.4 nm), and Au NPs (D = 6.9 nm) on
To this end,
n
4
,
2
6
and NaAuCl
4
syphoned into the glass capillary, the Au NPs spontaneously
adsorbed onto the micellar brushes through coordination
interactions. SEM images revealed a relatively even distribution
of Au NPs on the micellar brushes with a very small spacing of <
4
n
n
n
3
nm (Fig. 3b, Fig. S6a) while no obvious aggregation was
observed. Titanium dioxide (TiO ) NPs (D = 32.8 nm) were also
attached to the micellar brushes via H-bonding and electrostatic
interactions (Fig. S6b), although the intrinsic clustering of TiO
the micellar brushes (Figs. 3d,e, Fig. S10, size analysis was
based on SEM images). Compared to the direct immobilization
method, the in situ reduction approach generated smaller
nanocatalyst particles with denser packing on the micellar
brushes (Fig. 3). Notably, the loading capability of nancatalysts
by the micellar brushes was apparently higher than the sparsely
2
n
2
NPs resulted in a less uniform distribution. We also introduced
glucose oxidase (GOx) to the micellar brushes utilizing a similar
combination of interactions (the isoelectric point of GOx is pH =
coated cylindrical micelles or
a layer of block copolymer
4
.26, indicating that the enzyme is acidic). Although the GOx
(denoted as BCP film, which consisted of much more polymer,
see Figs. S3b, S4d, Table S1 for more details) (Figs. 3f-i).
enzyme was not detected by SEM due to its small size (Fig. 3c),
EDX mapping definitively demonstrated the presence of sulfur
3
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Figure 3. Decoration of nanocatalysts on micellar brushes in short glass capillaries. a. Schematic illustrations of direct immobilization (a solution of a
desired nanocatalyst was syphoned into a glass capillary coated with PFS30-b-P2VP226 micellar brushes and the nanocatalyst spontaneously adsorbed via
4
coordination, H-bonding, or electrostatic interactions) and in situ generation methods (the solutions of metallic salts and NaBH were sequentially added through
syphoning and soaking). b,c, SEM images of collapsed PFS30-b-P2VP226 micellar brushes in the dry state after direct immobilization of (b) Au NPs (inset is the
size distribution of the immobilized Au NPs) and (c) GOx (inset is the EDX mapping of S). d,e, SEM images of collapsed PFS30-b-P2VP226 micellar brushes in the
dry state after in situ generation of (d) Au NPs (inset is the size distribution of the generated Pd NPs) and (e) Pt NPs (inset is the size distribution of the generated
Pt NPs). For SEM analysis, the capillaries were broken into small pieces and then fixed on conductive tape with the internal surfaces facing up. f-i, Rough loading
amounts of (f) Au NPs, (g) GOx, (h) Pd NPs and (i) Pt NPs on the micellar brushes, sparsely coated cylindrical micelles and BCP film (see Supporting Information
for experimental details).
After the decoration of nanocatalysts, the PFS30-b-P2VP226
Fig. 4c, the Au NP-decorated micellar brushes demonstrated a
superior long-term stability compared to the controls with the
morphology of the micellar brushes and NPs well retained (Fig.
S12). No obvious leaching of Au NPs was detected after the
reaction was carried out for 24 h. However, ca. 11.8% and ca.
12% of leaching were detected in cylindrical micelle and BCP
film systems. Apparently, the Au NPs were much more firmly
immobilized by the micellar brushes. On the other hand, the
capillaries coated with Pd NP-decorated micellar brushes
demonstrated efficient catalytic performance for the Suzuki
micellar brush-coated glass capillaries (length = 10 cm, diameter
=
0.5 mm) were assembled as a reactor with other simple
accessories to form a continuous flow device (Fig. S11) to carry
out a rich array of flow reactions (Table S2). The capillary coated
with Au NP-decorated micellar brushes exhibited excellent flow
catalytic performance over the reduction of 4-nitrophenol
[
25]
(
Nip),
complete within a residence time (t
a,b). In contrast, the sparsely coverage achieved on the
internal surface with deposited pre-prepared cylindrical micelles
= 527 nm, L = 532 nm, L /L = 1.01) and BCP film treated
with an equivalent amount of Au NPs only gave a conversion of
60% under the same conditions (Fig. 4b). The micellar brush
a well-known model reaction, where the reaction was
R
) of 120 seconds (s) (Figs.
4
[
26]
coupling reactions (Figs. 4d–f, S13, S14),
a classic Pd-
(
L
n
w
w
n
catalyzed reaction, where a conversion of ca. 99% was achieved
within a residence time of 4800 s (Fig. 4e, Fig. S14). By contrast,
the capillaries that sparsely deposited with cylindrical micelles or
<
clearly significantly boosts the loading and performance of
catalysts, presumably on account of the erect structure in the
a BCP film which treated with the same amount of NaPdCl
4
and
NaBH only gave conversions of < 75% within a residence time
4
[
15]
presence of solvent. Besides, the micellar brushes effectively
raised the catalytic activity of the supported Au NPs as revealed
of 9600 s (Fig. 4e). The Pd NP loaded micelle brush system also
showed a consistent and durable catalytic performance with
conversion of ca. 99% over 72 h (Fig. 4f) and no obvious
leaching of Pd NP was detected. On the contrary, ca. 0.9% and
ca. 1.3% of leaching were detected in cylindrical micelle and
-
1
by the turnover frequency (TOF) values (61.88 h for the
-
1
micellar brushes, 41.80 h for the sparsely coated cylindrical
-
1
micelles and 45.69 h for the BCP film). Moreover, as shown in
4
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[
27,28]
BCP film systems. The above results illustrated that the micellar
brushes not only effectively raised the catalytic activity of the
immobilized nanocatalysts, but also provided a superior loading
stability during long-term flow reactions. Other reactions like
chemical and photodegradation of methyl orange (MO)
were
also successfully explored with the in situ generation of Au NPs
and direct decoration of TiO
S15, S16).
2
NPs on the micellar brushes (Figs.
Figure 4. Continuous flow reactions catalyzed by metal NPs supported on the micellar brushes, sparsely-coated cylindrical micelles and BCP film. a,
Schematic illustration for the reduction of Nip in water catalyzed by Au NPs that directly mounted on PFS30-b-P2VP226 micellar brushes (L > 400 nm, see Fig. 2d)
see the Supporting Information for experimental details). b, Conversion-residence time plot of the reactions conducted through glass capillaries that coated with
n
(
Au NP-decorated micellar brushes (L
n
> 400 nm, see Fig. 2d), Au NP-decorated sparsely coated cylindrical micelles, Au NP-decorated BCP film and pristine
was adjusted by varying the flow rate and the
conversions were calculated based on the UV-vis absorbance at 400 nm. c, Stability test of Au NP-decorated PFS30-b-P2VP226 micellar brushes, Au NP-
decorated sparsely coated cylindrical micelles and Au NP-decorated BCP film. For all reactions, flow rate = 10 µL/min, t = 120 s (the volume of the glass capillary
n R
micellar brush (L > 400 nm) on the internal surface. All reactions were conducted at room temperature, t
R
is ca. 20 µL). 0.080 mg of Nip were transformed after 24 h continuous flow reaction carried out through the glass capillary coated with Au NP-decorated micellar
brushes (turnover number, TON = 52.63). d, Schematic illustration of the Suzuki coupling reaction catalyzed by Pd NPs that in situ generated on PFS30-b-P2VP226
micellar brushes (L
conducted through glass capillaries that coated with Pd NP-decorated micellar brushes (L
micelles, Pd NP-decorated BCP film and pristine micellar brush (L > 400 nm) on the internal surface. All reactions were conducted at 35 °C, t
varying the flow rate and the conversions were calculated based on HPLC test. f, Stability test of Pd NP-decorated PFS30-b-P2VP226 micellar brushes, Pd NP-
decorated sparsely coated cylindrical micelles and Pd NP-decorated BCP film (flow rate = 1 µL/min, t = 4800 s, T = 35 °C). 54.240 mg of iodobenzene were
transformed after 72 h continuous flow reaction carried out through glass capillaries coated with Pd NP-decorated micellar brushes (TON = 221.57).
n
> 400 nm, see Fig. 2d) (see the Supporting Information for experimental details). e, Conversion-residence time plot of the reactions
> 400 nm, see Fig. 2d), Pd NP-decorated sparsely coated cylindrical
was adjusted by
n
n
R
R
[
30]
Multistep cascade reactions in continuous flow were also
explored by assembling different flow reactors in series. As a
proof of concept, the oxidation of glucose catalyzed by GOx and
imine derivative, which possesses an absorption at 450 nm,
was also detected. This experiment therefore demonstrated the
potential to oxidize TMB (to form ox-TMB) using the H
2
O
2
[
23,30]
the subsequent reaction of the resulting H
2
O
2
for the oxidation of
generated from the glucose oxidation.
decorated with in situ generated Au NPs was shown to exhibit
excellent catalytic activity for the oxidation of TMB by H (Fig.
Next, a micelle brush
3
,3’,5,5’-tetramethylbenzidine (TMB) catalyzed by Au NPs
[
29]
exhibiting peroxidase-like activity
were organized as
a
2 2
O
cascade reaction in the presence of micellar brushes. First, the
ability of the micellar brushes loaded with GOx through direct
immobilization to efficiently catalyze the oxidation of glucose
was demonstrated. After addition of TMB and horseradish
peroxidase (HRP) to the collected solution (Fig. 5a), intense
UV–vis peaks appeared at 370 nm and 652 nm (Fig. 5a, Fig.
S17a), indicating the formation of oxidized TMB (oxTMB) as a
5b, Fig. S17b). Finally, the two modules were connected to form
a cascade reaction system (Fig. 5c) with the first flow reactor
coated with a GOx-decorated micellar brush and the second
coated with a brush decorated with Au NPs. The solution
obtained after flowing through the two modules showed an
obvious absorbance at 652 nm (Fig. 5c) attributed to oxTMB,
which is fully consistent with the targeted cascade reaction.
Again, the micellar brush-based flow system showed excellent
durability as the micellar brushes in the two capillaries retained
[
29]
charge transfer complex (Fig. 5b).
In addition, due to the
acidic environment (PBS, pH = 5.05), some conversion to a di-
5
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the original morphology with neglectable leaching of the
nanocatalysts and micellar brushes after a 500 min-continuous
flow reaction (Fig. S18).
Figure 5. Cascade reaction sequentially catalyzed by GOx- and Au NP-decorated micellar brushes. a, Schematic illustration and UV–vis spectrum for the
oxidation of glucose in PBS (pH = 5.05) catalyzed by GOx that directly mounted on PFS30-b-P2VP226 micellar brushes (L > 1000 nm, see Fig. S2b) in a glass
capillary (flow rate = 5 µL/min, t = 240 s). b, Schematic illustration and UV–vis spectrum for the oxidation of TMB in PBS (pH = 5.05) catalyzed by Au NPs that in
situ generated on PFS30-b-P2VP226 micellar brushes (L > 400 nm, see Fig. 2d) in a glass capillary (flow rate = 5 µL/min, t = 240 s). c, Schematic illustration and
UV–vis spectrum for the cascade reaction in PBS (pH = 5.05) sequentially catalyzed by GOx-decorated micellar brushes (L > 1000 nm) and Au NP-decorated
micellar brushes (L > 400 nm) (flow rate = 5 µL/min, t = 480 s).
n
R
n
R
n
n
R
Substantially longer fused-silica capillaries (inner diameter =
.5 mm, length 57 cm vs 10 cm) were selected to enhance the
n
S5a, D = 13.3 nm) by injecting an aqueous solution of Au NPs
0
into the long capillary (Fig. S20b).The reduction of Nip was
carried out to evaluate the catalytic performance of the long
capillary that coated with Au NP-decorated micellar brushes.
With a longer reaction track (57 cm vs. 10 cm), the long capillary
reactor permitted a remarkably higher flow throughput after 24 h
continuous flow (780% increase of the mass of converted Nip
and 56% increase of TON, Figs. S20c,d vs. Figs. 4a,c, Table
productivity of the flow reactors (Fig. S19). The solutions of
PFS44-b-P2VP526 micelle seeds (L = 96 nm, L = 99 nm, L /L
.03) and PFS24-b-P2VP314 unimers were sequentially injected
n
w
w
n
=
1
to a long capillary, which led to the formation of dense and
uniform micellar brushes on the internal surface (Fig. S20a). The
micellar brushes were subsequently decorated with Au NPs (Fig.
6
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S2) than the short capillary reactor. The micelle brushes in the
long fused-silica capillaries also exhibited excellent durability
and were not eluted even under a relatively high flow rate (88
µL/min, Fig. S21).
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[
[
5]
6]
In summary, we have established a versatile continuous
flow catalysis platform through the facile growth of the cylindrical
micellar brushes on the internal wall of glass capillaries. A rich
array of reactions, either in single-step or cascade manner, can
be customized and conducted in flow simply by decorating
specific nanocatalysts onto the micellar brushes through direct
immobilization or in situ generation. Significantly, this strategy
can be readily applied to relatively long capillaries to
substantially increase the throughput, which is relevant for large-
scale industrial manufacture. In principle, the system developed
in this work should be viable in a wide range of applications in
the field of flow chemistry. This is attributed to the facile and
versatile decoration of functional units on micellar brushes,
leading to applicability that includes, but is not limited to, multi-
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This work was financially supported by the National Key R&D
Program of China (2020YFA0908100), the National Natural
Science Foundation of China (22075180, 92056110), the
Innovation Program of Shanghai Municipal Education
Commission (202101070002E00084) and the Science and
Technology Commission of Shanghai Municipality (195271040,
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2
0JC1415000, 21XD1421900). The authors thank the
3
Instrumental Analysis Center (Shanghai Jiao Tong University)
for TEM, SEM, EDX mapping, HPLC, ICP-MS and XPS. IM
thanks the Canadian Government for a Canada 150 Research
Chair at the University of Victoria and the Chinese Government
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Angewandte Chemie International Edition
10.1002/anie.202110206
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Forest-like micellar brushes fabricated under ambient environment in glass capillaries enable flexible decoration of various
nanocatalysts and subsequently permit a broad range of continuous flow transformations. Notably, this strategy is feasible for not
only short but also long capillaries, allowing the preparation of flow reactors with significantly higher throughput.
8
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