A dual-functional urea-linked conjugated porous polymer anchoring silver nanoparticles for highly efficient CO2conversion under mild conditions

Article abstract of DOI:10.1039/d0dt02559c

A dual-functional urea-linked conjugated porous polymer (UCPP) assembled by enol-imine with ordered unit arrays that act as potential anchoring sites in the networks was fabricated, and was further applied as a support for Ag nanoparticles by the coordinate interaction between them. The UCPP not only can well confine the Ag particle size and facilitate high dispersion, but also can afford special CO2-philic moieties to enhance the adsorption properties. The resulting Ag?UCPP as a heterogeneous catalyst exhibited excellent activity for the carboxylative cyclization of propargyl alcohols with CO2 under mild conditions, together with good recyclability, which is probably attributed to the synergistic effect of the UCPP on the adsorption and activation of CO2 and the immobilization of Ag nanoparticles. This work affords possible opportunities for the design and synthesis of a heterogeneous catalyst toward CO2 conversion.

Full text of DOI:10.1039/d0dt02559c

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DOI: 10.1039/D0DT02559C
ARTICLE
Dual-functional urea-linked conjugated porous polymer anchoring
silver nanoparticles for highly efficient CO conversion under mild
2
conditions
Xiaoji Wang,a,b* Wang Li, Jianxin Wang, Jie Zhu, Yuting Li, Xiaozhen Liu, Liping Wang, Lin Li
b
b
a
a
a
b*
a*
A dual-functional urea-linked conjugated porous polymer (UCPP) assembled by enol-imine with order unit arrays that act
as potential anchoring sites in the networks was fabricated, which was further applied as a platform for Ag nanoparticles
by the coordinate interaction between them. The UCPP not only can fine confine Ag particles size and facilitate the high
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
dispersion, but afford special CO
heterogeneous catalyst exhibited excellent activity for carboxylative cyclization of propargyl alcohols with CO
conditions, together with good recyclability, which are probably attributed to the synergistic effect of the UCPP in
adsorption and activation of CO and immobilization of Ag nanoparticles. This work affords possible opportunities for the
2
-philic moieties to enhance the adsorption property. The resulting Ag@UCPP as
2
under mild
2
2
design and synthesis of heterogeneous catalyst toward CO conversion.
7
stability, allowing for as attractive candidates for CO
2
capture and
8
Introduction
utilization (CCU). Significant progress has been achieved in CCU
field thus far because of readily tuneable structure of the CPPs by
9
With the increasing accumulation in the atmosphere of the
the introduction of specific CO
2
-philic moieties. Furthermore, recent
greenhouse gas carbon dioxide (CO
climate changes have been caused. The conversion of CO
2
), adverse global warming and
studies have revealed that CPPs possess a promising potential for
1
2
into high
1
0
heterogeneous catalysis, particularly, as a platform to host and
value-added chemicals represents a promising chemical process
that can also relieve CO rising level. Hence, considerable attention
has been paid to CO as C feedstocks for chemical synthesis, and
1
1
12
support catalytic sites. For instance, Cao et al. prepared a cyano-
pyridyl-functionalized conjugated microporous polymer, which
2
/
2
1
furnished high catalytic activity and superior recyclability by the
immobilization of ultrafine silver nanoparticles for the reduction of
numerous routes have also been exploited to convert CO
2
into
2
chemicals. Thereinto, the carboxylative cyclization of propargyl
1
3
nitrophenols. Wu et al. constructed a salen-porphyrin based
conjugated microporous polymer that was applied as palladium
nanoparticle support by the coordinate interactions, indicating
excellent catalytic performance towards Suzuki-Miyaura and Heck-
Mizoroki coupling reactions. In terms of this aspect, rational design
on the structure and pore environment of the CPPs is both crucial
and challenging. Fortunately, from the point of view of structural
design, CPPs can be easily tuned at the molecular level by
incorporating functional building blocks into the framework for
extended ability on purpose, which thus affords exciting
opportunities for the investigation in more meaningful
transformations.
3
alcohols with CO
2
is particularly appealing, because the resultant
products, α-alkylidene cyclic carbonates, are a kind of essential
4
building blocks for organic and pharmaceutical synthesis. To date,
tremendous efforts have been devoted to developing efficient
5
catalysts in the past few decades. Amongst these studies,
heterogeneous catalysts have attracted more attentions owing to
6
their merits in separation and recyclability. Despite that great
progress has been achieved, most still unavoidably suffer from
some limitations, such as low efficiency, harsh conditions and so
forth. It is thus challenging but desirable to discover robust catalysts
to accomplish the CO conversion through an environmental-
2
friendly and recyclable manner.
On combining these various properties, we herein designed and
constructed a novel urea-linked conjugated porous polymer (UCPP)
assembled by enol-imine via Schiff base condensation between
Conjugated porous polymers (CPPs) feature high specific surface
areas, permanent micropores and excellent physicochemical
1
,3,5-triformylphloroglucinol and 1,3-bis(4-aminophenyl)urea. The
resulting UCPP material possessed high surface area and
microporous nature as well as dual sites, urea and enol-imine units,
a. Engineering Research Center of Health Food Design & Nutrition Regulation,
School of Chemical Engineering and Energy Technology, Dongguan University of
Technology, Dongguan 523808, China
School of Life Science, Jiangxi Science and Technology Normal University,
Nanchang, 330013, China
E-mail: 2012207455@tju.edu.cn; 1147575323@qq.com; lilin@dgut.edu.cn;
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
which were beneficial for both CO
2
adsorption and the
b.
immobilization of metal species. Taking advantages of the abundant
urea and enol-imine units Ag nanoparticles could be further
anchored and stabilized on the surface or interlayer of UCPP
network by the coordinate interaction between them. The
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DOI: 10.1039/D0DT02559C
Figure 1. Schematic representations of the synthesis of UCPP and Ag@UCPP.
Ag nanoparticles supported UCPP (Ag@UCPP) catalyst
demonstrated excellent catalytic activity and stability for the
carboxylative cyclization of various propargyl alcohols with CO
under mild conditions.
2
Results and discussion
At the outset of our study, the UCPP was prepared through the
condensation of 1,3,5-triformylphloroglucinol (TFP) and 1,3-bis(4-
aminophenyl)urea (BAPU) in the mixture of mesitylene/1,4-dioxane
o
and 9M aqueous acetic acid (5/5/1 by volume) at 120 C for 3 days,
as shown in Figure 1. The as-obtained orange power is not soluble
in common solvents, such as acetone, ethanol, dichloromethane,
tetrahydrofuran and so on. The structure of UCPP was then
confirmed by Fourier transformed infrared spectroscopy (FT-IR) and
1
3
C cross-polarization magic angle spinning nuclear magnetic
resonance (CP/MAS NMR) analysis. In Figure 2a, FT-IR spectrum of
-1
UCPP shows the characteristic stretching absorptions at 1295 cm
for imine (C=N) bond, indicating that the polymer is linked by the
condensation of formyl and amine. The absorption peak observed
-1
-1
at 1615 cm and 3294 cm can be attributed to the urea unit and
enol-imine unit, respectively. Furthermore, the formyl at 1649 cm-1
belonged to TFP has almost disappeared in the UCPP, suggesting
the formation of the UCPP with an enol-imine linkage. In Figure 2b,
1
3
C CP/MAS NMR spectrum of the UCPP presents a down field
resonance signal appeared at 171 ppm, corresponding to the
hydroxyl groups bearing carbon atoms. The strong resonance peak
at 151 ppm is attributed to the carbonyl carbon atoms of urea units.
The resonance at 158 ppm appears owing to the existence of
enamine carbon atoms. These results strongly demonstrate that the
enol-imine form dominates the UCPP structure, and no
conventional keto-enol tautomerism occurs in the polymer.
Generally, all the carbonyl, hydroxyl and amino have strong binding
interactions with metal ions, which can act as nucleation sites to
facilitate the dispersion of metal species, thus, the material is
expected to serve as a platform to guide the growth of metal
nanoparticles. In this direction, we attempt to in-situ immobilize
silver nanoparticles on the material by the chemical reduction
strategy, furnishing the Ag@UCPP (Figure 1). The content of
Agspecies was 1.73 wt%, determined by inductively coupled plasma
Figure 2. (a) FT-IR spectra of TFP, BAUP and UCPP. (b) 13C CP/MAS NMR spectrum
of UCPP.
The powder X-ray diffraction (XRD) profile of UCPP presents
o
o
major broad diffraction peaks at about 13.6 and 30.7 , indicating
the amorphous nature of the material (Figure S1). The XRD pattern
of Ag@UCPP exhibits similar diffraction peaks, however, no
identifiably characteristic peaks belonged to Ag nanoparticles are
observed (Figure S1), which is probably ascribed to the high
2
dispersion or small size of Ag nanoparticles. Both the N adsorption-
desorption isotherm of UCPP and Ag@UCPP exhibited the type IV
isotherm characters with a rapid uptake at low pressure and a sharp
step increase in the high pressure in the curves (Figure S2). The
Brunauer-Emmett-Teller (BET) surface areas of UCPP and Ag@UCPP
(ICP) analysis.
2
-1
are calculated to be 174 and 102 m g , respectively. The pore size
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distributions calculated by nonlocal density functional theory states of UCPP and Ag@UCPP. The survey spectrumVioewf AArgtic@leUOCnlPinPe
method showed that the dominant pore width was centred in clearly reveals the presence of Ag, C, O andDONI:e1l0e.m10e3n9t/D(0FiDgTu0r2e5459aC).
about 1.2 nm and 4.2 nm, indicative of abundant micropores and The Ag content in the material estimated by XPS analysis was about
mesopores in the materials. Noticeably, the Ag@UCPP presented 1.51 wt%, which was very similar with the ICP data (1.73 wt%). The
less mesopores compared with the pristine UCPP. These decreased high-resolution C 1s XPS spectra show three dominant binding
2
physical characteristics demonstrated that the pores and/or energy peaks, corresponding to C=O, C-NH and sp C-C, and no
interlayer in the host framework are occupied by highly dispersed obvious changes in the C 1s are observed in the two materials
Ag nanoparticles located at the surface as well as inside the matrix.
The structural morphology of UCPP and Ag@UCPP are investigated
by the scanning electron microscopy (SEM) and transmission
electron microscopy (TEM). SEM images of UCPP suggest nanofibre-
like morphology, which are randomly distributed and tend to form a
knitted network (Figure 3a and S3), whereas the aggregation has
remarkably occurred after anchoring Ag nanoparticles (Figure 3b).
The TEM images of UCPP further exhibit the nanofibre-like and
abundant micropore structures (Figure S4). From the TEM
observation on Ag@UCPP, it can be clearly seen that the Ag
nanoparticles are evenly distributed in the framework (Figure 3c)
and average particle size is at about 5.23 nm (Figure S5), indicating
the UCPP can faciliate the dispersion of particles and confine their
size. The high-resolution TEM image shows clear lattice fringes with
an interplane distance of 0.236 nm, which is corresponded to the
Ag (111) lattice space.14 Further high-resolution X-ray photoelectron
spectroscopy (XPS) spectrum of Ag 3d indicates that the binding
energies of Ag 3d3/2 and Ag 3d5/2 appear at 374.4 and 368.4 eV
(Figure 4b). In the O 1s XPS spectra of UCPP, two distinctive peaks
1
5
(Figure 3d), respectively, strongly indicating the metallic state of
Figure 3. SEM images of (a) UCPP and (b) Ag@UCPP. (c) TEM image of Ag@UCPP
Ag on the UCPP.
XPS analysis is further performed to unveil the surface chemical
including the magnifying picture as an inset. (d) The high-resolution XPS spectrum of Ag
3
d for the Ag@UCPP.
Figure 4. (a) Survey scan XPS patterns of and Ag@UCPP. High-resolution XPS spectra of (b) C 1s, (c) O 1s and (d) N 1s of UCPP and Ag@UCPP.
This journal is © The Royal Society of Chemistry 20xx
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at the binding energies of 532.6 eV and 531.0 eV was assigned to C- obtained when using UCPP as catalyst (Entry 2), while Ag@UCPP
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1
6
17
which also further confirmed the enol- could remarkably enhance the product yiDeOldI: (1E0n.1t0r3y9/3D)0, DaTlt0h2o55u9gCh
OH and urea O=C-N
2
,
imine form for the material (Figure 4c), in good agreement with the which was unsatisfactory result for our request. In general, CO
2
1
3
FT-IR and C NMR analysis. Noticeably, the O 1s binding energy of pressure is a key parameter for affecting the CO
the C-OH and O=C-N
2
conversion. To our
2
in the Ag@UCPP present an obvious shift delight, increasing the pressure to 1.0 MPa, the Ag@UCPP could
compared to that of the UCPP, suggesting a strong interaction afford a 82% yield (Entry 5), which was much higher than that of as-
between Ag and the O atom from phenol and urea units. The N 1s prepared Ag@C under the same reaction conditions (Entry 6).
XPS spectra of UCPP can be deconvoluted into two peaks at the Furthermore, increasing the amount of catalyst could greatly boost
binding energies of 400.3 eV and 399.4 eV, corresponding to C=N the yield to 99% (Entry 7). By contrast, cutting down the reaction
and C-NH, respectively. As compared to the N 1s of pure UCPP, an time severely resulted in a decrease of yield (Entry 8). The
obvious shift towards lower binding energies is observed over the prominent advantages of Ag@UCPP are probably attributed to the
2 2
Ag@UCPP (Figure 4d). In comparison, the O1s spectrum is observed stronger interaction with CO molecules due to abundant CO -philic
to shift towards higher binding values in the Ag@UCPP. The XPS features and strong interaction with Ag nanoparticles in the UCPP.
analysis demonstrates that the reduced Ag not only acts as the The reusability of Ag@UCPP was then examined using the model
electron donor endowing electrons to nitrogen, but can serve as reaction under the optimal conditions, as depicted in Figure 6a.
5
f
electron acceptor accepting the electrons of oxygen in the UCPP.
Importantly, it was found that the Ag@UCPP still retained high
Thus, it is believed that the urea and enol-imine units of the UCPP catalytic activity after reused five runs, demonstrating its excellent
serve as anchoring sites in the frameworks to provide strong recyclability and stability. TEM analysis further confirmed that the
interaction for Ag nanoparticles, which is very beneficial for recovered catalyst well remained the high dispersion and small size
promoting the dispersion and immobilization of Ag nanoparticles, of most nanoparticles, but it was undeniable that slight aggregation
thereby giving rise to good catalytic activity and stability.
Due to abundant amide groups that have a certain affinity infulence for the catalytic activity. These results strongly suggested
toward CO in the UCPP framework, the CO adsorption/desorption the excellent stability of Ag@UCPP catalyst during the reaction
isotherms of UCPP and Ag@UCPP are investigated at 273 K and 298 process.
K, respectively. As shown in Figure 5, the UCPP shows a CO uptake To investigate the general application of Ag@UCPP, the
of 14.9 cm /g (273 K) and 13.5 cm /g (298 K), which is beneficial for carboxylative cyclization of various propargyl alcohols with CO
adsorbing CO molecules. Compared to the pristine UCPP, the were further examined under optimal conditions, and the results
Ag@UCPP gives a slightly decrease of CO uptake, which can be were summarized in Table 2. It could be clearly found that all the
was still inevitably occurred (Figure 6b), which had no significant
2
2
2
3
3
2
2
2
assigned to the specific surface area and porous structure. Even so, propargyl alcohols with chain and cyclic alkane substituents were
the Ag@UCPP still presents a good sorption capacity. In general, the converted smoothly into the target α-alkylidene cyclic carbonates
adsorption of CO2 gas in the materials is crucial for CO
since the interaction between CO molecule and amide groups is in
favour for the CO activation.
The catalytic activity of Ag@UCPP was first evaluated using the
carboxylative cyclization of 2-methyl-3-butyn-2-ol with CO as a
model reaction, as listed in the Table 1. Initially, the reaction was
carried out under atmospheric CO pressure and room temperature
2
conversion,
2
Table 1. Carboxylative cyclization of 2-methyl-3-butyn-2-ol with CO
2
.a
2
O
OH
O
2
+ CO2
O
Entry
Catalyst
none
UCPP
Ag@UCPP
Ag@UCPP
Ag@UCPP
Ag@C
CO
2
Pressure (MPa)
Yield (%)b
<1
5
18
52
82
56
99
78
2
1
2
3
4
5
6
0.1
0.1
0.1
0.5
1.0
1.0
1.0
1.0
with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). No product was
detected without any catalyst (Entry 1) and only poor yield was
c
7
8
Ag@UCPP
Ag@UCPP
d
a
Reaction conditions: 2-methylbut-3-yn-2-ol (0.5 mmol), catalyst (10 mg), DBU (1.0
o
b
equiv.), CH3CN (2 mL), 25 C for 24 h. GC yields were given using naphthalene as the
internal standard. 15 mg of catalyst. For 13 h.
c
d
Figure 5. CO2 adsorption/desorption of UCPP and Ag@UCPP at 273K and 298K.
Figure 6. (a) Stability of the Ag@UCPP catalyst. (b) TEM image of the used Ag@UCPP
catalyst after five cycles.
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On the basis of previous reports and experimental results,[5b,5f]
tentative mechanism for the carboxylative cyclization of propargyl
alcohols with CO2 over Ag@UCPP catalyst was proposed and
a
View Article Online
DOI: 10.1039/D0DT02559C
a
Table 2. Carboxylative cyclization of propargyl alcohols with CO
2
over Ag@UCPP
O
R1
15 mg Ag@UCMP
1.0 equiv DBU
O
OH
+
CO2
O
R1
R2
descripted in Figure 7. Owing to strong CO -philic feature of amide
2
2
mL CH3CN, rt
R2
2a-g
[18]
and imine groups,
adsorption of CO
CO2 adsorption/desorption isotherms, which is much beneficial for
CO activation and conversion. Meanwhile, the functional sites, Ag
nanoparticles, interact with the alkynyl to reduce activation energy
of C-H bond. With the assistance of DBU, the insertion of CO into
the material can greatly facilitate the
1a-g
2
molecules in the framework, as descripted in the
b
Entry
Substrate
Product
Yield (%)
2
O
OH
O
2
1
2
O
98
91
1
1
a
substrate to generate the carbamate salt proceeds, which quickly
attacks the alkynyl, resulting in the intramolecular cyclization and
then affording the target cyclic carbonate. The porosity and
structure of the framework are also significant factor for promoting
the substrate transport and the contact with catalytic sites, giving
rising to the efficient transformation.
2
a
O
OH
O
O
b
2
b
O
O
3
4
OH
O
95
93
1
c
2
c
Experimental
Materials
O
OH
i-Pr
O
O
Naphthamine, 1,3,5-trihydroxybenzene, trifluoroacetic acid, p-
1
d
i-Pr
2
d
e
phenylenediamine,
silver
nitrate
(AgNO
3
),
1,8-
O
diazabicyclo[5.4.0]undec-7-ene (DBU), available alcohols were
purchased from J&K scientific Ltd and Energy Chemicals. Sodium
bisulfite, acetic acid, and all the solvents were provided by the local
applier.
OH
O
5
6
7
O
97
92
Hep
1
e
Hep
2
O
O
O
Synthesis of 1,3,5-triformylphloroglucinol (TFP)
TFP was synthesized according to previously described protocol.
OH
OH
O
1
f
[19]
2
f
1
.3. Synthesis of 1,3-bis(4-aminophenyl)urea (BAPU)
O
96
BAPU was synthesized according to previously described
O
1
g
[17]
protocol.
2
g
a
Synthesis of UCPP
Reaction conditions: propargyl alcohols (0.5 mmol), Ag@UCPP (15 mg), DBU (1.0
(99.99%, 1.0 MPa), room temperature, 24 h. b Isolated
The UCPP was synthesized according to the following steps: Briefly,
thick-walled pressure tube equipped a vacuum switch (15 mL) was
charged with TFP (63 mg, 0.3 mmol) and BAPU (109.0 mg, 0.45
3 2
equiv.), CH CN (2 mL), CO
yields.
2
a-2g in >90% isolated yield. As a result, the Ag@UCPP as mmol) in 6 mL mesitylene/1,4-dioxane/9M aqueous acetic acid (6
heterogeneous catalyst can be efficiently and extensively used mL, 5/5/1 by volume. The mixture was sufficiently dispersed by
towards the carboxylative cyclization.
2
Figure 7. Proposed mechanism for carboxylative cyclization of propargyl alcohols with CO over Ag@UCPP catalyst.
This journal is © The Royal Society of Chemistry 20xx
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ultrasound for 10 min, and then filled with argon. Subsequently, the The Ag@UCPP as heterogeneous catalyst exhibited excellent
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o
DOI: 10.1039/D0DT02559C
tube was heated in an oil bath at 120 C for 3 days. Thereafter, the activity for carboxylative cyclization of propargyl alcohols with CO
resulting precipitate was collected by filtration and repeatedly under mild conditions, together with good recyclability with
2
washed with DMF, CH
2
Cl
2
, ethanol and acetone. The obtained successively used at least five runs. The outstanding catalytic
o
power was dried under vacuum at 70 C for 24 h to produce the performance could be attributed to the synergistic effect of the
orange power, which was referred as to UCPP.
2
UCPP in adsorption and activation of CO and immobilization of Ag
nanoparticles. This work highlighted the potential of functional CMP
as support for metal nanoparticles, also affording possible
Preparation of Ag@UCPP
The Ag@UCPP was prepared according to previous literature with a opportunities for the design and synthesis of heterogeneous
[
6c]
slight modification. Typically, the prepared UCPP (100 mg) was catalyst toward CO
2
conversion.
added to a solution of AgNO (7 mg) in methanol (5 mL). The
3
mixtures were continuously stirred for 3 hrs at room temperatue.
Conflicts of interest
There are no conflicts to declare.
The solid was filtered, washed with methanol, and activated at 100
o
C in vacuum, which then was reduced by excess NaBH
4
aqueous
solution (20 mg NaBH
4
in 3 mL water) for another 4 hrs. After that,
the obtained catalyst was filtered, washed with deionized water,
o
and dried at 70 C in vacuum, furnishing the final Ag@UCPP Acknowledgements
catalyst.
We thank the Institute of Science and Technology Innovation, DGUT
No. KCYCXPT2017007).
General procedure for catalytic activity test
(
Typically, the Ag@UCPP catalyst (15 mg), propargylic alcohols (0.5
mmol), DBU (1.0 equiv.), and acetonitrile (2.0 mL) was charged into
a stainless steel autoclave with 10 mL Teflon-lined tube. After
Notes and references
2
sealing, the reactor was charge CO until the desired pressure.
1
(a) G. Kupgan, L. J. Abbott, K. E. Hart, C. M. Colina, Chem. Rev
Afterwards, the reaction proceeded at room temperature for 24
hrs. After completion, the catalyst was removed and the mixture
was analyzed quantitatively using gas chromatography with
naphthalene as internal standard. All of the pure products were
identified by H NMR, C NMR and GC-MS.
Catalyst characterization
2
018, 118, 5488-5538. (b) A. E. Creamer B. Gao, Environ. Sci.
Technol. 2016, 50, 7276-7289. (c) O. Buyukcakir, S. H. Je, S. N.
Talapaneni, D. Kim, A. Coskun, ACS Appl. Mater. Interfaces 2017,
9, 7209-7216.
1
13
2 (a) Q. Liu, L. Wu, R, Jackstell, M. Beller. Nat. Commun. 2015, 6,
5
2
3
933. (b) S. Dabral, T. Schaub. Adv. Synth. Catal. 2019, 361, 223-
46. (c) Q. W. Song, Z. –H. Zhou, L.-N. He, Green Chem. 2017, 19,
707-3728. (d) J. Luo, I. Larrosa, ChemSusChem 2017, 10, 3317-
Fourier transform infrared spectroscopy (FT-IR) was obtained on a
1
3
Nicolet iS10 spectrometer. C CP-MAS solid-state NMR was
performed by JEOL JNM-ECZ600R at 300 MHz. The Ag loading was
determined by inductively coupled plasma-mass spectrometry (ICP-
MS; Varian Vista MPX). Power X-ray diffraction (XRD) was recorded
3332. (e) X. Lan, C. Du, L. Cao, T. She, Y. Li, G. Bai. ACS Appl.
Mater. Interfaces 2018, 10, 38953-38962. (f) X. Lan, Q. Li, L. Cao,
C. Du, L. Ricardez-Sandoval, G. Bai, Appl. Surf. Sci. 2020, 508,
1
45220.
M. Li, S. Abdolmohammadi, M. S. Hoseininezhad-Namin, F.
Behmagham, E. Vessally, J. CO Util. 2020, 38, 220-231.
3
o
on a Bruker D8 Advance with the scanning range of 3-80 at a rate
2
o
of 0.1 step/sec. N
2
adsorption-desorption isotherms were recorded 4 R. Méreau, B. Grignard, A. Boyaval, C. Detrembleur, C. Jerome, T.
a Micromeritics Tristar II 3020 apparatus at 77 K and the surface
areas was calculated by Brunauer-Emmett-Teller method. Scanning
electron microscope (SEM) was performed on the JSM-7500.
Transmission electron microscope (TEM) was achieved on Tecnai G2
F20 S-TWIN (FEI) under 200 KV. X-ray photoelectron spectroscopy
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3
(
(
XPS) was tested on the PHI 1600 X-ray photoelectron spectroscopy
PE company, USA). CO adsorption/desorption isotherms were
2
1
13
measured on Autosorb-iQ-MP at 273 K and 298 K. H and C NMR
was operated on BUXI-I NMR (400 M).
Conclusions
6
7
In summary, a urea-linked conjugated porous polymer (UCPP)
assembled by enol-imine with order dual-unit arrays in the
networks and high physicochemical stability has been successfully
fabricated, and further served as a platform for Ag nanoparticles.
The resultant Ag@UCPP material was systematically characterized,
revealing that the UCPP not only could facilitate the high
distribution of Ag nanoparticles and confine the growth of particles,
but could provide strong interaction for stabilizing Ag nanoparticles
in the surface or interlayer of networks by the dual anchoring sites.
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Dalton Transactions
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DOI: 10.1039/D0DT02559C
Table of Content
Dual-functional urea-based conjugated porous polymer (UCPP) linked by enol-imine supported
silver nanoparticles for CO conversion.
2