Research Article

www.acsami.org

Imparting Catalytic Activity to a Covalent Organic Framework

Material by Nanoparticle Encapsulation
Xiaofei Shi, Youjin Yao, Yulong Xu, Kun Liu, Guangshan Zhu,*, Lifeng Chi,*, and Guang Lu*,

Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials &
Devices, Soochow University, Suzhou 215123, China

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China

Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University,
Changchun 130024, China
*
S Supporting Information

ABSTRACT: Integrating covalent organic frameworks

(COFs) with other functional materials is a useful route to
enhancing their performances and extending their applications.
We report herein a simple encapsulation method for
incorporating catalytically active Au nanoparticles with dier-
ent sizes, shapes, and contents in a two-dimensional (2D)
COF material constructed by condensing 1,3,5-tris(4-amino-
phenyl)benzene (TAPB) with 2,5-dimethoxyterephthaldehyde
(DMTP). The encapsulation is assisted by the surface
functionalization of Au nanoparticles with polyvinyl-
pyrrolidone (PVP) and follows a mechanism based on the
adsorption of nanoparticles onto surfaces of the initially
formed polymeric precursor of COF. The incorporation of
nanoparticles does not alter obviously the crystallinity, thermal stability, and pore structures of the framework matrices. The
obtained COF composites with embedded but accessible Au nanoparticles possess large surface areas and highly open mesopores
and display recyclable catalytic performance for reduction of 4-nitrophenol, which cannot be catalyzed by the pure COF material,
with activities relevant to contents and geometric structures of the incorporated nanoparticles.
KEYWORDS: covalent organic framework, porous materials, nanoparticles, catalysis, composites

INTRODUCTION
Covalent organic frameworks (COFs) are a new class of porous
crystalline materials constructed by organic building blocks via
covalent bonds.18 The molecular engineering-based synthesis
strategy of COFs allows the exible design for achieving unique
structures and properties. Their two-dimensional (2D) or
three-dimensional (3D) open network structures yield high
surface areas and accessible cavities or channels with uniform
sizes ranging from angstroms to nanometers, which is attractive
for many applications including gas storage,913 separa-
tions,1416 drug delivery,1719 and energy conversion and
storage.2023 Built with functional moieties, COF materials can
be endowed with unique optical,2428 optoelectronic,2931 and
catalytic properties.3234 Alternately, noninherent functional-
ities and extended applications of COFs can be achieved by
reasonably integrating them with other functional materials.
The open porous structures and outstanding stability of
COFs make them excellent host matrices for many functional
species such as proton carriers,3537 electron acceptors,3840
and enzymes.41 The cavities themselves of COF materials have
also been explored as nanoreactors for chemical reactions.
Based on the conned synthesis, metal nanoparticles can be
produced within the cavities of COFs with ultrasmall sizes and
clean surfaces.4246 New and enhanced performances that are
relevant to the nanoparticle components have been observed
for the obtained nanoparticles/COF composites in organic
catalysis4245 and hydrogen storage applications.46 Alternately,
this kind of composite can be generated by encapsulating the
preprepared nanoparticles during the framework synthesis. This
strategy is attractive since the compositions, sizes, and shapes
associated with the chemical and physical properties of
nanoparticles can be feasibly tuned by their well-established
synthesis.47,48 COF materials can heterogeneously nucleate and
grow around the outer surfaces of some nanosized objects (e.g.,
carbon nanotubes with diameter of 50 nm,49 ZnO nanorods
with diameter of 100 nm,50 and 200 nm Fe3O4 spheres51)
to give the coreshell structures, just as they did on the surface
of a at substrate.5254 Nevertheless, although the encapsula-
tion strategy, in principle, is capable of incorporating any
nanoparticles with the desired chemical or physical properties
Received: December 19, 2016
Accepted: February 6, 2017

XXXX American Chemical Society A DOI: 10.1021/acsami.6b16267

ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces
Scheme 1. Schematic Illustration of the Encapsulation of PVP-Modied Nanoparticles in the 2D TAPB-DMTP-COF
in COF materials, the nanoparticle-relevant catalysis applica-
tions of the resulting COF composites have not been reported
yet. For 2D COF-based composites, the orientation of channels
and possible crystal defects (e.g., amorphous portion and
stacking faults) in the framework matrices may also raise doubts
about the accessibility and catalytic activity of the enshrouded
nanoparticles. In addition, for the systematic investigation on
the catalytic performance of the resulting composites, it is
highly desirable to develop new encapsulation methods that
enable the easy incorporation of smaller nanoparticles (<50
nm) (and even multiple types of nanoparticles) within COFs
with tunable contents.
In this study, we report a general encapsulation method for
incorporating nanoparticles with dierent sizes and shapes in a
2D COF material (Scheme 1). This strategy involves the
optimization of framework synthesis and the surface function-
alization of nanoparticles. The highly crystalline 2D TAPB-
DMTP-COF, we chose in this work, has been reported
previously and displays outstanding chemical robustness and
thermal stability.33 Au nanoparticles were chosen as examples
to demonstrate our encapsulation method due to their easy
synthesis and excellent catalytic activities for many chemical
reactions.55 The surfaces of nanoparticles used in our work
were functionalized with polyvinylpyrrolidone (PVP), an
amphiphilic surfactant, that has been widely used for
controlling the sizes, shapes, and surface properties of a variety
of nanoparticles.5658 Relying on the adsorption of PVP-
modied nanoparticles onto the initially formed polymeric
precursor of COF, instead of the heterogeneous nucleation
reported previously for the formation of coreshell-structured
composites,4951 nanoparticles with sizes ranging from 3.8 to
100 nm and with shapes in sphere and rod can be incorporated
with high eciency in TAPB-DMTP-COF during its synthesis
B DOI: 10.1021/acsami.6b16267
Research Article
under the optimized experimental conditions. The composites
display high crystallinity, excellent thermal stability, large
surface areas, and open mesopores that are substantially similar
to those of the pure TAPB-DMTP-COF. In the model reaction
of 4-nitrophenol reduction by NaBH4,43,5961 the composites
containing Au nanoparticles show recyclable catalytic capability,
but the pure COF material does not, establishing the
accessibility and activity of the encapsulated nanoparticles
within the 2D COF. In addition, systematic investigation with
samples incorporated with dierent Au nanoparticles reveals
the nanoparticle-relevant catalytic performances of the
composites, where higher activity (with rate constants of 0.46
and 0.36 min1) was observed for samples containing 15 nm Au
nanoparticles (0.20 and 0.10 wt %), moderate activity (with
rate constant of 0.36 min1) for that containing 25 100 nm
Au nanorods (0.26 wt %), and lower activity (with rate
constant of 0.12 min1) for that containing 50 nm Au
nanoparticles (0.38 wt %).
EXPERIMENTAL SECTION
General Procedure of Nanoparticle Encapsulation in TAPB-
DMTP-COF. A 20 mL borosilicate glass vial was charged with 1,3,5-
tris(4-aminophenyl)benzene (TAPB) (0.030 mmol, 10.5 mg), 2,5-
dimethoxyterephaldehyde (DMTP) (0.045 mmol, 8.7 mg), 4 mL of
1,4-dioxanebutanol (v/v, 1:1), 0.5 mL of solution of PVP-modied
nanoparticles in methanol, and 0.05 mL of 12 M aqueous acetic acid.
The mixture was allowed to react at room temperature for 2 h. After
adding 0.45 mL of 12 M aqueous acetic acid, the reaction was
conducted further at 70 C for 24 h. After cooling to room
temperature, the product was collected by centrifugation, washed
several times with tetrahydrofuran (THF) and acetone, and vacuum-
dried at room temperature overnight.
Other experiment and characterization details are provided in the
Supporting Information.
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces
RESULTS AND DISCUSSION
Nanoparticles were synthesized using established methods, and
their surfaces were functionalized with PVP during or after their
synthesis (see experimental details in the Supporting
Information). The PVP-modied nanoparticles can be
dispersed well in common polar solvents (for example, water
and methanol) and are also stable in a mixture of methanol/
butanol/1,4-dioxane (v/v/v, 1:4:4), which was optimized as
solvents for the synthesis of COF material in our experiment.
The encapsulation process was demonstrated with 15 nm Au
nanoparticles. Typically, a homogeneous solution containing
PVP-modied Au nanoparticles, 1,3,5-tris(4-aminophenyl)-
benzene (TAPB), and 2,5-dimethoxyterephthaldehyde
(DMTP) in methanol/butanol/1,4-dioxane was prepared, and
acetic acid aqueous solution was subsequently introduced to
trigger the condensation reaction between amino and aldehyde
monomers. The mixture was allowed to react at room
temperature for 2 h and then at 70 C for 24 h. The product
collected by centrifugation displays homogeneous color
(yellow), and the supernatant is transparent and absent of
the discernible UVvis absorption peak at 520 nm
(characteristic for 15 nm Au nanoparticles) (Figure S2),
implying that essentially all of the nanoparticles are
incorporated in the product. Scanning electron microscope
(SEM) images show that the product consists of spheres with
an average diameter of 1.03 m (Figure 1a). These spheres
Figure 1. Microscopy characterizations of COF composite containing
0.20 wt % 15 nm Au nanoparticles: (a) low-magnication SEM image,
(b) high-magnication SEM image, (c) low-resolution TEM image,
and (d) high-resolution TEM image.
exhibit rough surfaces on which convex domains with sizes of
50100 nm could be observed clearly (Figure 1b). Trans-
mission electron microscopy (TEM) measurements reveal that
each (brighter) polymer sphere contains either single or several
(darker) Au nanoparticles in their central regions (Figure 1c).
Essentially, no unencapsulated nanoparticles were observed
outside the spheres or on their outer surfaces. Close
observation at the edges of spheres under higher magnication
C DOI: 10.1021/acsami.6b16267
Research Article
indicates that the spheres consist of domains that contain
regular channels arranged along the radial direction of spheres
(Figure 1d). The grain sizes of domains are about 50 nm along
the orthogonal direction of channels, in consistent with that of
the convex domains observed in SEM. Previous studies on the
morphology evolution of the 2D Dha-Tab-COF have showed
that the stacking of 2D COF layers along the c-axis can
result in the formation of rod-like crystallites possessing the
hexagonally arrayed channels, which can self-assemble further
and evolve to form dense or hollow COF spheres.41 We
speculate that, similarly, the spheres in current work are
presumably aggregates of the rod-like crystallites. However,
more TEM investigation on the possible ordered structures
within bodies of spheres was frustrated by the large sizes of
spheres and the overlapping projections of channels.
High nanoparticle-encapsulation eciency (>99%) could be
achieved for polymer spheres using the current method. The
contents of nanoparticles can be tuned by changing the
concentration of nanoparticles in the stock solutions (Table
S1). The fraction of polymer spheres containing single Au
nanoparticle in the products was observed to increase as
lowering the concentration of nanoparticles used in the
synthesis, however, at the expense of a slight decrease in the
encapsulation eciency (Figure S3). The nal sizes of polymer
spheres do not change obviously on tuning nanoparticle
concentrations or even in the absence of nanoparticles in the
synthesis, suggesting that the presence of nanoparticles does
not alter substantially the homogeneous nucleation and
subsequent growth of polymer spheres under current synthetic
conditions. The encapsulation process was further investigated
by time-dependent TEM analysis (Figure S4). The adsorption
of Au nanoparticles onto surfaces of the gradually formed
oligomeric polymer precursors (with irregular shapes), instead
of the nanoparticle@polymer coreshell morphology, was
observed commonly in the early time (15 min) of the
encapsulation process (Figure S4b). The above results suggest
that the encapsulation of nanoparticles does not follow
predominantly the heterogeneous nucleation mechanism. We
speculate that in the current solution system the hydrophilic/
hydrophobic interactions between PVP molecules adsorbed on
the nanoparticle surfaces and the initially formed tiny
oligomeric polymer precursors (with high surface energy) are
responsible for the adsorption of nanoparticles on the surfaces
of polymeric precursor of COF, resulting in the nal
encapsulation of nanoparticles as polymer spheres subsequently
growing. In fact, the PVP-assisted encapsulation strategy has
been adopted previously for incorporating nanoparticles in
other materials such as silica62 and metalorganic frameworks
(MOFs)63 based on either heterogeneous nucleation or
nanoparticle adsorption. In an additional control experiment
with excess free PVP intentionally added in the reaction, severe
agglomeration of polymer spheres was observed in the product
(Figure S5), suggesting again the strong interactions between
PVP and polymer of spheres.
In principle, this encapsulation method is applicable to any
nanoparticles that are chemically stable in the acidic solution
system used in current work since the surface modication with
PVP is easy to operate and has proved to work well for various
nanoparticles diered in compositions, sizes, and shapes. In
fact, composites containing 50 nm Au nanoparticles, 25 100
nm Au nanorods, and 3.8 nm Pt nanoparticles were also
successfully prepared using this method (Figure 2ac). The
agglomeration of polymer spheres observed in the Pt
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces
Figure 2. TEM images of COF composites containing (a) 0.38 wt %
50 nm Au nanoparticles, (b) 0.26 wt % 25 100 nm Au nanorods, (c)
3.8 nm Pt nanoparticles, and (d) 15 and 50 nm Au nanoparticles.
nanoparticle-containing product is presumably due to the
existence of a small amount of free PVP in the nanoparticle
stock solution even after intensive washing process. In addition,
the simultaneous encapsulation of dierent types of nano-
particles within the composites can also be achieved easily.
Although we just demonstrated this exibility using 15 and 50
nm Au nanoparticles (Figure 2d), multifunctional composites
could be prepared by encapsulating more than one types of
nanoparticles with judicious selection.
The crystallinity of the obtained composites was investigated
by powder X-ray diraction (XRD) measurements. As shown in
Figure 3 and Figure S7, all the samples display an intense peak
at 2.79, moderate peaks at 4.84, 5.60, and 7.39, and weak
peaks at 9.73 and 25.42 in their diraction patterns, which is
Figure 3. Powder XRD patterns for as-synthesized COF and COF
composite containing of 0.20 wt % 15 nm Au nanoparticles and
simulated XRD pattern for TAPB-DMTP-COF. Inset is the same
XRD pattern for the Au/COF composite but with the adjusted
intensity scale, where weak peaks associated with diraction of COF
can be observed but those assignable to Au nanoparticles cannot.
D DOI: 10.1021/acsami.6b16267
Research Article
consistent with that of TAPB-DMTP-COF previously
reported,33 suggesting that the TAPB-DMTP-COF materials
synthesized using current protocol are highly crystalline and
that the incorporation of nanoparticles does not degrade
obviously the crystallinity of framework matrices. The
diraction peaks assignable to nanoparticles are too weak to
be observed clearly in the patterns of hybrid composites
presumably due to their low contents (and small sizes).
However, energy-dispersive X-ray microanalysis (EDX) (Figure
S9) and inductively coupled plasma analysis (ICP) conrm
explicitly their existence in the composites. Thermogravimetric
analysis (TGA) (Figure S11) shows that the nanoparticle/COF
composites are stable in nitrogen up to 400 C without obvious
weight loss, as the pure TAPB-DMTP-COF does.
The porosity of evacuated composites was investigated by
nitrogen-sorption measurements. All composites display type
IV isotherms (Figure 4a), as pure TAPB-DMTP-COF sample
Figure 4. (a) Nitrogen-sorption isotherms for the activated COF and
COF composites individually containing 0.10 and 0.20 wt % 15 nm Au
nanoparticles, 0.38 wt % 50 nm Au nanoparticles, and 0.26 wt % 25
100 nm Au nanorods at 77 K up to 1 bar. (b) Pore-size distributions
for COF and COF composite containing 0.20 wt % 15 nm Au
nanoparticles.
does, with steep increase in nitrogen uptake at low relative
pressure (<0.01), indicating the existence of micropores, and a
step in the relative pressure range of 0.100.20, corresponding
to the condensation of nitrogen in mesopores. By applying the
consistency criteria,64,65 their BrunauerEmmettTeller
(BET) surface areas were estimated. As shown in Table S1,
compared with the pure COF sample, composites display
slightly decreased BET surface areas due to the mass
contributions of nonporous nanoparticles and PVP. The pore
size distributions within composites were further evaluated
from their isotherms using nonlocal density functional theory
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces Research Article

(NLDFT, based on N2-cylindrical pores-oxide surface model).

All samples exhibit the similar distribution patterns with a main
pore width centered at 3.24 nm (Figure 4b and Figure S13),
suggesting that the incorporated nanoparticles functionalized
with PVP do not occupy the channels of the 2D TAPB-DMTP-
COF matrices due to their large sizes.
The accessibility and catalytic activity of the encapsulated Au
nanoparticles functionalized with PVP were probed in the well-
studied reduction reaction of 4-nitrophenol by NaBH4.43,5961
Although the aqueous solution of 4-nitrophenol undergoes a
rapid color change (with a UVvis absorption peak shift from
319 to 400 nm) after adding NaBH4 due to the formation of 4-
nitrophenolate ions, the reduction reaction does not proceed
substantially in the absence of suitable catalysts (such as Au, Ag,
Pd, and Pt nanoparticles). Figure 5a shows the UVvis spectra
of the reaction solution in the presence of COF composite
containing 0.20 wt % 15 nm Au nanoparticles. The absorption
peak at 400 nm characteristic for 4-nitrophenolate was
observed to decrease in intensity rapidly and disappear
eventually after 10 min, suggesting that the COF composite
does catalyze 4-nitrophenolate reduction. Since the COF itself,
in the control experiment, exhibits no propensity to catalyze the
reduction reaction, the above result indicates that the 4-
nitrophenol molecules can diuse quickly through the channels
of TAPB-DMTP-COF matrix and react on surfaces of the
active Au nanoparticles. In addition, the appearance of the new
peak at 300 nm and the well-dened isosbestic point at 315
nm in the UVvis spectra of the reaction solution suggests that
the COF composite selectively catalyzes the reduction of 4-
nitrophenol to give 4-aminophenol as the sole product.66 Given
that NaBH4 concentration used in the reaction is much higher
than that of 4-nitrophenol, pseudo-rst-order kinetics is
expected for the above catalytic reaction.43,59,61 Based on the
linear relationship between ln[At/A0] and time (where At and
A0 are the absorbance of reaction solution at 400 nm at time t
and 0, respectively) (Figure S14), the apparent rate constant k
was calculated to be 0.46 min1 for the reaction catalyzed by
COF composites containing 0.20 wt % 13 nm Au nanoparticles.
The catalytic activity (in terms of TOF) of the obtained 0.20 wt
% 13 nm Au/COF composite is higher than those of
composites of Au nanoparticles encapsulated in mesoporous
silica and porous carbon tested under similar conditions (Table Figure 5. Evaluation of catalytic performances of Au nanoparticle/
S2).67,68 COF composites in 4-nitrophenol reduction by NaBH4. (a) UVvis
Taking advantage of the exibility of current encapsulation spectra of the reaction solution in the presence of composite
method, we further investigated the eects of contents, sizes, containing 0.20 wt % 15 nm Au nanoparticles recorded at 2 min
and shapes of Au nanoparticles embedded in COF matrices on intervals. (b) Catalytic conversion of 4-nitrophenol versus reaction
time with composites containing individually 0.20 wt % 15 nm Au
the catalytic performances of composites under the same nanoparticles, 0.26 wt % 25 100 nm Au nanorods, and 0.38 wt % 50
conditions. As showed in Figure 5b and Figure S14, all nm Au nanoparticles, as catalysts. (c) The reusability of composite
composite samples can catalyze 4-nitrophenol reduction but containing 0.20 wt % 15 nm Au nanoparticles as catalyst for six
display dierent activities. On the one hand, when composites consecutive cycles of reactions.
contain the same type of Au nanoparticles, their catalytic
performances are nanoparticle content dependent. For
example, the composite containing 0.10 wt % 15 nm gold lower activity (with rate constant of 0.12 min1) (Figure S14e
nanoparticles displays lower catalytic activity (with a smaller h), respectively, in comparison with that incorporated with 15
rate constant of 0.36 min1) than the 0.20 wt % sample does nm nanoparticles (0.20 wt %). The 15 nm Au nanoparticles
(Figure S14ad). On the other hand, when dierent types of behave more active presumably as the result of their higher
Au nanoparticles are incorporated individually in TAPB- surface areavolume ratio, in comparison with 25 100 nm
DMTP-COF, the catalytic performances of the resulting rods and 50 nm nanoparticles.59,61
composites are inuenced predominantly by the sizes and The reusability of nanoparticle/COF composites as catalysts
shapes of nanoparticles. For example, even with higher Au for the reduction of 4-nitrophenol was further conrmed by the
contents, composites containing 25 100 nm rods (0.26 wt %) observation of the similar conversion for the same reaction time
and 50 nm nanoparticles (0.38 wt %) show a slightly decreased (10 min) for six consecutive cycles (the slightly decreased
catalytic activity (with rate constant of 0.36 min1) and much conversions in the later catalysis cycles are presumably caused
E DOI: 10.1021/acsami.6b16267
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces
by the loss of catalyst (nanoparticle/COF) during the washing
process between cycles) (Figure 5c). The XRD and TEM
measurements (Figure S16) show that the mesostructures and
crystallinity of nanoparticle/COF composites were preserved
after the catalytic reactions, and no obvious degradation was
observed, suggesting their excellent stability.
CONCLUSION
In summary, catalytically active Au nanoparticles with dierent
sizes and shapes have been encapsulated successfully in the 2D
TAPB-DMTP-COF with tunable contents based on the surface
functionalization of nanoparticles with PVP and the optimiza-
tion of COF synthesis. The framework matrix of the resulting
composites retains its thermal stability, high crystallinity, large
surface area, and open mesoporous structures. The accessibility
and catalytic activity of the embedded Au nanoparticles were
examined in the reaction of 4-nitrophenol reduction by NaBH4.
The COF composites display recyclable catalytic performance
with activities relevant to the contents, sizes, and shapes of the
encapsulated nanoparticles. With this simple model reaction,
we validated the feasibility of the nanoparticle-encapsulation
strategy for imparting catalytic functionality to 2D COF
materials for the rst time. The Au nanoparticle/TAPB-
DMTP-COF composites prepared here could be used for
other catalytic reactions where the framework matrix is still
chemically and thermally stable. In addition, the possible
molecular sieving eect originating from the framework
matrices for the catalytic applications has not been evaluated
further in this work due to the large pore sizes of TAPB-
DMTP-COF (3.24 nm), which, however, could be anticipated
for the composites prepared using current encapsulation
method with other 2D or 3D COFs possessing smaller pore
sizes (and with other nanoparticles). Finally, beyond the
traditional catalysis, this simple and exible encapsulation
method could be applied to prepare (multi)functional COF
composites integrated with other nanoparticle-relevant (e.g.,
optical and magnetic) properties for various applications such
as sensing, drug delivery, and bioimaging.
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.6b16267.
Synthetic procedures and characterization details, Figures
S1S17, and Tables S1 and S2 (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail zhugs100@nenu.edu.cn (G.Z.).
*E-mail chilf@suda.edu.cn (L.C.).
*E-mail glu@suda.edu.cn (G.L.).
ORCID
Kun Liu: 0000-0003-2940-9814
Guang Lu: 0000-0001-8392-2980
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work is supported by the National Natural Science
Foundation of China (Grant 21371127), the Collaborative
Innovation Center of Suzhou Nano Science and Technology, a
F DOI: 10.1021/acsami.6b16267
Research Article
project funded by the Priority Academic Program Development
of Jiangsu Higher Education Institutions (PAPD), and the
Young Thousand Talented Program.
REFERENCES
(1) Cote, A. P.; Benin, A. I.; Ockwig, N. W.; OKeeffe, M.; Matzger,
A. J.; Yaghi, O. M. Porous, Crystalline, Covalent Organic Frameworks.
Science 2005, 310, 11661170.
(2) El-Kaderi, H. M.; Hunt, J. R.; Mendoza-Cortes, J. L.; Cote, A. P.;
Taylor, R. E.; O Keeffe, M.; Yaghi, O. M. Designed Synthesis of 3D
Covalent Organic Frameworks. Science 2007, 316, 268272.
(3) Feng, X.; Ding, X. S.; Jiang, D. L. Covalent Organic Frameworks.
Chem. Soc. Rev. 2012, 41, 60106022.
(4) Colson, J. W.; Dichtel, W. R. Rationally Synthesized Two-
Dimensional Polymers. Nat. Chem. 2013, 5, 453465.
(5) Ding, S.-Y.; Wang, W. Covalent Organic Frameworks (COFs):
from Design to Applications. Chem. Soc. Rev. 2013, 42, 548568.
(6) Waller, P. J.; Gandara, F.; Yaghi, O. M. Chemistry of Covalent
Organic Frameworks. Acc. Chem. Res. 2015, 48, 30533063.
(7) Slater, A. G.; Cooper, A. I. Porous Materials. Function-Led
Design of New Porous Materials. Science 2015, 348, aaa8075.
(8) Kandambeth, S.; Mallick, A.; Lukose, B.; Mane, M. V.; Heine, T.;
Banerjee, R. Construction of Crystalline 2D Covalent Organic
Frameworks with Remarkable Chemical (Acid/Base) Stability via A
Combined Reversible and Irreversible Route. J. Am. Chem. Soc. 2012,
134, 1952419527.
(9) Han, S. S.; Furukawa, H.; Yaghi, O. M.; Goddard, W. A., III
Covalent Organic Frameworks as Exceptional Hydrogen Storage
Materials. J. Am. Chem. Soc. 2008, 130, 1158011581.
(10) Furukawa, H.; Yaghi, O. M. Storage of Hydrogen, Methane, and
Carbon Dioxide in Highly Porous Covalent Organic Frameworks for
Clean Energy Applications. J. Am. Chem. Soc. 2009, 131, 88758883.
(11) Doonan, C. J.; Tranchemontagne, D. J.; Glover, T. G.; Hunt, J.
R.; Yaghi, O. M. Exceptional Ammonia Uptake by A Covalent Organic
Framework. Nat. Chem. 2010, 2, 235238.
(12) Huang, N.; Chen, X.; Krishna, R.; Jiang, D. Two-Dimensional
Covalent Organic Frameworks for Carbon Dioxide Capture through
Channel-Wall Functionalization. Angew. Chem., Int. Ed. 2015, 54,
29862990.
(13) Zeng, Y.; Zou, R.; Zhao, Y. Covalent Organic Frameworks for
CO2 Capture. Adv. Mater. 2016, 28, 28552873.
(14) Lu, H.; Wang, C.; Chen, J.; Ge, R.; Leng, W.; Dong, B.; Huang,
J.; Gao, Y. A Novel 3D Covalent Organic Framework Membrane
Grown on A Porous -Al2O3 Substrate under Solvothermal
Conditions. Chem. Commun. 2015, 51, 1556215565.
(15) Fu, J.; Das, S.; Xing, G.; Ben, T.; Valtchev, V.; Qiu, S.
Fabrication of COF-MOF Composite Membranes and Their Highly
Selective Separation of H2/CO2. J. Am. Chem. Soc. 2016, 138, 7673
7680.
(16) Qian, H.-L.; Yang, C.-X.; Yan, X.-P. Bottom-up Synthesis of
Chiral Covalent Organic Frameworks and Their Bound Capillaries for
Chiral Separation. Nat. Commun. 2016, 7, 12104.
(17) Zhao, H.; Jin, Z.; Su, H.; Jing, X.; Sun, F.; Zhu, G. Targeted
Synthesis of A 2D Ordered Porous Organic Framework for Drug
Release. Chem. Commun. 2011, 47, 63896391.
(18) Fang, Q.; Wang, J.; Gu, S.; Kaspar, R. B.; Zhuang, Z.; Zheng, J.;
Guo, H.; Qiu, S.; Yan, Y. 3D Porous Crystalline Polyimide Covalent
Organic Frameworks for Drug Delivery. J. Am. Chem. Soc. 2015, 137,
83528355.
(19) Bai, L.; Phua, S. Z. F.; Lim, W. Q.; Jana, A.; Luo, Z.; Tham, H.
P.; Zhao, L.; Gao, Q.; Zhao, Y. Nanoscale Covalent Organic
Frameworks as Smart Carriers for Drug Delivery. Chem. Commun.
2016, 52, 41284131.
(20) DeBlase, C. R.; Silberstein, K. E.; Truong, T.-T.; Abruna, H. D.;
Dichtel, W. R. -Ketoenamine-Linked Covalent Organic Frameworks
Capable of Pseudocapacitive Energy Storage. J. Am. Chem. Soc. 2013,
135, 1682116824.
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces
(21) Vyas, V. S.; Haase, F.; Stegbauer, L.; Savasci, G.; Podjaski, F.;
Ochsenfeld, C.; Lotsch, B. V. A Tunable Azine Covalent Organic
Framework Platform for Visible Light-Induced Hydrogen Generation.
Nat. Commun. 2015, 6, 8508.
(22) Lin, S.; Diercks, C. S.; Zhang, Y.-B.; Kornienko, N.; Nichols, E.
M.; Zhao, Y.; Paris, A. R.; Kim, D.; Yang, P.; Yaghi, O. M.; Chang, C. J.
Covalent Organic Frameworks Comprising Cobalt Porphyrins for
Catalytic CO2 Reduction in Water. Science 2015, 349, 12081213.
(23) Liao, H.; Wang, H.; Ding, H.; Meng, X.; Xu, H.; Wang, B.; Ai,
X.; Wang, C. A 2D Porous Porphyrin-Based Covalent Organic
Framework for Sulfur Storage in LithiumSulfur Batteries. J. Mater.
Chem. A 2016, 4, 74167421.
(24) Huang, N.; Ding, X.; Kim, J.; Ihee, H.; Jiang, D. A
Photoresponsive Smart Covalent Organic Framework. Angew. Chem.,
Int. Ed. 2015, 54, 87048707.
(25) Crowe, J. W.; Baldwin, L. A.; McGrier, P. L. Luminescent
Covalent Organic Frameworks Containing a Homogeneous and
Heterogeneous Distribution of Dehydrobenzoannulene Vertex Units.
J. Am. Chem. Soc. 2016, 138, 1012010123.
(26) Dalapati, S.; Jin, E.; Addicoat, M.; Heine, T.; Jiang, D. Highly
Emissive Covalent Organic Frameworks. J. Am. Chem. Soc. 2016, 138,
57975800.
(27) Lin, G.; Ding, H.; Yuan, D.; Wang, B.; Wang, C. A Pyrene-
Based, Fluorescent Three-Dimensional Covalent Organic Framework.
J. Am. Chem. Soc. 2016, 138, 33023305.
(28) Ding, S.-Y.; Dong, M.; Wang, Y.-W.; Chen, Y.-T.; Wang, H.-Z.;
Su, C.-Y.; Wang, W. Thioether-Based Fluorescent Covalent Organic
Framework for Selective Detection and Facile Removal of Mercury-
(II). J. Am. Chem. Soc. 2016, 138, 30313037.
(29) Wan, S.; Guo, J.; Kim, J.; Ihee, H.; Jiang, D. A Belt-Shaped, Blue
Luminescent, and Semiconducting Covalent Organic Framework.
Angew. Chem., Int. Ed. 2008, 47, 88268830.
(30) Wan, S.; Guo, J.; Kim, J.; Ihee, H.; Jiang, D. A Photoconductive
Covalent Organic Framework: Self-Condensed Arene Cubes Com-
posed of Eclipsed 2D Polypyrene Sheets for Photocurrent Generation.
Angew. Chem., Int. Ed. 2009, 48, 54395442.
(31) Ding, H.; Li, Y.; Hu, H.; Sun, Y.; Wang, J.; Wang, C.; Wang, C.;
Zhang, G.; Wang, B.; Xu, W.; Zhang, D. A Tetrathiafulvalene-Based
Electroactive Covalent Organic Framework. Chem. - Eur. J. 2014, 20,
1461414618.
(32) Fang, Q.; Gu, S.; Zheng, J.; Zhuang, Z.; Qiu, S.; Yan, Y. 3D
Microporous Base-Functionalized Covalent Organic Frameworks for
Size-Selective Catalysis. Angew. Chem., Int. Ed. 2014, 53, 28782882.
(33) Xu, H.; Gao, J.; Jiang, D. Stable, Crystalline, Porous, Covalent
Organic Frameworks as A Platform for Chiral Organocatalysts. Nat.
Chem. 2015, 7, 905912.
(34) Wang, X.; Han, X.; Zhang, J.; Wu, X.; Liu, Y.; Cui, Y.
Homochiral 2D Porous Covalent Organic Frameworks for Heteroge-
neous Asymmetric Catalysis. J. Am. Chem. Soc. 2016, 138, 12332
12335.
(35) Xu, H.; Tao, S.; Jiang, D. Proton Conduction in Crystalline and
Porous Covalent Organic Frameworks. Nat. Mater. 2016, 15, 722
727.
(36) Ma, H.; Liu, B.; Li, B.; Zhang, L.; Li, Y.-G.; Tan, H.-Q.; Zang,
H.-Y.; Zhu, G. Cationic Covalent Organic Frameworks: A Simple
Platform of Anionic Exchange for Porosity Tuning and Proton
Conduction. J. Am. Chem. Soc. 2016, 138, 58975903.
(37) Chandra, S.; Kundu, T.; Dey, K.; Addicoat, M.; Heine, T.;
Banerjee, R. Interplaying Intrinsic and Extrinsic Proton Conductivities
in Covalent Organic Frameworks. Chem. Mater. 2016, 28, 14891494.
(38) Bertrand, G. H. V.; Michaelis, V. K.; Ong, T.-C.; Griffin, R. G.;
Dinca, M. Thiophene-Based Covalent Organic Frameworks. Proc. Natl.
Acad. Sci. U. S. A. 2013, 110, 49234928.
(39) Medina, D. D.; Werner, V.; Auras, F.; Tautz, R.; Dogru, M.;
Schuster, J.; Linke, S.; Doblinger, M.; Feldmann, J.; Knochel, P.; Bein,
T. Oriented Thin Films of A Benzodithiophene Covalent Organic
Framework. ACS Nano 2014, 8, 40424052.
(40) Cai, S.-L.; Zhang, Y.-B.; Pun, A. B.; He, B.; Yang, J.; Toma, F.
M.; Sharp, I. D.; Yaghi, O. M.; Fan, J.; Zheng, S.-R.; Zhang, W.-G.; Liu,
G DOI: 10.1021/acsami.6b16267
Research Article
Y. Tunable Electrical Conductivity in Oriented Thin Films of
Tetrathiafulvalene-Based Covalent Organic Framework. Chem. Sci.
2014, 5, 46934700.
(41) Kandambeth, S.; Venkatesh, V.; Shinde, D. B.; Kumari, S.;
Halder, A.; Verma, S.; Banerjee, R. Self-Templated Chemically Stable
Hollow Spherical Covalent Organic Framework. Nat. Commun. 2015,
6, 6786.
(42) Ding, S.-Y.; Gao, J.; Wang, Q.; Zhang, Y.; Song, W.-G.; Su, C.-
Y.; Wang, W. Construction of Covalent Organic Framework for
Catalysis: Pd/COF-LZU1 in SuzukiMiyaura Coupling Reaction. J.
Am. Chem. Soc. 2011, 133, 1981619822.
(43) Pachfule, P.; Kandambeth, S.; Daz, D. D.; Banerjee, R. Highly
Stable Covalent Organic Framework-Au Nanoparticles Hybrids for
Enhanced Activity for Nitrophenol Reduction. Chem. Commun. 2014,
50, 31693172.
(44) Pachfule, P.; Panda, M. K.; Kandambeth, S.; Shivaprasad, S. M.;
Daz, D. D.; Banerjee, R. Multifunctional and Robust Covalent
Organic Framework-Nanoparticle Hybrids. J. Mater. Chem. A 2014, 2,
79447952.
(45) Mullangi, D.; Nandi, S.; Shalini, S.; Sreedhala, S.; Vinod, C. P.;
Vaidhyanathan, R. Pd Loaded Amphiphilic COF as Catalyst for Multi-
fold Heck Reactions, C-C Couplings and CO Oxidation. Sci. Rep.
2015, 5, 10876.
(46) Kalidindi, S. B.; Oh, H.; Hirscher, M.; Esken, D.; Wiktor, C.;
Turner, S.; Van Tendeloo, G.; Fischer, R. A. Metal@COFs: Covalent
Organic Frameworks as Templates for Pd Nanoparticles and
Hydrogen Storage Properties of Pd@COF-102 Hybrid Material.
Chem. - Eur. J. 2012, 18, 1084810856.
(47) Cushing, B. L.; Kolesnichenko, V. L.; OConnor, C. J. Recent
Advances in the Liquid-Phase Syntheses of Inorganic Nanoparticles.
Chem. Rev. 2004, 104, 38933946.
(48) Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E. Shape-Controlled
Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex
Physics? Angew. Chem., Int. Ed. 2009, 48, 60103.
(49) Xu, F.; Jin, S.; Zhong, H.; Wu, D.; Yang, X.; Chen, X.; Wei, H.;
Fu, R.; Jiang, D. Electrochemically Active, Crystalline, Mesoporous
Covalent Organic Frameworks on Carbon Nanotubes for Synergistic
Lithium-Ion Battery Energy Storage. Sci. Rep. 2015, 5, 8225.
(50) Pachfule, P.; Kandmabeth, S.; Mallick, A.; Banerjee, R. Hollow
Tubular Porous Covalent Organic Framework (COF) Nanostructures.
Chem. Commun. 2015, 51, 1171711720.
(51) Tan, J.; Namuangruk, S.; Kong, W.; Kungwan, N.; Guo, J.;
Wang, C. Manipulation of Amorphous-to-Crystalline Transformation:
Towards the Construction of Covalent Organic Framework Hybrid
Microspheres with NIR Photothermal Conversion Ability. Angew.
Chem., Int. Ed. 2016, 55, 1397913984.
(52) Colson, J. W.; Woll, A. R.; Mukherjee, A.; Levendorf, M. P.;
Spitler, E. L.; Shields, V. B.; Spencer, M. G.; Park, J.; Dichtel, W. R.
Oriented 2D Covalent Organic Framework Thin Films on Single-
Layer Grapheme. Science 2011, 332, 228231.
(53) Spitler, E. L.; Colson, J. W.; Uribe-Romo, F. J.; Woll, A. R.;
Giovino, M. R.; Saldivar, A.; Dichtel, W. R. Lattice Expansion of
Highly Oriented 2D Phthalocyanine Covalent Organic Framework
Films. Angew. Chem., Int. Ed. 2012, 51, 26232627.
(54) Gou, X.; Zhang, Q.; Wu, Y.; Zhao, Y.; Shi, X.; Fan, X.; Huang,
L.; Lu, G. Preparation and Engineering of Oriented 2D Covalent
Organic Framework Thin Films. RSC Adv. 2016, 6, 3919839203.
(55) Corma, A.; Garcia, H. Supported Gold Nanoparticles as
Catalysts for Organic Reactions. Chem. Soc. Rev. 2008, 37, 20962126.
(56) Sun, Y.; Xia, Y. Shape-Controlled Synthesis of Gold and Silver
Nanoparticles. Science 2002, 298, 21762179.
(57) Li, Z.; Zhang, Y. Monodisperse Silica-Coated Polyvinylpyrro-
lidone/NaYF4 Nanocrystals with Multicolor Upconversion Fluores-
cence Emission. Angew. Chem., Int. Ed. 2006, 45, 77327735.
(58) Koczkur, K. M.; Mourdikoudis, S.; Polavarapu, L.; Skrabalak, S.
E. Polyvinylpyrrolidone (PVP) in Nanoparticle Synthesis. Dalton
Trans. 2015, 44, 1788317905.
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces Research Article

(59) Lee, J.; Park, J. C.; Song, H. A Nanoreactor Framework of A

Au@SiO2 Yolk/Shell Structure for Catalytic Reduction of p-Nitro-
phenol. Adv. Mater. 2008, 20, 15231528.
(60) Yuan, C.; Luo, W.; Zhong, L.; Deng, H.; Liu, J.; Xu, Y.; Dai, L.
Gold@Polymer Nanostructures with Tunable Permeability Shells for
Selective Catalysis. Angew. Chem., Int. Ed. 2011, 50, 35153519.
(61) Herves, P.; Perez-Lorenzo, M.; Liz-Marzan, L. M.; Dzubiella, J.;
Lu, Y.; Ballauff, M. Catalysis by Metallic Nanoparticles in Aqueous
Solution: Model Reactions. Chem. Soc. Rev. 2012, 41, 55775587.
(62) Liz-Marzan, L. M.; Giersig, M.; Mulvaney, P. Synthesis of
Nanosized Gold-Silica Core-Shell Particles. Langmuir 1996, 12, 4329
4335.
(63) Lu, G.; Li, S.; Guo, Z.; Farha, O. K.; Hauser, B. G.; Qi, X.;
Wang, Y.; Wang, X.; Han, S.; Liu, X.; DuChene, J. S.; Zhang, H.;
Zhang, Q.; Chen, X.; Ma, J.; Joachim Loo, S. C.; Wei, W. D.; Yang, Y.;
Hupp, J. T.; Huo, F. Imparting Functionality to A Metal-Organic
Framework Material by Controlled Nanoparticle Encapsulation. Nat.
Chem. 2012, 4, 310316.
(64) Thommes, M.; Kaneko, K.; Neimark, A. V.; Olivier, J. P.;
Rodriguez-Reinoso, F.; Rouquerol, J.; Sing, K. S. W. Physisorption of
Gases, with Special Reference to The Evaluation of Surface Area and
Pore Size Distribution (IUPAC Technical Report). Pure Appl. Chem.
2015, DOI: 10.1515/pac-2014-1117.
(65) Gomez-Gualdron, D. A.; Moghadam, P. Z.; Hupp, J. T.; Farha,
O. K.; Snurr, R. Q. Application of Consistency Criteria To Calculate
BET Areas of Micro- And Mesoporous MetalOrganic Frameworks. J.
Am. Chem. Soc. 2016, 138, 215224.
(66) Zhang, W.; Lu, G.; Cui, C.; Liu, Y.; Li, S.; Yan, W.; Xing, C.;
Chi, Y. R.; Yang, Y.; Huo, F. A Family of Metal-Organic Frameworks
Exhibiting Size-Selective Catalysis with Encapsulated Noble-Metal
Nanoparticles. Adv. Mater. 2014, 26, 40564060.
(67) Chen, J.; Zhang, R.; Han, L.; Tu, B.; Zhao, D. One-Pot
Synthesis of Thermally Stable Gold@Mesoporous Silica Core-Shell
Nanospheres with Catalytic Activity. Nano Res. 2013, 6, 871879.
(68) Guo, J.; Suslick, K. S. Gold Nanoparticles Encapsulated in
Porous Carbon. Chem. Commun. 2012, 48, 1109411096.

H DOI: 10.1021/acsami.6b16267
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX