Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
www.acsami.org
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
INTRODUCTION
Covalent organic frameworks (COFs) are a new class of porous
produced within the cavities of COFs with ultrasmall sizes and
clean surfaces.4246 New and enhanced performances that are
crystalline materials constructed by organic building blocks via relevant to the nanoparticle components have been observed
covalent bonds.18 The molecular engineering-based synthesis for the obtained nanoparticles/COF composites in organic
strategy of COFs allows the exible design for achieving unique catalysis4245 and hydrogen storage applications.46 Alternately,
structures and properties. Their two-dimensional (2D) or this kind of composite can be generated by encapsulating the
three-dimensional (3D) open network structures yield high preprepared nanoparticles during the framework synthesis. This
surface areas and accessible cavities or channels with uniform strategy is attractive since the compositions, sizes, and shapes
sizes ranging from angstroms to nanometers, which is attractive associated with the chemical and physical properties of
for many applications including gas storage,913 separa- nanoparticles can be feasibly tuned by their well-established
tions,1416 drug delivery,1719 and energy conversion and synthesis.47,48 COF materials can heterogeneously nucleate and
storage.2023 Built with functional moieties, COF materials can grow around the outer surfaces of some nanosized objects (e.g.,
be endowed with unique optical,2428 optoelectronic,2931 and carbon nanotubes with diameter of 50 nm,49 ZnO nanorods
catalytic properties.3234 Alternately, noninherent functional- with diameter of 100 nm,50 and 200 nm Fe3O4 spheres51)
ities and extended applications of COFs can be achieved by to give the coreshell structures, just as they did on the surface
reasonably integrating them with other functional materials. of a at substrate.5254 Nevertheless, although the encapsula-
The open porous structures and outstanding stability of tion strategy, in principle, is capable of incorporating any
COFs make them excellent host matrices for many functional nanoparticles with the desired chemical or physical properties
species such as proton carriers,3537 electron acceptors,3840
and enzymes.41 The cavities themselves of COF materials have Received: December 19, 2016
also been explored as nanoreactors for chemical reactions. Accepted: February 6, 2017
Based on the conned synthesis, metal nanoparticles can be
in COF materials, the nanoparticle-relevant catalysis applica- under the optimized experimental conditions. The composites
tions of the resulting COF composites have not been reported display high crystallinity, excellent thermal stability, large
yet. For 2D COF-based composites, the orientation of channels surface areas, and open mesopores that are substantially similar
and possible crystal defects (e.g., amorphous portion and to those of the pure TAPB-DMTP-COF. In the model reaction
stacking faults) in the framework matrices may also raise doubts of 4-nitrophenol reduction by NaBH4,43,5961 the composites
about the accessibility and catalytic activity of the enshrouded containing Au nanoparticles show recyclable catalytic capability,
nanoparticles. In addition, for the systematic investigation on but the pure COF material does not, establishing the
the catalytic performance of the resulting composites, it is accessibility and activity of the encapsulated nanoparticles
highly desirable to develop new encapsulation methods that within the 2D COF. In addition, systematic investigation with
enable the easy incorporation of smaller nanoparticles (<50 samples incorporated with dierent Au nanoparticles reveals
nm) (and even multiple types of nanoparticles) within COFs the nanoparticle-relevant catalytic performances of the
with tunable contents. composites, where higher activity (with rate constants of 0.46
In this study, we report a general encapsulation method for and 0.36 min1) was observed for samples containing 15 nm Au
incorporating nanoparticles with dierent sizes and shapes in a nanoparticles (0.20 and 0.10 wt %), moderate activity (with
2D COF material (Scheme 1). This strategy involves the rate constant of 0.36 min1) for that containing 25 100 nm
optimization of framework synthesis and the surface function- Au nanorods (0.26 wt %), and lower activity (with rate
alization of nanoparticles. The highly crystalline 2D TAPB- constant of 0.12 min1) for that containing 50 nm Au
DMTP-COF, we chose in this work, has been reported nanoparticles (0.38 wt %).
previously and displays outstanding chemical robustness and
thermal stability.33 Au nanoparticles were chosen as examples EXPERIMENTAL SECTION
to demonstrate our encapsulation method due to their easy
General Procedure of Nanoparticle Encapsulation in TAPB-
synthesis and excellent catalytic activities for many chemical DMTP-COF. A 20 mL borosilicate glass vial was charged with 1,3,5-
reactions.55 The surfaces of nanoparticles used in our work tris(4-aminophenyl)benzene (TAPB) (0.030 mmol, 10.5 mg), 2,5-
were functionalized with polyvinylpyrrolidone (PVP), an dimethoxyterephaldehyde (DMTP) (0.045 mmol, 8.7 mg), 4 mL of
amphiphilic surfactant, that has been widely used for 1,4-dioxanebutanol (v/v, 1:1), 0.5 mL of solution of PVP-modied
controlling the sizes, shapes, and surface properties of a variety nanoparticles in methanol, and 0.05 mL of 12 M aqueous acetic acid.
of nanoparticles.5658 Relying on the adsorption of PVP- The mixture was allowed to react at room temperature for 2 h. After
modied nanoparticles onto the initially formed polymeric 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
precursor of COF, instead of the heterogeneous nucleation temperature, the product was collected by centrifugation, washed
reported previously for the formation of coreshell-structured several times with tetrahydrofuran (THF) and acetone, and vacuum-
composites,4951 nanoparticles with sizes ranging from 3.8 to dried at room temperature overnight.
100 nm and with shapes in sphere and rod can be incorporated Other experiment and characterization details are provided in the
with high eciency in TAPB-DMTP-COF during its synthesis Supporting Information.
B DOI: 10.1021/acsami.6b16267
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces Research Article
by the loss of catalyst (nanoparticle/COF) during the washing project funded by the Priority Academic Program Development
process between cycles) (Figure 5c). The XRD and TEM of Jiangsu Higher Education Institutions (PAPD), and the
measurements (Figure S16) show that the mesostructures and Young Thousand Talented Program.
crystallinity of nanoparticle/COF composites were preserved
after the catalytic reactions, and no obvious degradation was REFERENCES
observed, suggesting their excellent stability.
(1) Cote, A. P.; Benin, A. I.; Ockwig, N. W.; OKeeffe, M.; Matzger,
CONCLUSION A. J.; Yaghi, O. M. Porous, Crystalline, Covalent Organic Frameworks.
Science 2005, 310, 11661170.
In summary, catalytically active Au nanoparticles with dierent (2) El-Kaderi, H. M.; Hunt, J. R.; Mendoza-Cortes, J. L.; Cote, A. P.;
sizes and shapes have been encapsulated successfully in the 2D Taylor, R. E.; O Keeffe, M.; Yaghi, O. M. Designed Synthesis of 3D
TAPB-DMTP-COF with tunable contents based on the surface Covalent Organic Frameworks. Science 2007, 316, 268272.
functionalization of nanoparticles with PVP and the optimiza- (3) Feng, X.; Ding, X. S.; Jiang, D. L. Covalent Organic Frameworks.
tion of COF synthesis. The framework matrix of the resulting Chem. Soc. Rev. 2012, 41, 60106022.
composites retains its thermal stability, high crystallinity, large (4) Colson, J. W.; Dichtel, W. R. Rationally Synthesized Two-
surface area, and open mesoporous structures. The accessibility Dimensional Polymers. Nat. Chem. 2013, 5, 453465.
and catalytic activity of the embedded Au nanoparticles were (5) Ding, S.-Y.; Wang, W. Covalent Organic Frameworks (COFs):
examined in the reaction of 4-nitrophenol reduction by NaBH4. from Design to Applications. Chem. Soc. Rev. 2013, 42, 548568.
(6) Waller, P. J.; Gandara, F.; Yaghi, O. M. Chemistry of Covalent
The COF composites display recyclable catalytic performance Organic Frameworks. Acc. Chem. Res. 2015, 48, 30533063.
with activities relevant to the contents, sizes, and shapes of the (7) Slater, A. G.; Cooper, A. I. Porous Materials. Function-Led
encapsulated nanoparticles. With this simple model reaction, Design of New Porous Materials. Science 2015, 348, aaa8075.
we validated the feasibility of the nanoparticle-encapsulation (8) Kandambeth, S.; Mallick, A.; Lukose, B.; Mane, M. V.; Heine, T.;
strategy for imparting catalytic functionality to 2D COF Banerjee, R. Construction of Crystalline 2D Covalent Organic
materials for the rst time. The Au nanoparticle/TAPB- Frameworks with Remarkable Chemical (Acid/Base) Stability via A
DMTP-COF composites prepared here could be used for Combined Reversible and Irreversible Route. J. Am. Chem. Soc. 2012,
other catalytic reactions where the framework matrix is still 134, 1952419527.
chemically and thermally stable. In addition, the possible (9) Han, S. S.; Furukawa, H.; Yaghi, O. M.; Goddard, W. A., III
molecular sieving eect originating from the framework Covalent Organic Frameworks as Exceptional Hydrogen Storage
matrices for the catalytic applications has not been evaluated Materials. J. Am. Chem. Soc. 2008, 130, 1158011581.
further in this work due to the large pore sizes of TAPB- (10) Furukawa, H.; Yaghi, O. M. Storage of Hydrogen, Methane, and
Carbon Dioxide in Highly Porous Covalent Organic Frameworks for
DMTP-COF (3.24 nm), which, however, could be anticipated
Clean Energy Applications. J. Am. Chem. Soc. 2009, 131, 88758883.
for the composites prepared using current encapsulation (11) Doonan, C. J.; Tranchemontagne, D. J.; Glover, T. G.; Hunt, J.
method with other 2D or 3D COFs possessing smaller pore R.; Yaghi, O. M. Exceptional Ammonia Uptake by A Covalent Organic
sizes (and with other nanoparticles). Finally, beyond the Framework. Nat. Chem. 2010, 2, 235238.
traditional catalysis, this simple and exible encapsulation (12) Huang, N.; Chen, X.; Krishna, R.; Jiang, D. Two-Dimensional
method could be applied to prepare (multi)functional COF Covalent Organic Frameworks for Carbon Dioxide Capture through
composites integrated with other nanoparticle-relevant (e.g., Channel-Wall Functionalization. Angew. Chem., Int. Ed. 2015, 54,
optical and magnetic) properties for various applications such 29862990.
as sensing, drug delivery, and bioimaging. (13) Zeng, Y.; Zou, R.; Zhao, Y. Covalent Organic Frameworks for
*
ASSOCIATED CONTENT
S Supporting Information
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
The Supporting Information is available free of charge on the Conditions. Chem. Commun. 2015, 51, 1556215565.
ACS Publications website at DOI: 10.1021/acsami.6b16267. (15) Fu, J.; Das, S.; Xing, G.; Ben, T.; Valtchev, V.; Qiu, S.
Synthetic procedures and characterization details, Figures Fabrication of COF-MOF Composite Membranes and Their Highly
S1S17, and Tables S1 and S2 (PDF) 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
AUTHOR INFORMATION Chiral Covalent Organic Frameworks and Their Bound Capillaries for
Corresponding Authors Chiral Separation. Nat. Commun. 2016, 7, 12104.
*E-mail zhugs100@nenu.edu.cn (G.Z.). (17) Zhao, H.; Jin, Z.; Su, H.; Jing, X.; Sun, F.; Zhu, G. Targeted
*E-mail chilf@suda.edu.cn (L.C.). Synthesis of A 2D Ordered Porous Organic Framework for Drug
*E-mail glu@suda.edu.cn (G.L.). Release. Chem. Commun. 2011, 47, 63896391.
(18) Fang, Q.; Wang, J.; Gu, S.; Kaspar, R. B.; Zhuang, Z.; Zheng, J.;
ORCID Guo, H.; Qiu, S.; Yan, Y. 3D Porous Crystalline Polyimide Covalent
Kun Liu: 0000-0003-2940-9814 Organic Frameworks for Drug Delivery. J. Am. Chem. Soc. 2015, 137,
Guang Lu: 0000-0001-8392-2980 83528355.
Notes (19) Bai, L.; Phua, S. Z. F.; Lim, W. Q.; Jana, A.; Luo, Z.; Tham, H.
The authors declare no competing nancial interest. P.; Zhao, L.; Gao, Q.; Zhao, Y. Nanoscale Covalent Organic
F DOI: 10.1021/acsami.6b16267
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces Research Article
(21) Vyas, V. S.; Haase, F.; Stegbauer, L.; Savasci, G.; Podjaski, F.; Y. Tunable Electrical Conductivity in Oriented Thin Films of
Ochsenfeld, C.; Lotsch, B. V. A Tunable Azine Covalent Organic Tetrathiafulvalene-Based Covalent Organic Framework. Chem. Sci.
Framework Platform for Visible Light-Induced Hydrogen Generation. 2014, 5, 46934700.
Nat. Commun. 2015, 6, 8508. (41) Kandambeth, S.; Venkatesh, V.; Shinde, D. B.; Kumari, S.;
(22) Lin, S.; Diercks, C. S.; Zhang, Y.-B.; Kornienko, N.; Nichols, E. Halder, A.; Verma, S.; Banerjee, R. Self-Templated Chemically Stable
M.; Zhao, Y.; Paris, A. R.; Kim, D.; Yang, P.; Yaghi, O. M.; Chang, C. J. Hollow Spherical Covalent Organic Framework. Nat. Commun. 2015,
Covalent Organic Frameworks Comprising Cobalt Porphyrins for 6, 6786.
Catalytic CO2 Reduction in Water. Science 2015, 349, 12081213. (42) Ding, S.-Y.; Gao, J.; Wang, Q.; Zhang, Y.; Song, W.-G.; Su, C.-
(23) Liao, H.; Wang, H.; Ding, H.; Meng, X.; Xu, H.; Wang, B.; Ai, Y.; Wang, W. Construction of Covalent Organic Framework for
X.; Wang, C. A 2D Porous Porphyrin-Based Covalent Organic Catalysis: Pd/COF-LZU1 in SuzukiMiyaura Coupling Reaction. J.
Framework for Sulfur Storage in LithiumSulfur Batteries. J. Mater. Am. Chem. Soc. 2011, 133, 1981619822.
Chem. A 2016, 4, 74167421. (43) Pachfule, P.; Kandambeth, S.; Daz, D. D.; Banerjee, R. Highly
(24) Huang, N.; Ding, X.; Kim, J.; Ihee, H.; Jiang, D. A Stable Covalent Organic Framework-Au Nanoparticles Hybrids for
Photoresponsive Smart Covalent Organic Framework. Angew. Chem., Enhanced Activity for Nitrophenol Reduction. Chem. Commun. 2014,
Int. Ed. 2015, 54, 87048707.
50, 31693172.
(25) Crowe, J. W.; Baldwin, L. A.; McGrier, P. L. Luminescent
(44) Pachfule, P.; Panda, M. K.; Kandambeth, S.; Shivaprasad, S. M.;
Covalent Organic Frameworks Containing a Homogeneous and
Daz, D. D.; Banerjee, R. Multifunctional and Robust Covalent
Heterogeneous Distribution of Dehydrobenzoannulene Vertex Units.
Organic Framework-Nanoparticle Hybrids. J. Mater. Chem. A 2014, 2,
J. Am. Chem. Soc. 2016, 138, 1012010123.
(26) Dalapati, S.; Jin, E.; Addicoat, M.; Heine, T.; Jiang, D. Highly 79447952.
Emissive Covalent Organic Frameworks. J. Am. Chem. Soc. 2016, 138, (45) Mullangi, D.; Nandi, S.; Shalini, S.; Sreedhala, S.; Vinod, C. P.;
57975800. Vaidhyanathan, R. Pd Loaded Amphiphilic COF as Catalyst for Multi-
(27) Lin, G.; Ding, H.; Yuan, D.; Wang, B.; Wang, C. A Pyrene- fold Heck Reactions, C-C Couplings and CO Oxidation. Sci. Rep.
Based, Fluorescent Three-Dimensional Covalent Organic Framework. 2015, 5, 10876.
J. Am. Chem. Soc. 2016, 138, 33023305. (46) Kalidindi, S. B.; Oh, H.; Hirscher, M.; Esken, D.; Wiktor, C.;
(28) Ding, S.-Y.; Dong, M.; Wang, Y.-W.; Chen, Y.-T.; Wang, H.-Z.; Turner, S.; Van Tendeloo, G.; Fischer, R. A. Metal@COFs: Covalent
Su, C.-Y.; Wang, W. Thioether-Based Fluorescent Covalent Organic Organic Frameworks as Templates for Pd Nanoparticles and
Framework for Selective Detection and Facile Removal of Mercury- Hydrogen Storage Properties of Pd@COF-102 Hybrid Material.
(II). J. Am. Chem. Soc. 2016, 138, 30313037. Chem. - Eur. J. 2012, 18, 1084810856.
(29) Wan, S.; Guo, J.; Kim, J.; Ihee, H.; Jiang, D. A Belt-Shaped, Blue (47) Cushing, B. L.; Kolesnichenko, V. L.; OConnor, C. J. Recent
Luminescent, and Semiconducting Covalent Organic Framework. Advances in the Liquid-Phase Syntheses of Inorganic Nanoparticles.
Angew. Chem., Int. Ed. 2008, 47, 88268830. Chem. Rev. 2004, 104, 38933946.
(30) Wan, S.; Guo, J.; Kim, J.; Ihee, H.; Jiang, D. A Photoconductive (48) Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E. Shape-Controlled
Covalent Organic Framework: Self-Condensed Arene Cubes Com- Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex
posed of Eclipsed 2D Polypyrene Sheets for Photocurrent Generation. Physics? Angew. Chem., Int. Ed. 2009, 48, 60103.
Angew. Chem., Int. Ed. 2009, 48, 54395442. (49) Xu, F.; Jin, S.; Zhong, H.; Wu, D.; Yang, X.; Chen, X.; Wei, H.;
(31) Ding, H.; Li, Y.; Hu, H.; Sun, Y.; Wang, J.; Wang, C.; Wang, C.; Fu, R.; Jiang, D. Electrochemically Active, Crystalline, Mesoporous
Zhang, G.; Wang, B.; Xu, W.; Zhang, D. A Tetrathiafulvalene-Based Covalent Organic Frameworks on Carbon Nanotubes for Synergistic
Electroactive Covalent Organic Framework. Chem. - Eur. J. 2014, 20, Lithium-Ion Battery Energy Storage. Sci. Rep. 2015, 5, 8225.
1461414618. (50) Pachfule, P.; Kandmabeth, S.; Mallick, A.; Banerjee, R. Hollow
(32) Fang, Q.; Gu, S.; Zheng, J.; Zhuang, Z.; Qiu, S.; Yan, Y. 3D Tubular Porous Covalent Organic Framework (COF) Nanostructures.
Microporous Base-Functionalized Covalent Organic Frameworks for Chem. Commun. 2015, 51, 1171711720.
Size-Selective Catalysis. Angew. Chem., Int. Ed. 2014, 53, 28782882. (51) Tan, J.; Namuangruk, S.; Kong, W.; Kungwan, N.; Guo, J.;
(33) Xu, H.; Gao, J.; Jiang, D. Stable, Crystalline, Porous, Covalent Wang, C. Manipulation of Amorphous-to-Crystalline Transformation:
Organic Frameworks as A Platform for Chiral Organocatalysts. Nat. Towards the Construction of Covalent Organic Framework Hybrid
Chem. 2015, 7, 905912. Microspheres with NIR Photothermal Conversion Ability. Angew.
(34) Wang, X.; Han, X.; Zhang, J.; Wu, X.; Liu, Y.; Cui, Y. Chem., Int. Ed. 2016, 55, 1397913984.
Homochiral 2D Porous Covalent Organic Frameworks for Heteroge- (52) Colson, J. W.; Woll, A. R.; Mukherjee, A.; Levendorf, M. P.;
neous Asymmetric Catalysis. J. Am. Chem. Soc. 2016, 138, 12332
Spitler, E. L.; Shields, V. B.; Spencer, M. G.; Park, J.; Dichtel, W. R.
12335.
Oriented 2D Covalent Organic Framework Thin Films on Single-
(35) Xu, H.; Tao, S.; Jiang, D. Proton Conduction in Crystalline and
Porous Covalent Organic Frameworks. Nat. Mater. 2016, 15, 722 Layer Grapheme. Science 2011, 332, 228231.
(53) Spitler, E. L.; Colson, J. W.; Uribe-Romo, F. J.; Woll, A. R.;
727.
(36) Ma, H.; Liu, B.; Li, B.; Zhang, L.; Li, Y.-G.; Tan, H.-Q.; Zang, Giovino, M. R.; Saldivar, A.; Dichtel, W. R. Lattice Expansion of
H.-Y.; Zhu, G. Cationic Covalent Organic Frameworks: A Simple Highly Oriented 2D Phthalocyanine Covalent Organic Framework
Platform of Anionic Exchange for Porosity Tuning and Proton Films. Angew. Chem., Int. Ed. 2012, 51, 26232627.
Conduction. J. Am. Chem. Soc. 2016, 138, 58975903. (54) Gou, X.; Zhang, Q.; Wu, Y.; Zhao, Y.; Shi, X.; Fan, X.; Huang,
(37) Chandra, S.; Kundu, T.; Dey, K.; Addicoat, M.; Heine, T.; L.; Lu, G. Preparation and Engineering of Oriented 2D Covalent
Banerjee, R. Interplaying Intrinsic and Extrinsic Proton Conductivities Organic Framework Thin Films. RSC Adv. 2016, 6, 3919839203.
in Covalent Organic Frameworks. Chem. Mater. 2016, 28, 14891494. (55) Corma, A.; Garcia, H. Supported Gold Nanoparticles as
(38) Bertrand, G. H. V.; Michaelis, V. K.; Ong, T.-C.; Griffin, R. G.; Catalysts for Organic Reactions. Chem. Soc. Rev. 2008, 37, 20962126.
Dinca, M. Thiophene-Based Covalent Organic Frameworks. Proc. Natl. (56) Sun, Y.; Xia, Y. Shape-Controlled Synthesis of Gold and Silver
Acad. Sci. U. S. A. 2013, 110, 49234928. Nanoparticles. Science 2002, 298, 21762179.
(39) Medina, D. D.; Werner, V.; Auras, F.; Tautz, R.; Dogru, M.; (57) Li, Z.; Zhang, Y. Monodisperse Silica-Coated Polyvinylpyrro-
Schuster, J.; Linke, S.; Doblinger, M.; Feldmann, J.; Knochel, P.; Bein, lidone/NaYF4 Nanocrystals with Multicolor Upconversion Fluores-
T. Oriented Thin Films of A Benzodithiophene Covalent Organic cence Emission. Angew. Chem., Int. Ed. 2006, 45, 77327735.
Framework. ACS Nano 2014, 8, 40424052. (58) Koczkur, K. M.; Mourdikoudis, S.; Polavarapu, L.; Skrabalak, S.
(40) Cai, S.-L.; Zhang, Y.-B.; Pun, A. B.; He, B.; Yang, J.; Toma, F. E. Polyvinylpyrrolidone (PVP) in Nanoparticle Synthesis. Dalton
M.; Sharp, I. D.; Yaghi, O. M.; Fan, J.; Zheng, S.-R.; Zhang, W.-G.; Liu, Trans. 2015, 44, 1788317905.
G DOI: 10.1021/acsami.6b16267
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
ACS Applied Materials & Interfaces Research Article
H DOI: 10.1021/acsami.6b16267
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX