Expansion of the Graphdiyne Family: A Triphenylene-Cored Analogue

Mar 6, 2018 - This article is part of the Graphdiyne Materials: Preparation, Structure, and Function special issue. ... ACS Applied Materials & Interf...
2 downloads 3 Views 1MB Size
Download PDF
Subscriber access provided by UNIV OF NEW ENGLAND ARMIDALE

Expansion of the Graphdiyne Family: A Triphenylene-Cored Analogue Ryota Matsuoka, Ryojun Toyoda, Ryo Shiotsuki, Naoya Fukui, Keisuke Wada, Hiroaki Maeda, Ryota Sakamoto, Sono Sasaki, Hiroyasu Masunaga, Kosuke Nagashio, and Hiroshi Nishihara ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b00743 • Publication Date (Web): 06 Mar 2018 Downloaded from http://pubs.acs.org on March 6, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Expansion of the Graphdiyne Family: A Triphenylene-Cored Analogue Ryota Matsuoka,† Ryojun Toyoda,† Ryo Shiotsuki,† Naoya Fukui,† Keisuke Wada,† Hiroaki Maeda,† Ryota Sakamoto†,‡,* Sono Sasaki,⊥,║ Hiroyasu Masunaga,▷ Kosuke Nagashio,‡,O and Hiroshi Nishihara†,* †

Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

‡

JST-PRESTO, 4-1-8, Honcho, Kawaguchi, Saitama 332-0012, Japan

⊥

Faculty of Fiber Science and Engineering, Kyoto Institute of Technology, Matsugasaki Hashikami-cho 1, Sakyo-ku, Kyoto 606-8585, Japan

║

RIKEN SPring-8 Center, Hyogo 679-5148, Japan

▷

Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan

O

Department of Materials Engineering, The University of Tokyo, Tokyo 113-8656, Japan

ABSTRACT: Graphdiyne (GDY) comprises an important class in functional covalent organic nanosheets based on carbon-carbon bond formation, and recent focus has collected in the expansion of its variations. Here we report on the synthesis of a GDY analogue, TP-GDY, which has triphenylene as the aromatic core. Our liquid/liquid interfacial synthesis for GDY (J. Am. Chem. Soc. 2017, 139, 3145) was modified for hexaethynyltriphenylene monomer to afford a TP-GDY film with a free-standing morphology, a smooth texture, a domain size of >1 mm, and a thickness of 220 nm. Resultant TP-GDY is characterized by series of microscopies and spectroscopies, thermogravimetric and gas adsorption analyses.

KEYWORDS: graphdiyne, interfacial synthesis, nanosheets, two-dimensional materials, triphenylene

covalent-organic

Recent attention of two-dimensional (2D) materials has been chiefly supported by inorganic nanosheets, such as graphene1 and transition metal dichalcogenides.2 Their counterpart corresponds to moleculebased nanosheets, including metal-organic nanosheets (MONs) and covalent organic nanosheets (CONs).3-5 The significant feature of MONs and CONs lies in diversity in compositions and structures, being designed at will by tuning molecular components. In tethering constitutive monomers, the rational strategy for molecule-based nanosheets is to employ reversible chemical bonding, such as metal-ligand coordination6-8 and imine condensation between amino and formyl groups.9,10 Reversible bonding/dissociation allows us to repair potential errors and defects. Therefore, CONs based on carbon-carbon bond formation remains a big challenge: carbon-carbon bonds afford chemical and physical durability, π-conjugation, and versatility, thereby being indispensable factors for CONs. For example, topochemical reactions have been employed to

Figure 1. Synthetic scheme and ideal structure for TP-GDY from HETP monomer. form carbon-carbon CONs.11-13 In this context, graphdiyne (GDY) comprises an important class in carbon-carbon CONs (Figure S1), which is synthesized through multiple alkyne-alkyne dimerization of hexaethynylbenzene. GDY is an allotrope of graphene, featuring a hexagonal 2D lattice. The distinctive feature of GDY lies in the bonding nature, containing both sp and sp2 carbon atoms. Li and coworkers reported the first synthesis of GDY,14-17 having developed a series of applications. 18-22 the other hand, our group have demonstrated the synthesis of a GDY nanosheet.23 Liquid/liquid or gas/liquid interfacial synthesis allows hexaethynylbenzene monomers to undergo ordered oxidative polymerization, producing a thin GDY nanosheet with high quality. Herein, as a demonstration of the advantage of molecule-based nanosheets, broad variations, we synthesize a GDY analogue that possesses triphenylene core (TP-GDY, Figure 1). We note the expansion of the variation is one of the recent significant topics in GDYs.24-27 To produce TP-GDY, here we adopted a liquid/liquid interfacial synthesis similar to that used for GDY. Under an argon atmosphere, a dichloromethane solution of freshly prepared HETP28 was layered with a catalytic phase, a mixture of aqueous copper(II) acetate and pyridine

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 2. (a) Improved liquid/liquid interfacial synthesis for TP-GDY. (b) Photograph of the liquid/liquid interfacial synthesis that holds TPGDY film at the interface. (Figure S2). However, the biphasic system gave no polymeric matter at the liquid/liquid interface. To increase the reactivity of HETP, modifications were applied to the liquid/liquid interfacial synthesis (Figure 2a). The Cu source was substituted with di-μ-hydroxy-bis(N,N,N',N'-tetramethylenediamine) copper(II) ([Cu(OH)TMEDA]2Cl2), which is known as a good catalyst for Hay coupling. Under an argon atmosphere, a liquid/liquid interfacial was composed using an o-dichlorobenzene solution of HETP (0.1 mM) and an ethylene glycol solution of [Cu(OH)TMEDA]2Cl2 (5 mM). The biphase system was then kept undistributed at 60°C for 24 h, generating TP-GDY as a thin yellow film at the liquid/liquid interface (Figure 2b). The viscous and high boiling point solvents were chosen to maintain the calm liquid/liquid interface at the elevated temperature. TP-GDY was insoluble in any solvent, which reflects the polymeric nature. Optical microscopy for the TP-GDY film on a 1,1,1,3,3,3-Hexamethyldisilazane-modified silicon(100) substrate [HMDS/Si(100)] disclosed a flat and smooth sheet morphology with a lateral dimension exceeding 1 mm (Figure 3a). Figure 3b shows a typical SEM micrograph

Figure 3. (a) Optical microscopic image of the TP-GDY film on a HMDS/Si(100) substrate. (b) SEM micrograph of the TP-GDY film on a molybdenum grid with a mesh size of 100 μm. (c,d) AFM topographic image of the TP-GDY film on HMDS/Si(100) and cross-sectional analysis along the blue line. (e) TEM micrograph of the TP-GDY film.

Page 2 of 5

of TP-GDY on a molybdenum grid with a mesh size of 100 μm. The sheet was freestanding enough to traverse the holes of the grid, ensuring the polymeric nature of TP-GDY. On the other hand, AFM for TPGDY transferred on a Si substrate revealed its thickness to be 220 nm (Figure 3c,d). The thickness can be controlled to some extent by the concentration of HETP monomer and [Cu(OH)TMEDA]2Cl2 catalyst (Figure S3, 60 and 130 nm). A typical TEM image for TP-GDY also disclosed the sheet morphology (Figure 3e), while selected area electron diffraction was not observed because of poor crystallinity (vide infra) and a plausible electron-beam damage to TP-DGY. Thermogravimetric analysis (TGA) for TP-GDY showed good thermal durability at least up to 250°C under a nitrogen atmosphere (Figure S4). TP-GDY exhibits peculiar gas adsorption behavior (Figure S5). The N2 uptake ability of TP-GDY was poor, with a Brunauer–Emmett–Teller (BET) surface area of 17.4 m2g-1, while TP-GDY features water uptake ability with a BET surface area of 304 m2g-1 irrespective of the absence of heteroatoms and polar functional groups. The elemental composition and chemical bonding of TP-GDY were analyzed using XPS, SEM, and Raman spectroscopy. The XPS survey spectrum in Figure 4a displays the presence of constitutive carbon, as well as oxygen. No copper peaks are visible therein (e.g. Cu 2p3/2 at around 935 eV), indicating the copper catalyst was not persistent in the TP-GDY film. High-resolution XPS may discern the chemical environment of carbon. Herein, the C 1s envelope is deconvoluted into four Gaussian curves (Figure 4b), with major contributions from C≡C and C=C species. The abundance ratio of the sp2/sp carbons is 1.5, which is in good agreement with the chemical structure of the TP-GDY lattice (Figure 1). Minor contributions to the C 1s envelope are ascribable to C–O and C=O species. The oxygen/carbon ratio of was calculated to be 0.24, comparable to that of multilayer GDY (~0.2),14,15 and graphene grown by CVD.29,30 Elemental mapping by energy dispersive X-ray spectrometry associated with SEM (SEM/EDS) are depicted in Figure 4c-f. Carbon is distributed chiefly on the TP-GDY film, while oxygen and molybdenum on the grid. Therefore, the TP-GDY film comprises carbon predominantly. The presence of sp carbon was also confirmed by

Figure 4. (a) XPS Survey scan for TP-GDY on HMDS/Si(100). (b) C1s narrow scan. (c-f) SEM image for TP-GDY on a molybdenum grid, and accompanying EDS mapping for C, O, and Mo. (g) Raman spectrum of TP-GDY on HMDS/Si(100).

ACS Paragon Plus Environment

Page 3 of 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

Raman spectroscopy (Figure 4g). The spectrum features three bands corresponding to the aromatic sp2 carbon stretching (1347, 1447, and 1591 cm−1). In addition, two bands derived from the vibration of the conjugated butadiyne linkage (1928 and 2192 cm − 1)23 are observed. Terminal alkyne stretching (2100–2120 cm−1) is absent at all. Synchrotron-radiated grazing incidence X-ray diffraction (GI-XD) for TP-GDY found a broad diffraction derived from the in-plane periodicity, thereby showing not good crystallinity but still the existence of the 2D ordering of TP-GDY (Figures S6,S7). Here we employed solvents and a catalyst different from, and a higher temperature than the previous GDY synthesis26 to compensate the lower reactivity of HETP monomer, which could cause the poorer periodicity. The UV/vis absorption spectra for trimethylsilyl-protected HETP monomer and TP-GDY are shown in Figure S8. Compared with the monomer, the absorption band of TPGDY is broadened and redshifted, which reflects the narrowed bandgap derived from the π-conjugated polymer structure of TP-GDY. In conclusion, a modified liquid/liquid interfacial protocol was applied to the synthesis of a GDY analogue, TP-GDY, featuring a triphenylene core. A biphasic system composed of an o-dichlorobenzene solution of monomer HETP and an ethylene glycol solution of catalyst [Cu(OH)TMEDA]2Cl2 afforded TP-GDY. The resultant TP-GDY film exhibited a free-standing, sheet morphology with a smooth texture, a domain size of >1 mm, and thicknesses of 60-220 nm, in OM, SEM and AFM. Gas adsorption isotherms featured water uptake behavior of TP-GDY. XPS disclosed the absence of a copper residue, and the bonding nature of the carbon element consistent with the chemical structure of TP-GDY. The existence of the butadiyne linker, and the absence of the terminal alkyne were confirmed by Raman spectroscopy. UV/vis spectroscopy verified a narrowed bandgap in TP-GDY upon the polymerization compared with trimethylsilyl-protected HETP monomer. The present letter has contributed to the expansion of the variation of the GDY family, which will accelerate its applications as nanomaterials.

ASSOCIATED CONTENT Supporting Information Experimental details; structure of GDY, schematic illustration for the conventional liquid/liquid interfacial synthesis; AFM images for thinner TP-GDY; TGA chart for TP-GDY; N2 and water adsorption and desorption isotherms for TP-GDY; experimental and simulated GI-XD patterns for TP-GDY; optimized 2D lattice of TP-GDY; absorption spectra of HETP monomer and TP-GDY. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author [email protected] (R.S.); [email protected] (H.N.)

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was mainly JST PRESTO Grant Number JPMJPR1516, Japan. This work was also supported by JST CREST Grant Number JPMJCR15F2, and JSPS KAKENHI Grant Numbers JP17H05354, JP17H03028, JP16H00900, JP15H00862, JP26708005, JP26620039,

JP26220801. R.S. acknowledges The Asahi Glass Foundation, Foundation Advanced Technology Institute, Hitachi Metals ⋅ Materials Science Foundation, The Murata Science Foundation, Kato foundation for Promotion of Science, and Yashima Environment Technology Foundation for financial supports.

REFERENCES (1) Allen, M. J.; Tung, V. C.; Kaner, R. B., Honeycomb Carbon: A Review of Graphene. Chem. Rev. 2010, 110, 132-145. (2) Chhowalla, M.; Shin, H. S.; Eda, G.; Li, L.-J.; Loh, K. P.; Zhang, H., The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 2013, 5, 263-275. (3) Sakamoto, J. a. v. H. J. a. L. O. a. S. A. D., Two-Dimensional Polymers: Just a Dream of Synthetic Chemists? Angew. Chem. Int. Ed. 2009, 48, 1030-1069. (4) Rodriguez-San-Miguel, D.; Amo-Ochoa, P.; Zamora, F., MasterChem: cooking 2D-polymers. Chem. Commun. 2016, 52, 4113-4127. (5) Sakamoto, R.; Takada, K.; Pal, T.; Maeda, H.; Kambe, T.; Nishihara, H., Coordination nanosheets (CONASHs): strategies, structures and functions. Chem. Commun. 2017, 53, 5781-5801. (6) Zheng, Z.; Opilik, L.; Schiffmann, F.; Liu, W.; Bergamini, G.; Ceroni, P.; Lee, L.-T.; Schütz, A.; Sakamoto, J.; Zenobi, R.; VandeVondele, J.; Schlüter, A. D., Synthesis of Two-Dimensional Analogues of Copolymers by Site-to-Site Transmetalation of Organometallic Monolayer Sheets. J. Am. Chem. Soc. 2014, 136, 6103-6110. (7) Sakamoto, R.; Hoshiko, K.; Liu, Q.; Yagi, T.; Nagayama, T.; Kusaka, S.; Tsuchiya, M.; Kitagawa, Y.; Wong, W.-Y.; Nishihara, H., A photofunctional bottom-up bis(dipyrrinato)zinc(II) complex nanosheet. Nat. Commun. 2015, 6, 6713. (8) Kambe, T.; Sakamoto, R.; Hoshiko, K.; Takada, K.; Miyachi, M.; Ryu, J.H.; Sasaki, S.; Kim, J.; Nakazato, K.; Takata, M.; Nishihara, H., π-Conjugated Nickel Bis(dithiolene) Complex Nanosheet. J. Am. Chem. Soc. 2013, 135, 24622465. (9) Tanoue, R.; Higuchi, R.; Enoki, N.; Miyasato, Y.; Uemura, S.; Kimizuka, N.; Stieg, A. Z.; Gimzewski, J. K.; Kunitake, M., Thermodynamically Controlled Self-Assembly of Covalent Nanoarchitectures in Aqueous Solution. ACS Nano 2011, 5, 3923-3929. (10) Liu, X.-H.; Guan, C.-Z.; Ding, S.-Y.; Wang, W.; Yan, H.-J.; Wang, D.; Wan, L.-J., On-Surface Synthesis of Single-Layered Two-Dimensional Covalent Organic Frameworks via Solid–Vapor Interface Reactions. J. Am. Chem. Soc. 2013, 135, 10470-10474. (11) Kissel, P.; Erni, R.; Schweizer, W. B.; Rossell, M. D.; King, B. T.; Bauer, T.; Götzinger, S.; Schlüter, A. D.; Sakamoto, J., A two-dimensional polymer prepared by organic synthesis. Nat. Chem. 2012, 4, 287-291. (12) Kissel, P.; Murray, D. J.; Wulftange, W. J.; Catalano, V. J.; King, B. T., A nanoporous two-dimensional polymer by single-crystal-to-single-crystal photopolymerization. Nat. Chem. 2014, 6, 774-778. (13) Kory, M. J.; Wörle, M.; Weber, T.; Payamyar, P.; van de Poll, S. W.; Dshemuchadse, J.; Trapp, N.; Schlüter, A. D., Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction. Nat. Chem. 2014, 6, 779-784. (14) Li, G.; Li, Y.; Liu, H.; Guo, Y.; Li, Y.; Zhu, D., Architecture of graphdiyne nanoscale films. Chem. Commun. 2010, 46, 3256-3258. (15) Zhou, J.; Gao, X.; Liu, R.; Xie, Z.; Yang, J.; Zhang, S.; Zhang, G.; Liu, H.; Li, Y.; Zhang, J.; Liu, Z., Synthesis of Graphdiyne Nanowalls Using Acetylenic Coupling Reaction. J. Am. Chem. Soc. 2015, 137, 7596-7599. (16) Qian, X.; Liu, H.; Huang, C.; Chen, S.; Zhang, L.; Li, Y.; Wang, J.; Li, Y., Self-catalyzed Growth of Large-Area Nanofilms of Two-Dimensional Carbon. Sci. Rep. 2015, 5, 7756. (17) Li, Y.; Xu, L.; Liu, H.; Li, Y. Graphdiyne and graphyne: from theoretical predictions to practical construction. Chem. Soc. Rev. 2014, 43, 2572-2586. (18) Jia, Z.; Li, Y.; Zuo, Z.; Liu, H.; Huang, C.; Li, Y., Synthesis and Properties of 2D Carbon-Graphdiyne. Acc. Chem. Res. 2017, 50, 2470-2478. (19) Shang, H. Zuo, Z.; Li, L.; Wang, F.; Liu, H.; Li, Y.; Li, Y., Ultrathin Graphdiyne Nanosheets Grown In Situ on Copper Nanowires and Their Performance as Lithium-Ion Battery Anodes. Angew. Chem. Int. Ed. doi:10.1002/anie.201711366.

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(20) Kuang, C.; Tang, G.; Jiu, T.; Yang, H.; Liu, H.; Li, B.; Luo, W.; Li, X.; Zhang, W.; Lu, F.; Fang, J.; Li, Y., Highly Efficient Electron Transport Obtained by Doping PCBM with Graphdiyne in Planar-Heterojunction Perovskite Solar Cells. Nano Lett. 2015, 15, 2756-2762. (21) Zuo, Z.; Shang, H.; Chen, Y.; Li, J.; Liu, H.; Li, Y.; Li, Y. A facile approach for graphdiyne preparation under atmosphere for an advanced battery anode. Chem. Commun. 2017, 53, 8074-8077. (22) Wang, N.; He, J.; Tu, Z.; Yang, Z.; Zhao, F.; Li, X.; Huang, C.; Wang, K.; Jiu, T.; Yi, Y.; Li, Y. Synthesis of Chlorine-Substituted Graphdiyne and Applications for Lithium-Ion Storage. Angew. Chem. Int. Ed. 2017, 56, 10740-10745. (23) Matsuoka, R.; Sakamoto, R.; Hoshiko, K.; Sasaki, S.; Masunaga, H.; Nagashio, K.; Nishihara, H., Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface. J. Am. Chem. Soc. 2017, 139, 3145-3152. (24) Kan, X.; Ban, Y.; Wu, C.; Pan, Q.; Liu, H.; Song, J.; Zuo, Z.; Li, Z.; Zhao, Y., Interfacial Synthesis of Conjugated Two-Dimensional N-Graphdiyne. ACS Appl. Mater. Interfaces doi:10.1021/acsami.7b17326. (25) Shang, H.; Zuo, Z.; Zheng, H.; Li, K.; Tu, Z.; Yi, Y.; Liu, H.; Li, Y.; Li, Y., N-doped graphdiyne for high-performance electrochemical electrodes. Nano Energy 2018, 44, 144-154.

Page 4 of 5

(26) Prabakaran, P.; Satapathy, S.; Prasad, E.; Sankararaman, S., Architecting pyrediyne nanowalls with improved inter-molecular interactions, electronic features and transport characteristics. J. Mater. Chem. C doi:10.1039/c7tc04655c. (27) He, J.; Wang, N.; Cui, Z.; Du, H.; Fu, L.; Huang, C.; Yang, Z.; Shen, X.; Yi, Y.; Tu, Z.; Li, Y. Hydrogen substituted graphdiyne as carbon-rich flexible electrode for lithium and sodium ion batteries. Nat. Commun. 2017, 8, 1172. (28) Zhang, X.-M.; Ding, X.; Hu, A.; Han, B.-H., Facile approach for preparing porous organic polymers through Bergman cyclization. Polym. Chem. 2015, 6, 4734-4741. (29) Bae, S.; Kim, H.; Lee, Y.; Xu, X.; Park, J.-S.; Zheng, Y.; Balakrishnan, J.; Lei, T.; Ri Kim, H.; Song, Y. Il; Kim, Y.-J.; Kim, K. S.; Özyilmaz, B.; Ahn, J.-H.; Hong, B. H.; Iijima, S., Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol. 2010, 5, 574–578. (30) Gao, G.; Liu, D.; Tang, S.; Huang, C.; He, M.; Guo, Y.; Sun, X.; Gao, B., Heat-Initiated Chemical Functionalization of Graphene. Sci. Rep. 2016, 6, 20034.

ACS Paragon Plus Environment

Page 5 of 5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

TOC Graphic

Insert Table of Contents artwork here

5 ACS Paragon Plus Environment