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Facile Synthesis of Potassium Poly(Heptazine Imide) (PHIK)

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Facile Synthesis of Potassium Poly(Heptazine Imide) (PHIK) Subscriber access provided by CORNELL UNIVERSITY LIBRARY Article Facile synthesis of potassium poly(heptazine imide) (PHIK) / Ti-based Metal- Organic Framework (MIL-125-NH2) composites for photocatalytic applications Nicolás Artemio Rodríguez, Aleksandr Savateev, Maria Alejandra Grela, and Dariya Dontsova ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 13 Jun 2017 Downloaded from http://pubs.acs.org on June 14, 2017 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. 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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. ACS Applied Materials & Interfaces 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 32 ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 Facile synthesis of potassium poly(heptazine imide) 9 10 11 12 (PHIK) / Ti-based Metal-Organic Framework (MIL- 13 14 15 16 125-NH2) composites for photocatalytic applications 17 18 19 20 21 Nicolás A. Rodríguez1,2, Aleksandr Savateev3, María A. Grela1,2*, Dariya Dontsova3* 22 23 24 1 25 Departamento de Química, Facultad de Ciencias Exactas y Naturales (FCEyN), Universidad 26 27 Nacional de Mar del Plata (UNMdP), 7600 Mar del Plata, Argentina. 28 29 30 2Instituto de Física de Mar del Plata (IFIMAR), FCEyN, UNMdP – CONICET, 7600 Mar del 31 32 33 Plata, Argentina. 34 35 36 3Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces, 14476 37 38 Potsdam, Germany. 39 40 41 42 KEYWORDS: Carbon nitride, Metal-Organic Framework, poly(heptazine imide), MIL-125- 43 44 NH2, Composite, Photocatalysis, photochromic effect 45 46 47 48 ABSTRACT. Photocatalytically active composites comprising potassium poly(heptazine imide) 49 50 (PHIK) and a Ti-based Metal-Organic Framework (MOF, MIL-125-NH ) are prepared in-situ by 51 2 52 53 simply dispersing both materials in water. The driving forces of composite formation are the 54 55 electrostatic interactions between the solids and the diffusion of potassium ions from PHIK to 56 57 58 MIL-125-NH2. This mechanism implies that other composites of poly(heptazine imide) salts and 59 60 ACS Paragon Plus Environment 1 ACS Applied Materials & Interfaces Page 2 of 32 1 2 3 4 different MOFs bearing positive surface charge can potentially be obtained in a similar fashion. 5 6 The suggested strategy thus opens a new avenue for the facile synthesis of such materials. The 7 8 composites are shown to have a superior photocatalytic activity in Rhodamine B degradation 9 10 11 under visible light irradiation. The reaction rate is doubled compared to that of pure MOF 12 13 compound and is seven times higher than the activity of the pristine PHIK. The results of the 14 15 Electron Paramagnetic Resonance (EPR) investigations and the analysis of the electronic 16 17 18 structures of the solids suggest the electron transfer from MIL-125-NH2 to PHIK in the 19 20 composite. The possible pathways for the dye degradation and the rationalization of the 21 22 increased activity of the composites are elaborated. 23 24 25 26 INTRODUCTION 27 28 29 30 The synthesis of composite materials is an area of much interest in photocatalysis, since the 31 32 presence of different functional materials facilitates charge separation inducing charge carrier 33 34 transfer between the components that enhances photocatalytic and photoelectrochemical 35 36 1,2 37 efficiencies of the integral system. 38 39 40 Many materials have been tested in the synthesis of composites. In particular, there is a recent 41 42 43 interest in graphitic carbon nitrides (g-CN) / Metal-Organic Frameworks (MOF) 44 3–5 45 heterostructures. Carbon nitrides are polymeric metal-free semiconductors extensively studied 46 47 for photocatalytic applications.6–8 One of the main advantages of carbon nitrides is that they 48 49 50 absorb a high energy fraction of the visible light, however, they typically have low surface areas 51 52 and are characterized by high charge carrier recombination rates.9 g-CN is usually obtained by 53 54 heating cyanamide4/dicyanamide3,5 under inert atmosphere at high temperatures (550°C). 55 56 57 However, it has been reported that related polymers with better photocatalytic activities are 58 59 60 ACS Paragon Plus Environment 2 Page 3 of 32 ACS Applied Materials & Interfaces 1 2 3 4 obtained by heating substituted 1,2,4-triazole derivatives in LiCl/KCl eutectics. Such a procedure 5 6 leads to the formation of a carbon nitride polymer salt composed of layers of poly(heptazine 7 + 9 8 imide) with K ions within the interstices. MOFs are hybrid coordination polymers whose 9 10 11 optical and electronic properties can be tuned, e.g. by changing an organic or inorganic precursor 12 10,11 4,5 3 13 to obtain isoreticular materials. ZIF-9 and MIL-125 have been employed to produce 14 15 carbon nitride containing composites in order to benefit from the high CO2 adsorption capability 16 17 18 of ZIF-9, and the additional catalytically active titanium centers of MIL-125, respectively. MIL- 19 20 125-NH2 is isoreticular to MIL-125, but the replacement of terephthalic acid by 21 22 aminoterephthalic acid leads to the decrease of the material bandgap and higher retention of 23 24 11,12 25 CO2. 26 27 28 In general, the synthesis of composites is not straightforward and depends on the properties of 29 30 31 the individual components. Possible strategies for the synthesis of metal oxides deposited on 32 13 14 33 other semiconductors are pulsed laser deposition, chemical vapor deposition, etc. Using these 34 35 approaches it is possible to deposit nanometric particles over films or micrometric structures. 36 37 15 38 Solvothermal synthesis under controlled conditions is also suitable to obtain composites. 39 9,11 40 However, PHIK and MIL-125-NH2 are both obtained as micrometric particles. That makes it 41 42 more difficult to ensure the crystallization of one material over the other. Many proposed routes 43 44 45 in such cases involve a sol-gel synthesis in which a powder is dispersed in a sol of the reagents 46 47 needed to synthesize the second material. This is especially feasible for metal oxides and TiO2 in 48 49 particular.16–19 Other possibility is to obtain the desired composite by the impregnation 50 51 20 5 52 technique, as reported by Zhou et al. to prepare a g-CN/ ZIF-9 composite. 53 54 55 In this work, a simple and straightforward way to prepare PHIK/MIL-125-NH2 composites 56 57 58 with enhanced photocatalytic activity is reported. The suggested strategy involves only the 59 60 ACS Paragon Plus Environment 3 ACS Applied Materials & Interfaces Page 4 of 32 1 2 3 4 dispersion of both materials in water. The analysis of the surface ζ-potentials of the pure solids 5 6 shows that the components can attract each other by means of electrostatic forces. The 7 8 comparative analysis of FTIR and photoluminescence spectra, together with the morphological 9 10 11 changes observed by SEM proves the formation of a composite. The possible influence of the 12 + 13 migration of K ions from PHIK to MIL-125-NH2 within the composite is discussed. The 14 15 superior photocatalytic activity of the composite compared to pure semiconductors is 16 17 18 exemplified in Rhodamine B (RhB) degradation. EPR studies and Mott-Schottky analysis are 19 20 used to reveal the electronic structure of the composite. Based on these findings, possible 21 22 pathways for Rhodamine B degradation are discussed. We suggest that the charge transfer from 23 24 25 MIL-125-NH2 to PHIK is responsible for the increase of Rhodamine B photodegradation rates in 26 27 the presence of composites as compared to pure materials. 28 29 30 31 MATERIALS AND METHODS 32 33 34 Chemicals. LiCl (99%, Roth), KCl (99%, Sigma-Aldrich), 3-amino-1,2,4-triazole-5-thiol 35 36 (98%, Alfa Aesar), N,N-dimethylformamide (DMF, 99.8%, Sigma-Aldrich), acetonitrile (99.9 37 38 39 %, Merck), methanol (99.9%, Merck), titanium (IV) isopropoxide (97 %, Aldrich), pivalic acid 40 41 (99%, Roth), 2-aminoterephthalic acid (97%, Aldrich), sodium sulfate (99%, Acros Organics) 42 43 and Rhodamine B (95 %, Sigma Aldrich) were used as received. 44 45 46 9 47 Synthesis of the materials.
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