On a new FeOF polymorph: Synthesis and stability |
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| Institution: | 1. Institut de Ciència de Materials de Barcelona (ICMAB-CSIC) Campus UAB, E-08193 Bellaterra, Catalonia, Spain;2. Laboratoire de Réactivité et Chimie des Solides, UPJV, CNRS UMR 7314, 33 Rue Saint Leu, 80039 Amiens, France;3. FRE 3677 “Chimie du Solide et Energie”, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France;4. Sorbonne Universités, UPMC Univ Paris 06, 4 Place Jussieu, F-75005 Paris, France;1. State Research Institute Center of Physical Sciences and Technology, Savanorių 231, LT-02300 Vilnius, Lithuania;2. Vilnius Gediminas Technical University, Scientific Institute of Thermal Insulation, Linkmenų 28, LT-08217 Vilnius, Lithuania;1. School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, PR China;2. Center for Programmable Materials, School of Materials Science & Engineering, Nanyang Technological University, Singapore 639798, Singapore;3. Institute of Materials Research and Engineering, Agency for Science, Technology and Research (A*STAR), 2 Fusionopolis Way, Innovis, Singapore 138634, Singapore;4. Centre for Micro-/Nano-electronics (NOVITAS), School of Electrical & Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore;5. CINTRA CNRS/NTU/THALES, UMI 3288, Research Techno Plaza, 50 Nanyang Drive, Border X Block, Level 6, Singapore 637553, Singapore;6. Environmental Chemistry and Materials Centre, Nanyang Environment & Water Research Institute, 1 Cleantech Loop, Singapore 637141, Singapore;1. School of Civil Engineering, Southeast University, Nanjing 210096, China;2. Key Laboratory of Concrete and Prestressed Concrete Structures of the Ministry of Education, Southeast University, Nanjing 210096, China;3. Depart of Civil and Environmental Engineering, University of Washington, Seattle, WA 98195-2007, United States;4. State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092, China;5. School of Environmental and Safety Engineering, Changzhou University, Changzhou 213164, China;6. College of Civil Engineering and Architecture, Zhejiang University of Technology, Hangzhou 310014, China;1. Key Laboratory of Low-grade Energy Utilization Technologies and Systems of Ministry of Education, School of Energy and Power Engineering, Chongqing University, Chongqing 400044, China;2. Guizhou Institute of Technology, Guiyang 550003, China;1. School of Energy Materials and Chemical Engineering, Hefei University, Hefei, Anhui 230601, PR China;2. Anhui Provincial Engineering Research Center for Green Coatings High-performance Additives, Hefei University, Hefei, Anhui 230601, PR China;1. Helmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, Germany;2. Institut für theoretische Chemie, Universität Ulm, Albert-Einstein-Allee 11, 89069 Ulm, Germany;3. Institut für Technikfolgenabschätzung und Systemanalyse (ITAS), Karlsruhe Institute of Technology (KIT), P.O. Box 3640, D-76021 Karlsruhe, Germany;4. Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), P.O. Box 3640, D-76021 Karlsruhe, Germany |
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| Abstract: | A new polymorph of FeOF (up to now only known in its rutile type structure) was prepared by using a new synthesis approach formally based on anionic exchange using the well-known layered FeOCl as precursor. The synthesis was achieved using CH3C(CH2O–)2(COO–)B] to vehicle fluorine through the formation of soluble (CH3)4N+ CH3C(CH2O–)2(COO–)BF]− and using N,N-dimethylformamide (DMF) as the reacting medium. The XRD pattern of layered FeOF can be indexed with an orthorhombic cell which doubles along the b axis (which is the direction perpendicular to the layers) with respect to that of pristine FeOCl (a = 3.792(1) Å, b = 12.699(1) Å, c = 3.321(1) Å). Both thermal analysis and diffraction indicate similar stability for the layered and rutile polymorphs. Such findings are rationalized through Density Functional Theory calculations. It is found that the energy difference between the more stable rutile and layered polymorphs is practically nul. The origin of the similar stability lies in the fact that although the number of Fe–F and Fe–O bonds is different in the two structures, the strength of both the total number of Fe–O as well as Fe–F bonds are found to be almost identical. Even if the crystal and electronic structures are considerably different, the total bonding and thus, the stability of the two polymorphs, is comparable. The stability of different FeOF rutile type structures is also analyzed. |
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| Keywords: | FeOF Oxyfluorides FeOCl Ion exchange DFT |
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