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A simple solvent- and catalyst-free method is presented for the synthesis of the mesoporous metal-organic framework (MOF) MAF-6 (RHO-Zn(eIm)2) based on the reaction of ZnO with 2-ethylimidazole vapor at temperatures ≤ 100 °C. By translating this method to a chemical vapor deposition (CVD) protocol, mesoporous crystalline films could be deposited for the first time entirely from the vapor phase. A combination of PALS and Kr physisorption measurements confirmed the porosity of these MOF-CVD films and the size of the MAF-6 supercages (diam. ~2 nm), in close agreement with powder data and calculations. MAF-6 powders and films were further characterized by XRD, TGA, SEM, FTIR, PDF and EXAFS. The exceptional uptake capacity of the mesoporous MAF-6 in comparison to the microporous ZIF-8 is demonstrated by vapor-phase loading of a molecule larger than the ZIF-8 windows.
T.S., R.V. and I.S. thank the Research Foundation Flanders (FWO) for SB-PhD and postdoctoral fellowships (1S53316N, 1S00917N and 12L5417N). R.A. acknowledges the funding from the European Research Council (No. 716472, acronym: VAPORE) and the Research Foundation Flanders (FWO) for funding in the research projects G083016N, G0E6319N and 1501618N and the infrastructure project G0H0716N. We acknowledge the Elettra Synchrotron Trieste for allocation of beamtime and thank Luisa Barba and Nicola Demitri for assis-tance in using beamline XRD1. We acknowledge the European Synchrotron Radiation Facility for provision of synchrotron radia-tion facilities and we would like to thank Oleg Konovalov and Andrey Chumakov for assistance in using beamline ID10, and Dipanjan Banerjee for assistance in using the Dutch-Belgian (DUBBLE) beamline BM26. We acknowledge Benedikt Schrode and Sabina Rodríguez Hermida for assistance with the in situ PXRD experiment and data processing. PALS measurements are based upon experiments performed at the PLEPS instrument op-erated by FRM-II at the Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany. The authors would like to thank Diamond Light Source for beamtime (proposal EE17279), and the staff of beamline I15-1, in particular Philip Chater, with data collection and treatment. Thomas D. Bennett is acknowledged for useful insights in total scattering data processing and analysis. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.