Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 37, Pages 12844-12847Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja507119n
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Funding
- BASF SE (Ludwigshafen, Germany)
- U.S. Department of Defense, Defense Threat Reduction Agency [HDTRA 1-12-1-0053]
- Office of Science, Office of Basic Energy Sciences, of the U.S. DOE [DE-AC02-05CH11231]
- Chevron Energy Technology Company
- Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geological and Biosciences of the US DOE [DE-AC02-05CH11231]
- Basic Science Research Program through the National Research Foundation (NRF) in Korea - Ministry of Education [2012R1A6A3A03039602]
- National Research Foundation of Korea [2012R1A6A3A03039602] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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Superacids, defined as acids with a Hammett acidity function H-0 <=-12, are useful materials, but a need exists for new, designable solid state systems. Here, we report superacidity in a sulfated metal-organic framework (MOP) obtained by treating the microcrystalline form of MOF-808 [MOF-808-P: Zr6O5(OH)(3)-(BTC)(2)(HCOO)(5)(H2O)(2), BTC = 1,3,5-benzenetricarboxylate] with aqueous sulfuric acid to generate its sulfated analogue, MOF-808-2.5SO(4) [Zr6O5(OH)(3)(BTC)(2)-(SO4)(2.5)(H2O)(2.5)]. This material has a Hammett acidity function H-0 <= -14.5 and is thus identified as a superacid, providing the first evidence for superacidity in MOFs. The superacidity is attributed to the presence of zirconium-bound sulfate groups structurally characterized using single-crystal X-ray diffraction analysis.
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