Materials capable of the safe and efficient capture or degradation of toxic chemicals, including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs), are critically important in the modern age due to continuous threats of these chemicals to human life, both directly and indirectly. Metal−organic frameworks (MOFs), atomically precise hybrid materials that are synthesized via the self-assembly of metal cations or clusters and organic linkers, offer a unique solid adsorbent design platform due to their great synthetic versatility. This review will focus on recent advancements in MOF-based adsorbent design for protection against chemical warfare agents (organophosphorus nerve agents, blistering agents, and their simulants) and toxic industrial chemicals such as H 2 S, NH 3 , SO 2 , CO, NO 2 , and NO. CONTENTS 1. Introduction 8130 2. Capture of Chemical Warfare Agents and Simulants 8132 2.1. Organophosphorous Agents and Their Simulants 8132 2.2. Mustard Gas (HD) and Its Simulants 8135 3. Capture of Toxic Industrial Chemicals (TICs) 8137 3.1. Hydrogen Sulfide (H 2 S) 8137 3.2. Ammonia (NH 3 ) 8141 3.3. Sulfur Dioxide (SO 2 ) 8144 3.4. Carbon Monoxide (CO) 8147 3.5. Nitrogen Oxides (NO x ) 8150 4. Conclusions and Outlook 8152
Synthesis and activation of phase-pure and defect-free metal–organic frameworks (MOFs) are essential for establishing accurate structure–property relationships.
We report the syntheses, structures, and oxidation catalytic activities of a single-atom-based vanadium oxide incorporated in two highly crystalline MOFs, Hf-MOF-808 and Zr-NU-1000. These vanadium catalysts were introduced by a postsynthetic metalation, and the resulting materials (Hf-MOF-808-V and Zr-NU-1000-V) were thoroughly characterized through a combination of analytic and spectroscopic techniques including single-crystal X-ray crystallography. Their catalytic properties were investigated using the oxidation of 4-methoxybenzyl alcohol under an oxygen atmosphere as a model reaction. Crystallographic and variable-temperature spectroscopic studies revealed that the incorporated vanadium in Hf-MOF-808-V changes position with heat, which led to improved catalytic activity.
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