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

Chemical warfare agents (CWAs), and in particular organophosphorus nerve agents, still pose a significant threat to society due to their continued use despite international bans. While nature has constructed a variety of enzymes that are capable of rapidly hydrolyzing organophosphorus substrates, the poor stability of enzymes outside of buffered solutions has limited their use in practical applications, such as in filters or on protective suits. As a result, we have explored the use of metal−organic frameworks (MOFs) as robust and tunable catalytic materials in which the nodes can be tailored to resemble the active sites found in these enzymes. We identified the Zn-based MOF, MFU-4l, as a promising hydrolysis catalyst due to the presence of Zn(II)−OH groups on the nodes, which are structurally reminiscent of the active sites in carbonic anhydrase (CA), a Zn-based enzyme that has been shown to efficiently catalyze the hydrolysis of phosphate esters. Indeed, MFU-4l can rapidly hydrolyze both the organophosphorus nerve agent, GD, and its simulant, DMNP, with half-lives as low as <1 min, which is competitive with the some of best heterogeneous hydrolysis catalysts reported to date.

A thermally stable and highly electrically conductive Pd(iii) 1D complex [Pd(dabdOH)2Cl]Cl2 was newly synthesized.