Abstract: During the process of combat, emergency rescue and accident handling, both chemical warfare agents (CWAs) and toxic industrial chemicals (TICs) diffusion will pose a serious threat to the breathing safety of personnel. Therefore, the respirators are required to provide broad-spectrum protection against CWAs and TICs at the same time. The activated carbon impregnated with copper, silver, zinc, molybdenum, and triethy-lenediamine, known as the ASZM-TEDA carbon, is the main protection material used in current gas masks for military and emergency response personnel. Although a variety of chemicals are added, the ASZM-TEDA carbon still has some limitations such as poor protection performance against TICs and a high risk of physically adsorbed toxic molecules releasing at room temperature. It is thus urgent to develop novel respiratory protection materials with broad-spectrum protection and in-situ degradation capabilities against both CWAs and TICs. Metal-organic frameworks (MOFs), characterized by their huge specific surface areas, diverse structures and on-demand modular design, are considered as the novel respiratory protection materials with the greatest potential to achieve broad-spectrum protection and in-situ degradation against toxic chemicals. In recent years, the zirconium-based metal-organic frameworks (Zr-MOFs) have been extensively studied due to their high specific surface areas, various surface active sites, remarkable stabilities, as well as excellent CWAs/TICs adsorption and catalytic degradation performance. In terms of Zr-MOFs used for the adsorption removal of CWAs and TICs, current research work mainly focuses on UiO-66-NH2. Researchers have systematically studied the adsorption properties of UiO-66-NH2 powders and granules. They found that UiO-66-NH2 powders shows excellent intrinsic adsorption capacities for many TICs, such as NH3, Cl2, and NO2. The hierarchical structure was further developed in UiO-66-NH2 to increase the diffusion rates of toxic molecules through the pores of UiO-66-NH2 granules. In terms of Zr-MOFs used for the catalytic degradation of CWAs and TICs, current research work mainly focuses on a series of Zr-MOFs with different node connectivity. By optimizing the pore size, node connectivity and types of organic ligands, researchers have effectively regulated the catalytic degradation performance of Zr-MOFs against toxic chemicals. They further investigated the catalytic degradation behavior of toxic chemicals in heterogeneous buffer and pure liquid environment, so as to promote the practical application of Zr-MOFs as protection materials. This review focuses on the Zr-MOFs respiratory protection materials. Based on analysis of the structures and surface chemistry of Zr-MOFs, this paper summarized the research progress on the application of Zr-MOFs in toxic chemicals adsorption and degradation. The structure-activity relationship of Zr-MOFs respiratory protection materials was discussed and the future research trend was also prospected.
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