Evaluation of HKUST-1 as Volatile Organic Compound Adsorbents for Respiratory Filters

Cyclohexane is a representative of volatile organic compounds (VOCs). VOCs can cause serious health problems in case of continuous exposure; therefore, it is essential to develop efficient personal protective equipment. Historically, activated carbons are used as VOC adsorbents. However, the emergence of promising novel adsorbents, such as metal-organic frameworks, has pushed the research to study their behavior under the same conditions. In this work, the use of the well-known HKUST-1 MOF of different particle sizes (20 μm, 300-600 μm, and 1-1.18 mm) for the adsorption of low-grade (5000 ppm) cyclohexane combined with different water concentrations (dry, 27 and 80% RH) in a fixed bed is proposed. The results were compared under the same conditions for a typically used activated carbon, PICACTIF TA 60. HKUST-1 has higher affinity to cyclohexane than PICACTIF for the whole pressure range studied, especially at low partial pressures. It begins to adsorb much earlier (0.0025 kPa) than the activated carbon (0.01 kPa). However, a different adsorption behavior is evidenced for both materials in the presence of water vapor since HKUST-1 is very hydrophilic in the zone near to the copper open metal sites, whereas PICACTIF is hydrophobic. After three consecutive cycles, good stability results were obtained for the MOF, comparable to activated carbon, even in the presence of water. As the main finding, although the unstability of HKUST-1 is well established under high humid conditions, the kinetic of degradation has not been established so far. Here, it is shown that the time usage of HKUST-1 as the adsorbent for respiratory mask (single pass) is not affected by the degradation of the structure, which may occur on a longer time scale. Finally, shaping by tableting provides good results since it is possible to increase the MOF density by around 69% with minor loss of adsorption capacity. The best fraction is 300-600 μm, reaching cyclohexane breakthrough times around 85 min/cm³ at 80% RH, comparable with PICACTIF-activated carbon and promising for practical applications.