ABSTRACT
Ammonia (NH3) is a viable candidate for the storage and distribution of hydrogen (H2) due to its exceptional volumetric and gravimetric hydrogen energy density. Therefore, it is desirable to develop NH3 storage materials that exhibit robust stability across numerous adsorption-desorption cycles. While porous materials with polymeric frameworks are often used for NH3 capture, achieving reversible NH3 uptake remains a formidable challenge, primarily due to the high reactivity of NH3. Here, we advocate the use of CO2H-functionalized cyclic oligophenylene 1a with high chemical stability as a novel single-molecule-based adsorbent for NH3. Simple reprecipitation of 1a selectively yielded microporous crystalline solid 1a (N). Crystalline 1a (N) adsorbs up to 8.27 mmol/g of NH3 at 100 kPa and 293 K. Adsorbed NH3 in the pore of 1a (N) has a packing density of 0.533 g/cm3 at 293 K, which is close to the density of liquid NH3 (0.681 g/cm3 at 240 K). Crystalline 1a (N) also exhibits reversible NH3 adsorption over at least nine cycles, sustaining its storage capacity (1st cycle: 8.27 mmol/g; 9th cycle: 8.25 mmol/g at 100 kPa and 293 K) and crystallinity. During each desorption cycle, NH3 was removed from 1a (N) under reduced pressure (â¼65 Pa), leaving <3% of the total uptake, and 1a (N) was fully purged under dynamic vacuum conditions (â¼5 × 10-4 Pa at 293 K for 1 h) before the subsequent adsorption cycles. Thus, microporous crystalline 1a (N) can reliably adsorb and desorb NH3 repeatedly, which avoids the need for heat-based activation between cycles.
