Enhancing toxic gas uptake performance of Zr-based MOF through uncoordinated carboxylate and copper insertion; ammonia adsorption

摘要

This study reports the development of a new type of Zr-based MOF by inserting copper and carboxylate into HCl modulated UiO-67 (UiO-67-vac) which gained higher surface area/vacant than UiO-67. Copper was inserted into MOF containing uncoordinated carboxylate group, to create open metal site in the form of -COOCu which called UiO-67-ox-Cu. PXRD, FTIR, BET, SEM, EDS, UV-Vis and XPS were used to characterize the obtained MOFs. As expected, UiO-67-ox-Cu exhibits the highest ammonia capacity (178.3 mg/g) among UiO-67 (104 mg/g) and UiO-67-vac (121 mg/g) at 298 K and 1 bar pressure. In fact, the significant increase in ammonia uptake of UiO-67-ox-Cu is related to the modified binding affinity of -COOCu groups with ammonia. Moreover, UiO-67-vac with the highest surface area showed the hydrogen adsorption capacity of 18.75 mg/g at 77 K, which is comparable or even superior to the previously reported value. Interestingly, adsorption capacities were retained with slight changes around five cycles and three regeneration temperatures, 25, 60 and 120 degrees C under vacuum pressure which were proved by PXRD after ammonia adsorption/desorption. The good results obtained in the current work clearly show the role of postsynthesis functionalization approach for creation of new metal/active sites into MOFs.