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

Highlights: • UiO-67 modulated by acid along with copper insertion was developed. • OMS emerge through Cu coordination with carboxylate group. • UiO-67-ox-Cu achieved a maximum NH₃ adsorption of 178.3 mg/g at 298 K. • UiO-67-vac showed a maximum H₂ adsorption of 18.75 mg/g at 1 bar and 77 K. • MOF containing −COOCu achieved a higher gas uptake capacity than pristine MOF. 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 °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.