Photo-switchable metal-organic frameworks(PMOFs)as energy-saving adsorbents for tailorable guest capture show admirable potentials for various applications like adsorptive desulfurization.However,the regulation behavi...Photo-switchable metal-organic frameworks(PMOFs)as energy-saving adsorbents for tailorable guest capture show admirable potentials for various applications like adsorptive desulfurization.However,the regulation behavior of most reported PMOFs is based on weak physical interaction,and it is highly desired to introduce specific active sites to satisfy the demand of higher adsorption capacity and selectivity.Herein,for the first time,we prepared the PMOFs,azobenzene-functionalized HKUST-1(HK-Azo),simultaneously decorated with Cu_(2)O active sites that possess strong interaction with guest molecules.Due toπ-complexation interaction of Cu^(+)with aromatic sulfur compounds,the obtained HK-Azo shows obviously higher adsorption capacity on benzothiophene compared with HKUST-1.Upon ultraviolet(UV)and visible irradiation,azobenzene moieties in the PMOFs can transform their configuration freely and reversibly.Such trans/cis isomerization of azobenzene causes exposure/shelter of Cu_(2)O active sites,leading to controllable benzothiophene capture.The HK-Azo exhibits the change of benzothiophene uptake up to 29.7%upon trans and cis isomerization,which is obviously higher than HKUST-1 with negligible change.This work may inspire the development of new adsorption process regulated by light for adsorptive desulfurization that is impossible to realize by conventional PMOFs.展开更多
基金supproted by the National Science Fund for Distinguished Young Scholars(No.22125804)the National Natural Science Foundation of China(Nos.22001122,22178163,22078155,and 21878149)we were also grateful to the High Performance Computing Center of Nanjing Tech University for providing the computational resources.
文摘Photo-switchable metal-organic frameworks(PMOFs)as energy-saving adsorbents for tailorable guest capture show admirable potentials for various applications like adsorptive desulfurization.However,the regulation behavior of most reported PMOFs is based on weak physical interaction,and it is highly desired to introduce specific active sites to satisfy the demand of higher adsorption capacity and selectivity.Herein,for the first time,we prepared the PMOFs,azobenzene-functionalized HKUST-1(HK-Azo),simultaneously decorated with Cu_(2)O active sites that possess strong interaction with guest molecules.Due toπ-complexation interaction of Cu^(+)with aromatic sulfur compounds,the obtained HK-Azo shows obviously higher adsorption capacity on benzothiophene compared with HKUST-1.Upon ultraviolet(UV)and visible irradiation,azobenzene moieties in the PMOFs can transform their configuration freely and reversibly.Such trans/cis isomerization of azobenzene causes exposure/shelter of Cu_(2)O active sites,leading to controllable benzothiophene capture.The HK-Azo exhibits the change of benzothiophene uptake up to 29.7%upon trans and cis isomerization,which is obviously higher than HKUST-1 with negligible change.This work may inspire the development of new adsorption process regulated by light for adsorptive desulfurization that is impossible to realize by conventional PMOFs.
