TY - JOUR
T1 - Cr-Ti Mixed Oxide Molecular Cages
T2 - Synthesis, Structure, Photoresponse, and Photocatalytic Properties
AU - Wang, Dexin
AU - Said, Amir
AU - Liu, Yanshu
AU - Niu, Huihui
AU - Liu, Caiyun
AU - Wang, Guo
AU - Li, Zhaoyang
AU - Tung, Chen Ho
AU - Wang, Yifeng
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/9/19
Y1 - 2022/9/19
N2 - The solvothermal reaction of titanium isopropoxide and chromate in the presence of benzoate produced two novel host-guest clusters encapsulating Cs+or H3O+, (H3O)@Ti7Cr14and Cs@Ti7Cr14. The most remarkable feature is that the Ti7O7ring is concentrically embraced by a Cr14O14ring to form a rigid Ti7Cr14host. ESI-MS and 133Cs NMR revealed that the overall framework structures are preserved, whereas the benzoate ligands on the two clusters may be labile in solutions. Both (H3O)@Ti7Cr14and Cs@Ti7Cr14exhibit good UV-vis light-responsive properties and photocatalytic activities, with absorption edges extending up to 780 nm. Cs@Ti7Cr14is an effective visible-light-responsive photocatalyst in both the heterogeneous methylene dye degradation and homogeneous CO2cycloaddition reaction under mild conditions like room temperature and 1 bar of CO2. According to the mechanism studies, Cs+, as a rigid guest, can significantly improve the photogenerated charge separation efficiency of the Ti7Cr14host, thereby improving its interface charge separation properties, photocurrent, and photocatalytic activities. Our findings not only provide new members of heterometallic titanium oxide clusters to enrich the metal oxide cluster family but also open up new possibilities for their photoresponses, which may play an important role in solar energy harvesting for sustainable chemistry.
AB - The solvothermal reaction of titanium isopropoxide and chromate in the presence of benzoate produced two novel host-guest clusters encapsulating Cs+or H3O+, (H3O)@Ti7Cr14and Cs@Ti7Cr14. The most remarkable feature is that the Ti7O7ring is concentrically embraced by a Cr14O14ring to form a rigid Ti7Cr14host. ESI-MS and 133Cs NMR revealed that the overall framework structures are preserved, whereas the benzoate ligands on the two clusters may be labile in solutions. Both (H3O)@Ti7Cr14and Cs@Ti7Cr14exhibit good UV-vis light-responsive properties and photocatalytic activities, with absorption edges extending up to 780 nm. Cs@Ti7Cr14is an effective visible-light-responsive photocatalyst in both the heterogeneous methylene dye degradation and homogeneous CO2cycloaddition reaction under mild conditions like room temperature and 1 bar of CO2. According to the mechanism studies, Cs+, as a rigid guest, can significantly improve the photogenerated charge separation efficiency of the Ti7Cr14host, thereby improving its interface charge separation properties, photocurrent, and photocatalytic activities. Our findings not only provide new members of heterometallic titanium oxide clusters to enrich the metal oxide cluster family but also open up new possibilities for their photoresponses, which may play an important role in solar energy harvesting for sustainable chemistry.
UR - http://www.scopus.com/inward/record.url?scp=85137895589&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.2c02605
DO - 10.1021/acs.inorgchem.2c02605
M3 - Article
C2 - 36063420
AN - SCOPUS:85137895589
SN - 0020-1669
VL - 61
SP - 14887
EP - 14898
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 37
ER -