TY - JOUR
T1 - Photophysical and photocatalytic properties of structurally modified UiO-66
AU - Zeama, Mostafa
AU - Morsy, Mohamed
AU - Abdel-Azeim, Safwat
AU - Abdelnaby, Mahmoud
AU - Alloush, Ahmed
AU - Yamani, Zain
N1 - KAUST Repository Item: Exported on 2022-06-13
Acknowledgements: We are grateful to Prof. Omar M. Yaghi (University of California, Berkeley Global Science Institute) and Mr. Kyle E. Cordova (formerly of University of California, Berkeley Global Science Institute) for their helpful comments and guidance in this research work as well as for their support of global science activities. For computer time, this research used the resources of the Supercomputing Laboratory (Project k1276) at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia. We are thankful for CENT at KFUPM for allowing us to use their facilities in our experimental work. We are also thankful to Dr. Bassem A. Al-Maythalony (TIC on CCSKFUPM) for access to gas sorption measurements. The research team also acknowledges the support by Saudi Aramco, through KFUPM Project No. ORCP2390. This work was supported by Saudi Aramco, through KFUPM Project No. ORCP2390.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.
PY - 2019/12/9
Y1 - 2019/12/9
N2 - UiO-66 metal-organic-frameworks (MOFs) are well known for their stability and photoactivity, especially for CO2 reduction. This work reports different incorporation methods of titanium metal into UiO-66-NH2 based frameworks via post-synthetic as well as in situ metal exchange. Each method successfully produced crystalline material with enhancement in photophysical and photocatalytic properties. The origin of the enhanced photophysical was investigated with electron paramagnetic resonance and ultraviolet-visible diffuse reflectance spectroscopy measurements. The observed decrease in the electronic band gaps of the modified UiO-66-based MOFs is supported by density functional theory (DFT)-electronic structure calculations. The DFT-simulations also confirmed the synergistic effect between –NH2 functionalization and titanium metal incorporation that boosts the reactivity of the respective resulting MOFs. A detailed investigation of CO2 reduction was then carried out with the different MOFs models. A remarkable enhancement of the photocatalytic activity was observed by using the UiO-66-NH2 based frameworks compared to the pristine UiO-66. A nearly doubled photocatalytic activity was obtained by the Ti-Zr mixed MOF materials regardless of the method or the ratio of incorporated titanium metal loading.
AB - UiO-66 metal-organic-frameworks (MOFs) are well known for their stability and photoactivity, especially for CO2 reduction. This work reports different incorporation methods of titanium metal into UiO-66-NH2 based frameworks via post-synthetic as well as in situ metal exchange. Each method successfully produced crystalline material with enhancement in photophysical and photocatalytic properties. The origin of the enhanced photophysical was investigated with electron paramagnetic resonance and ultraviolet-visible diffuse reflectance spectroscopy measurements. The observed decrease in the electronic band gaps of the modified UiO-66-based MOFs is supported by density functional theory (DFT)-electronic structure calculations. The DFT-simulations also confirmed the synergistic effect between –NH2 functionalization and titanium metal incorporation that boosts the reactivity of the respective resulting MOFs. A detailed investigation of CO2 reduction was then carried out with the different MOFs models. A remarkable enhancement of the photocatalytic activity was observed by using the UiO-66-NH2 based frameworks compared to the pristine UiO-66. A nearly doubled photocatalytic activity was obtained by the Ti-Zr mixed MOF materials regardless of the method or the ratio of incorporated titanium metal loading.
UR - http://hdl.handle.net/10754/678926
UR - https://linkinghub.elsevier.com/retrieve/pii/S0020169319314677
UR - http://www.scopus.com/inward/record.url?scp=85075987363&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2019.119287
DO - 10.1016/j.ica.2019.119287
M3 - Article
SN - 0020-1693
VL - 501
SP - 119287
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
ER -