Photophysical and photocatalytic properties of structurally modified UiO-66

Mostafa Zeama; Mohamed Morsy; Safwat Abdel-Azeim; Mahmoud Abdelnaby; Ahmed Alloush; Zain Yamani

doi:10.1016/j.ica.2019.119287

Photophysical and photocatalytic properties of structurally modified UiO-66

Mostafa Zeama, Mohamed Morsy, Safwat Abdel-Azeim, Mahmoud Abdelnaby, Ahmed Alloush, Zain Yamani

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	119287
Journal	Inorganica Chimica Acta
Volume	501
DOIs	https://doi.org/10.1016/j.ica.2019.119287
State	Published - Dec 9 2019
Externally published	Yes

Bibliographical note

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.

ASJC Scopus subject areas

Materials Chemistry
Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1016/j.ica.2019.119287

Cite this

@article{a39d7a8726b94ee18b3993cede10116c,

title = "Photophysical and photocatalytic properties of structurally modified UiO-66",

abstract = "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.",

author = "Mostafa Zeama and Mohamed Morsy and Safwat Abdel-Azeim and Mahmoud Abdelnaby and Ahmed Alloush and Zain Yamani",

note = "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.",

year = "2019",

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doi = "10.1016/j.ica.2019.119287",

language = "English (US)",

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pages = "119287",

journal = "Inorganica Chimica Acta",

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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.

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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 -

Photophysical and photocatalytic properties of structurally modified UiO-66

Abstract

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