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Engineering the Electronic Microenvironment with Bromine Functionalization for High-Selectivity Photocatalytic CO2
Junhui He1,2, Zhansheng Wang2, Jiang Xue1
1CAEA Innovation Center of Nuclear Environmental Safety Technology, School of Environment and Resource, School of National Defense & Nuclear Science and Technology, Southwest University of Science and Technology, Mianyang, Sichuan, P. R. China.
Surface bromine modification of covalent organic frameworks (COFs) enhances CO2 photoreduction. This strategy improves catalyst activity and selectivity for efficient carbon dioxide conversion.
Area of Science:
- Materials Science
- Photocatalysis
- Green Chemistry
Background:
- Covalent organic frameworks (COFs) are promising materials for photocatalysis.
- Tuning the electronic structure of COFs is crucial for enhancing their performance.
- Surface modification offers a route to optimize COF properties.
Purpose of the Study:
- To investigate the effect of surface bromine atom modification on TzPm-COF.
- To enhance the activity and selectivity of CO2 photoreduction using modified COFs.
- To elucidate the mechanism behind the improved photocatalytic performance.
Main Methods:
- Synthesis of bromine-modified TzPm-COF (TzPm-COF-2Br).
- In situ Kelvin probe force microscopy (KPFM) and spectral analysis.
- Density functional theory (DFT) calculations.
Main Results:
- Bromine functionalization of TzPm-COF significantly enhanced CO2 photoreduction activity (155 µmol g⁻¹ h⁻¹).
- The modified COF exhibited high selectivity (99.4%) for CO production.
- Bromine atoms facilitated charge carrier separation and migration, improving CO2 adsorption and activation.
Conclusions:
- Surface bromine modification is an effective strategy for tuning COF donor-acceptor structures.
- The enhanced TzPm-COF-2Br shows superior performance for visible-light-driven CO2 reduction.
- This work provides a rational design approach for developing advanced COF photocatalysts.
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