Khojastegi Anahita, Khosropour Ahmadreza, Amirjalayer Saeed, Mosleh Imann, Abbaspourrad Alireza
Department of Food Science, College of Agriculture and Life Sciences, Cornell University, Ithaca, New York, USA.
Institute for Solid State Theory, Center for Multiscale Theory and Computation, Center for Nanotechnology, University of Münster, 48149 Münster, Germany.
Adv Funct Mater. 2024 Mar 11;34(11). doi: 10.1002/adfm.202309367. Epub 2023 Dec 2.
Woven covalent organic frameworks (COF) possess three dimensional frameworks with spatially isolated Cu(I) centers and have promising optoelectronic properties because of metal to ligand charge transfer (MLCT). However, despite their potential, woven COFs have not yet been investigated as photocatalysts. In this study, we developed a new woven COF, Cu-PhenBDA-COF, functionalized with diacetylene bonds. Cu-PhenBDA-COF was fully characterized, and the optoelectronic and photocatalytic properties were compared to previously reported Cu-COF-505. The diacetylene bonds of the linker positively impacted the optoelectronic properties of Cu-PhenBDA-COF and resulted in a narrower band gap and better charge separation efficiency. When the Cu(I) center was removed from both woven COFs, the absorption edge was blue shifted, resulting in a wider band gap, and there was a considerable decrease in the charge separation efficiency, underscoring the pivotal role of MLCT. This trend was reflected in the photocatalytic activity of the woven COFs toward the degradation of sulfamethoxazole in water, where the highest reaction rate constant ( ) was recorded for the metallated diacetylene functionalized woven COF, Cu-PhenBDA-COF.
编织共价有机框架（COF）具有三维框架结构，其中铜（I）中心在空间上相互隔离，并且由于金属到配体的电荷转移（MLCT）而具有良好的光电性能。然而，尽管编织COF具有潜力，但尚未对其作为光催化剂进行研究。在本研究中，我们开发了一种新的用二乙炔键官能化的编织COF，即Cu-PhenBDA-COF。对Cu-PhenBDA-COF进行了全面表征，并将其光电和光催化性能与先前报道的Cu-COF-505进行了比较。连接体的二乙炔键对Cu-PhenBDA-COF的光电性能产生了积极影响，导致带隙变窄和电荷分离效率提高。当从两种编织COF中去除铜（I）中心时，吸收边缘发生蓝移，导致带隙变宽，并且电荷分离效率显著降低，这突出了MLCT的关键作用。这种趋势反映在编织COF对水中磺胺甲恶唑降解的光催化活性上，其中金属化二乙炔官能化的编织COF，即Cu-PhenBDA-COF，记录到最高的反应速率常数（ ）。
