钴
光催化
化学
催化作用
共价键
卟啉
选择性
自旋态
光化学
密度泛函理论
纳米技术
自旋(空气动力学)
计算化学
有机化学
无机化学
材料科学
热力学
物理
作者
Yun‐Nan Gong,Wenhui Zhong,Li Yang,Yunze Qiu,Lirong Zheng,Jun Jiang,Hai‐Long Jiang
摘要
While catalysis is highly dependent on the electronic structure of the catalyst, the understanding of catalytic performance affected by electron spin regulation remains challenging and rare. Herein, we have developed a facile strategy to the manipulation of the cobalt spin state over covalent organic frameworks (COFs), COF-367-Co, by simply changing the oxidation state of Co centered in the porphyrin. Density functional theory (DFT) calculations together with experimental results confirm that CoII and CoIII are embedded in COF-367 with S = 1/2 and 0 spin ground states, respectively. Remarkably, photocatalytic CO2 reduction results indicate that COF-367-CoIII exhibits favorable activity and significantly enhanced selectivity to HCOOH, accordingly much reduced activity and selectivity to CO and CH4, in sharp contrast to COF-367-CoII. The results highlight that the spin-state transition of cobalt greatly regulates photocatalytic performance. Theoretical calculations further disclose that the presence of CoIII in COF-367-Co is preferable to the formation of HCOOH but detrimental to its further conversion, which clearly accounts for its distinctly different photocatalysis over COF-367-CoII. To the best of our knowledge, this is the first report on regulating photocatalysis by spin state manipulation in COFs.
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