Key Laboratory of Photochemistry, Institute of Chemistry Chinese Academy of Sciences, Beijing National Laboratory for Molecular Sciences, 100190, Beijing, P. R. China.
University of Chinese Academy of Sciences, 100049, Beijing, P. R. China.
Angew Chem Int Ed Engl. 2023 Mar 1;62(10):e202216717. doi: 10.1002/anie.202216717. Epub 2023 Jan 25.
Herein, we fabricated a π-π stacking hybrid photocatalyst by combining two two-dimensional (2D) materials: g-C N and a Cu-porphyrin metal-organic framework (MOF). After an aerobic photocatalytic pretreatment, this hybrid catalyst exhibited an unprecedented ability to photocatalytically reduce CO to CO and CH under the typical level (20 %) of O in the air. Intriguingly, the presence of O did not suppress CO reduction; instead, a fivefold increase compared with that in the absence of O was observed. Structural analysis indicated that during aerobic pretreatment, the Cu node in the 2D-MOF moiety was hydroxylated by the hydroxyl generated from the reduction of O . Then the formed hydroxylated Cu node maintained its structure during aerobic CO reduction, whereas it underwent structural alteration and was reductively devitalized in the absence of O . Theoretical calculations further demonstrated that CO reduction, instead of O reduction, occurred preferentially on the hydroxylated Cu node.
在此，我们通过结合两种二维（2D）材料：g-C3N4和铜卟啉金属有机骨架（MOF），制备了一种π-π 堆积杂化光催化剂。在有氧光催化预处理后，该杂化催化剂表现出在空气中典型的（20%）O2水平下将 CO 光催化还原为 CO 和 CH4的前所未有的能力。有趣的是，O2的存在并没有抑制 CO 的还原，反而观察到比没有 O2存在时增加了五倍。结构分析表明，在有氧预处理过程中，二维 MOF 部分中的 Cu 节点被 O2还原产生的羟基羟基化。然后，形成的羟基化 Cu 节点在有氧 CO 还原过程中保持其结构，而在没有 O2存在时，它会发生结构改变并被还原失活。理论计算进一步表明，CO 还原而不是 O2还原优先发生在羟基化的 Cu 节点上。
