Dong Hong, Fang Liang, Chen Ke-Xin, Wei Jian-Xin, Li Jia-Xin, Qiao Xiu, Wang Ya, Zhang Feng-Ming, Lan Ya-Qian
Heilongjiang Provincial Key Laboratory of CO2 Resource Utilization and Energy Catalytic Materials, School of Material Science and Chemical Engineering, Harbin University of Science and Technology, Harbin, 150040, PR China.
School of Chemistry, South China Normal University, Guangzhou, 510006, PR China.
Angew Chem Int Ed Engl. 2025 Jan 10;64(2):e202414287. doi: 10.1002/anie.202414287. Epub 2024 Nov 6.
Directly converting CO in flue gas using artificial photosynthetic technology represents a promising green approach for CO resource utilization. However, it remains a great challenge to achieve efficient reduction of CO from flue gas due to the decreased activity of photocatalysts in diluted CO atmosphere. Herein, we designed and synthesized a series of dual metallosalen-based covalent organic frameworks (MM-Salen-COFs, M: Zn, Ni, Cu) for artificial photosynthetic diluted CO reduction and confirmed their advantage in comparison to that of single metal M-Salen-COFs. As a results, the ZnZn-Salen-COF with dual Zn sites exhibits a prominent visible-light-driven CO-to-CO conversion rate of 150.9 μmol g h under pure CO atmosphere, which is ~6 times higher than that of single metal Zn-Salen-COF. Notably, the dual metal ZnZn-Salen-COF still displays efficient CO conversion activity of 102.1 μmol g h under diluted CO atmosphere from simulated flue gas conditions (15 % CO), which is a record high activity among COFs- and MOFs-based photocatalysts under the same reaction conditions. Further investigations and theoretical calculations suggest that the synergistic effect between the neighboring dual metal sites in the ZnZn-Salen-COF facilitates low concentration CO adsorption and activation, thereby lowering the energy barrier of the rate-determining step.
利用人工光合技术直接转化烟气中的一氧化碳是一种很有前景的一氧化碳资源利用绿色方法。然而，由于光催化剂在稀释一氧化碳气氛中的活性降低，实现从烟气中高效还原一氧化碳仍然是一个巨大的挑战。在此，我们设计并合成了一系列基于双金属水杨醛络合物的共价有机框架材料（MM-Salen-COFs，M：Zn、Ni、Cu）用于人工光合稀释一氧化碳还原，并证实了它们相对于单金属M-Salen-COFs的优势。结果，具有双锌位点的ZnZn-Salen-COF在纯一氧化碳气氛下表现出显著的可见光驱动一氧化碳到一氧化碳的转化率，为150.9 μmol g⁻¹ h⁻¹，比单金属Zn-Salen-COF高约6倍。值得注意的是，在模拟烟气条件（15 % CO）的稀释一氧化碳气氛下，双金属ZnZn-Salen-COF仍表现出102.1 μmol g⁻¹ h⁻¹的高效一氧化碳转化活性，这是在相同反应条件下基于COF和MOF的光催化剂中的创纪录高活性。进一步的研究和理论计算表明，ZnZn-Salen-COF中相邻双金属位点之间的协同效应促进了低浓度一氧化碳的吸附和活化，从而降低了速率决定步骤的能垒。
