Wang Fu-Xue, Zhang Zi-Wei, Wang Fei, Li Ya, Zhang Zi-Chen, Wang Chong-Chen, Yu Baoyi, Du Xuedong, Wang Peng, Fu Huifen, Zhao Chen
Beijing Key Laboratory of Functional Materials for Building Structure and Environment Remediation, Beijing University of Civil Engineering and Architecture, Beijing 100044, China; Beijing Energy Conservation & Sustainable Urban and Rural Development Provincial and Ministry Co-construction Collaboration Innovation Center, Beijing University of Civil Engineering and Architecture, Beijing 100044, China.
Beijing Key Laboratory of Functional Materials for Building Structure and Environment Remediation, Beijing University of Civil Engineering and Architecture, Beijing 100044, China; Beijing Energy Conservation & Sustainable Urban and Rural Development Provincial and Ministry Co-construction Collaboration Innovation Center, Beijing University of Civil Engineering and Architecture, Beijing 100044, China.
J Colloid Interface Sci. 2023 Nov;649:384-393. doi: 10.1016/j.jcis.2023.06.083. Epub 2023 Jun 17.
Constructing Fe-Cu bimetal catalysts is an efficient strategy to promote Fe(III)/Fe(II) cycle, whereas there is still a long way to go before fully understanding the role of the Cu in the catalysts. Herein, a new Fe-MOF namely BUC-96(Fe) was fabricated from FeSO·7HO, 4,4'-bipyridine (bpy) and 2,5-dihydroxyterephthalic acid (Hdhtp) by both hydrothermal reaction and microwave-assisted method. Also, bimetal BUC-96(FeCu-x) were obtained when the CuSO was added into the system identical to the synthesis process of BUC-96(Fe). Series BUC-96 MOFs showed good organics elimination performance via Fenton-like process, where 88.1% (k = 0.0672 min) of chloroquine phosphate (CQ, 20 mg/L) was decomposed over pristine BUC-96(Fe) within 30 min. Interestingly, nearly 100% CQ was degraded over BUC-96(FeCu-5) as catalyst under the identical conditions within 5 min, whose reaction rate (1.3527 min) was 20.1-fold higher than that of BUC-96. Additionally, BUC-96(FeCu-5) exhibited excellent Fenton-like oxidation degradation performance for 10 selected emerging organic pollutants. The reaction mechanism was studied in detail by experiments, and density functional theory (DFT) calculation. The results revealed that the introduced Cu not only accelerated Fe(III)/Fe(II) cycles, hydroxyl radical (·OH) generation, electron transfer, but also lowered HO dissociated energy barrier. This work advanced the bimetal MOFs construction and application in wastewater treatment via Fenton-like process.
构建铁铜双金属催化剂是促进Fe(III)/Fe(II)循环的有效策略，然而在充分理解铜在催化剂中的作用之前，仍有很长的路要走。在此，通过水热反应和微波辅助方法，由FeSO₄·7H₂O、4,4'-联吡啶（bpy）和2,5-二羟基对苯二甲酸（H₂dhtp）制备了一种新型铁基金属有机框架材料BUC-96(Fe)。此外，在与BUC-96(Fe)合成过程相同的体系中加入CuSO₄时，得到了双金属BUC-96(FeCu-x)。系列BUC-96金属有机框架材料通过类芬顿过程表现出良好的有机物去除性能，其中在原始BUC-96(Fe)上，30分钟内88.1%（k = 0.0672 min⁻¹）的磷酸氯喹（CQ，20 mg/L）被分解。有趣的是，在相同条件下，以BUC-96(FeCu-5)为催化剂，5分钟内近100%的CQ被降解，其反应速率（1.3527 min⁻¹）比BUC-96高20.1倍。此外，BUC-96(FeCu-5)对10种选定的新兴有机污染物表现出优异的类芬顿氧化降解性能。通过实验和密度泛函理论（DFT）计算对反应机理进行了详细研究。结果表明，引入的铜不仅加速了Fe(III)/Fe(II)循环、羟基自由基（·OH）的产生、电子转移，还降低了H₂O₂的解离能垒。这项工作推进了双金属金属有机框架材料在类芬顿法废水处理中的构建和应用。
