Limited electrooxidation efficiency and high energy consumption restrict the application of Ti4O7 reactive electrochemical membrane (REM). This study aimed to improve the electrooxidation reactivity of Ti4O7 REM through tailoring CeO2 transition layer into the interface of Ti4O7 loaded with Pt. We found that 1Pt/CeO2-Ti4O7 REM (1 wt% Pt) operation in single pass achieved more than 31 times enhancement for dichlorophen (DCP) removal rates compared with pristine Ti4O7 at 0.5 mA cm−2, accompanied by over 98 % energy consumption reduction. Characterization results showed that CeO2 loaded on Ti4O7 could uniformly disperse Pt clusters by anchoring effect on Pt atoms to exhibit stable and efficient electrooxidation activity. Density functional theory simulations and well-designed experiments elucidated that direct electron transfer (DET) anodic oxidation drove the electrooxidation process of DCP in Pt/CeO2-Ti4O7 REM due to the increased charge transfer efficiency, active sites and the adsorption energy for DCP. This differs from the joint action of DET reaction and hydroxyl radicals mediated reaction in pristine Ti4O7 anode. More pronounced charge redistribution and accumulation at DCP-Pt/CeO2-Ti4O7 interface especially around Cl atoms facilitated nucleophilic substitution of the hydroxyl group for Cl atoms to realize less containing chlorine intermediate products and greater mineralization rates. These findings provide insights into interface engineering strategies for preparing Ti4O7 REM with excellent reactivity and low energy consumption.

中文翻译：

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定制有序 CeO2/Pt 负载 Ti4O7 反应电化学膜，用于抗菌二氯酚的高效电氧化


有限的电氧化效率和高能耗限制了Ti4O7反应电化学膜（REM）的应用。本研究旨在通过在负载 Pt 的 Ti4O7 界面上定制 CeO2 过渡层来提高 Ti4O7 REM 的电氧化反应活性。我们发现，与原始 Ti4O7 相比，在 0.5 mA cm−2 下，1Pt/CeO2-Ti4O7 REM (1 wt% Pt) 单次操作对二氯酚 (DCP) 的去除率提高了 31 倍以上，同时能耗降低了 98% 以上减少。表征结果表明，Ti4O7上负载的CeO2可以通过对Pt原子的锚定效应均匀分散Pt团簇，从而表现出稳定高效的电氧化活性。密度泛函理论模拟和精心设计的实验表明，直接电子转移（DET）阳极氧化由于电荷转移效率、活性位点和DCP吸附能的增加而驱动了Pt/CeO2-Ti4O7 REM中DCP的电氧化过程。这与原始 Ti4O7 阳极中 DET 反应和羟基自由基介导的反应的联合作用不同。 DCP-Pt/CeO2-Ti4O7界面上更明显的电荷重新分布和积累，尤其是在Cl原子周围，促进了羟基对Cl原子的亲核取代，从而实现了含氯中间产物的减少和矿化速率的提高。这些发现为制备具有优异反应性和低能耗的 Ti4O7 REM 的界面工程策略提供了见解。