Zhang Ting, Pan Zhelun, Wang Jianying, Qian Xufang, Yamashita Hiromi, Bian Zhenfeng, Zhao Yixin
School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai200240, China.
Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita565-0871, Osaka, Japan.
JACS Au. 2023 Jan 17;3(2):516-525. doi: 10.1021/jacsau.2c00644. eCollection 2023 Feb 27.
Fenton chemistry has been widely studied in a broad range from geochemistry, chemical oxidation to tumor chemodynamic therapy. It was well established that Fe/HO resulted in a sluggish initial rate or even inactivity. Herein, we report the homogeneous carbon dot-anchored Fe(III) catalysts (CD-COOFe) wherein CD-COOFe active center activates HO to produce hydroxyl radicals (OH) reaching 105 times larger than that of the Fe/HO system. The key is the OH flux produced from the O-O bond reductive cleavage boosting by the high electron-transfer rate constants of CD defects and its self-regulated proton-transfer behavior probed by operando ATR-FTIR spectroscopy in DO and kinetic isotope effects, respectively. Organic molecules interact with CD-COOFe via hydrogen bonds, promoting the electron-transfer rate constants during the redox reaction of CD defects. The antibiotics removal efficiency in the CD-COOFe/HO system is at least 51 times large than the Fe/HO system under equivalent conditions. Our findings provide a new pathway for traditional Fenton chemistry.
芬顿化学在从地球化学、化学氧化到肿瘤化学动力疗法的广泛领域中得到了深入研究。众所周知，Fe/H₂O₂体系初始反应速率缓慢甚至无活性。在此，我们报道了均相碳点锚定的Fe(III)催化剂（CD-COOFe），其中CD-COOFe活性中心激活H₂O₂生成羟基自由基（·OH），其生成量比Fe/H₂O₂体系高出105倍。关键在于，通过CD缺陷的高电子转移速率常数促进O-O键还原裂解产生的·OH通量，以及分别通过原位ATR-FTIR光谱在D₂O中的动力学同位素效应探测到的其自调节质子转移行为。有机分子通过氢键与CD-COOFe相互作用，提高了CD缺陷氧化还原反应过程中的电子转移速率常数。在同等条件下，CD-COOFe/H₂O₂体系中抗生素的去除效率比Fe/H₂O₂体系至少高51倍。我们的研究结果为传统芬顿化学提供了一条新途径。
