Abstract: Titanium suboxide is an excellent electrode material for many oxidization reactions. In this article, the electrodes of pure Ti₄O₇, doped Ti₄O₇ and the mixed-crystal of Ti₄O₇ and Ti₅O₉ were prepared to evaluate their activities and doping effects in the electro-degradation of phenol. It was revealed by the HPLC analysis results that the degradation intermediates and routes were significantly affected by the doping element. On the pure Ti₄O₇ anode, a series of classic intermediates were obtained from benzoquinone and hydroquinone to various carboxylic acids. These intermediates were degraded gradually to the final organic intermediate of oxalate in all experiments. At last, oxalate was oxidized to CO₂ and H₂O. Distinctively, the Y-doped Ti₄O₇ anode directly broke phenol to α-ketoglutaric acid without the intermediates of benzoquinone and hydroquinone. The strong oxidization ability of the Y-doped Ti₄O₇ anode might be responsible for the highest COD removal ratio. In contrast, the Ga-doped Ti₄O₇ anode showed the worst degradation activity in this article. Three intermediates of benzoquinone, hydroquinone and maleic acid were found during the degradation. Benefiting from the weak ability, oxalate was efficiently accumulated with a very high yield of 74.6%. The results demonstrated promising applications from electrochemical preparation to wastewater degradation by adjusting the doping reagent of Ti₄O₇ electrodes.

Key words: Titanium suboxide, Electro-oxidation, Doping effect, Phenol, Oxalate

摘要： Titanium suboxide is an excellent electrode material for many oxidization reactions. In this article, the electrodes of pure Ti₄O₇, doped Ti₄O₇ and the mixed-crystal of Ti₄O₇ and Ti₅O₉ were prepared to evaluate their activities and doping effects in the electro-degradation of phenol. It was revealed by the HPLC analysis results that the degradation intermediates and routes were significantly affected by the doping element. On the pure Ti₄O₇ anode, a series of classic intermediates were obtained from benzoquinone and hydroquinone to various carboxylic acids. These intermediates were degraded gradually to the final organic intermediate of oxalate in all experiments. At last, oxalate was oxidized to CO₂ and H₂O. Distinctively, the Y-doped Ti₄O₇ anode directly broke phenol to α-ketoglutaric acid without the intermediates of benzoquinone and hydroquinone. The strong oxidization ability of the Y-doped Ti₄O₇ anode might be responsible for the highest COD removal ratio. In contrast, the Ga-doped Ti₄O₇ anode showed the worst degradation activity in this article. Three intermediates of benzoquinone, hydroquinone and maleic acid were found during the degradation. Benefiting from the weak ability, oxalate was efficiently accumulated with a very high yield of 74.6%. The results demonstrated promising applications from electrochemical preparation to wastewater degradation by adjusting the doping reagent of Ti₄O₇ electrodes.

关键词: Titanium suboxide, Electro-oxidation, Doping effect, Phenol, Oxalate