Titanium suboxide is an excellent electrode material for many oxidization reactions. In this article

the electrodes of pure Ti

4

O

7

doped Ti

4

O

7

and the mixed-crystal of Ti

4

O

7

and Ti

5

O

9

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 Ti

4

O

7

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 CO

2

and H

2

O. Distinctively

the Y-doped Ti

4

O

7

anode directly broke phenol to α-ketoglutaric acid without the intermediates of benzoquinone and hydroquinone. The strong oxidization ability of the Y-doped Ti

4

O

7

anode might be responsible for the highest COD removal ratio. In contrast

the Ga-doped Ti

4

O

7

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 Ti

4

O

7

electrodes.