Pd/C气体扩散电极用于电生成H2O2降解苯酚的研究

采用自制的Pd/C气体扩散阴极和Ti/IrO2/RuO2阳极,在无隔膜电解槽中对苯酚模拟废水降解效果及机制进行了研究,采用电子自旋共振法(ESR)对电解体系中产生的羟自由基(·OH)进行了检测.结果表明,在Pd/C气体扩散体系中掺杂Pd催化剂可以促进H2 O2的生成(H2 O2的稳定浓度是7.5 mg/L),有利于·OH的产生.经电化学氧化处理120 min后,苯酚和COD的去除率分别达到97.2%和50%,表明在电催化氧化过程中苯酚被氧化生成了大量低分子量中间产物.废水的BOD5/COD值达到0.73是处理前的9.1倍,苯酚废水的可生化降解性通过电化学氧化处理后显著提高.在该电化学体系中苯酚的降解是在阳极直接、间接氧化及阴极产生的H2 O2、·OH的氧化共同作用下完成的.通过对紫外扫描光谱图的分析推断出苯酚在电解过程中有醌类物质生成;由GC-MS检测到了邻苯二酚、对苯二酚、苯醌等芳香族化合物和己二酸、顺丁烯二酸、反丁烯二酸、丁二酸、丙二酸、乙二酸等短链羧酸,据此提出了苯酚降解的可能历程.

Degradation Mechanism of Phenol with Electrogenerated Hydrogen Peroxide on a Pd/C Gas-diffusion Electrode

Using a self-made Pd/C gas-diffusion electrode as the cathode and Ti/IrO₂/RuO₂ as the anode, the degradation of phenol was investigated in an undivided electrolysis device by the electrochemical oxidation process. Hydroxyl radical (·OH) was determined in the reaction mixture by the electron spin resonance spectrum (ESR). The result indicated that the Pd/C catalyst in Pd/C gas-diffusion electrode system accelerated the two-electron reduction of O₂ to H₂O₂ when feeding air, which is in favor of producing ·OH. After 120 min electrolysis in Pd/C gas-diffusion electrode system, the steady concentration of H₂O₂ was 7.5 mg/L. The removal efficiency of phenol and COD reached about 97.2% and 50% after 120 min electrolysis, respectively, which suggested that most of phenol were oxidized to intermediates using the Pd/C gas-diffusion electrode. Furthermore, the ratio of BOD₅/COD of the solutions was 9.1 times larger than the initial ones. Hence the electrochemical oxidation can enhance the biodegradation character of the phenol solution. The degradation of phenol was supposed to be cooperative oxidation by direct and/or indirect electrochemical oxidation at the anode and H₂O₂, ·OH produced by oxygen reduction at the cathode. UV-Vis and GC-MS identified catechol, hydroquinone, and benzoquinone as the main aromatic intermediates, and adipic, maleic, fumaric, succinic, malonic, and oxalic acids as the main aliphatic carboxylic intermediates. A reaction scheme involving all these intermediates was proposed.