Improvement of stability and reduction of energy consumption for Ti-based MnOx electrode by Ce and carbon black co-incorporation in electrochemical degradation of ammonia nitrogen.

Ti-based electrode coated with MnOx catalytic layer has presented superior electrochemical activity for degradation of organic pollution in wastewater, however, the industrial application of Ti-based MnOx electrode is limited by the poor stability of the electrode. In this study, the novel Ti-based MnOx electrodes co-incorporated with rare earth (Ce) and conductive carbon black (C) were prepared by spraying-calcination method. The Ti/Ce:MnOx-C electrode, with uniform and integrated surface and enhanced Mn(IV) content by C and Ce co-incorporation, could completely remove ammonia nitrogen (NH4+-N) with N2 as the main product. The cell potential and energy consumption of Ti/Ce:MnOx-C electrode during the electrochemical process was significantly reduced compared with Ti/MnOx electrode, which mainly originated from the enhanced electrochemical activity and reduced charge transfer resistance by Ce and C co-incorporation. The accelerated lifetime tests in sulfuric acid showed that the actual service lifetime of Ti/Ce:MnOx-C was ca. 25 times that of Ti/MnOx, which demonstrated the significantly promoted stability of MnOx-based electrode by Ce and C co-incorporation.

Preparation of novel Ti-based MnOx electrodes by spraying method for electrochemical oxidation of Acid Red B.

At different calcination conditions, titanium-based manganese oxides (MnOx) electrodes were fabricated by spraying method without adhesive. The MnOx/Ti electrodes were applied in electrochemical oxidation of wastewater treatment for the first time. The surface morphologies of electrodes were tested by scanning electron microscopy. The formation of different manganese oxidation states on electrodes was confirmed by X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical properties of the electrodes have been performed by means of cyclic voltammetry and electrochemical impedance spectroscopy. The characterizations revealed that the MnOx/Ti-350(20) electrode, prepared at calcination temperature of 350 °C for 20 min, exhibited fewer cracks on the electrode surface, larger electrochemically effective surface area and lower charge transfer resistance than electrodes prepared at other calcination conditions. Moreover, Acid Red B was used as target pollutant to test the electrode activity via monitoring the concentration changes by UV spectrophotometer. The results showed that the MnOx/Ti-350(20) electrode presented the best performance on decolorization of Acid Red B with the lowest cell potential during the process of electrochemical oxidation, and the chemical oxygen demand (COD) conversion was 50.7%. Furthermore, the changes of Acid Red B during the electrochemical oxidation process were proposed by the UV-vis spectra.

Promotion of catalytic ozonation of aniline with Mn-Ce-Ox/γ-Al2O3.

In this study, Mn-Ce-Ox/γ-Al2O3 supported catalysts were adopted to promote the removal efficiency of aniline in simulated wastewater with ozone. Mn-Ce-Ox/γ-Al2O3 catalysts were prepared by the impregnation-calcination method. Its phase structure, specific surface area, loading amount and distribution of active units were analyzed by XRD, BET, ICP-AES and TEM/SEM respectively. The characterization results demonstrated that the catalysts had a good dispersion of Mn-Ce-Ox active sites and an abundant porous structure from the γ-Al2O3 support. The catalytic ozonation results showed that with Mn3-Ce1-Ox/γ-Al2O3(1.0), the aniline removal efficiency was highly improved, 15.0% higher than that of ozonation without a catalyst. Furthermore, from the variation in loading amounts of Mn and Ce, it can be seen that the molar ratio of Mn and Ce within the Mn-Ce-Ox plays a key role in accelerating the ozonation of aniline in simulated wastewater with ozone, while Mn:Ce = 1.9:1 showed the best performance. More importantly, the catalysts showed high recycling performance and could be reused at least 12 times without obvious loss of activity.