School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China.
School of Chemical Engineering, Xiangtan University, Xiangtan 411105, China.
J Hazard Mater. 2016 Mar 15;305:15-20. doi: 10.1016/j.jhazmat.2015.11.028. Epub 2015 Nov 28.
A new microwave catalytic oxidation process based on two kinds of catalysts, the commercially available activated carbon (AC) and Mn2O3 nanoparticle modified AC (Mn2O3/AC), was reported for the degradation of 4-nitrophenol (4-NP) without adding any oxidant. Effects of microwave power, catalyst dosage, irradiation time, and initial concentration for the degradation efficiency were studied. Results indicated that catalyst of Mn2O3/AC showed much higher catalytic activity than pure AC and Mn2O3 particles. Significantly, 4-NP degradation efficiency reached 99.6%, corresponding to 93.5% TOC removal under optimal conditions with microwave power of 400W, Mn2O3/AC dosage of 2g, reaction time of 5min, and initial concentration of 100mg/L. Hydroxyl radicals (OH) generated during catalytic reaction is the main oxidant, and O2 can not effectively improve removal rate. We proposed the microwave 'photoelectric effect' to interpret the generation of OH in view that microwave irradiation can directly excite the catalyst to produce electron-hole pairs and then transform H2O into OH on the surface of catalyst in solution. The obtained kinetic equation for microwave catalytic oxidation degradation of 4-NP was in line with pseudo-first-order kinetic model, that is, apparent rate constant increased as microwave power density increase.
一种新型的微波催化氧化工艺,基于两种催化剂,即市售的活性炭(AC)和 Mn2O3 纳米颗粒改性的 AC(Mn2O3/AC),被报道用于在不添加任何氧化剂的情况下降解 4-硝基苯酚(4-NP)。研究了微波功率、催化剂用量、辐照时间和初始浓度对降解效率的影响。结果表明,Mn2O3/AC 催化剂比纯 AC 和 Mn2O3 颗粒具有更高的催化活性。重要的是,在最佳条件下,微波功率为 400W、Mn2O3/AC 用量为 2g、反应时间为 5min、初始浓度为 100mg/L 时,4-NP 的降解效率达到 99.6%,对应的总有机碳(TOC)去除率为 93.5%。在催化反应过程中产生的羟基自由基(OH)是主要的氧化剂,而 O2 不能有效地提高去除率。我们提出了微波“光电效应”来解释 OH 的产生,因为微波辐射可以直接激发催化剂产生电子-空穴对,然后在溶液中催化剂表面将 H2O 转化为 OH。获得的微波催化氧化降解 4-NP 的动力学方程符合准一级动力学模型,即表观速率常数随着微波功率密度的增加而增加。