State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University , Beijing 100084, China.
Collaborative Innovation Center for Regional Environmental Quality, School of Environment, Tsinghua University , Beijing 100084, China.
Environ Sci Technol. 2015 Oct 20;49(20):12372-9. doi: 10.1021/acs.est.5b02085. Epub 2015 Oct 8.
Layered manganese oxide, i.e., birnessite was prepared via the reaction of potassium permanganate with ammonium oxalate. The water content in the birnessite was adjusted by drying/calcining the samples at various temperatures (30 °C, 100 °C, 200 °C, 300 °C, and 500 °C). Thermogravimetry-mass spectroscopy showed three types of water released from birnessite, which can be ascribed to physically adsorbed H2O, interlayer H2O and hydroxyl, respectively. The activity of birnessite for formaldehyde oxidation was positively associated with its water content, i.e., the higher the water content, the better activity it has. In-situ DRIFTS and step scanning XRD analysis indicate that adsorbed formaldehyde, which is promoted by bonded water via hydrogen bonding, is transformed into formate and carbonate with the consumption of hydroxyl and bonded water. Both bonded water and water in air can compensate the consumed hydroxyl groups to sustain the mineralization of formaldehyde at room temperature. In addition, water in air stimulates the desorption of carbonate via water competitive adsorption, and accordingly the birnessite recovers its activity. This investigation elucidated the role of water in oxidizing formaldehyde by layered manganese oxides at room temperature, which may be helpful for the development of more efficient materials.
层状氧化锰,即水钠锰矿,是通过高锰酸钾与草酸铵反应制备的。通过在不同温度(30°C、100°C、200°C、300°C 和 500°C)下干燥/煅烧样品来调节水钠锰矿中的含水量。热重-质谱联用表明,水钠锰矿中释放出三种类型的水,分别归因于物理吸附的 H2O、层间 H2O 和羟基。水钠锰矿对甲醛氧化的活性与其含水量呈正相关,即含水量越高,活性越好。原位 DRIFTS 和分步扫描 XRD 分析表明,通过氢键与结合水结合的吸附甲醛转化为甲酸盐和碳酸盐,同时消耗羟基和结合水。结合水和空气中的水可以补偿消耗的羟基,以维持甲醛在室温下的矿化。此外,空气中的水通过水竞争吸附刺激碳酸盐的解吸,从而使水钠锰矿恢复其活性。这项研究阐明了层状氧化锰在室温下氧化甲醛过程中水分的作用,这可能有助于开发更高效的材料。