Cobalt(Co)exists in significant quantities in naturally occurring manganese(Mn)oxides and alters the growth of Mn oxide crystals.Four-layered Mn oxides,Na-buserite(Na-bus)and three Co-doped Na-buserite samples prepared from oxidation of Mn(OH)2 with 5%,10%,and 20% Co/(Mn+Co)molar ratios(5Co-Na-bus,10Co-Na-bus,and 20Co-Na-bus),were used to prepare todorokite,a common Mn oxide on the Earth's surface,using Mg2+/Co2+ ions as a template.The results showed that todorokites could be obtained by reflux treatment of Mg2+-exchanged non-doped Na-buserite and three Co-doped Na-buserites at atmospheric pressure.However,the formation of todorokites was prohibited by reflux treatment of Co2+-exchanged Na-bus,5Co-Na-bus,and 10Co-Na-bus samples.Instead,todorokite was obtained by the reflux treatment of Co2+-exchanged 20Co-Na-bus samples under atmospheric pressure.X-ray photoelectron spectroscopy analysis showed that doped Co existed as Co3+in the MnO6 layers of doped Na-buserites.The amount of substituted Co3+ in the MnO6 layers may play a key role in the conversion of buserite to todorokite using Co2+ ions as a template.
Manganese oxides are known as one type of semiconductors,but their photocatalysis characteristics have not been deeply explored.In this study,photocatalytic degradation of phenol using several synthesized manganese oxides,i.e,acidic birnessite (BIR-H),alkaline birnessite (BIR-OH),cryptomelane (CRY) and todorokite (TOD),were comparatively investigated.To elucidate phenol degradation mechanisms,X-ray diffraction (XRD),ICP-AES (inductively coupled plasma-atomic emission spectroscopy),TEM (transmission electronic microscope),N 2 physisorption at 77 K and UV-visible diffuse reflectance spectroscopy (UV-Vis DRS) were employed to characterize the structural,compositional,morphological,specific surface area and optical absorption properties of the manganese oxides.After 12 hr of UV-Vis irradiation,the total organic carbon (TOC) removal rate reached 62.1%,43.1%,25.4%,and 22.5% for cryptomelane,acidic birnessite,todorokite and alkaline birnessite,respectively.Compared to the reactions in the dark condition,UV- Vis exposure improved the TOC removal rates by 55.8%,31.9%,23.4% and 17.9%.This suggests a weak ability of manganese oxides to degrade phenol in the dark condition,while UV-Vis light irradiation could significantly enhance phenol degradation.The manganese minerals exhibited photocatalytic activities in the order of:CRY > BIR-H > TOD > BIR-OH.There may be three possible mechanisms for photochemical degradation:(1) direct photolysis of phenol;(2) direct oxidation of phenol by manganese oxides;(3) photocatalytic oxidation of phenol by manganese oxides.Photocatalytic oxidation of phenol appeared to be the dominant mechanism.
Qin ZhangXiaodi ChengChen ZhengXionghan FengGuohong QiuWenfeng TanFan Liu
