Coprecipitation mechanisms of Zn by birnessite formation and its mineralogy under neutral pH conditions

Birnessite (δ-Mn(IV)O₂) is a great manganese (Mn) adsorbent for dissolved divalent metals. In this study, we investigated the coprecipitation mechanism of δ-MnO₂ in the presence of Zn(II) and an oxidizing agent (sodium hypochlorite) under two neutral pH values (6.0 and 7.5). The mineralogical characteristics and Zn–Mn mixed products were compared with simple surface complexation by adsorption modeling and structural analysis. Batch coprecipitation experiments at different Zn/Mn molar ratios showed a Langmuir-type isotherm at pH 6.0, which was similar to the result of adsorption experiments at pH 6.0 and 7.5. X-ray diffraction and X-ray absorption fine structure analysis revealed triple-corner-sharing inner-sphere complexation on the vacant sites was the dominant Zn sorption mechanism on δ-MnO₂ under these experimental conditions. A coprecipitation experiment at pH 6.0 produced some hetaerolite (ZnMn(III)₂O₄) and manganite (γ-Mn(III)OOH), but only at low Zn/Mn molar ratios (< 1). These secondary precipitates disappeared because of crystal dissolution at higher Zn/Mn molar ratios because they were thermodynamically unstable. Woodruffite (ZnMn(IV)₃O₇•2H₂O) was produced in the coprecipitation experiment at pH 7.5 with a high Zn/Mn molar ratio of 5. This resulted in a Brunauer–Emmett–Teller (BET)-type sorption isotherm, in which formation was explained by transformation of the crystalline structure of δ-MnO₂ to a tunnel structure. Our experiments demonstrate that abiotic coprecipitation reactions can induce Zn–Mn compound formation on the δ-MnO₂ surface, and that the pH is an important controlling factor for the crystalline structures and thermodynamic stabilities.     

Spectroscopic characterization and photochemistry of the Criegee intermediate CF3C(H)OO

Criegee intermediates (CIs), also known as carbonyl oxide, are reactive intermediates that play an important role in the atmospheric chemistry. Investigation on the structures and reactivity of CIs is of fundamental importance in understanding the underlying mechanism of their atmospheric reactions. In sharp contrast to the intensively studied parent molecule (CH₂OO) and the alkyl-substituted derivatives, the knowledge about the fluorinated analogue CF₃C(H)OO is scarce. By carefully heating the triplet carbene CF₃CH in an O₂-doped Ar-matrix to 35 K, the elusive carbonyl oxide CF₃C(H)OO in syn- and anti-conformations has been generated and characterized with infrared (IR) and ultraviolet-visible (UV-vis) spectroscopy. The spectroscopic identification is supported by ¹⁸O-labeling experiments and quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(2d,2p) levels. Upon the long-wavelength irradiation (λ > 680 nm), both conformers of CF₃C(H)OO decompose to give trifluoroacetaldehyde CF₃C(H)O and simultaneously rearrange to the isomeric dioxirane, cyclic-CF₃CH(OO), which undergoes isomerization to the lowest-energy carboxylic acid CF₃C(O)OH upon UV-light excitation at 365 nm. The O₂-oxidation of CF₃CH via the intermediacy of CF₃C(H)OO and cyclic-CF₃CH(OO) might provide new insight into the mechanism for the degradation of hydro-chlorofluorocarbon CF₃CHCl₂ (HCFC-123) in the atmosphere.