ABSTRACT
The band structure of multicomponent semiconductor photocatalysts, as well as their reactivity distinction under different wavelengths of light, is still unclear. BiOBr, which is a typical multicomponent semiconductor, may have two possible valence-band structures, that is, two discrete valence bands constructed respectively from O 2p and Br 4p orbitals, or one valence band derived from the hybridization of these orbitals. In this work, aqueous photocatalytic hydroxylation is applied as the probe reaction to investigate the nature and reactions of photogenerated holes in BiOBr. Three organic compounds (microcystin-LR, aniline, and benzoic acid) with different oxidation potentials were selected as substrates. Isotope labeling (H(2)(18)O as the solvent) was used to determine the source of the O atom in the hydroxyl group of the products, which distinguishes the contribution of different hydroxylation pathways. Furthermore, a spin-trapping ESR method was used to quantify the reactive oxygen species ((.)OH and (.)OOH) formed in the reaction system. The different isotope abundances of the hydroxyl O atom of the products formed, as well as the reverse trend of the (.)OH/(.)OOH ratio with the oxidative resistance of the substrate under UV and visible irradiation, reveal that BiOBr has two separate valence bands, which have different oxidation ability and respond to UV and visible light, respectively. This study shows that the band structure of semiconductor photocatalysts can be reliably analyzed with an isotope labeling method.
ABSTRACT
To test whether the altitudinal distribution of trees is determined by a carbon shortage or an insufficient sugar fraction (sugar:starch ratio) in treeline trees, we studied the status of nonstructural carbohydrates (NSC) and their components (total soluble sugars and starch) in Abies fabri (Mast.) Craib and Picea balfouriana var. hirtella Rehd. et Wils. trees along three elevational gradients, ranging from lower elevations to the alpine treeline, on the eastern edge of the Tibetan Plateau. For comparison, we investigated a low-altitude species (Tsuga yunnanensis (Franch.) Pritz.) which served as a warm-climate reference because it is distributed in closed montane forests below 3100 m a.s.l. in the study area. The carbon status of T. yunnanensis responded to altitude differently from that of the treeline species. At the species level, total NSC was not consistently more abundant in treeline trees than in trees of the same species growing at lower elevations. Thus there was no consistent evidence for carbon limitation of growth in treeline trees. For the three treeline species studied (P. balfouriana and A. fabri in the Kang-Ding Valley and A. fabri in the Mo-Xi Valley), winter NSC concentrations in treeline trees were significantly lower than in lower-elevation trees of the same species, suggesting that, in winter, carbon is limited in treeline trees. However, in no case was there total overwinter depletion of NSC or its components in treeline trees. Treeline and low-altitude species had similar sugar:starch ratios of about three at their upper-elevational limits in April. We conclude that survival and growth of trees at the elevational or latitudinal climate limit depend not only on NSC concentration in perennial tissues, but also on the maintenance of an overwintering sugar:starch ratio greater than three.
