To probe the phase structure–reactivity relationship of A2B2O7 catalysts for the oxidative coupling of methane (OCM), three model La2B2O7 compounds with Ti4+, Zr4+, or Ce4+ at the B-site have been purposely designed. By decreasing the r A/r B ratios in the order of La2Ti2O7 > La2Zr2O7 > La2Ce2O7, typical monoclinic layered perovskite, cubic ordered pyrochlore, and disordered defective cubic fluorite phase are formed, respectively. The reaction performance of the catalysts based on CH4 conversion and C2 product yield follow the order of La2Ce2O7 > La2Zr2O7 > La2Ti2O7. It has been discovered that superoxide O2 – is the active oxygen species detected on all the catalysts and is responsible for the OCM reaction, whose amount follows also the sequence of La2Ce2O7 > La2Zr2O7 > La2Ti2O7. Moreover, the surface alkalinity related to the superoxide anions observes the same order. This testifies that the amount of surface superoxide O2 – determines the OCM reaction performance over the La2B2O7 compounds. On the basis of the characterization results, the formation of active O2 – species could follow two pathways. For La2Zr2O7 and La2Ce2O7 possessing intrinsic 8a oxygen vacancies, O2 – anions are formed by activating the oxygen species entering into the vacancies in the bulk and then migrating to the catalyst surface. For La2Ti2O7 possessing no oxygen vacancies, they are formed directly by transforming the O2 molecules adsorbed on its surface. Usually, the former pathway generates more abundant O2 – species than the latter one. La2Ce2O7 displays not only promising reaction performance in the low-temperature region, but also potent sulfur and lead poisoning resistance, thus having the potential for application after further optimization.

A series of phosphorus-doped titania samples with different phosphorus contents have been prepared by a simple, modified sol-gel method. The obtained samples were characterized by X-ray diffraction spectrometry, Brunauer-Emmett-Teller surface area, differential thermal analysis-thermogravimetry, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and UV-vis diffuse reflectance spectroscopy, and the photodegradation of methylene blue (MB) on the samples was tested under both UV and visible light irradiation. It was found that the doped phosphorus existed in a pentavalent oxidation state, replacing part of Ti 4+ in the anatase lattice in the form of Ti-O-P bonds. Increased calcination temperature gave an enrichment of P species on the titania surface. The P species in the titania lattice should be the dominant group responsive to visible light, whereas the P species on the surface could retard the phase transition of anatase to rutile and increase the surface area and adsorption capability. The photocatalytic activity of P-doped titania with the optimal P content was 4-fold higher than that of pure TiO 2 and was 41% higher than that of commercial Degussa P-25 under UV irradiation. Furthermore, P-doped titania presented significant photocatalytic activity under visible light (>400 nm) irradiation.

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