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Heterogeneous solid base catalysis is valuable and promising in chemical industry, however it is insufficiently developed compared to solid acid catalysis due to the lack of satisfied solid base ca...

Heterogeneous solid base catalysis is valuable and promising in chemical industry, however it is insufficiently developed compared to solid acid catalysis due to the lack of satisfied solid base catalysts. To gain the strong basicity, the previous strategy was to basify oxides with alkaline metals to create surficial vacancies or defects, which suffers from the instability under catalytic conditions. Monocomponent basic oxides like MgO are literally stable but deficient in electron-withdrawing ability. Here we prove that a special connectivity of atoms could enhance the Lewis basicity of oxygen in monocomponent solids exemplified by Ga

An octahedron-based gallium borate (Ga-PKU-1) with an open framework was prepared by the boric acid flux method and studied by XRD, SEM, FT-IR, TGA-DSC, BET and NH3-TPD. The borate hydroxyl groups in the 18-ring membered channels functioned as Bronsted acid centers and were proved to play an important role in the dehydration of isopropanol to propylene with high selectivity. However, the other two gallium borates, Ga4B2O9 and GaBO3, with similar elemental compositions showed completely different acidities and catalytic performance for isopropanol decomposition. Our results indicated that such a great difference in selectivity most probably originated from the changes in the coordination microenvironment from GaO6 to GaO5. The relationship between the structure and activity was discussed in detail, and an intrinsic mechanism for the selectivity preference was proposed according to the obtained results.

PKU-5 (Al 4 B 6 O 15 ) is potentially a solid acid catalyst, and it possesses an interesting open-framework composed of [AlO 6 ] and [B 2 O 5 ] groups. PKU-5 shows a high thermal stability, while no physical and chemical properties were investigated thus far, because of the difficulty in its synthesis. Cr-stabilized PKU-5 with the formula (Al 1− x Cr x ) 4 B 6 O 15 (0.08 ≤ x ≤ 0.14) can be easily prepared by annealing Cr-doped PKU-1 precursors. XRD and TEM experiments demonstrate Cr 3+ has been successively incorporated into the framework of PKU-5. NH 3 -TPD measurements indicate that the partial substitution of Al 3+ by Cr 3+ leads to a small change of acid sites in total amounts and distributions. Cr-PKU-5 shows a good catalytic activity for methanol dehydration from 300 to 450 °C. Other operation conditions, such as the Cr 3+ content, space velocity of methanol were also discussed in detail to evaluate its catalytic performance.

Ga4B2O9 is prepared by hydrothermal (HY), sol-gel (SG), and high-temperature solid state (HTSSR) reactions.

Borates are well-known candidates for optical materials, but their potentials in photocatalysis are rarely studied. Ga(3+)-containing oxides or sulfides are good candidates for photocatalysis applications because the unoccupied 4s orbitals of Ga usually contribute to the bottom of the conducting band. It is therefore anticipated that Ga4B2O9 might be a promising photocatalyst because of its high Ga/B ratio and three-dimensional network. Various synthetic methods, including hydrothermal (HY), sol-gel (SG), and high-temperature solid-state reaction (HTSSR), were employed to prepare crystalline Ga4B2O9. The so-obtained HY-Ga4B2O9 are micrometer single crystals but do not show any UV-light activity unless modified by Pt loading. The problem is the fast recombination of photoexcitons. Interestingly, the samples obtained by SG and HTSSR methods both possess a fine micromorphology composed of well-crystalline nanometer strips. Therefore, the excited e(-) and h(+) can move to the surface easily. Both samples exhibit excellent intrinsic UV-light activities for pure water splitting without the assistance of any cocatalyst (47 and 118 μmol/h/g for H2 evolution and 22 and 58 μmol/h/g for O2 evolution, respectively), while there is no detectable activity for P25 (nanoparticles of TiO2 with a specific surface area of 69 m(2)/g) under the same conditions.