Kondratowicz Tomasz, Gajewska Marta, Li Jiangtong, Li Molly Meng-Jung, Turner Zoë R, Chen Chunping, O'Hare Dermot
Chemistry Research Laboratory, Department of Chemistry, University of Oxford 12 Mansfield Road Oxford OX1 3TA UK
Academic Centre for Materials and Nanotechnology, AGH University of Krakow Mickiewicza 30 30-059 Krakow Poland.
Chem Sci. 2024 Dec 17;16(3):1327-1335. doi: 10.1039/d4sc07292h. eCollection 2025 Jan 15.
We report a new synthetic strategy for preparing well-organised, spherical and mesoporous, mixed-metal, hollow-core@layered double hydroxides. Hollow-SiO@Cu Zn Mg Al-LDHs ( + + = 2.32 ± 0.06) were prepared by exploiting a unique "memory effect" feature of LDH materials. The reconstruction with simultaneous incorporation of Cu and Zn into the LDH shell was achieved by exposing hollow-SiO@MgAl-LDO to an aqueous solution containing Cu and Zn cations. The effect of a single reconstruction step with various concentrations of Cu and Zn solutions (20-80 mM), as well as the implementation of five successive cycles of calcination-reconstruction on the chemical composition, morphology, texture and structure of the resulting materials are described. Hollow-SiO@Cu Zn Mg Al-LDHs are precursors to active catalysts for CO hydrogenation to methanol. The most active catalyst exhibits a space-time yield for methanol of 1.68 g g h at 270 °C (3 : 1 CO : H, 30 bar) which represents a 1.7-fold increase in space-time yield compared to commercial Cu/ZnO/AlO catalyst under the same conditions.
我们报道了一种制备结构规整、球形且具有介孔的混合金属中空核@层状双氢氧化物的新合成策略。通过利用层状双氢氧化物（LDH）材料独特的“记忆效应”特性，制备了中空二氧化硅@铜锌镁铝层状双氢氧化物（Cu + Zn + Mg + Al = 2.32 ± 0.06）。通过将中空二氧化硅@镁铝层状双金属氧化物（LDO）暴露于含有铜和锌阳离子的水溶液中，实现了在LDH壳层中同时掺入铜和锌的重构。描述了使用不同浓度（20 - 80 mM）的铜和锌溶液进行单次重构步骤的效果，以及对所得材料进行五个连续煅烧 - 重构循环对其化学成分、形态、织构和结构的影响。中空二氧化硅@铜锌镁铝层状双氢氧化物是用于将一氧化碳加氢制甲醇的活性催化剂的前体。在270°C（一氧化碳与氢气比例为3:1，30巴）条件下，最具活性的催化剂甲醇时空产率为1.68 g g⁻¹ h⁻¹，与相同条件下的商业铜/氧化锌/氧化铝催化剂相比，时空产率提高了1.7倍。
