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Physico-chemical properties and catalytic activity of the sol-gel prepared Ce-ion doped LaMnO3 perovskites

机译:溶胶-凝胶制备的铈离子掺杂LaMnO3钙钛矿的理化性质和催化活性

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摘要

Ce-doped LaMnO3 perovskite ceramics (La1−xCexMnO3) were synthesized by sol-gel based co-precipitation method and tested for the oxidation of benzyl alcohol using molecular oxygen. Benzyl alcohol conversion of ca. 25–42% was achieved with benzaldehyde as the main product. X-ray diffraction (XRD), thermogravimetric analysis (TGA), BET surface area, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (H2-TPR), temperature-programmed oxidation (O2-TPO), FT-IR and UV-vis spectroscopic techniques were used to examine the physiochemical properties. XRD analysis demonstrates the single phase crystalline high purity of the perovskite. The Ce-doped LaMnO3 perovskite demonstrated reducibility at low-temperature and higher mobility of surface O2-ion than their respective un-doped perovskite. The substitution of Ce3+ ion into the perovskite matrix improve the surface redox properties, which strongly influenced the catalytic activity of the material. The LaMnO3 perovskite exhibited considerable activity to benzyl alcohol oxidation but suffered a slow deactivation with time-on-stream. Nevertheless, the insertion of the A site metal cation with a trivalent Ce3+ metal cation led to an enhanced in catalytic performance because of atomic-scale interactions between the A and B active site. La0.95Ce0.05MnO3 catalyst demonstrated the excellent catalytic activity with a selectivity of 99% at 120 °C.
机译:通过基于溶胶-凝胶的共沉淀法合成了Ce掺杂的LaMnO3钙钛矿陶瓷(La1-xCexMnO3),并利用分子氧测试了苄醇的氧化。苯甲醇的转化率约为以苯甲醛为主要产物,可达到25-42%。 X射线衍射(XRD),热重分析(TGA),BET表面积,透射电子显微镜(TEM),X射线光电子能谱(XPS),程序升温还原(H2-TPR),程序升温氧化(O2 -TPO),FT-IR和UV-vis光谱技术用于检查理化性质。 XRD分析表明钙钛矿的单相晶体高纯度。铈掺杂的LaMnO3钙钛矿与未掺杂的钙钛矿相比,在低温下具有还原性,并且表面O2-离子的迁移率更高。 Ce 3 + 离子取代钙钛矿基质改善了表面氧化还原性能,这强烈影响了材料的催化活性。 LaMnO3钙钛矿对苯甲醇的氧化表现出相当大的活​​性,但随着生产时间的延长而缓慢失活。尽管如此,由于A和B活性位之间的原子尺度相互作用,A位金属阳离子与三价Ce 3 + 金属阳离子的插入导致催化性能的增强。 La0.95Ce0.05MnO3催化剂具有出色的催化活性,在120 C下的选择性为99%。

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