多金属BiFeCo-MOFs材料活化空气氧高效催化松油烯氧化脱氢性能

Air Oxygen-activated and Efficient Oxidative Dehydrogenation of Terpinene Catalyzed by Multi-metallic BiFeCo-MOFs

摘要

多金属MOFs材料具备多种金属活性中心, 不同金属间的电子协同效应使其在催化活化分子氧领域表现出宽广的研究前景. 本文通过静态溶剂热法成功构建了以Bi³⁺, Fe³⁺和Co²⁺为多金属中心的BiFeCo-MOFs材料, 并应用于松油烯的高效空气氧化脱氢反应. 所制备的Bi₂Fe₂Co₄-MOF-BDC-150-24催化剂经X射线衍射(XRD)、红外光谱(IR)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和氨气吸附-脱附(NH₃-TPD)等系统表征, 证实其结构稳定且存在多金属电子协同效应. 在近室温条件下, 该催化剂可在无外加助剂条件下实现松油烯中C—C单键向C=C双键的选择性转化, 转化率达96.1%. 此外, 该材料表现出良好的底物普适性, 对γ-松油烯和水芹烯的转化率分别为97.2%和93.9%. 循环实验表明, 催化剂在连续使用5次后仍保持高活性, 具备优异的循环稳定性与潜在应用价值.

Abstract

Multi-metallic MOFs, characterized by multiple metal active centers, exhibit promising potential in the catalytic activation of molecular oxygen owing to the synergistic electronic effects between different metal species. In this work, a BiFeCo-MOF material with Bi³⁺, Fe³⁺ and Co²⁺ as multi-metal centers was successfully constructed via a static solvothermal method and applied to the efficient aerobic oxidative dehydrogenation of terpinene. The as-prepared Bi₂Fe₂Co₄-MOF-BDC-150-24 catalyst was systematically characterized by X-ray diffraction (XRD), Infrared (IR), scanning electronic microscope (SEM), X-ray photoelectron spectroscopy (XPS), and NH₃ temperature programmed desorption (NH₃-TPD), confirming its stable structure and the presence of multi-metal electronic synergy. Under near-ambient conditions, the catalyst enabled the selective conversion of the C—C single bond in terpinene to a C=C double bond without any external additives, achieving a conversion of 96.1%. Moreover, the material exhibited good substrate versatility, providing conversions of 97.2% for γ-terpinene and 93.9% for phellandrene. Recycling tests showed that the catalyst maintained high activity after five consecutive runs, demonstrating excellent cycling stability and promising potential applications.

关键词

多金属BiFeCo-MOFs / 空气氧活化 / 松油烯 / 氧化脱氢 / 协同催化

Key words

Multi-metallic BiFeCo-MOFs / Air oxygen activation / Terpinene / Oxidative dehydrogenation / Synergistic catalyst

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基金资助

国家自然科学基金(22072038)

国家自然科学基金(22272045)

药物合成与优化湖北省重点实验室开放基金(ZD202502)

小分子原料药精准制造湖北省重点实验室开放基金项目(HKLB2414)