Pt-Mg-MOF-74-R的开放金属位点微环境调控及其储氢性能研究

Research on the Microenvironment Regulation of Open Metal Sites and Hydrogen Storage Performance of Pt-Mg-MOF-74-R

  • 摘要: 针对金属有机框架(MOFs)储氢材料存在的吸附位点不足及稳定性问题,本文以Mg-MOF-74为基体,采用原位引入铂(Pt)源结合热还原策略,成功制备了一系列具有不同Pt负载量及缺陷程度的Pt-Mg-MOF-74-R复合储氢材料。通过XRD、FT-IR、SEM、TG、TEM及XPS等手段,系统表征了材料的微观形貌与晶体结构,揭示了热还原温度与Pt负载量对框架缺陷形成及金属价态的影响规律。研究表明,热还原过程在将Pt离子还原为高活性Pt0纳米颗粒的同时,有效脱除溶剂分子并诱导部分配体缺失,构筑了丰富的MgO5开放金属位点。储氢性能测试显示,在298 K、100 bar条件下,4-Pt-Mg-MOF-74-R200的重量储氢量达到0.35 wt%,吸附焓为-22.35 kJ/mol。机理分析证实,Pt0触发的“氢溢流”效应促进了H2的解离,并加速氢原子向邻近MgO5位点迁移,这种解离-吸附协同机制是提升储氢性能的关键。

     

    Abstract: To address the issues of insufficient adsorption sites and poor stability in metal-organic frameworks (MOFs) for hydrogen storage, a series of Pt-Mg-MOF-74-R composite materials with varying Pt loadings and defect degrees were synthesized using an in-situ platinum (Pt) incorporation strategy combined with thermal reduction, based on the Mg-MOF-74 framework. The micromorphology and crystal structure of the materials were systematically characterized by XRD, FT-IR, SEM, TG, TEM, and XPS. The regulatory effects of thermal reduction temperature and Pt loading on the framework defect formation and metal valence states were investigated. The results indicate that the thermal reduction process effectively reduces Pt ions into highly active Pt0 nanoparticles while removing solvent molecules and inducing partial ligand loss, thereby constructing abundant MgO5 open metal sites (OMSs). Hydrogen storage performance tests show that the 4-Pt-Mg-MOF-74-R200 sample achieves a gravimetric hydrogen storage capacity of 0.35 wt% with an adsorption enthalpy of -22.35 kJ/mol at 298 K and 100 bar. Mechanism analysis confirms that the “hydrogen spillover” effect triggered by Pt0 promotes the dissociation of \textH_2 and accelerates the migration of hydrogen atoms to adjacent MgO5 sites. This synergistic dissociation-adsorption mechanism is the key to enhancing the hydrogen storage performance.

     

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