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    CeO2-rGO复合催化剂改性MgH2的储氢性能

    Hydrogen storage performance of MgH2 modified by CeO2-rGO composite catalyst

    • 摘要: 镁氢化物(MgH2)因高理论储氢容量成为极具潜力的固态储氢材料,但其吸放氢动力学迟缓、热力学稳定性过高等问题,以及单一催化剂改性易出现的颗粒团聚现象,限制了其实际应用。针对上述问题,采用水热法制备CeO2-rGO复合催化剂,通过高能球磨法将其与MgH2复合得到CeO2-rGO@MgH2储氢复合材料。CeO2纳米颗粒均匀负载于rGO褶皱片层表面,二者与MgH2发生界面电子相互作用,诱导产生更多氧空位活性位点,并形成Ce4+/Ce3+氧化还原电对,从而弱化Mg-H键强度、缩短氢原子扩散路径、降低反应活化能。储氢性能测试表明,CeO2-rGO@MgH2的起始放氢温度降至278 ℃,较MgH2显著降低;在150 ℃、4 MPa条件下,该复合材料1 000 s内可完成完全吸氢,吸氢容量质量分数达5.71%;在300 ℃下,80 min内即可实现完全放氢,放氢容量是6.14%。动力学计算结果显示,CeO2-rGO@MgH2的放氢表观活化能为114.78 kJ/mol,较MgH2降低125.35 kJ/mol,有效提升了MgH2的吸放氢动力学性能。该结果为MgH2基储氢材料的催化剂改性设计提供了新的思路与实验依据。

       

      Abstract: Magnesium hydride (MgH2) is a promising solid-state hydrogen storage material due to its high theoretical capacity. However, its practical application is hindered by sluggish kinetics, high thermodynamic stability, and particle agglomeration, especially when modified with a single catalyst. To address these problems, a CeO2-rGO composite catalyst was prepared by a hydrothermal method, and the CeO2-rGO@ MgH2 hydrogen storage composite was fabricated by compounding the catalyst with MgH2 via high-energy ball milling. CeO2 nanoparticles are uniformly anchored on the wrinkled rGO nanosheets. Interfacial electronic interactions among CeO2, rGO, and MgH2 induce more oxygen vacancies and the Ce4+/Ce3+ redox couple, which weaken Mg-H bonds, shorten hydrogen diffusion paths, and reduce the activation energy for dehydrogenation. Hydrogen storage performance tests demonstrate that the initial dehydrogenation temperature of CeO2-rGO@ MgH2 is reduced to 278 ℃, which is significantly lower than that of pure MgH2; The composite can accomplish complete hydrogen absorption within 1 000 s with a hydrogen absorption capacity of 5.71% by mass at 150 ℃ and 4 MPa, and achieve full dehydrogenation within 80 min with a dehydrogenation capacity of 6.14% at 300 ℃. Kinetic calculation results indicate that the apparent dehydrogenation activation energy of CeO2-rGO@ MgH2 is 114.78 kJ/mol, 125.35 kJ/mol lower than that of MgH2, which effectively enhances the hydrogen sorption kinetic properties of MgH2. These results provide a new idea and experimental basis for the catalyst modification design of MgH2-based hydrogen storage materials.

       

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