Institute of New Energy Material Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University, Tianjin 300071, PR China.
Nanoscale. 2013 Feb 7;5(3):1074-81. doi: 10.1039/c2nr33347c. Epub 2012 Dec 20.
Highly crumpled graphene nanosheets (GNS) with a BET surface area as high as 1159 m(2) g(-1) was fabricated by a thermal exfoliation method. A systematic investigation was performed on the hydrogen sorption properties of MgH(2)-5 wt% GNS nanocomposites acquired by ball-milling. It was found that the as-synthesized GNS exhibited a superior catalytic effect on hydrogenation/dehydrogenation of MgH(2). Differential Scanning Calorimetry (DSC) and isothermal hydrogenation/dehydrogenation measurements indicated that both hydrogen sorption capacity and dehydrogenation/hydrogenation kinetics of the composites improved with increasing milling time. The composites MgH(2)-GNS milled for 20 h can absorb 6.6 wt% H(2) within 1 min at 300 °C and 6.3 wt% within 40 min at 200 °C, even at 150 °C, it can also absorb 6.0 wt% H(2) within 180 min. It was also demonstrated that MgH(2)-GNS-20 h could release 6.1 wt% H(2) at 300 °C within 40 min. In addition, microstructure measurements based on XRD, SEM, TEM as well as Raman spectra revealed that the grain size of thus-prepared MgH(2)-GNS nanocomposites decreased with increasing milling time, moreover, the graphene layers were broken into smaller graphene nanosheets in a disordered and irregular manner during milling. It was confirmed that these smaller graphene nanosheets on the composite surface, providing more edge sites and hydrogen diffusion channels, prevented the nanograins from sintering and agglomerating, thus, leading to promotion of the hydrogenation/dehydrogenation kinetics of MgH(2).
采用热剥离法制备了比表面积高达 1159 m(2) g(-1)的高度褶皱石墨烯纳米片(GNS)。通过球磨法获得了 MgH(2)-5wt%GNS 纳米复合材料的吸氢性能进行了系统研究。结果表明,合成的 GNS 对 MgH(2)的加氢/脱氢具有优异的催化作用。差示扫描量热法(DSC)和等温加氢/脱氢测量表明,随着球磨时间的增加,复合材料的吸氢容量和脱氢/加氢动力学均得到提高。复合材料 MgH(2)-GNS 经 20 h 球磨后,在 300°C 下 1 min 内可吸收 6.6wt%H(2),在 200°C 下 40 min 内可吸收 6.3wt%H(2),甚至在 150°C 下 180 min 内也可吸收 6.0wt%H(2)。还证明 MgH(2)-GNS-20 h 在 300°C 下 40 min 内可释放 6.1wt%H(2)。此外,基于 XRD、SEM、TEM 和拉曼光谱的微观结构测量表明,随着球磨时间的增加,所制备的 MgH(2)-GNS 纳米复合材料的晶粒尺寸减小,而且,在球磨过程中,石墨烯层被无序且不规则地破碎成更小的石墨烯纳米片。证实了复合材料表面这些更小的石墨烯纳米片提供了更多的边缘位和氢扩散通道,防止了纳米颗粒的烧结和团聚,从而促进了 MgH(2)的加氢/脱氢动力学。