Nanoscale Synthesis and Characterization Laboratory, Lawrence Livermore National Laboratory , Livermore, California 94550, United States.
ACS Appl Mater Interfaces. 2017 Aug 2;9(30):25615-25622. doi: 10.1021/acsami.7b05648. Epub 2017 Jul 19.
Many application-relevant properties of nanoporous metals critically depend on their multiscale architecture. For example, the intrinsically high step-edge density of curved surfaces at the nanoscale provides highly reactive sites for catalysis, whereas the macroscale pore and grain morphology determines the macroscopic properties, such as mass transport, electrical conductivity, or mechanical properties. In this work, we systematically study the effects of alloy composition and dealloying conditions on the multiscale morphology of nanoporous copper (np-Cu) made from various commercial Zn-Cu precursor alloys. Using a combination of X-ray diffraction, electron backscatter diffraction, and focused ion beam cross-sectional analysis, our results reveal that the macroscopic grain structure of the starting alloy surprisingly survives the dealloying process, despite a change in crystal structure from body-centered cubic (Zn-Cu starting alloy) to face-centered cubic (Cu). The nanoscale structure can be controlled by the acid used for dealloying with HCl leading to a larger and more faceted ligament morphology compared to that of HPO. Anhydrous ethanol dehydrogenation was used as a probe reaction to test the effect of the nanoscale ligament morphology on the apparent activation energy of the reaction.
许多与应用相关的纳米多孔金属性能取决于其多尺度结构。例如,纳米尺度下弯曲表面固有的高台阶密度为催化提供了高反应性位点,而宏观尺度的孔和晶粒形态决定了宏观性能,如质量传输、电导率或机械性能。在这项工作中,我们系统地研究了合金成分和脱合金条件对由各种商业 Zn-Cu 前驱体合金制成的纳米多孔铜(np-Cu)的多尺度形貌的影响。我们使用 X 射线衍射、电子背散射衍射和聚焦离子束截面分析相结合的方法,结果表明,尽管晶体结构从体心立方(Zn-Cu 起始合金)转变为面心立方(Cu),起始合金的宏观晶粒结构在脱合金过程中出人意料地得以保留。纳米尺度结构可以通过用于脱合金的酸来控制,与 HPO 相比,HCl 导致更大和更具面的连接体形态。无水乙醇脱氢被用作探针反应来测试纳米级连接体形态对反应表观活化能的影响。