A Direct Dry Synthesis Route for High Purity Catalytic Nanoporous Metallic Films

Abstract

Control of catalyst morphology is important because it affects many catalytic related properties such as, active sites, surface energy, and surface area, which can lead to tunable catalytic activity. Nanoporous metallic networks (NPMs), a morphology of interest for catalysis, contain many uncoordinated atoms at the surface and highly curved ligaments that can have a large effect on catalytic performance. Nanoporous self-supported metal structures have been synthesized in the past by dealloying of a master alloy,[1] which is a wet chemical method. This technique uses an Au-Ag alloy, from which Ag is etched away and which always results in NPMs containing residual amounts of the sacrificial metal (Ag) preventing the formation of high-purity structures. It follows that the catalytic properties of pure NPMs formed by dealloying can not be studied due to metal 'impurities' remaining in the structure. Although these 'impurities' contribute to catalytic activity and stability, it is difficult to control their amount and the systematic investigation of the 'impurity' effect is almost impossible for these NPMs.Here, we present results obtained by using physical vapor deposition, in the form of glancing angle deposition (GLAD), together with plasma etching to form nanoporous ultra-thin metal mesh structures, in a unique and facile dry synthesis method,[2] unlike most wet chemical synthesis methods used to prepare catalysts, which result chemical waste. The nanostructured metal mesh films are suitable for catalysis as they are extremely pure and highly porous, and contain high curvature ligaments, different crystal motifs, and many grain boundaries. We present nanoporous gold films (NPGF) prepared by our method as an example material. We show that the electrochemical structural stability of the NPGF is remarkably higher than that of dealloyed nanoporous gold, which is a result of the high amount of grain boundaries. Furthermore, the electrocatalytic performance of CH3OH oxidation is measured and the results show high catalytic activity for pure NPGF.[3] Our GLAD method can be applied to various metals and enables precise mixing or doping of different materials composing the NPMs. The high porosity, active sites, and potential elemental mixing will lead to new catalysts, especially suitable for CO2 reduction to fuels and value-added chemicals.[1] G. Wittstock, M. Bäumer, W. Dononelli, T. Klüner, L. Lührs, C. Mahr, L. V. Moskaleva, M. Oezaslan, T. Risse, A. Rosenauer, A. Staubitz, J. Weissmüller, A. Wittstock, Chem. Rev. 2023, 123, 6716.[2] H. Kwon, H.-N. Barad, A. R. Silva Olaya, M. Alarcón-Correa, K. Hahn, G. Richter, G. Wittstock, P. Fischer, ACS Appl. Mater. Interfaces 2023, 15, 5620.[3] H. Kwon, H.-N. Barad, A. R. Silva Olaya, M. Alarcón-Correa, K. Hahn, G. Richter, G. Wittstock, P. Fischer, ACS Catal. 2023, 11656.