Ionic transports in nanopores hold the key to unlocking the full potential of bi-continuous nanoporous (NP) metals as advanced electrodes in electrochemical devices. The precise control of the uniform NP metal structures also provides us a unique opportunity to understand how complex structures determine transports at nanoscales. For NP Au from the dealloying of a Ag-Au alloy, we can tune the pore size in the range of 13 nm to 2.4 microns and the porosity between 38% and 69% via isothermal coarsening. For NP Ag from the reduction-induced decomposition of AgCl, we can control additionally its structural hierarchy and pore orientation. We measure the effective ionic conductivities of 1 M NaClO4 through these NP metals as membranes, which range from 7% to 44% of that of a free solution, corresponding to calculated pore tortuosities between 2.7 and 1.3. The tortuosity of NP Au displays weak dependences on both the pore size and the porosity, consistent with the observed self-similarity in the coarsening, except for those of pores < 25 nm, which we consider deviating from the well-coarsened pore geometry. For NP Ag, the low tortuosity of the hierarchical structure can be explained with the Maxwell-Garnett equation and that of the oriented structure underlines the random orientation as the cause of slow transport in other NP metals. At last, we achieve high current densities of CO2 reduction with these two low-tortuosity NP Ags, demonstrating the significance of the structure-transport relationships for designing functional NP metals.
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