Metallic and catalytically active materials with high surface area and large porosity are a long-desired goal in both industry and academia. In this Account, we summarize the strategies for making a variety of self-supported noble metal aerogels consisting of extended metal backbone nanonetworks. We discuss their outstanding physical and chemical properties, including their three-dimensional network structure, the simple control over their composition, their large specific surface area, and their hierarchical porosity. Additionally, we show some initial results on their excellent performance as electrocatalysts combining both high catalytic activity and high durability for fuel cell reactions such as ethanol oxidation and the oxygen reduction reaction (ORR). Finally, we give some hints on the future challenges in the research area of metal aerogels. We believe that metal aerogels are a new, promising class of electrocatalysts for polymer electrolyte fuel cells (PEFCs) and will also open great opportunities for other electrochemical energy systems, catalysis, and sensors. The commercialization of PEFCs encounters three critical obstacles, viz., high cost, insufficient activity, and inadequate long-term durability. Besides others, the sluggish kinetics of the ORR and alcohol oxidation and insufficient catalyst stability are important reasons for these obstacles. Various approaches have been taken to overcome these obstacles, e.g., by controlling the catalyst particle size in an optimized range, forming multimetallic catalysts, controlling the surface compositions, shaping the catalysts into nanocrystals, and designing supportless catalysts with extended surfaces such as nanostructured thin films, nanotubes, and porous nanostructures. These efforts have produced plenty of excellent electrocatalysts, but the development of multisynergetic functional catalysts exhibiting low cost, high activity, and high durability still faces great challenges. In this Account, we demonstrate that the sol–gel process represents a powerful “bottom-up” strategy for creating nanostructured materials that tackles the problems mentioned above. Aerogels are unique solid materials with ultralow densities, large open pores, and ultimately high inner surface areas. They magnify the specific properties of nanomaterials to the macroscale via self-assembly, which endow them with superior properties. Despite numerous investigations of metal oxide aerogels, the investigation of metal aerogels is in the early stage. Recently, aerogels including Fe, Co, Ni, Sn, and Cu have been obtained by nanosmelting of hybrid polymer–metal oxide aerogels. We report here exclusively on mono-, bi- and multimetallic noble metal aerogels consisting of Ag, Au, Pt, and Pd and their application as electrocatalysts.

The quantitative analysis of the different surface sites on platinum samples is attempted from pure voltammetric data. This analysis requires independent knowledge of the fraction of two-dimensional (111) and (100) domains. Specific site-probe reactions are employed to achieve this goal. Irreversibly-adsorbed bismuth and tellurium have been revealed to be sensitive to the presence of (111) terrace domains of different width whereas almost all sites involved in (100) ordered domains have been characterized through germanium adatoms. The experimental protocol follows that used with well-defined single-crystal electrodes and, therefore, requires careful control of the surface cleanliness. Platinum basal planes and their vicinal stepped surfaces have been employed to obtain calibration plots between the charge density measured under the adatom redox peak, specific for the type of surface site, and the corresponding terrace size. The evaluation of the (100) bidimensional domains can also be achieved using the voltammetric profiles, once the fraction of (111) ordered domains present in the polyoriented platinum has been determined and their featureless contribution has been subtracted from the whole voltammetric response. Using that curve, it is possible to perform a deconvolution of the adsorption states of the polycrystalline sample different from those related to (111) domains. The fraction of (100)-related states in the deconvoluted voltammogram can then be compared to that expected from the independent estimation coming from the charge involved in the redox process undergone by the irreversibly-adsorbed germanium and thus check the result of the deconvolution. The information about the surface-site distribution can also be applied to analyze the voltammetric profile of nanocrystalline platinum electrodes.