Morphological and Elemental Analyses of Supported Palladium (Pd)/Silver (Ag) Composite Membranes

Abstract

Supported palladium (Pd)/silver (Ag) composite membranes have been investigated for hydrogen separation mainly in order to avoid hydrogen embrittlement, improve hydrogen permeance and reduce membrane cost. The electroless method is recommended for the co-plating of Pd and Ag on a substrate surface. However, Ag precursor has a higher redox potential than Pd and, thus, Ag is preferentially deposited, which compromises the membrane selectivity to hydrogen. Here we investigated the morphology and elemental composition of supported palladium (Pd)/silver (Ag) composite membranes produced by different methods. The first membrane was produced from a plating solution of 80 wt% of Pd and 20 wt% of Ag. The membrane surface presented several large dendritic crystals that not grown in a direction to form a dense metallic film. According to EDS results, the membrane surface presented similar Pd and Ag composition, which confirms the preferential Ag deposition. At room temperature, this membrane presented a nitrogen flux of 0.35 mol m^-2 s^-1 at 200 kPa of transmembrane pressure. Thus, the formed membrane is not suitable for hydrogen separation. The second membrane was formed by adding small amounts of Ag to the plating solution during the electroless process. The final plating solution contained 75 wt% of Pd and 25 w% of Ag. The membrane thickness was 2 µm, but the membrane morphology was not totally dense. According to EDS results, the Ag composition was greater than the Pd composition, especially at the membrane top surface. This membrane also presented high nitrogen permeance probably due to the holes formed on the membrane surface. Thus, although the controlled addition of Ag is recommended to form dense membranes, the Ag was preferentially deposited over the Pd when starting with the highest rate of Ag addition. Adding lower Ag rates at the beginning could be helpful to avoid the preferential Ag deposition.