Electronic supplementary material:The online version of this article (doi: 10.1007/s11144-017-1152-8) contains supplementary material, which is available to authorized users. Abstract Alloy-type Sn-Pt/C electrocatalysts with desired Pt/Sn= 3.0 ratio have been prepared by Controlled Surface Reactions using home-made 20 wt.% Pt/C (20Pt/C) catalysts with different Pt dispersion. Reaction conditions were found for the preparation of highly dispersed 20Pt/C catalysts by modified NaBH 4 -assisted ethylene-glycol reduction method using ethanol as a solvent. It has been demonstrated that the increase of the heating time in ethanol up to 2 h results in decreasing dispersion of Pt. Upon using highly dispersed 20Pt/C catalyst the exclusive incorporation of Sn onto the Pt sites was achieved resulting in exclusive formation of the Pt-Sn alloy phase. According to in situ XPS studies pre-treatment of the air exposed catalyst in H 2 even at 170°C resulted in complete reduction of the ionic tin to Sn 0 , suggesting alloy formation. In contrast, the catalyst with lower Pt dispersion cannot be completely reduced even at 350°C, as 10 % of tin still remains in the form of Sn 4+ surface species. The electrocatalytic performance of both Sn-20Pt/C catalysts in the CO electrooxidation and the oxygen reduction reaction is superior to that of the parent 20Pt/C catalysts. Our data obtained for the oxygen reduction reaction indicate that the small size of the bimetallic nanoparticles in the highly dispersed Sn-20Pt/C catalyst, along with their optimal surface composition, result in increased activity compared to the catalyst with lower dispersion.Keywords SnPt/C electrocatalysts, Controlled surface reactions, Pt 3 Sn, Oxygen reduction reaction, CO electrooxidation
IntroductionPolymer electrolyte membrane fuel cells (PEMFC) offer a very promising solution for environmentally sustainable electric power generation in mobile applications. A major challenge in PEMFC development is the choice of the cathode and anode electrocatalysts, which usually consist of platinum supported on carbon. The Pt/C system is, however, prone to corrosion at high potentials occurring during rapid load change conditions, and sensitive to poisoning by CO, which is a common low level impurity of the hydrogen fuel. As a result, electrocatalysts with acceptable lifetime can only be manufactured with very high Pt loadings. Therefore, a main development goal is to find electrocatalysts with reduced Pt content, enhanced long term stability under operating conditions and affordable price. CO tolerance of the anode electrocatalysts also has to be improved, as CO adsorbs very strongly on Pt, blocking the active sites for the hydrogen oxidation reaction and causing a large decrease in the electrode performance. In order to reduce this poisoning issue, a common approach consists of the utilization of a second oxophilic metal such as Ru, Mo, Ni or Sn [1][2][3][4][5], which are less noble than Pt and thus activate water at lower potential leading to accelerated CO 2