Intermetallic PtBi Nanoplates with High Catalytic Activity towards Electro‐oxidation of Formic Acid and Glycerol

Abstract

Despite considerable progress made for direct liquid fuel cells, developing efficient electrocatalysts for the oxidation of small organic molecules reaction remains a challenge. Herein, we employed a facile one‐pot method to synthesize hexagonal intermetallic PtBi nanoplates. Benefiting from the unique structure and third body effect, the mass activity of formic acid oxidation on PtBi/C at peak potential reaches 9.06 A ⋅ mgPt−1, which is 10.4 times higher than that of commercial Pt/C catalyst, making it the most efficient electrocatalyst ever reported. In situ FTIR spectroscopic studies revealed that the introduction of Bi suppresses dramatically CO‐poisoning, which effectively improves the activity and stability towards formic acid oxidation. Furthermore, in situ FTIR spectra of glycerol oxidation indicate that much more oxalate and tartronate are produced on PtBi/C than that on Pt/C, and a plausible reaction mechanism for the oxidation of glycerol on PtBi/C catalyst in alkaline solution was proposed.

Electrochemical Deposition of PdBiSn Catalyst for Glycerol Oxidation in Alkaline Medium

“…. PtBi/C was found to have 3.2 times higher mass activity compared to Pt/C for glycerol oxidation in alkaline media [21]. Polycrystalline Pt−Bi catalysts demonstrated a five fold activity increase compared to polycrystalline Pt catalyst [22].…”

Recent Progress in Electrocatalytic Glycerol Oxidation

“…Moreover, the in situ FTIR can be used to fleetly detect the key intermediates during reaction processes, which is conducive to investigate the reaction mechanism and propose the corresponding reaction pathway. [ 29,30 ]…”

“…Coutanceau et al investigated the influence of introduced Bi on the GOR performance of carbon‐supported or unsupported Pt, Pd, and PtPd alloy nanoparticles in alkaline media by combining cyclic voltammograms and in situ FTIR. [ 58 ] They found that Bi adatoms did not bring much improvement on the catalytic activity of non‐supported Pd nanospheres toward GOR, but greatly enhanced the reactivity of carbon‐supported Pd x Bi 10− x /C, Pt 9 Bi 1 /C, and Pd 4.5 Pt 4.5 Bi 1 /C catalysts. Moreover, they also found that the introduced Bi had no influence on the selectivity of Pd, but significantly affected the selectivity of Pt containing catalysts at low potential.…”

Benchmarking Catalysts for Formic Acid/Formate Electrooxidation

“…The greatest dissolution features were observed when the experiments were performed in a CO-saturated electrolyte implying that the indirect oxidation pathway (i.e., through CO adsorption and oxidation) plays a key role in formate electrooxidation using PtRu as the catalyst. Other Pt-based alloys have been tested in formic acid/formate electrooxidation such as PtFe [79], PtAu [67,90], PtAg [65], PtCo [66], PtCu [68], PdPt [39,71,73,91,92], PtBi [69,93] or PtSn [68,93,94] (Table 2). Indeed, the use of Bi, Sb, As, Pb, Sn and Ge as dopants for Pt has been investigated from several decades ago, finding optimum loadings of around 50% in most cases [93,94].…”