Trimetallic Synergy in Intermetallic PtSnBi Nanoplates Boosts Formic Acid Oxidation

Abstract

Platinum is the most effective metal for a wide range of catalysis reactions, but it fails in the formic acid electrooxidation test and suffers from severe carbon monoxide poisoning. Developing highly active and stable catalysts that are capable of oxidizing HCOOH directly into CO2 remains challenging for commercialization of direct liquid fuel cells. A new class of PtSnBi intermetallic nanoplates is synthesized to boost formic acid oxidation, which greatly outperforms binary PtSn and PtBi intermetallic, benefiting from the synergism of chosen three metals. In particular, the best catalyst, atomically ordered Pt45Sn25Bi30 nanoplates, exhibits an ultrahigh mass activity of 4394 mA mg−1 Pt and preserves 78% of the initial activity after 4000 potential cycles, which make it a state‐of‐the‐art catalyst toward formic acid oxidation. Density functional theory calculations reveal that the electronic and geometric effects in PtSnBi intermetallic nanoplates help suppress CO* formation and optimize dehydrogenation steps.

Recent advances in formic acid electro-oxidation: from the fundamental mechanism to electrocatalysts

“…This view has been widely accepted, and many efforts have been made to construct discontinuous platinum sites to mitigate the poisoning of platinum. 14,66,67 Except for FAEO, palladium is less reactive than platinum in most electrochemical reactions. 68 The reasons are not yet known, perhaps because palladium has a more specific affinity for hydrogen, allowing rapid dehydrogenation of formic acid molecules on the palladium surface.…”

“…The low formic acid crossover allows to using high concentration of formic acid as fuel, which compensates for the lower energy density of formic acid compared to other liquid fuels. [12][13][14] Moreover, the theoretical open have been achieved in the above mentioned two aspects for formic acid oxidation, i.e. reaction mechanism and electrocatalysts.…”

Atomic Thickness Catalysts: Synthesis and Applications

“…However, low stability under harsh reaction conditions and the significant degradation of FAOR activity caused by the intermediate products, for example, CO molecules have limited the practical application of DFAFCs. To solve this problem, oxophilic metals (e.g., Cu, Ag, Sn, Bi) [114,115] were brought into the Pt or Pd metals to improve the CO tolerance. Generally, direct and indirect pathways have involved in the FAOR.…”

Promoting formic acid oxidation performance of Pd nanoparticles via Pt and Ru atom mediated surface engineering

“…Aforementioned issues have been addressed by multidirectional efforts. More specically, electronic properties of Ptbased NCs have been modied via introducing foreign atoms to generate multi-element nano-architectures including Pt-M alloys [11][12][13][14][15] (where M denotes foreign metals e.g. Pd, Pb, Ru, Sn, Ni etc.…”