Pt3Co@Pt Core@shell Nanoparticles as Efficient Oxygen Reduction Electrocatalysts in Direct Methanol Fuel Cell

• Published in: ChemCatChem 2021-03, Vol.13 (6), p.1587-1594
• Main Authors: Yang, Yongchao, Tan, Chunhui, Yang, Yuwei, Zhang, Lei, Zhang, Bin‐Wei, Wu, Kuang‐Hsu, Zhao, Shenlong
• Format: Article
• Language: English
• Subjects: Bimetals; Clean energy; core@shell alloy; Electrocatalysts; Electronic structure; Energy technology; fuel cell; Fuel cells; Intermetallic compounds; in situ FTIR; Methanol; methanol tolerance; Nanoparticles; Nuclear fuels; oxygen reduction; Oxygen reduction reactions; Platinum; Poisoning; Scanning transmission electron microscopy
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202001868

Core‐shell structured bimetallic platinum‐metal (Pt−M) nanoparticles, as a new class of active and stable nanocatalysts, have shown many advantages in increasing the utilization of precious Pt and improving electrocatalytic performances. Here, a core‐shell Pt3Co@Pt supported on porous graphitic carbon (denoted as Pt3Co@Pt/C) is synthesized via a simple thermal method, and further used as an efficient electrocatalyst for oxygen reduction reaction (ORR) in the direct methanol fuel cell. An atomic‐resolution high‐angle annular dark‐field scanning transmission electron microscopy (HAADF‐STEM) measurement combining with line‐profile analysis reveals that the average thickness of Pt‐shell is around 0.4–0.6 nm, forming an ultrathin catalytic layer. Given its unique geometric and electronic structure, the as‐prepared Pt3Co@Pt/C displays highly enhanced electrocatalytic ORR activity and stability, boosted anti‐methanol poisoning ability with a high onset potential and an exceptional half‐wave potential in 0.1 M HClO4 solution. Impressively, its mass activity (0.71 mA mgPt−1) and specific activity (2.75 mA cmPt−2) for ORR are 3.7‐ and 8.1‐fold higher than those of commercial Pt/C catalyst, respectively. The Pt3Co@Pt/C nanocatalysts show remarkable tolerance against methanol poisoning, evidenced by the in situ Fourier‐transform infrared (FTIR) spectroscopy. This work points out a path for the design of high‐performance nanocatalysts for accelerating the development of clean energy technologies involving ORR. Core@shell alloy: A core@shell structured Pt3Co@Pt nanoparticle with a 0.4‐0.6 nm thickness Pt‐shell supported on porous graphitic carbon, is synthesized as an efficient electrocatalyst via a simple thermal method. Due to its unique core@shell structure and favorable composition, this as‐prepared catalyst shows superior electrocatalytic performance and highly enhanced methanol tolerance for oxygen reduction in direct methanol fuel cells, compared with commercial Pt/C catalyst. This work proposes a new direction for the design of high‐performance nanocatalysts for the development of methanol fuel cells.