Ultrathin ternary PtNiRu nanowires for enhanced oxygen reduction and methanol oxidation catalysis via d-band center regulation

• Published in: Journal of colloid and interface science 2025-01, Vol.678 (Pt B), p.599-608
• Main Authors: Cai, Guopu, Hua, Chun, Ren, Hongji, Yu, Renqin, Xu, Deying, Khan, Muhammad Arif, Guo, Jian, Sun, Yu, Tang, Ya, Qian, Huidong, Xia, Zhonghong, Ye, Daixin, Zhang, Jiujun, Zhao, Hongbin
• Format: Article
• Language: English
• Subjects: D-band center; Electrocatalyst; Ruthenium; Ternary alloy; Ultrathin nanowires
• ISSN: 0021-9797; 1095-7103; 1095-7103
• DOI: 10.1016/j.jcis.2024.09.054

The ultrafine PtNiRu ternary alloy nanowires exhibit exceptional catalytic activity and durability for both oxygen reduction reaction and methanol oxidation reaction. The incorporation of Ru modulates the d-band center of Pt atoms, facilitating the desorption of oxygenated intermediates and enhancing stability through the formation of robust PtRu metal bonds. [Display omitted] Direct methanol fuel cells rely on the efficiency of their anode/cathode electrocatalysts to facilitate the methanol oxidation reaction and oxygen reduction reaction, respectively. Platinum-based nanocatalysts are at the forefront due to their superior catalytic properties. However, the high-cost, scarcity, and low CO tolerance of platinum pose challenges for the scalable application of DMFCs. Herein, we report novel ultrathin ternary PtNiRu alloy nanowires to improve Pt utilization and CO tolerance. These novel electrocatalysts incorporate the oxophilic metal Ru into ultrathin PtNi nanowires, aiming to enhance the intrinsic activity of platinum while leveraging the long-term durability and high utilization efficiency provided by the bimetallic synergistic effect. The PtNiRu NWs significantly enhance both mass activity and specific activity for ORR, performing about 6.9 times and 3.9 times better than commercial Pt/C, respectively. After a rigorous durability test of 10,000 cycles, the PtNiRu NWs only exhibited a 25.2 % loss in mass activity. Additionally, for MOR, the MA and SA of PtNiRu NWs exceed that of Pt/C catalyst by 4.30 and 2.72 times, respectively, and exhibit exceptional resistance to CO poisoning. Theoretical insights from density functional theory calculations suggest that the introduction of Ru modulates the d-band center of the surface Pt atoms, which contributes to decreased binding strength of oxygenated species and an elevated dissolution potential, substantiating the enhanced performance metrics, and the durability enhancement stems from the stronger PtM bonds than those in PtNiRu NWs resulted from PtRu covalent interactions. These findings not only provide a new perspective on platinum-based nanocatalysts but also significantly advance the quest for more efficient and durable electrocatalysts for DMFCs, representing a substantial stride in fuel cell technology.