IC2MP, UMR-CNRS 7285, University of Poitiers, 14 rue Michel Brunet, 86022, Poitiers, France.
Institute of Electrochemistry, Ulm University, Albert Einstein-Allee 47, 89081, Ulm, Germany.
ChemSusChem. 2018 Jan 10;11(1):193-201. doi: 10.1002/cssc.201701822. Epub 2017 Dec 12.
Improving the efficiency of Pt-based oxygen reduction reaction (ORR) catalysts while also reducing costs remains an important challenge in energy research. To this end, we synthesized highly stable and active carbon-supported Mo-doped PtCu (Mo-PtCu/C) nanoparticles (NPs) from readily available precursors in a facile one-pot reaction. Mo-PtCu/C displays two-to-fourfold-higher ORR half-cell kinetics than reference PtCu/C and Pt/C materials, a trend that was confirmed in proof-of-concept experiments by using a H /O microlaminar fuel cell. This Mo-induced activity increase mirrors observations for Mo-PtNi/C NPs and possibly suggests an emerging trend. Electrochemical-accelerated stability tests revealed that dealloying was greatly reduced in Mo-PtCu/C in contrast to the binary alloys PtCu/C and PtMo/C. Supporting DFT studies suggested that the exceptional stability of Mo-PtCu could be attributed to oxidative resistance of the Mo-doped atoms. Furthermore, our calculations revealed that oxygen could induce segregation of Mo to the catalytic surface, at which it effected beneficial changes to the surface oxygen adsorption energetics in the context of the Sabatier principle.
提高基于铂的氧还原反应 (ORR) 催化剂的效率同时降低成本仍然是能源研究中的一个重要挑战。为此,我们从易得的前体中通过简便的一锅法反应合成了高度稳定和高效的碳负载 Mo 掺杂 PtCu(Mo-PtCu/C)纳米颗粒 (NPs)。Mo-PtCu/C 的 ORR 半电池动力学比参考 PtCu/C 和 Pt/C 材料高出两到四倍,这一趋势在使用 H/O 微层流燃料电池的概念验证实验中得到了证实。这种 Mo 诱导的活性增加与 Mo-PtNi/C NPs 的观察结果一致,可能表明出现了一种新兴趋势。电化学加速稳定性测试表明,与二元合金 PtCu/C 和 PtMo/C 相比,Mo-PtCu/C 中的脱合金化大大减少。支持的 DFT 研究表明,Mo-PtCu 的非凡稳定性可归因于 Mo 掺杂原子的抗氧化性。此外,我们的计算表明,氧可以诱导 Mo 向催化表面的分离,在 Sabatier 原理的背景下,它对表面氧吸附能产生有益的变化。