Highly Selective Synthesis of Monoclinic-Phased Platinum-Tellurium Nanotrepang for Direct Formic Acid Oxidation Catalysis

Chengyuan Dong; Xinyao Wang; Zhipeng Zhu; Changhong Zhan; Xin Lin; Lingzheng Bu; Jinyu Ye; Yucheng Wang; Wei Liu; Xiaoqing Huang

doi:10.1021/jacs.3c03317

Highly Selective Synthesis of Monoclinic-Phased Platinum-Tellurium Nanotrepang for Direct Formic Acid Oxidation Catalysis

J Am Chem Soc. 2023 Jul 19;145(28):15393-15404. doi: 10.1021/jacs.3c03317. Epub 2023 Jul 10.

Authors

Chengyuan Dong¹, Xinyao Wang^{2

3}, Zhipeng Zhu¹, Changhong Zhan¹, Xin Lin⁴, Lingzheng Bu⁴, Jinyu Ye¹, Yucheng Wang¹, Wei Liu^{2

3}, Xiaoqing Huang¹

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
² Nano and Heterogeneous Materials Center, School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
³ State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China.
⁴ College of Energy, Xiamen University, Xiamen 361102, China.

PMID: 37429024
DOI: 10.1021/jacs.3c03317

Abstract

Designing efficient formic acid oxidation reaction (FAOR) catalysts with remarkable membrane electrode assembly (MEA) performance in a direct formic acid fuel cell (DFAFC) medium is significant yet challenging. Herein, we report that the monoclinic-phased platinum-tellurium nanotrepang (m-PtTe NT) can be adopted as a highly active, selective, and stable FAOR catalyst with a desirable direct reaction pathway. The m-PtTe NT exhibits the high specific and mass activities of 6.78 mA cm^-2 and 3.2 A mg_Pt^-1, respectively, which are 35.7/22.9, 2.8/2.6, and 3.9/2.9 times higher than those of commercial Pt/C, rhombohedral-phased Pt₂Te₃ NT (r-Pt₂Te₃ NT), and trigonal-phased PtTe₂ NT (t-PtTe₂ NT), respectively. Simultaneously, the highest reaction tendency for the direct FAOR pathway and the best tolerance to poisonous CO intermediate can also be realized by m-PtTe NT. More importantly, even in a single-cell medium, the m-PtTe NT can display a much higher MEA power density (171.4 mW cm^-2) and stability (53.2% voltage loss after 5660 s) than those of commercial Pt/C, demonstrating the great potential in operating DFAFC device. The in-situ Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy jointly demonstrate that the unique nanostructure of m-PtTe NT can effectively optimize dehydrogenation steps and inhibit the CO intermediate adsorption, as well as promote the oxidation of noxious CO intermediate, thus achieving the great improvement of FAOR activity, poisoning tolerance, and stability. Density functional theory calculations further reveal that the direct pathway is the most favorable on m-PtTe NT than r-Pt₂Te₃ NT and t-PtTe₂ NT. The higher activation energy to produce CO and the relatively weaker binding with CO of m-PtTe NT result in the better CO tolerance. This work achieves remarkable FAOR and MEA performances of advanced Pt-based anodic catalysts for DFAFCs via a phase engineering strategy.