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理解Nb掺杂TiO负载的Pt的氧还原反应活性和氧化稳定性。

Understanding the Oxygen Reduction Reaction Activity and Oxidative Stability of Pt Supported on Nb-Doped TiO.

作者信息

He Cheng, Sankarasubramanian Shrihari, Matanovic Ivana, Atanassov Plamen, Ramani Vijay

机构信息

Center for Solar Energy and Energy Storage, Department of Energy, Environmental, and Chemical Engineering, Washington University in St. Louis, 1 Brookings Dr., St. Louis, MO, 63130, USA.

Department of Chemical and Biological Engineering, Center for Micro-Engineered Materials, University of New Mexico, Albuquerque, NM 87131, USA.

出版信息

ChemSusChem. 2019 Aug 8;12(15):3468-3480. doi: 10.1002/cssc.201900499. Epub 2019 Mar 5.

Abstract

Commercial fuel cell electrocatalyst degradation results from carbon electrocatalyst support oxidation at high operating potential transients. Guided by density functional theory (DFT) calculations, Nb-doped TiO (NTO) was synthesized, which exhibits a unique combination of high surface area, high electrical conductivity, and high porosity. This catalyst retained 78 % of its initial electrochemically active surface area compared with 57.6 % retained by Pt/C following the DOE/FCCJ protocol for accelerated stability test. Strong metal-support interactions, which were predicted by DFT calculations and confirmed experimentally by X-ray photoelectron spectroscopy and kinetics measurements, resulted in 21 % higher oxygen reduction reaction mass activity (at 0.9 V vs. reversible hydrogen electrode) on Pt/NTO compared with commercial Pt/C. The ex situ activity and durability of Pt/NTO translated to a fuel cell. The rise in electrode ohmic resistance and non-electrode concentration overpotential indicate that improving the conductivity of NTO and optimizing the catalyst ink formulation are critical next steps in the development of Pt/NTO-catalyzed proton exchange membrane fuel cells.

摘要

商用燃料电池电催化剂的降解是由于在高操作电位瞬变时碳电催化剂载体发生氧化所致。在密度泛函理论(DFT)计算的指导下,合成了Nb掺杂的TiO(NTO),它具有高表面积、高电导率和高孔隙率的独特组合。按照美国能源部/燃料电池技术联合中心(DOE/FCCJ)的加速稳定性测试协议,这种催化剂保留了其初始电化学活性表面积的78% , 相比之下,Pt/C仅保留了57.6% 。DFT计算预测并通过X射线光电子能谱和动力学测量实验证实的强金属-载体相互作用,使得Pt/NTO上氧还原反应的质量活性(相对于可逆氢电极在0.9 V时)比商用Pt/C高21% 。Pt/NTO的非原位活性和耐久性转化到了燃料电池中。电极欧姆电阻和非电极浓度过电位的增加表明,提高NTO的电导率和优化催化剂油墨配方是开发Pt/NTO催化的质子交换膜燃料电池的关键下一步。

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