Amino Functionalization Approach to Synthesis of Carbon Supported Intermetallic Platinum Based Alloy Catalysts for Fuel Cell Application

Abstract

Platinum (Pt) is a critical element in the electrocatalysts for oxygen reduction reaction (ORR) occurring in the cathode of polymer electrolyte membrane fuel cells (PEMFCs). To address the Pt abundance issue and to enhance Pt ORR activity, Pt is often alloyed with another transition metal M (i.e., M=Fe, Co, and Ni, etc). (1-3) Generally, the atoms in PtM alloys are randomly distributed in the Pt fcc lattice. In the corrosive working environment of a PEMFC cathode, these transition metals are rapidly etched, thus leading to the reduced catalytic activity and stability. In these regards, ordered intermetallic PtM alloys are considered as one of the most promising candidates to achieve both high activity and stability in practical fuel cell applications. (4) The transition metals in ordered intermetallic PtM alloys occupy specific sites, and are stabilized by both metallic and ionic bonding. Ordered intermetallic structures are formed via high temperature (>600 °C) annealing of disordered PtM alloys, as the atomic ordering is a thermodynamically driven process. However, the high temperature annealing inevitably leads to the migration and agglomeration of the catalyst nanoparticles forming randomly alloyed particles with poor dispersion and broad size distributions, due to weak adhesions to the carbon support under typical synthesis conditions. To prevent this coalescence during annealing, protective coating of the nanoparticles with inorganic shells or physical barriers has been suggested. (5-10) However, these studies were limited to the synthesis of intermetallic nanoparticles on carbon supports at low metal loadings, or require an additional step of removing the protective coating layer from the surface of the nanoparticles to expose the active sites. Thus, it is essential to develop a general approach that can produce highly dispersed, structurally ordered nanoparticles while achieving controls over the size and size distribution.We propose to use the functionalized carbon supports to control PtM alloy nanoparticle size and prevent nanoparticles from aggregating during the high temperature annealing through improving the metal-support interactions. A strong electrostatic attraction between the negative charge from Pt precursor (PtCl6 2 -) and positive charge from the amino groups (C-NH2+) on the surface of the functionalized carbon will be established during the wet impregnation synthesis. Such bonds will help to make the PtM nanoparticle size smaller and more uniformly distributed over the surface of support. The ordered intermetallic 30 wt.% PtCo/KB-NH2 catalyst demonstrated an average size of 2.7 nm and uniform size distribution. In addition, 30 wt.% PtCo/KB-NH2 catalyst exhibited a mass activity of 535 A/gPt (H2/O2) and a rated power density of 1.05 W/cm2 at 0.67 V (H2/air), meeting/exceeding the DOE targets.(1) V. Stamenkovic, B.S. Mun, K.J.J. Mayrhofer, P.N. Ross, N.M. Markovic, J. Rossmeisl, J. Greeley, J.K. Nørskov, Angew. Chem. Int. Ed. 2006, 118, 2963–2967.(2) P. Strasser, S. Koh, T. Anniyev, J. Greeley, K. More, C. Yu, Z. Liu, S. Kaya, D. Nordlund, H. Ogasawara, M.F. Toney, A. Nilsson, Nat. Chem. 2010, 2, 454–460.(3) D. Wu, X. Shen, Y. Pan, L. Yao, Z. Peng, ChemNanoMat 2019, 6, 32–41.(4) X. Wang, M. T. Swihart, G. Wu, Nat. Catal. 2019, 2, 578–589.(5) D. C. Lee, F. V. Mikulec, J. M. Pelaez, B. Koo, B. Korgel, J. Phys. Chem. B 2006, 110, 11160−11166.(6) H. Chen, D. Wang, Y. Yu, K. A. Newton, D. A. Muller, H. Abruna, F. J. Disalvo, J. Am. Chem. Soc. 2012, 134, 18453−18459.(7) E. F. Holby, W. Sheng, Y. Shao-Horn, D. Morgan, Energy Environ. Sci. 2009, 2, 865−871. (8) L. Guo, W. J. Jiang, Y. Zhang, J. S. Hu, Z. D. Wei, L Wan, J. ACS Catal. 2015, 5, 2903−2909. (9) N. Cheng, Banis, N. M. J. Liu, A. Riese, X. Li, R. Li, S. Ye, S. Knights, X. Sun, Adv. Mater. 2015, 27, 277−281.(10) J. Li, S. Sharma, X. Liu, Yung-Tin Pan, J. S. Spendelow, M. Chi, Y. Jia, P. Zhang, D. A. Cullen, Z. Xi, Joule 2019, 3, 124-135.