Supporting Information. MOF Templated Nitrogen Doped Carbon Stabilized Pt-Co Bimetallic

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1 Supporting Information MOF Templated Nitrogen Doped Carbon Stabilized Pt-Co Bimetallic Nanoparticles: Low Pt Contents and Robust Activity towards Electrocatalytic Oxygen Reduction Reaction Li-Li Ling, Wu-Jun Liu, Si-Qin Chen, Xiao Hu, Hong Jiang* CAS Key Laboratory of Urban Pollutant Conversion, Department of Chemistry, University of Science and Technology of China, Hefei , China S-1

2 S1. Calculation of the parameters of ORR The electron transfer number (n) in ORR can be calculated based on the Koutecky-Levich equations (S1-4) at different electrode potentials: 33 1/J = 1/J k +1/J L = 1/J k + 1/Bω 1/2 (S1) B = 0.2nFC o (D o ) 2/3 υ -1/6 J k = nfkc o J L= 0.2nFC o (D o ) 2/3 υ -1/6 ω 1/2 (S2) (S3) (S4) where J, J k, and J L are the total current density, kinetic- and diffusion-limiting current densities, respectively. ω and n are the angular velocity and electron transfer number in ORR, respectively. F (96485 C mol 1 ) is the Faraday constant. C o and D o are the bulk O 2 concentration of ( mol cm 3 in 0.1 M of KOH) and O 2 diffusion coefficient ( cm 2 /s in 0.1 M of KOH), respectively. ν and k are the kinematic electrolyte viscosity (0.01 cm 2 s 1 ) the electron transfer rate constant, respectively. The H 2 O 2 yield and the electron transfer number (n) were calculated by the followed Eqs. S5 and 6, respectively: %HO - I r / N 2 = 200 (S5) I + I / N d r I d n= 4 (S6) I + I / N d r where I d and Ir are the disk and ring current, respectively. N is determined as 0.4 from the reduction of K 3 Fe[CN] 6. S-2

3 Table S1. Comparison of the Pt contents and ORR performances between the state-of-art Pt based ORR catalysts and the Pt-Co/NC synthesized in this work catalyst Pt content (%) E 1/2 (V) Ref. 5% Pt/FeCo OMPC 5% Pd-P 11% Pt NW/C 40% Pt 3 Co/C 20% Au-rod@Pt 34% Pt-Co 6 Mo 6 C 2 /gc 40% Pt-Co/NC 0.51% 0.87 This work S-3

4 Figure S1. XRD pattern and SEM image of the ZIF-67 S-4

5 Figure S2. (a) XPS Co 2p spectra of the Co/NC (b) XPS Co 2p spectra of the Pt-Co/NC. Figure S3. XPS Pt 4f spectra of the Pt-Co/NC S-5

6 Figure S4. Ring and disk current densities of the Pt-Co/NC in RRDE measurements. S-6

7 Figure S5. The LSV profiles collected from the catalysts with different Pt contents. S-7

8 Figure S6. (a) LSV profiles of the Co/NC, Pt-Co/NC, and benchmark 20% Pt/C catalyst in O 2 -saturated 0.1 M HClO 4 solution at room temperature (rotation speed 1600 rpm, sweep rate 5 mv s -1 ); (b) current-time (i-t) chronoamperometric response of NPMAC-495 and Pt/C electrodes at V (vs. RHE) in O 2 -saturatured 0.1 M HClO 4 solution at a rotation rate of 900 rpm with the introduction of methanol;(c) current-time (i-t) chronoamperometric response of NC and Pt/C electrodes at V (vs. RHE) in O 2 -saturatured 0.1 M HClO 4 solution at a rotation rate of 900 rpm. S-8

9 References 1. Wu, R.; Qian, X.; Rui, X.; Liu, H.; Yadian, B.; Zhou, K.; Wei, J.; Yan, Q.; Feng, X. Q.; Long, Y.; Wang, L.; Huang, Y., Zeolitic Imidazolate Framework 67-Derived High Symmetric Porous Co(3)O(4) Hollow Dodecahedra with Highly Enhanced Lithium Storage Capability. Small 2014, 10, Papadimitriou, S.; Armyanov, S.; Valova, E.; Hubin, A.; Steenhaut, O.; Pavlidou, E.; Kokkinidis, G.; Sotiropoulos, S., Methanol Oxidation at Pt Cu, Pt Ni, and Pt Co Electrode Coatings Prepared by a Galvanic Replacement Process. J. Phys. Chem. C 2010, 114, Cheon, J. Y.; Kim, T.; Choi, Y.; Jeong, H. Y.; Kim, M. G.; Sa, Y. J.; Kim, J.; Lee, Z.; Yang, T.-H.; Kwon, K., Ordered Mesoporous Porphyrinic Carbons with very High Electrocatalytic Activity for the Oxygen Reduction Reaction. Scientific reports 2013, 3, Poon, K. C.; Tan, D. C.; Vo, T. D.; Khezri, B.; Su, H.; Webster, R. D.; Sato, H., Newly Developed Stepwise Electroless Deposition enables a Remarkably Facile Synthesis of Highly Active and Stable Amorphous Pd Nanoparticle Electrocatalysts for Oxygen Reduction Reaction. J. Am. Chem. Soc. 2014, 136, Sun, S.; Zhang, G.; Geng, D.; Chen, Y.; Li, R.; Cai, M.; Sun, X., A Highly Durable Platinum Nanocatalyst for Proton Exchange Membrane Fuel Cells: Multiarmed Starlike Nanowire Single Crystal. Angew. Chem. 2011, 50, Dubau, L.; Durst, J.; Maillard, F.; Guétaz, L.; Chatenet, M.; André, J.; Rossinot, E., Further Insights into the Durability of Pt 3 Co/C Electrocatalysts: Formation of Hollow Pt Nanoparticles Induced by the Kirkendall Effect. Electrochim. Acta 2011, 56, Kim, Y.; Hong, J. W.; Lee, Y. W.; Kim, M.; Kim, D.; Yun, W. S.; Han, S. W., Synthesis of AuPt Heteronanostructures with Enhanced Electrocatalytic Activity toward Oxygen Reduction. Angew. Chem. Int. Ed. 2010, 49, Ma, X.; Meng, H.; Cai, M.; Shen, P. K., Bimetallic Carbide Nanocomposite Enhanced Pt Catalyst with High Activity and Stability for the Oxygen Reduction Reaction. J. Am. Chem. Soc. 2012, 134, S-9

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