Thermal Stability and Potential Cycling Durability of Nitrogen-Doped Graphene Modified by Metal-Organic Framework for Oxygen Reduction Reactions

Harsimranjit Singh, Shiqiang Zhuang , Bharath Babu Nunna and Eon Soo Lee *

Abstract: Here we report a nitrogen-doped graphene modified metal-organic framework (N-G/MOF)

catalyst, a promising metal-free electrocatalyst exhibiting the potential to replace the noble

metal catalyst from the electrochemical systems; such as fuel cells and metal-air batteries.

The catalyst was synthesized with a planetary ball milling method, in which the precursors

nitrogen-functionalized graphene (N-G) and ZIF-8 are ground at an optimized grinding speed

and time. The N-G/MOF catalyst not only inherited large surface area from the ZIF-8 structure,

but also had chemical interactions, resulting in an improved Oxygen Reduction Reaction (ORR)

electrocatalyst. Thermogravimetric Analysis (TGA) curves revealed that the N-G/MOF catalyst

still had some unreacted ZIF-8 particles, and the high catalytic activity of N-G particles decreased

the decomposition temperature of ZIF-8 in the N-G/MOF catalyst. Also, we present the durability

study of the N-G/MOF catalyst under a saturated nitrogen and oxygen environment in alkaline

medium. Remarkably, the catalyst showed no change in the performance after 2000 cycles in the

N2 environment, exhibiting strong resistance to the corrosion. In the O2 saturated electrolyte,

the performance loss at lower overpotentials was as low compared to higher overpotentials. It is

expected that the catalyst degradation mechanism during the potential cycling is due to the oxidative

attack of the ORR intermediates.

Keywords: oxygen reduction reaction; metal-organic framework; nitrogen-doped graphene;

rotating disk electrode; durability study; potential cycling