Engineering S, N-doped carbon nanosheets derived from thiazolothiazole-based conjugated polymer for efficient electrocatalytic oxygen evolution and Zn-air battery

Abstract

Electrochemical oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) by using metal-free electrocatalysts is an emerging research interest for clean energy due to its cost affordability and eco-friendliness. However, only a few metal-free electrocatalysts are reported to exhibit robust OER and ORR performances, although OER and ORR are very important in various energy technology like metal-air batteries, fuel cells, etc. Herein, we have developed a rigid thiazolo [5,4-d] thiazole-based organic conjugated polymer, P-TzTz, and its polymer-derived N and S-doped carbon nanosheets for metal-free electrocatalytic OER and ORR. The polymer possesses a unique two-dimensional nanosheet structure with a moderate surface area of 72.6 m2/g and a wide range of pore sizes. The synthesized P-TzTz displayed a reasonable electrocatalytic OER performance with excellent long-term stability. The OER performance was further enhanced by pyrolyzing the P-TzTz at 800 °C to prepare the N and S-doped carbon nanosheet, P-TzTz-CNS800. The elevated surface area (228 m2/g) with uniform mesopores, enhanced electrical conductivity of P-TzTz-CNS800, and the presence of N, and S as the dopants for improving active sites made the P-TzTz-CNS800 a promising OER/ORR electrocatalyst as it showed the OER overpotential of 347 mV@10 mA/cm2 current density with more than 45 h long-range durability and 98% Faradic efficiency of oxygen evolution. Finally, to utilize the good OER efficacy of P-TzTz-CNS800-based metal-free electrocatalyst, a rechargeable Zn-air battery was fabricated as a proof of concept by taking P-TzTz-CNS800 as the air cathode. The Zn-air battery revealed a constant open circuit potential of 1.44 V and high charging/discharging stability over 40 h with a minimal loss in round trip frequency. Thus, the report corroborates the promising potential of P-TzTz derived N and S-doped carbon nanosheets as an efficient metal-free electrocatalyst as an air cathode for Zn-air battery for clean energy conversion.