Electrochemical impacts of sheet-like hafnium phosphide and hafnium disulfide catalysts bonded with reduced graphene oxide sheets for bifunctional oxygen reactions in alkaline electrolytes

Non-noble metal-based catalysts with efficient catalytic activities for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are critical for energy conversion devices, including fuel cells and metal-air batteries. In this work, novel hafnium phosphide-reduced graphene oxide nanosheets (HfP-rGO NS) and hafnium disulfide-reduced graphene oxide nanosheets (HfS2-rGO NS) were synthesized and investigated as bifunctional electrocatalysts for OER and ORR. The prepared HfP-rGO NS and HfS2-rGO NS catalysts showed nanosheet structures, where the HfP or HfS2 nanosheet was closely packed with rGO. A unique methodology was adopted to lodge the non-metal oxide catalytic sheets (i.e., HfP and HfS2) over the rGO sheets, which positioned the oxide layer on the catalytic sheet surface for instant oxygen evolution. Low intensity X-ray diffraction patterns and Raman spectra confirmed the sheet-like structure of HfP-rGO NS and HfS2-rGO NS. Scanning electron microscope mapping images revealed that all elements (i.e., Hf, P, C and O for HfP-rGO NS and Hf, S, C and O for HfS2-rGO NS) were equally distributed in the synthesized heteroatomic nanosheets. Moreover, both the HfP-rGO NS and HfS2-rGO NS demonstrated excellent durability for both ORR and OER. This outperforms the most state-of-the-art non-precious-metal-based bifunctional catalysts, which is attributed to the synergistic effect of rGO and Hf-based catalysts. The different ORR and OER reaction potentials in HfP-rGO NS and HfS2-rGO NS likely result from the influence of HfP and HfS2.