Hollow-Structured Co-MoSx/Graphene Trifunctional Electrocatalyst for Self-Powered Hydrogen Production System.
Authors: Kim Dong Won , Kim Jihoon , CHOI Jong Hui , Adhyatma Abdurrahman , Kang Jeung Ku 
Published: August 2024

Developing a single electrocatalyst that can facilitate both rechargeable aqueous metal-air batteries and water splitting has become a crucial focus in renewable-energy technologies. This necessitates addressing the three distinct electrocatalytic reactions: the electrochemical oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Despite significant efforts, the creation of a alkaline medium based trifunctional catalyst with high activity at a low cost has proven to be a considerable challenge. Currently, Pt and its alloys have been considered as the most active catalysts for the ORR and HER, whereas noble-metal oxides such as IrO2 and RuO2 are considered as the golden standards of OER catalyst. However, noble-metals based catalyst have been suffered from their high cost, limited reserves in the Earth’s crust, and poor electrocatalytic stability. Moreover, these noble metals face challenges in simultaneously exhibiting trifunctional catalytic activity for ORR, OER, and HER. In recent study, Transiton metal sulfides(TMSs) have great attraction as trifunctional catalyts due to their eqrth abudance, tunnable band structure, and crystal structure. especially, one of widely used TMCs is MoS2 because of their Pt-like high catalytic activity for HER as well as thermodynamic electrochemical stability and rich catalytic sites in the planar nature. However, the most stable 2H (hexagonal) phase MoS2 suffers from poor electrical conductivity, low wettability, and aggregation indced reducing active catalytic sites and resulting high resistance. 2H MoS2 also shows poor activity for OER and ORR, thereby hampering its practical applications as trifunctional catalyst. To overcome this threshold, various strategies have been conducted to improve their electrochemical charateristics, such as defect engineering, heterojunction foramtion, phase transform and integrating porosity control. However, commonly considered method to synthesis requires complex multi-steps with high temperature, vaccum system, explosive gas, and toxic etchant.

In this study, we successfully synthesized the homogeneous growth of a Co-based nanometer-scale metal-organic framework (MOF) on graphene oxide at room temperature. Furthermore, a facile one-pot solvothermal method was employed to synthesize Co-MoSx/Graphene, which consists of a hollow, heterogeneous bimetallic sulfide (Co3S4/MoS2 with Co-S-Mo bonding) within a sandwiched graphene/MoS2 layer, demonstrating superior trifunctional activity and stability. Incorporating a conductive graphene layer between MoS2 layers is an effective strategy for not only realizing high electrical conduction to MoS2 layers, but also increasing MoS2 interlayer spacing for high ion accessibility. Besides, a variety of techniques, including Cs-corrected scanning transmission electron microscope (Cs-STEM), X-ray diffraction(XRD), and X-ray absorption spectroscopy (XAS), are used to confirm the atomic configurations of Co-MoSx/Graphene structure and morphologies. Also, Raman, Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) were conducted to investigating the binding structure and chemical states. Furthermore, The internal electric field (IEF) within heterojunction, which induced from the differing electron density of the bimetallic species and the sandwiched graphene are contribute not only electron density structure optimization for enhancing reaction kinetics but also accelerating electron-hole exchange. The IEF in the microporous-heterostructure accelerates the diffusion of reaction intermediate with sufficient mass transport and facilitates a Graphene/MoS2-to-Co-MoSx pathway for enhancing redox kinetics of sluggish OER and ORR. Consequently, the OER and ORR-inactive MoS2, HER, and ORR-inactive Co3S4, along with less catalytically effective graphene, demonstrate outstanding performance when combined in the bimetallic sulfide based highly active heterojunctional structure. To investigate the electrochemical catalytic properties of Co-MoSx/Graphene, Rotating disk electrode(RDE) was used with three electrode measurment. The presence of MoS2/Graphene on Co3S4 and Co-MoSx bonding species in Co-MoSx/Graphene enhances the alkaline electrochemical catalytic activity by reducing overpotential and Tafel slopes(220 mV, 110 mV dec-1 in HER and 320 mV, 55.8 mV dec-1 in OER) under 1M KOH solution. Moreover, the ORR performance was evaluated by using Koutecky-Levich (K-L) Plot with different rotating speeds under 0.1M KOH. The electron transfer number (n) is closed theoretical value of 4.0 also shows outstanding performance of the onset potential, half-wave potential and kinetic current density (0.88 V, 0.67 V, and 10.4 mA cm-2), which is comparable that of Pt/C (0.92 V, 0.8 V, and 10.3 mA cm-2). Furthermore, Co-MoSx/G based rechargeable Zinc-Air battery achieve over 85% of theoretical zinc utilization efficiency and 1.4 times higher power density than a Pt/C + RuO2 air cathode based system. We believe that this work could provide a rational strategy for achieve trifunctional electrocatalyst and high performance self-powered hydrogen production system.

This research was supported by the National Research Foundation of Korea (2022M3H4A1A04096482, RS-2023-00229679) funded by the Ministry of Science and ICT.