Demystifying Synergistic Multifunctional Electrocatalysis of N-Doped Graphene/WS2 Heterostructure with Single-Atom Catalysts for Water Splitting and Fuel Cells

As the demand for sustainable energy continues to rise, electrocatalysis has become increasingly prominent in the advancement of clean energy technologies. By scrutinizing the material to function as a multifunctional catalyst, the effectiveness of energy conversion processes is significantly enhanced. This study focuses on harnessing graphene/WS2 van der Waals heterostructures for overall water splitting and fuel cell applications, using transition metals (TMs) from Sc–Zn as single-atom catalysts (SACs). Additionally, the research explores the synergistic effect of nitrogen doping combined with SACs to modify the material into multifunctional catalysts. The stability of all TMs as SACs in the vdW heterostructure (TM@GW) and nitrogen-doped TM@GW (TM@NGW) is validated with negative cohesive and formation energies, and thermodynamic stability is also corroborated with ab initio molecular dynamics (AIMD) analysis at both 300 and 500 K for 5 ps. The observed electrocatalytic performance of TM@GW and TM@NGW depicts that the Ni@NGW system exhibits trifunctional property with the lowest overpotentials {ηHER; ηOER; ηORR = 0.21; 0.42; 0.27 V}. Additionally, the Cr@NGW material displays bifunctional catalytic activity for the OER and ORR, with overpotentials of 0.53 and 0.37 V, respectively. The synergistic effect between N doping and SACs is further studied with the d, p band centers and density of states calculations. Furthermore, the scaling relation between the adsorption of intermediates and reaction kinetics is studied, which validates the coaction of N and SACs in the TM@NGW heterostructure. This study demonstrates that the inclusion of SACs and nitrogen atoms in the GW heterostructure significantly enhances the catalytic performance by approximately 26%, effectively transforming the system into a multifunctional catalyst. These findings emphasize the role of SACs in vdW heterostructures and N doping effects, providing valuable insights to guide the design of advanced catalysts for water splitting and fuel cell applications.