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By performing DFT computations, we proposed a promising strategy to tune the ORR/OER catalytic performance of transition metal-nitrogen-carbon by constructing heterostructure with graphdiyne. We found the d-band center and charge transfer of the TM active sites can correlate the ORR/OER catalytic activity and their electronic properties for TM N C/GDY. [Display omitted] • The catalytic activities of the heterostructure between TM N C with GDY (TM N C/GDY) for ORR/OER were studied by means of density functional theory. • Co N C/GDY can be proposed as a bifunctional catalyst for ORR/OER with low overpotential. • According to the constant-potential method, the acidic condition is conducive to boost bifunctional catalytic activity for Co N C/GDY. Exploring high-efficiency electrocatalysts to boost the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is pivotal to the large-scale applications for clean and renewable energy technologies, such as fuel cells, water splitting, and metal–air batteries. Herein, by means of density functional theory (DFT) computations, we proposed a strategy to modulate the catalytic activity of transition metal-nitrogen-carbon catalysts through their interface engineering with graphdiyne (TM N C/GDY). Our results revealed that these hybrid structures exhibit good stability and excellent electrical conductivity. Especially, Co N C/GDY was identified as a promising bifunctional catalyst for ORR/OER with rather low overpotentials in acidic conditions according to the constant-potential energy analysis. Moreover, the volcano plots were established to describe the activity trend of the ORR/OER on TM N C/GDY using the adsorption strength of the oxygenated intermediates. Remarkably, the d-band center and charge transfer of the TM active sites can be utilized to correlate the ORR/OER catalytic activity and their electronic properties. Our findings not only suggested an ideal bifunctional oxygen electrocatalyst, but also provided a useful strategy to obtain highly efficient catalysts by interface engineering of two-dimensional heterostructures. [ABSTRACT FROM AUTHOR]

[Display omitted] • M-N-C/MoS 2 heterostructures exhibit good structural stability, excellent electrical conductivity, and improved stiffness. • The anchored Ir-N-C, Rh-N-C, and Co-N-C are identified as eligible bifunctional ORR/OER electrocatalysts. • The optimal binding strength with the oxygenated intermediates endow anchored M-N-C good catalytic performance. The development of highly-efficient bifunctional oxygen electrocatalysts is essential to the large-scale commercialization of energy-related conversion and storage technologies. In this work, using first-principle computations, we systematically investigated the catalytic activities of a variety of metal-N-C/MoS 2 heterostructures (M-N-C/MoS 2 , M = Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Os, Ir, and Pt) towards the oxygen reduction/evolution reactions (ORR/OER). Our result revealed that these M-N-C/MoS 2 heterostructures exhibit good structural stability, excellent electrical conductivity, and improved stiffness. Furthermore, the anchored Ir-N-C was identified as the best bifunctional ORR/OER electrocatalyst due to its lowest overpotentials (0.28/0.38 V) among all candidates, which were well rationalized by its optimal binding strength with the oxygenated intermediates. Thus, by combining M-N-C and MoS 2 monolayer, the highly-efficient bifunctional ORR/OER electrocatalysts can be achieved, which offers a new strategy to further explore heterostructures-based materials for other electrochemical processes. [ABSTRACT FROM AUTHOR]