RESUMO
In oxygen electrocatalysis, how to rationally design low-cost catalysts with reasonable structure and long-term stability is a crucial issue. Here, an in-situ growth strategy is used to construct a shaped structure encapsulating a uniformly-dispersed Co/Co3Fe7 heterojunction in nitrogen-doped carbon nanotubes (Co/Co3Fe7@NCNTs). Hollow CoFe layered-double-hydroxide prisms act as sacrifices for in-situ growth of Co/Co3Fe7 nanoparticles, which also catalyze the growth of bamboo-like NCNTs. Tubular structure not only accelerates the charge transfer through the interactions between Co and Co3Fe7, but also limits the aggregation of the particles, thereby promoting the 4e- oxygen reduction/evolution reactions (ORR/OER) kinetics and stabilizing the bifunctional activity. Co/Co3Fe7@NCNTs-800 (pyrolyzed at 800 °C) shows exceptional ORR activity (half-wave potential of 0.89 V) and methanol tolerance. Meanwhile, Co/Co3Fe7@NCNTs-800 shows a small OER overpotential of 280 mV, which increases by only 9 mV after 1000 cyclic voltammetry (CV) cycles. The outstanding bifunctionality (potential gap of 0.62 V) is ascribed to the electronic structure modulation at the Co/Co3Fe7 heterointerface. Notably, it also has a high performance as an air-cathode for rechargeable zinc-air battery, showing high power density (165 mW cm-2) and specific capacity (770.5 m Ah kg-1). This work provides a new reference for promoting the development of alloy catalysts with heterogeneous interfaces.
RESUMO
Phase transformation of cobalt selenide (CoSe2 ) can effectively modulate its intrinsic electrocatalytic activity. However, enhancing electroconductivity and catalytic activity/stability of CoSe2 still remains challenging. Heterostructure engineering may be feasible to optimize interfacial properties to promote the kinetics of oxygen electrocatalysis on a CoSe2 -based catalyst. Herein, a heterostructure consisting of CoSe2 and cobalt nitride (CoN) embedded in a hollow carbon cage is designed via a simultaneous phase/interface engineering strategy. Notably, the phase transition of orthorhombic-CoSe2 to cubic-CoSe2 (c-CoSe2 ) accompanied by in situ CoN formation is realized to build the c-CoSe2 /CoN heterointerface, which exhibits excellent/highly stable activities for oxygen reduction/evolution reactions (ORR/OER). Notably, heterostructure can modulate the local coordination environment and increase Co-Se/N bond lengths. Theoretical calculations show that Co-site (c-CoSe2 ) with an electronic state near Fermi energy level is the main active site for ORR/OER.Energetical tailoring of the d-orbital electronic structure of the Co atom of c-CoSe2 in heterostructure by in situ CoN incorporation lowers thermodynamic barriers for ORR/OER. Attractively, a zinc-air battery with a c-CoSe2 -CoN cathode displays excellent cycling stability (250 h) and charge/discharge voltage loss (0.953/0.96 V). It highlights that heterointerface engineering provides an option for modulating the bifunctional activity of metal selenides with controlled phase transformation.
