Designing stable and efficient electrocatalysts for both oxygen reduction and evolution reactions (ORR/OER) at low-cost is challenging. Here, a carbon-based bifunctional catalyst of magnetic catalytic nanocages that can direct enhance the oxygen catalytic activity by simply applying a moderate (350 mT) magnetic field is reported. The catalysts, with high porosity of 90% and conductivity of 905 S m-1 , are created by in situ doping metallic cobalt nanodots (≈10 nm) into macroporous carbon nanofibers with a facile electrospinning method. An external magnetic field makes the cobalt magnetized into nanomagnets with high spin polarization, which promote the adsorption of oxygen-intermediates and electron transfer, significantly improving the catalytic efficiency. Impressively, the half wave-potential is increased by 20 mV for ORR, and the overpotential at 10 mA cm-2 is decreased by 15 mV for OER. Compared with the commercial Pt/C+IrO2 catalysts, the magnetic catalyzed Zn-air batteries deliver 2.5-fold of capacities and exhibit much longer durability over 155 h. The findings point out a very promising strategy of using electromagnetic induction to boost oxygen catalytic activity.

Direct Magnetic Reinforcement of Electrocatalytic ORR/OER with Electromagnetic Induction of Magnetic Catalysts

Oxygen evolution reaction (OER) plays a determining role in electrochemical energy conversion devices, but challenges remain due to the lack of effective low-cost electrocatalysts and insufficient understanding about sluggish reaction kinetics. Distinguish from complex nano-structuring, this work focuses on the spin-related charge transfer and orbital interaction between catalysts and intermediates to accelerate catalytic reaction kinetics. Herein, we propose a simple magnetic-stimulation approach to rearrange spin electron occupation in noble-metal-free metal-organic frameworks (MOFs) with a feature of thermal-differentiated superlattice, in which the localized magnetic heating in periodic spatial distribution makes the spin flip occur at particular active sites, demonstrating a spin-dependent reaction pathway. As a result, the spin-rearranged Co0.8Mn0.2 MOF displays mass activities of 3514.7 A gmetal−1 with an overpotential of ~0.27 V, which is 21.1 times that of pristine MOF. Our findings provide a new paradigm for designing spin electrocatalysis and steering reaction kinetics. The oxygen evolution reaction in magnetic catalysts is related with their spin configuration. Here, the authors propose a magnetic-stimulation method to rearrange spin electron occupation in thermal-differentiated superlattices.

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Spin-sate reconfiguration induced by alternating magnetic field for efficient oxygen evolution reaction.

Tuning Charge Distribution of FeN4 via External N for Enhanced Oxygen Reduction Reaction

The development of efficient and stable catalysts for the oxygen reduction reaction (ORR) at low cost is crucial for realizing the large-scale application of metal-air batteries. Herein, we report an efficient ORR catalyst of bimetallic copper and cobalt fluoride heterojunctions, which are uniformly dispersed in nitrogen-fluorine-oxygen triply doped porous carbon nanofibers (PCNFs) that contain hierarchical macro-meso-micro pores. The composite catalyst materials are fabricated with a facile and green method of electrospinning with water as the solvent. By using poly(tetrafluoroethylene) as the pore inducer to anchor electropositive copper and cobalt salts in the electrospun hybrid nanofibers, bimetallic fluoride heterojunctions can be directly formed in PCNFs after calcination. The hierachical porous structures provide an effective way to transport matter, while the bimetallic fluorides expose abundant electroactive sites, both of which result in stable ORR activities with a high half-wave potential of 0.84 V. The study proposes a feasible strategy for the fabrication of nonprecious catalysts.

Ying Wang

Papers

Direct Magnetic Reinforcement of Electrocatalytic ORR/OER with Electromagnetic Induction of Magnetic Catalysts

One-step synthesis of a macroporous Cu-g/C3N4 nanofiber electrocatalyst for efficient oxygen reduction reaction.