RESUMO
The realization of the membrane-free two-step water electrolysis is particularly important yet challenging for the low-cost and large-scale supply of hydrogen energy. In this effort, Co-doped Ni(OH)2 nanosheets were successfully anchored onto the nickel foam (NF) substrate through the in-situ growth of metal-organic frame material and the subsequent alkali-etching technique. Using the well-regulated Co-doping Ni(OH)2@NF electrodes as a charge mediator, electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were decoupled on time scales, thus affording a membrane-free two-step route for H2 and O2 productions. In this architecture, the first HER process on the cathode could be maintained for 1300 s at a current of 100 mA, while the corresponding Ni(OH)2 charge mediator was simultaneously oxidized to NiOOH, with a decent cell voltage of 1.542 V. The subsequent OER process involved a reduction/regeneration of Ni(OH)2 (from NiOOH to Ni(OH)2) and an anodic O2-production, with an operating voltage of 0.291 V. Moreover, the Ni-Zn battery assembled through the combination of NiOOH and Zn sheet could replace the second step of OER to achieve the coupling of continuous H2-production and battery discharge, thus also providing a new way for hydrogen production without an external power supply. Experiment and theoretical calculations have shown that the cobalt-doping not only improved the conductivity of the charge-buffer electrode, but also shifted its redox potential cathodically and boosted the adsorption affinity of the buffer medium to OH- ions, both contributing to promoted HER and OER activity. Therefore, this decoupled water electrolysis device affords a promising pathway to support the efficient conversion of renewables to hydrogen.
RESUMO
To meet the application needs of rechargeable Zn-air battery and electrocatalytic overall water splitting (EOWS), developing high-efficiency, cost-effective, and durable trifunctional catalysts for the hydrogen evolution reaction (HER), oxygen evolution, and reduction reaction (OER and ORR) is extremely paramount yet challenging. Herein, the interface engineering concept and nanoscale hollowing design were proposed to fabricate N-doping carbon nanoboxes confined with Co/MoC nanoparticles. Uniform zeolitic imidazolate framework nanocube was employed as the starting material to construct the trifunctional electrocatalyst through the conformal polydopamine-Mo layer coating and the subsequent pyrolysis treatment. The Co@IC/MoC@PC catalyst displayed superior electrochemical ORR performances with a positive half-wave potential of 0.875 V and a high limiting current density of 5.89 mA/cm2. When practically employed as an electrocatalyst in regenerative Zn-air battery, a high specific capacity of 728 mAh/g, a large peak power density of 221 mW/cm2, a high open-circuit voltage of 1.482 V, and a low charge/discharge voltage gap of 0.41 V were obtained. Moreover, its practicability was further exploited by overall water splitting, affording low overpotentials of 277 and 68 mV at 10 mA/cm2 for the OER and HER in 1 M KOH solution, respectively, and a decent operating potential of 1.57 V for EOWS. Ultraviolet photoelectron spectroscopy and density functional theory calculation revealed that the Co/MoC interface synergistically facilitated the charge-transfer, thereby contributing to the enhancements of electrocatalytic ORR/OER/HER processes. More importantly, this catalyst design concept can offer some interesting prospects for the construction of outstanding trifunctional catalysts toward various energy conversion and storage devices.