Biphasic Transition Metal Nitride Electrode Promotes Nucleophile Oxidation Reaction for Practicable Hybrid Water Electrocatalysis

Abstract

Glycerol electrooxidation (GOR), as a typical nucleophile oxidation reaction, is deemed as a promising alternative anodic route to assist cathodic hydrogen evolution reaction. However, the investigations of high-performance catalysts and industrial-scale application of GOR remain a grand challenge. Herein, biphasic Ni 3 N/Co 3 N heterostructure nanowires (denoted as Ni 3 N/ Co 3 N-NWs) are proposed as an efficient bifunctional catalyst, which realizes a high Faradaic efficiency of 94.6% toward formate production. Importantly, the flow electrolyzer achieves an industry-level current density of 1 A cm −2 at 2.01 V with impressive stability for steady running over 200 h, realizing lower electricity expense of 4.82 kWh m −3 H2 and energy saving efficiency of 9.7%, as well as outstanding co-production rates of 11 and 21.4 mmol cm −2 h −1 toward formate and H 2 , respectively. Theoretical calculations reveal that the efficient electron transfer on Ni 3 N/Co 3 N heterointerfaces simultaneously optimizes nucleophile reaction tendency and glycerol dehydrogenation kinetics, thus contributing to excellent GOR performance.

Regulating Reaction Intermediate Adsorption of Co0.5NiS2–Ni3S2 Nanorods for Efficient Urea Electrolysis

“…It is reported that the electronic structure of the active sites can affect the charge transfer property of the catalysts to optimize the adsorption/desorption of reactants and products, accompanied by accelerating reaction kinetics, thus facilitating catalytic efficiency . In recent years, various strategies, such as interface engineering, defect engineering, and heteroatom doping, have been used to tune the electron configuration of catalysts to enhance the catalytic activity. − Combining suitable components with different energy structures to construct heterogeneous catalysts could generate an internal electric field and induce the formation of oppositely charged regions, , thus facilitating proton transport and local charge density redistribution at the heterointerface. In addition, the introduction of sulfur vacancies could change the electronic structure of adjacent metal atoms due to the different electronegativity, resulting in the adjacent metal active sites losing electrons, which could optimize the adsorption of reaction intermediates .…”

Water electrolysis for hydrogen production: from hybrid systems to self-powered/catalyzed devices

“…Recently, Zhang et al reported a biphasic transition metal nitride electrode by in situ growing Ni 3 N/Co 3 N heterostructure nanowires with abundant heterointerfaces on Ni foam. 34 This electrode exhibited remarkable activity for nucleophilic reaction electrocatalysis, achieving an ultrasmall work potential of 1.26 V to reach a current density of 50 mA cm −2 for the GOR and an excellent FE of 94.6% for formate production. Importantly, under a two-electrode configuration, the electrode enabled the concurrent production of formate and H 2 , delivering current densities of 50 and 400 mA cm −2 at 1.47 and 2.04 V, respectively, which surpass those required forthe OWS for O 2 and H 2 generation (1.72 and 2.22 V at 50 and 400 mA cm −2 , respectively).…”

Screening potential anodic chemistry in lieu of the oxygen evolution reaction in electrolysis systems: the road to practical application

“…7,15 Data for the above two critical performance indicators of the electrolyzer were obtained from the literature (Fig. 8c), 15,110,130,148,151,191,192,237–251 from the widely studied systems including methanol, 11 and glycerol oxidation. In most reports, the E E of the AAC-incorporated electrolyzer is 20% lower than that of the alkaline water electrolyzer, but the R P is much lower due to the limited current density.…”