Controlled Growth of Donor–Bridge–Acceptor Interface for High‐Performance Ammonia Production

Abstract

The intrinsic catalytic activity and active sites of the catalyst originate from the interface efficient charge transfer. A 2D graphdiyne (GDY) layer grown on the surface of zeolitic imidazolate framework nanocubes (ZIFNC@GDY) forms a novel structure of a perfect “donor–bridge–acceptor” interface, in which the ZIFNC and GDY act as electron donor and acceptor, respectively, linked by the sp‐C–Co and sp‐C–N bonds as bridges. Importantly, the as‐prepared catalyst exhibits intrinsically high reactivity for ammonia production through the nitrate reduction reaction (NtRR) in neutral aqueous solutions at ambient pressures and temperatures. The NtRR performance of the as‐prepared electrocatalyst is confirmed by the high NH3 yield rate (YNH3) of 0.40 ± 0.02 mmol h–1 cm–2 at potential of −0.745V versus RHE and Faradaic efficiency (FE) of 98.51 ± 0.75%, as well as the excellent stability. We show that such unique interfacial structures can accelerate the efficient electron transfers between the zeolitic imidazolate framework nanocubes (ZIFNC) core and GDY shell, enrich the electron density on the GDY surface, and thereby promote fast redox switching, creating more active sites, and improving the catalytic performances.

Iron‐Based Nanocatalysts for Electrochemical Nitrate Reduction

“…The implementation of electrochemical NO 3 RR ammonia production via a simple post-treatment process is expected to solve the problems of massive energy consumption and serious environmental pollution caused by traditional ammonia production methods, as well as to produce NH 3 efficiently under environmental conditions. [140][141][142][143][144][145][146][147] For example, Fang et al through in situ electrochemical reduction prepared a 2D ferricyanyl coordination polymer nanosheet. [53] This ironbased catalyst can exhibit high electrocatalytic NO 3 RR activity towards NH 3 with a yield of 42.1 mg h −1 mg cat −1 due to the strong adsorption of nitrate on the active sites of zero-valent iron generated by topological transformation and in situ electroreduction (Figure 9d-f).…”

“…The implementation of electrochemical NO 3 RR ammonia production via a simple post‐treatment process is expected to solve the problems of massive energy consumption and serious environmental pollution caused by traditional ammonia production methods, as well as to produce NH 3 efficiently under environmental conditions. [ 140–147 ] For example, Fang et al. through in situ electrochemical reduction prepared a 2D ferricyanyl coordination polymer nanosheet.…”

Graphdiyne Electrochemistry: Progress and Perspectives

“…Its yield rate is actually low. [191] Differently, electrochemical NRR only utilizes N 2 and H 2 O as the reactants to achieve sustainable and high-yield ammonia. For example, a GDY electrocatalyst was synthesized for electrochemical NNR using a one-step hydrothermal method, namely uniformly dispersed and zero-valent Mo atoms on the GDY (Mo 0 /GDY).…”

Interfacial Engineering of Bimetallic Ni/Co-MOFs with H-Substituted Graphdiyne for Ammonia Electrosynthesis from Nitrate

“…In addition, the available application environment of MOFs with both wide pH and potential operation windows is additional criteria that have to be qualified. Given all of this, some functional species are expected to couple with bimetallic MOFs to maximize their capability utilization in practical applications. − Recently, a microporous organic network of hydrogen-substituted graphdiyne (HsGDY) with an extended π-conjugation system is emerging as a versatile support of many host materials to improve their conductivity, stability, and mass transfer. − Of note, the cross-linking nature of HsGDY under a low temperature (60 °C) makes it available to engineer the surface of many functional materials sensitive to temperature, which distinguishes it from many other carbonaceous materials. In view of this, it is promising to engineer the surface of bimetallic MOFs with HsGDY, where a multifunctional interface could be achieved to improve the kinetics of the deoxygenation and hydrogenation of nitrate .…”