Trilayer Metal–Organic Frameworks as Multifunctional Electrocatalysts for Energy Conversion and Storage Applications

Abstract

The need for enhanced energy storage and improved catalysts has led researchers to explore advanced functional materials for sustainable energy production and storage. Herein, we demonstrate a reductive electrosynthesis approach to prepare a layer-by-layer (LbL) assembled trimetallic Fe−Co−Ni metal−organic framework (MOF) in which the metal cations within each layer or at the interface of the two layers are linked to one another by bridging 2-amino-1,4-benzenedicarboxylic acid linkers. Tailoring catalytically active sites in an LbL fashion affords a highly porous material that exhibits excellent trifunctional electrocatalytic activities toward the hydrogen evolution reaction (η j=10 = 116 mV), oxygen evolution reaction (η j=10 = 254 mV), as well as oxygen reduction reaction (half-wave potential = 0.75 V vs reference hydrogen electrode) in alkaline solutions. The dispersion-corrected density functional theory calculations suggest that the prominent catalytic activity of the LbL MOF toward the HER, OER, and ORR is due to the initial negative adsorption energy of water on the metal nodes and the elongated O−H bond length of the H 2 O molecule. The Fe−Co−Ni MOF-based Zn−air battery exhibits a remarkable energy storage performance and excellent cycling stability of over 700 cycles that outperform the commercial noble metal benchmarks. When assembled in an asymmetric device configuration, the activated carbon||Fe−Co−Ni MOF supercapacitor provides a superb specific energy and a power of up to 56.2 W h kg −1 and 42.2 kW kg −1 , respectively. This work offers not only a novel approach to prepare an LbL assembled multimetallic MOF but also provides a benchmark for a multifunctional electrocatalyst for water splitting and Zn−air batteries.

A Critical Review on Artificial Intelligence for Fuel Cell Diagnosis

“…It is critical to employ innovative materials and technologies to increase the performance of sustainable energy conversion systems and fulfill the fast-growing energy demand. In addition to being low-cost, ideal nanostructure materials for electrocatalysis must have the following characteristics: large surface area, porous structure, high ion and electron mobility, large electrolyte-electrode contact area, high durability, and good thermal and chemical stability [31,58,59].…”

A novel porous graphitic carbon nitride (g-C7N3) substrate: prediction of metal-based π–d conjugated nanosheets toward the highly active and selective electrocatalytic nitrogen reduction reaction

“…To date, a single TM atom adsorbed on a substrate, which acts as a single-atom catalyst (SAC), has attracted increasing attention and has been studied widely for various electrochemical reactions. 16–20 SACs, were first proposed by Qiao et al 21 and featured well-defined and uniformly dispersed single atoms on a substrate; 22–26 they contribute a promising solution, escaping the low activity and selectivity dilemma faced by the electrocatalytic NRR. They are a class of newly emerged catalysts that not only maximize the efficiency of metal atom usage to 100% and dramatically diminish the metal consumption, especially for noble metals, such as Pt, Pd, Ir, and Au, but also present rosy prospects to achieve high activity and selectivity resulting from the high-ratio of the low-coordinated metal atoms.…”

Rationalizing Structural Hierarchy in the Design of Fuel Cell Electrode and Electrolyte Materials Derived from Metal-Organic Frameworks

“…For the development of durable fuel cells, the search for electrocatalysts with superior efficiencies is therefore a significant hurdle. More recently, MOFs have been attractive for ORR applications [38][39][40] where the use of metal ions or clusters and organic connectors can aid the PEMFC technology can be made more efficient by using MOF materials that possess appropriate physical and chemical properties. The most commercially studied and applied proton-exchange membranes are composition-based nafion membranes.…”

“…For the development of durable fuel cells, the search for electrocatalysts with superior efficiencies is therefore a significant hurdle. More recently, MOFs have been attractive for ORR applications [38][39][40] where the use of metal ions or clusters and organic connectors can aid the development of advanced catalysts. The porous structure of MOF electrocatalysts facilitates mass transfer in electrochemical reactions, and as a result of the uniform distribution of metal throughout the MOF precursors, the active sites of the catalyst are efficiently utilized [41][42][43][44].…”