Interdiffusion Reaction-Assisted Hybridization of Two-Dimensional Metal–Organic Frameworks and Ti₃C₂T_x Nanosheets for Electrocatalytic Oxygen Evolution

Abstract

Two-dimensional (2D) metal-organic framework (MOF) nanosheets have been recently regarded as the model electrocatalysts due to their porous structure, fast mass and ion transfer through the thickness, and large portion of exposed active metal centers. Combining them with electrically conductive 2D nanosheets is anticipated to achieve further improved performance in electrocatalysis. In this work, we in situ hybridized 2D cobalt 1,4-benzenedicarboxylate (CoBDC) with TiCT (the MXene phase) nanosheets via an interdiffusion reaction-assisted process. The resulting hybrid material was applied in the oxygen evolution reaction and achieved a current density of 10 mA cm at a potential of 1.64 V vs reversible hydrogen electrode and a Tafel slope of 48.2 mV dec in 0.1 M KOH. These results outperform those obtained by the standard IrO-based catalyst and are comparable with or even better than those achieved by the previously reported state-of-the-art transition-metal-based catalysts. While the CoBDC layer provided the highly porous structure and large active surface area, the electrically conductive and hydrophilic TiCT nanosheets enabled the rapid charge and ion transfer across the well-defined TiCT-CoBDC interface and facilitated the access of aqueous electrolyte to the catalytically active CoBDC surfaces. The hybrid nanosheets were further fabricated into an air cathode for a rechargeable zinc-air battery, which was successfully used to power a light-emitting diode. We believe that the in situ hybridization of MXenes and 2D MOFs with interface control will provide more opportunities for their use in energy-based applications.

In Situ Coupling Strategy for the Preparation of FeCo Alloys and Co4N Hybrid for Highly Efficient Oxygen Evolution

“…[39,40] Interestingly, the battery shows an open-circuit voltage of about 1.4 V. The peak power density for FeCo-Co 4 N/N-C at 19.3 mA cm −2 reaches 11.4 mW cm −2 (Figure 3a). [39,40] Interestingly, the battery shows an open-circuit voltage of about 1.4 V. The peak power density for FeCo-Co 4 N/N-C at 19.3 mA cm −2 reaches 11.4 mW cm −2 (Figure 3a).…”

Advanced Architectures and Relatives of Air Electrodes in Zn–Air Batteries

“…Besides, rechargeable Zn–air battery assembled by ZIF‐selenized Co 0.85 Se nanocrystal showed a narrow discharge/charge voltage gap (0.8 V) and stable cycling performance (180 h) at current density of 10 mA cm −2 235. Hybridizing with other functional materials such as graphene,236 Mxene,237 and metal oxides,238 MOFs‐derived nanocomposites further demonstrated better oxygen electrochemical performance.…”

MXene‐Based Composites: Synthesis and Applications in Rechargeable Batteries and Supercapacitors

“…In addition to metals, carbon-based materials, metal oxides, metal sulfides, and polymers, many other materials have been used to compound with MXene, such as metal-organic frameworks, [223] metal organics, [224,225] metal hydrides, [226,227] sulfur, [228] glass fibers, [229] graphene-like carbon nitride (g-C 3 N 4 ), [230] etc.…”

“…[223] In a similar manner, Luo et al synthesized Ti 3 C 2 T x /PVP-Sn(IV) composite. In a mixture of Co 2+ , Ti 3 C 2 T x , and 1,4-benzene dicarboxylate (BDC), functional groups adsorbed on the Ti 3 C 2 T x surface cause Ti 3 C 2 T x to be negatively charged, Co 2+ ions were adsorbed onto Ti 3 C 2 T x , which enables a continuous reaction of BDC with the adsorbed Co 2+ ions to form MOF, thus forming the Ti 3 C 2 T x /CoBDC (MOF) composite.…”

“…Moreover, the hydrophilic or oxygen-terminated groups are firmly attached to the surface of the composite giving it a contact angle of 14.1°, which is an advantageous reserve of transformational energy in inorganic electrolyte. [228] In summary, in addition to metals, carbon-based materials, metal oxides, metal sulfides, and polymers, many other materials have been used to compound with MXene, such as metal-organic frameworks, [223] metal organics, [224,225] metal hydrides, [226,227] sulfur, [228] glass fibers, [229] graphene-like carbon nitride (g-C 3 N 4 ), [230] etc., in rechargeable batteries system and have shown remarkable electrical performance. [232] Both MgH 2 and NaAlH 4 have a reversible hydrogen storage property, so Liu et al and Wu et al combined Ti 3 C 2 T x with these metal hydrides by ball milling to obtain a composite material with excellent hydrogen storage properties.…”