The Synthesis of Hexaazatrinaphthylene‐Based 2D Conjugated Copper Metal‐Organic Framework for Highly Selective and Stable Electroreduction of CO₂ to Methane

Abstract

2D conjugated MOFs have attracted significant interests in recent years owing to their special structural features and promising physical and chemical properties. These intriguing attributes, to a large extent, stem from the nature of incorporated ligands. The available ligands for the construction of 2D conjugated MOFs are still limited, especially those that have heteroatoms included and exposed to the pores. In this work, we designed and synthesized a highly symmetric hexaazatrinaphthylene (HATNA)-based ligand with two different coordination sites. Through selective coordination, a highly crystalline and porous 2D conjugated copper metal-organic framework was constructed. Due to the synergic effects of HATNA and copper catecholate node, this HATNAbased 2D conjugated MOF can mediate the electrocatalytic reduction of CO 2 to methane with high selectivity of 78 % at high current density of 8.2 milliamperes per square centimetre (mA cm À2 ) for long durability over 12 hours.

A novel 3D terbium metal–organic framework as a heterogeneous Lewis acid catalyst for the cyanosilylation of aldehyde

“…Two- or three-dimensional porous metal–organic frameworks (MOFs) are an important kind of functional materials, which have an inherent advantage of being readily self-assembled via suitable organic linkers and inorganic metal ions/clusters. 1 Due to the unlimited coordinated bonds through the metal ions/clusters and the organic linkers, they usually appear as infinite multiple dimension networks, which endow the MOFs with diversified structures and functional applications. 2 Meanwhile they usually have high porosity, large surface area and considerable capacity, 3 which offer a wide range of potential applications in gas storage, 4 gas capture, 5 separation, 6 chemical catalysis, 7 luminescence, 8 magnetism, 9 drug delivery, 10 and so on.…”

Low‐dimensional material supported single‐atom catalysts for electrochemical CO2 reduction

“…The porosity and diversity of MOFs make them not only can serve as the precursors for synthesizing SACs but also can be directly used as the SACs support for ECR. [113][114][115][116] However, a significant hurdle in the door to use MOFs as support for ECR is the poor conductivity of MOFs, which inevitably leads to low current density and suboptimal efficiency. To this end, it is highly desired to develop LD MOFs with highly single-active sites for the ECR.…”

Utilizing Metal-Organic Frameworks to Achieve High-Efficiency CO2 Electroreduction

“…When it comes to the methane transformation, Liu et al developed and synthesized a hexaazatrinaphthylene (HATNA)-based ligand with two distinct coordination sites that are very symmetric [42]. This HATNA-Cu-MOF can mediate the electrocatalytic CO 2 RR to methane with good selectivity of 78 % and extended durability of over 12 hours at a high current density of 8.2 mA cm -2 .…”

“…7f, is comparable to HATNA-Cu-MOF, which has a maximum of 25 % at -1.5 V. At -1.5 V, HATNA-Cu-MOF has 3 times greater CH 4 selectivity than the model compound, indicating the impact of a 2D conjugated extended framework on product selectivity. between HATNA-Cu-MOF, HATNA-6OH and the model compound [42].…”