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.
Two‐dimensional conductive metal‐organic frameworks (2D‐c‐MOFs) have attracted extensive attention owing to their unique structures and physical‐chemical properties. However, the planarly extended structure of 2D‐c‐MOFs usually limited the accessibility of the active sites. Herein, we designed a triptycene‐based 2D vertically conductive MOF (2D‐vc‐MOF) by coordinating 2,3,6,7,14,15‐hexahydroxyltriptycene (HHTC) with Cu2+. The vertically extended 2D‐vc‐MOF(Cu) possesses a weak interlayer interaction, which leads to a facile exfoliation to the nanosheet. Compared with the classical 2D‐c‐MOFs with planarly extended 2D structures, 2D‐vc‐MOF(Cu) exhibits a 100 % increased catalytic activity in terms of turnover number and a two‐fold increased selectivity. Density functional theory (DFT) calculations further revealed that higher activity originated from the lower energy barriers of the vertically extended 2D structures during the CO2 reduction reaction process.
Ag triangle-nanoplates and potassium cations can synergistically promote electrocatalytic nitrogen fixation in aqueous solutions under ambient conditions.
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.
Electrochemical
CO2 reduction reaction (CO2RR) yielding value-added
chemicals provides a sustainable approach
for renewable energy storage and conversion. Bismuth-based catalysts
prove to be promising candidates for converting CO2 and
water into formate but still suffer from poor selectivity and activity
and/or sluggish kinetics. Here, we report that ultrathin porous Bi
nanosheets (Bi-PNS) can be prepared through a controlled solvothermal
protocol. Compared with smooth Bi nanoparticles (Bi-NPs), the ultrathin,
rough, and porous Bi-PNS provide more active sites with higher intrinsic
reactivities for CO2RR. Moreover, such high activity further
increases the local pH in the vicinity of the catalyst surfaces during
electrolysis and thus suppresses the competing hydrogen evolution
reaction. As a result, the Bi-PNS exhibit significantly boosted CO2RR properties, showing a Faradaic efficiency of 95% with an
effective current density of 45 mA cm–2 for formate
evolution at the potential of −1.0 V versus reversible hydrogen
electrode.
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