An rht-type metal-organic framework (MOF) prepared from M(2)(carboxylate)(4) (M = Cu, Co) paddlewheel clusters and a flexible C(3)-symmetric hexacarboxylate ligand with acylamide groups exhibits larger CO(2) uptake, an enhanced heat of adsorption, and higher selectivity toward CO(2)/N(2) in comparison with what was previously observed for an analogous MOF with alkyne groups.

An amide-inserted metal-organic framework (NJU-Bai3) presents high storage and high selectivity toward CO(2) and combines these two interesting characters which strongly support our expectation that amide groups can significantly enhance the CO(2) binding ability and selectivity of MOFs.

Two mesoporous and flexible acylamide-functionalized rht-type MOFs exhibit not only high excess unsaturation CO(2) uptake (157 wt%) at 20 bar and 273 K, but also good selectivity of CO(2)/CH(4) (8.6) and CO(2)/N(2) (34.3). The advantages of acylamide groups for CO(2) capture have been further confirmed by GCMC and first-principles calculations.

methods to suppress the release of CO 2 , using photo-or electrocatalysis. [7-10] Particularly, the electrocatalytic reduction can be a promising method for managing the global carbon balance and issues regarding energy generation, as it can convert CO 2 to C1 or C2 chemical products as fuel. [11,12] However, this reduction process faces significant challenges due to the chemical inertness of CO 2 , as there are high thermodynamic and kinetic barriers to obtain a successful electrocatalytic reduction of CO 2. Additionally, the CO 2-to-CO pathway is usually selected, because CO is the raw material of the Fisher-Tropsch process and other added-value hydrocarbons with wide distribution (C1-C3 products). [13-17] On the other hand, the competing hydrogen evolution reaction (HER) and the stable CO bond of CO 2 can optimize the catalytic system through the activity and selectivity during the CO 2-to-CO electrocatalytic process. [18-21] Metal-and nitrogen-coordinated materials dispersed on carbon matrix (M-N x-C), with a high density of active sites, have attracted increased interests in the field of electrocatalytic reduction of CO 2 , due to their low cost and high abundance of raw material. [22-28] Nitrogen coordinated metal as catalytic sites that could be designable to fit the especial functionality. As is already known, the Cu-N x-C sites can have much more interaction with the oxygen of the CO 2 , which can enhance the enthalpy of the CO 2 and inhibit the HER but results in sluggish kinetics of the CO 2 + H + + e − → COOH* process. [29,30] Besides, the Fe-N x-C materials are often applied in CO 2 reduction with low onset potential. Nevertheless, the desorption of *CO into the gas phase can reduce the reactivity, due to the strong binding of CO to the Fe-N x-C sites in the step of COOH* + H + + e − → CO* + H 2 O and CO* → CO+ *. [31-33] Considering the issues mentioned above, to maximize the potential of single-atom catalysts for multistep catalytic reaction, we design and synthesize biatomic active sites of Cu-Fe-N 6-C catalyst by pyrolysis of PcCu-Fe-ZIF-8 under an argon atmosphere at 1000 °C (the detail can be found in the Supporting Information). The configuration and coordination environment of the diatomic catalyst are evidenced by the aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (STEM) (AC HAADF-STEM) and X-ray adsorption spectroscopy. The experimental results show To relieve the green gas emission and involve the carbon neutral cycle, electrochemical reduction of CO 2 attracts more and more attention. Herein, a biatomic site catalyst of Cu-Fe coordinated with the nitrogen, which is doped in the carbon matrix (denoted as Cu-Fe-N 6-C), is designed. The as-obtained Cu-Fe-N 6-C exhibits higher performance than that of Cu-N-C and Fe-N-C, owing to bimetallic sites, proving synergistic functions based on different molecules and their interfaces. Cu-Fe-N 6-C shows high selectivity toward CO, with high Faradaic efficiency (98% at −0.7 V), and maintaining 98% of its in...

A new expanded microporous NbO-type metal-organic framework [Cu 2 (BDPT 42 )] n with inserted acylamide groups has been designed and synthesized, which shows both a large CO 2 -uptake capacity (156.4 cm 3 g 21 at 1 bar) and a high selectivity for CO 2 over N 2 (39.8) and CH 4 (7.2) at 273 K.