Conversion from CO2 to C2H4 is important for the development of energy and environment, but high barrier hydrogenation *CO intermediate C–C coupling step tend result in C1 compounds as main product thus restrict generation C2H4. Here, we report a metal–organic framework (denoted PcCu-Cu-O), composed 2,3,9,10,16,17,23,24-octahydroxyphthalo-cyaninato)copper(II) (PcCu-(OH)8) ligands square-planar CuO4 nodes, electrocatalyst Compared with discrete molecular copper-phthalocyanine (Faradaic...

Reducing CO2 into fuels via photochemical reactions relies on highly efficient photocatalytic systems. Herein, we report a new and system for reduction. Driven by electrostatic attraction, an anionic metal-organic framework Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) as host cationic photosensitizer [Ru(phen)3]2+ (phen 1,10-phenanthroline) guest were self-assembled Ru@Cu-HHTP, which showed high activity reduction under laboratory light source (CO production rate of 130(5) mmol g-1...

Electroreduction of CO2 to acetate provides a promising strategy reduce emissions and store renewable energy, but is usually by-product. Here, we show stable conductive two-dimensional phthalocyanine-based covalent-organic framework (COF) as an electrocatalyst for reduction with single-product Faradaic efficiency (FE) 90.3(2)% at -0.8 V (vs. RHE) current density 12.5 mA cm-2 in 0.1 M KHCO3 solution. No obvious degradation was observed over 80 hours continuous operation. Combined the...

It is of great significance to reveal the influence small differences in coordination environments metal ions catalytic active centers on selectivity products electrocatalytic CO2 reduction reaction (CO2RR). Here, two types metal–organic frameworks (MOFs) based square-pyramidal CuO5 and square-planar CuO4 nodes, respectively, are compared regard their performances CO2RR. The MOF (Cu-DBC, H8DBC = dibenzo-[g,p]chrysene-2,3,6,7,10,11,14,15-octaol) constructed by nodes catechol-derived ligands...

Crystalline porous materials sustained by supramolecular interactions (e.g., π–π stacking interactions) are a type of molecular crystals showing considerable stability, but their applications rarely reported due to the high difficulty construction. Herein, stable framework formed trinuclear copper(I) compound [Cu3(HBtz)3(Btz)Cl2] (CuBtz, HBtz = benzotriazole) with pyrazolate-bridged dicopper(I) sites is and employed for electrochemical CO2 reduction, an impressive performance 73.7 ± 2.8%...

Electroreduction of CO2 to CO is a promising approach for the cycling use , while it still suffers from impractical current density and durability. Here we report single-atom nanozyme (Ni-N5 -C) that achieves industrial-scale performance -to-CO conversion with Faradaic efficiency (FE) exceeded 97 % over -0.8--2.4 V vs. RHE. The at -2.4 RHE reached maximum 1.23 A cm-2 (turnover frequency 69.7 s-1 ) an FE 99.6 %. No obvious degradation was observed 100 hours continuous operation. Compared...

Conversion from CO2 to the more desirable and valuable C2+ products under neutral conditions is important for development of energy environment, but it a challenging work. In this work, we demonstrate that bi-copper sites on crystal surface metal–organic framework Cu-HITP (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) are very suitable catalyzing low-energy pathway *CO coupling with *COH form *OCCOH. The in situ infrared spectroscopy, theoretic calculations, controlled experiments show...

It is crucial to achieve continuous production of highly concentrated and pure C2 chemicals through the electrochemical CO2 reduction reaction (eCO2RR) for artificial carbon cycling, yet it has remained unattainable until now. Despite one-pot tandem catalysis (dividing eCO2RR into two catalytical reactions CO C2) offering potential significantly enhancing efficiency, its mechanism remains unclear performance unsatisfactory. Herein, we selected different CO2-to-CO catalysts CO-to-acetate...

High-purity CO2 rather than dilute (15 vol %, CO2/N2/O2 = 15:80:5, v/v/v) similar to the flue gas is currently used as feedstock for electroreduction of CO2, and liquid products are usually mixed up with cathode electrolyte, resulting in high product separation costs. In this work, we showed that a microporous conductive Bi-based metal–organic framework (Bi-HHTP, HHTP 2,3,6,7,10,11-hexahydroxytriphenylene) can not only efficiently capture from under humidity but also catalyze adsorbed into...

Here we review the synthetic methods and applications of 2D-MOF architectures, especially some novel strategies applications. In addition, outlook architectures are also proposed.

High-efficiency electrocatalysts for CO2 reduction reaction are extremely desirable to produce valuable hydrocarbon productions, as well addressing the current environmental challenges. In this work, we introduce a Cu-based metal–organic framework catalyst efficient and selective of CH4 in neutral aqueous electrolytes. Detailed examination [Cu4ZnCl4(btdd)3] (Cu4-MFU-4l, H2btdd = bis(1H-1,2,3-triazolo-[4,5-b],[4′,5′-i])dibenzo-[1,4]-dioxin) revealed highest activity yielding methane with...

The electrochemical reduction of CO2 into multicarbon (C2+) products is important and challenging. Here, we show a stable low-cost metal-azolate framework, namely, [Cu3(μ3-OH)(μ3-trz)3(OH)2(H2O)4] (Cutrz, Htrz = 1,2,4-triazole), based on the cyclic trinuclear clusters {Cu3(μ3-OH)(trz)3}2+ as electrocatalyst for highly efficient selective electroreduction to C2+ hydrocarbons (Faradaic efficiencies C2H4 are 80 50%, respectively) current density 280 mA cm–2 at potential −0.8 V vs reversible...

Integration of CO2 capture capability from simulated flue gas and electrochemical reduction reaction (eCO2 RR) active sites into a catalyst is promising cost-effective strategy for carbon neutrality, but great difficulty. Herein, combining the mixed breakthrough experiments eCO2 RR tests, we showed that an Ag12 cluster-based metal-organic framework (1-NH2 , aka bpy-NH2 ), simultaneously possessing as "CO2 relays" sites, can not only utilize its micropores to efficiently (CO2 : N2 =15 85, at...

Melt-quenched glasses of organic-inorganic hybrid crystals, i.e., glasses, have attracted increasing attention as an emerging class materials with beneficial processability and formability in the past years. Herein, we present a new crystal, (Ph3 PEt)3 [Ni(NCS)5 ] (1, Ph3 PEt+ =ethyl(triphenyl)phosphonium), crystallizing polar space group P1 exhibiting thermal-induced reversible crystal-liquid-glass-crystal transitions relatively low melting temperature 132 °C, glass-transition 40...

It is challenging and important to achieve high performance for an electrochemical CO2 reduction reaction (eCO2RR) yield CH4 under neutral conditions. So far, most of the reported active sites eCO2RR are single metal sites; performances far below commercial requirements. Herein, we a nanosheet metal-organic layer in single-layer, namely, [Cu2(obpy)2] (Cuobpy-SL, Hobpy = 1H-[2,2']bipyridinyl-6-one), possessing dicopper(I) aqueous solution. Detailed examination Cuobpy-SL revealed production...

Since the discovery of metal–organic frameworks (MOFs), covalent–organic (COFs) and zeolite–imidazole (ZIFs), many their outstanding properties have been explored such as large specific surface area, significant gas adsorption, high catalytic activity.

Here, we report an improved tandem catalytic mechanism for electroreduction of CO2 to C2H4. Cu(111) nanoparticles with average size 5.5 ± 0.9 nm were anchored on a conductive Cu-based metal-organic framework (Cu-THQ) by in situ electrochemical synthesis. Compared nanoparticles, the C2H4 faradaic efficiency catalyst Cu(111)@Cu-THQ was increased doubly.

Abstract Electroreduction of CO 2 to acetate provides a promising strategy reduce emissions and store renewable energy, but is usually by‐product. Here, we show stable conductive two‐dimensional phthalocyanine‐based covalent‐organic framework (COF) as an electrocatalyst for reduction with single‐product Faradaic efficiency (FE) 90.3(2)% at −0.8 V (vs. RHE) current density 12.5 mA cm −2 in 0.1 M KHCO 3 solution. No obvious degradation was observed over 80 hours continuous operation. Combined...

Abstract In recent decades, metal–organic frameworks (MOFs) have achieved rapid development owing to the considerable concern from researchers. As one of most intensely studied MOFs, HKUST‐1 has shown remarkable performance which is considered feasible apply in actual applications. However, weak mechanical properties and water instability hinder its are mainly ascribed lattice defects surface barriers that impede mass transfer molecular diffusion as well electronic transmission. This review...

Exploring the interactions between oxygen molecules and metal sites has been a significant topic. Most previous studies concentrated on enzyme-mimicking interacting with O2 to form M-OO species, leaving development of new types O2-activating novel adsorption mechanisms largely overlooked. In this study, we reported an Fe(II)-doped metal-organic framework (MOF) [Fe3Zn2H4(bibtz)3] (MAF-203, H2bibtz = 1H,1'H-5,5'-bibenzo[d][1,2,3]triazole), featuring unprecedented tetrahedral Fe(II)HN3 site....