Crystalline and porous covalent organic frameworks (COFs) metal-organic (MOFs) materials have attracted enormous attention in the field of photocatalytic H2 evolution due to their long-range order structures, large surface areas, outstanding visible light absorbance, tunable band gaps. In this work, we successfully integrated two-dimensional (2D) COF with stable MOF. By covalently anchoring NH2 -UiO-66 onto TpPa-1-COF, a new type MOF/COF hybrid high area, framework, crystallinity was...

Imidazole molecules were frequently incorporated into porous materials to improve their proton conductivity. To investigate how different arrangements of imidazoles in metal–organic frameworks (MOFs) affect the overall conduction, we designed and prepared a MOF-based model system. It includes an Fe–MOF as blank, imidazole@Fe–MOF (Im@Fe–MOF) with physically adsorbed imidazole, imidazole–Fe–MOF (Im–Fe–MOF), which contains chemically coordinated imidazole molecules. The parent Fe–MOF,...

Solar energy-driven conversion of CO2 into fuels with H2 O as a sacrificial agent is challenging research field in photosynthesis. Herein, series crystalline porphyrin-tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used photocatalysts for reducing O, the absence additional photosensitizer, agents, noble metal co-catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by bonding, resulting separated holes, respectively,...

A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors create stable organic-inorganic Z-scheme heterojunctions for artificial photosynthesis is presented. series of COF-semiconductor photocatalysts combining water-oxidation (TiO2 , Bi2 WO6 and α-Fe2 O3 ) CO2 reduction COFs (COF-316/318) was synthesized exhibited high photocatalytic -to-CO conversion efficiencies (up 69.67 μmol g-1 h-1 ), H2 O as the electron donor in gas-solid reduction, without...

Abstract Efficient conversion of carbon dioxide (CO 2 ) into value-added products is essential for clean energy research. Design stable, selective, and powerful electrocatalysts CO reduction reaction RR) highly desirable yet largely unmet. In this work, a series metalloporphyrin-tetrathiafulvalene based covalent organic frameworks (M-TTCOFs) are designed. Tetrathiafulvalene, serving as electron donator or carrier, can construct an oriented transmission pathway with metalloporphyrin....

Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion single-cluster catalyst is challenging. In this work, for first time, we present versatile strategy uniformly dispersed polyoxometalates (POMs) covalent organic frameworks (COFs) through confining POM cluster into regular nanopores COF by linkage. These COF-POM composites combine properties light absorption, electron transfer, and suitable catalytic active...

Abstract In this work, we rationally designed a series of crystalline and stable dioxin‐linked metallophthalocyanine covalent organic frameworks (COFs; MPc‐TFPN COF, M=Ni, Co, Zn) under the guidance reticular chemistry. As novel single‐site catalysts (SSCs), NiPc/CoPc‐TFPN COF exhibited outstanding activity selectivity for electrocatalytic CO 2 reduction (ECR; Faradaic efficiency (FE )=99.8(±1.24) %/ 96.1(±1.25) % COF). More importantly, when coupled with light, FE current density ( j ) were...

Abstract A series of stable heterometallic Fe 2 M cluster‐based MOFs ( NNU‐31‐M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion CO and H O into HCOOH without assistance additional sacrificial agent photosensitizer. The cluster units photosensitive ligands excited by visible light generate separated electrons holes. Then, low‐valent metal accepts to reduce high‐valent uses holes oxidize O. This is first MOF photocatalyst system finish artificial...

Solar-driven overall water splitting is an ideal way to generate renewable energy while still challenging. For the first time, this work combined covalent organic frameworks (COFs) and piezoelectric material by linkages form Z-scheme core@shell heterostructure for splitting. Benefiting from synergistic effect between polarized electric field photo-generated charges, as well precise adjustment of shell thickness, carrier separation utilization efficiency greatly improved. The optimal BiFeO3...

Covalent organic frameworks (COFs) are an emerging type of crystalline and porous photocatalysts for hydrogen evolution, however, the overall water splitting activity COFs is rarely known. In this work, we firstly realized β-ketoamine by systematically engineering N-sites, architecture, morphology. By in situ incorporating sub-nanometer platinum (Pt) nanoparticles co-catalyst into pores nanosheets, both Pt@TpBpy-NS Pt@TpBpy-2-NS show visible-light-driven activity, with optimal H

2D nanomaterials with flexibly modifiable surfaces are highly sought after for various applications, especially in room-temperature chemiresistive gas sensing. Here, we have prepared a series of COF (porphyrin-based nanosheets (NS)) that enabled sensitive and specific-sensing NO2 at room temperature. Different from the traditional sensing materials, H2 -TPCOF was designed largely reduced interlayer interaction predesigned porphyrin rings as sites on its post-metallization. After...

Abstract Metal–covalent organic frameworks (MCOFs) have been recently received wide attention owing to the homogeneous distribution of active metal centers that are beneficial for enhancing application potentials. However, complex based functional building blocks MCOFs synthesis limited. Herein, two new (Ni‐Py‐COF and Ni‐Bn‐COF) were constructed via a novel nickel glyoximate block. Splendid photocatalytic activity on hydrogen evolution from water great long‐term recyclability achieved using...

Artificial photosynthetic diluted CO2 reduction directly driven by natural sunlight is a challenging, but promising way to realize carbon-resources recycling utilization. Herein, three-in-one photocatalytic system of enrichment, and H2 O oxidation sites designed for reduction. A Zn-Salen-based covalent organic framework (Zn-S-COF) with reductive synthesized; then, ionic liquids (ILs) are loaded into the pores. As result, [Emim]BF4 @Zn-S-COF shows visible-light-driven -to-CO conversion rate...

The selective photo-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is important due its substitute-role in polyester-fabrication. Here, a titanium-cluster based metal-covalent organic framework nanosheet has been synthesized through the covalent-coupling between Ti6 -NH2 and benzotrithiophene tricarbaldehyde (BTT). integration them endows with visible-light-adsorption region, effective electron-hole separation-efficiency suitable ability....

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy)32+ /Fe(bpy)32+ ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer suitable band gap for highly photocatalytic hydrogen (H2 evolution. Rubpy-ZnPor COF...

Covalent organic frameworks (COFs), with the features of flexible structure regulation and easy introduction functional groups, have aroused broad interest in field photocatalysis. However, due to low light absorption intensity, photoelectron conversion efficiency, lack suitable active sites, it remains a great challenge achieve efficient photocatalytic aerobic oxidation reactions. Herein, based on reticular chemistry, we rationally designed series three-motif molecular junction type COFs,...

Electrocatalytic CO2 reduction (ECR) to high value-added chemicals by using renewable electricity presents a promising strategy realize "carbon neutrality". However, the ECR system is still limited its low current density and poor utilization efficiency. Herein, confinement effect of covalent organic frameworks (COFs) confine in-situ growth metal nanoclusters (NCs), we develop series Cu NCs encapsulated on COF catalysts ([email protected]) for ECR. Among them, [email protected] as gas...

The precise tuning of components, spatial orientations, or connection modes for redox units is vital gaining deep insight into efficient artificial photosynthetic overall reaction, yet it still hard achieve heterojunction photocatalysts. Here, we have developed a series molecular junction covalent organic frameworks (COFs) (M-TTCOF-Zn, M = Bi, Tri, and Tetra) reaction. between TAPP-Zn multidentate TTF endows various water photo-oxidation (multidentate TTF) CO2 photoreduction (TAPP-Zn)...

The high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO2 photoreduction reaction. However, systematic studies on structure-functional relationship regarding above based precisely structure model rarely reported. Herein, as a proof-of-concept, we developed new strategy evaluation of by controlling relative electron-deficient (ED) electron-rich (ER) intensity monomer at molecular level three...

In recent years, significant progress has been achieved in the field of three-dimensional covalent organic frameworks (3D COFs). However, there is still a great challenge to use flexible building units synthesize high-connectivity 3D COFs. this work, we showed that [6 + 3] COFs could be constructed by inducing highly planar blocks from C3 antitriangular prismed blocks. Herein, two with spn topology based on cyclotriphosphazene were and denoted as TAA/TAB-CTP-COF, their redox ability...

Abstract Solar energy‐driven conversion of CO 2 into fuels with H O as a sacrificial agent is challenging research field in photosynthesis. Herein, series crystalline porphyrin‐tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used photocatalysts for reducing O, the absence additional photosensitizer, agents, noble metal co‐catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by bonding, resulting separated holes,...

The sluggish kinetics and unclear mechanism have significantly hindered the development of Li-CO2 batteries. Here, a battery cathode catalyst based on porphyrin-based covalent organic framework (TTCOF-Mn) with single metal sites is reported to reveal intrinsic catalytic aprotic CO2 conversion from molecular level. TTCOF-Mn exhibits low overpotential 1.07 V at 100 mA/g as well excellent stability 300 mA/g, which one best catalysts date. unique features including uniform single-Mn(II)-sites,...