Covalent organic frameworks (COFs) have emerged as an important class of organic semiconductors and photocatalysts for the hydrogen evolution reaction (HER)from water. To optimize their ...photocatalytic activity, typically the organic moieties constituting the frameworks are considered and the most suitable combinations of them are searched for. However, the effect of the covalent linkage between these moieties on the photocatalytic performance has rarely been studied. Herein, we demonstrate that donor‐acceptor (D‐A) type imine‐linked COFs can produce hydrogen with a rate as high as 20.7 mmol g−1 h−1 under visible light irradiation, upon protonation of their imine linkages. A significant red‐shift in light absorbance, largely improved charge separation efficiency, and an increase in hydrophilicity triggered by protonation of the Schiff‐base moieties in the imine‐linked COFs, are responsible for the improved photocatalytic performance.
Protonation of imine‐linked COFs yields significant variations of their (opto)electronic properties and results in a largely enhanced performance in photocatalytic hydrogen evolution from water. This is attributed to an enhanced light absorption ability, charge separation efficiency, and hydrophilicity of imine‐linked COFs upon protonation.
A room‐temperature, visible‐light‐driven N‐centered iminyl radical‐mediated and redox‐neutral C−C single bond cleavage/radical addition cascade reaction of oxime esters and unsaturated systems has ...been accomplished. The strategy tolerates a wide range of O‐acyl oximes and unsaturated systems, such as alkenes, silyl enol ethers, alkynes, and isonitrile, enabling highly selective formation of various chemical bonds. This method thus provides an efficient approach to various diversely substituted cyano‐containing alkenes, ketones, carbocycles, and heterocycles.
A visible‐light‐driven room‐temperature N‐centered iminyl radical‐mediated and redox‐neutral C−C single bond cleavage/radical addition cascade reaction of oxime esters and unsaturated systems has been accomplished. The strategy tolerates a wide range of O‐acyl oximes and alkenes, silyl enol ethers, alkynes, and isonitrile. This method allows access to various cyano‐containing alkenes, ketones, carbocycles, and heterocycles.
Abstract
The fabrication of macroscopic objects from covalent organic frameworks (COFs) is challenging but of great significance to fully exploit their chemical functionality and porosity. Herein, ...COF/reduced graphene oxide (rGO) aerogels synthesized by a hydrothermal approach are presented. The COFs grow in situ along the surface of the 2D graphene sheets, which are stacked in a 3D fashion, forming an ultralight aerogel with a hierarchical porous structure after freeze-drying, which can be compressed and expanded several times without breaking. The COF/rGO aerogels show excellent absorption capacity (uptake of >200 g organic solvent/g aerogel), which can be used for removal of various organic liquids from water. Moreover, as active material of supercapacitor devices, the aerogel delivers a high capacitance of 269 F g
−1
at 0.5 A g
−1
and cycling stability over 5000 cycles.
0D/2D heterojunctions, especially quantum dots (QDs)/nanosheets (NSs) have attracted significant attention for use of photoexcited electrons/holes due to their high charge mobility. Herein, ...unprecedent heterojunctions of vanadate (AgVO3, BiVO4, InVO4 and CuV2O6) QDs/graphitic carbon nitride (g‐C3N4) NSs exhibiting multiple unique advances beyond traditional 0D/2D composites have been developed. The photoactive contribution, up‐conversion absorption, and nitrogen coordinating sites of g‐C3N4 NSs, highly dispersed vanadate nanocrystals, as well as the strong coupling and band alignment between them lead to superior visible‐light‐driven photoelectrochemical (PEC) and photocatalytic performance, competing with the best reported photocatalysts. This work is expected to provide a new concept to construct multifunctional 0D/2D nanocomposites for a large variety of opto‐electronic applications, not limited in photocatalysis.
Vanadate quantum dots including AgVO3, BiVO4, InVO4, and CuV2O6 were strongly coupled with graphitic carbon nitride nanosheets using an in situ growth strategy. These quantum dots displayed a much better visible‐light‐driven photoelectrochemical activity and photocatalytic degradation efficiency than single vanadate quantum dots, carbon nitride nanosheets or previously reported highly active photocatalysts.
Covalent organic frameworks (COFs) are promising materials for applications in photocatalysis, due to their conjugated, porous and chemically stable architectures. Alternating electron ...donor-acceptor-type structures are known to enhance charge carrier transport mobility and stability in polymers and are therefore also interesting building units for COFs used as photocatalysts but also as photoinitiator. In this work, two donor-acceptor COFs using electron deficient 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)trianiline and electron rich thiophene-based thieno3,2-
b
thiophene-2,5-dicarbaldehyde or 2,2′-bithiophene-5,5′-dicarbaldehyde linkers are presented. The resulting crystalline and porous COFs have been applied as photoinitiator for visible light induced free radical polymerization of methyl methacrylate (MMA) to poly-methyl methacrylate (PMMA). These results pave the way to the development of robust and heterogeneous systems for photochemistry that offers the transfer of radicals induced by visible light.
Crystalline and porous covalent organic frameworks (COFs) with donor-acceptor moieties in their backbone are utilized as initiators for visible light induced radical polymerization. The COFs are efficient photoinitiators, maintaining their structural integrity for several cycles.
Abstract
When new covalent organic frameworks (COFs) are designed, the main efforts are typically focused on selecting specific building blocks with certain geometries and properties to control the ...structure and function of the final COFs. The nature of the linkage (imine, boroxine, vinyl, etc.) between these building blocks naturally also defines their properties. However, besides the linkage type, the orientation,
i.e
., the constitutional isomerism of these linkages, has rarely been considered so far as an essential aspect. In this work, three pairs of constitutionally isomeric imine-linked donor-acceptor (D-A) COFs are synthesized, which are different in the orientation of the imine bonds (D-C=N-A (DCNA) and D-N=C-A (DNCA)). The constitutional isomers show substantial differences in their photophysical properties and consequently in their photocatalytic performance. Indeed, all DCNA COFs show enhanced photocatalytic H
2
evolution performance than the corresponding DNCA COFs. Besides the imine COFs shown here, it can be concluded that the proposed concept of constitutional isomerism of linkages in COFs is quite universal and should be considered when designing and tuning the properties of COFs.
Poly(heptazine imides) hosting cobalt ions as countercations are presented as promising electrocatalysts for the oxygen evolution reaction (OER). A facile mixed‐salt melt‐assisted condensation is ...developed to prepare such cobalt poly(heptazine imides) (PHI‐Co). The Co ions can be introduced in well‐controlled amounts using this method, and are shown to be atomically dispersed within the imide‐linked heptazine matrix. When applied to electrocatalytic OER, PHI‐Co shows a remarkable activity with an overpotential of 324 mV and Tafel slope of 44 mV dec−1 in 1 m KOH.
Poly(heptazine imides) hosting cobalt ions (PHI‐Co) are synthesized by a mixed molten salt method. Due to the abundant, well‐distributed Co ions within the PHI matrix, these materials are promising electrocatalysts for the oxygen evolution reaction (OER) with an overpotential of 324 mV and Tafel slope of 44 mV dec−1 in 1 m KOH.
Metal carbides are promising materials for electrocatalytic reactions such as water electrolysis. However, for application in catalysis for the oxygen evolution reaction (OER), protection against ...oxidative corrosion, a high surface area with facile electrolyte access, and control over the exposed active surface sites are highly desirable. This study concerns a new method for the synthesis of porous tungsten carbide films with template‐controlled porosity that are surface‐modified with thin layers of nickel oxide (NiO) to obtain active and stable OER catalysts. The method relies on the synthesis of soft‐templated mesoporous tungsten oxide (mp. WOx) films, a pseudomorphic transformation into mesoporous tungsten carbide (mp. WCx), and a subsequent shape‐conformal deposition of finely dispersed NiO species by atomic layer deposition (ALD). As theoretically predicted by density functional theory (DFT) calculations, the highly conductive carbide support promotes the conversion of Ni2+ into Ni3+, leading to remarkably improved utilization of OER‐active sites in alkaline medium. The obtained Ni mass‐specific activity is about 280 times that of mesoporous NiOx (mp. NiOx) films. The NiO‐coated WCx catalyst achieves an outstanding mass‐specific activity of 1989 A gNi−1 in a rotating‐disc electrode (RDE) setup at 25 °C using 0.1 m KOH as the electrolyte.
ALD‐fashioned: A highly active and stable electrocatalyst for the alkaline oxygen evolution reaction based on a mesoporous tungsten carbide film surface‐modified with a conformal NiO layer by atomic layer deposition is presented. The electrocatalyst reaches a record high mass activity of 1989 A gNi−1 in 0.1 m KOH electrolyte, which is more than 280 times higher than that of a mesoporous NiOx film.
An iridium dihydride pincer complex IrH2(POCOP) is immobilized in a hydroxy‐functionalized microporous polymer network using the concepts of surface organometallic chemistry. The introduction of this ...novel, truly innocent support with remote OH‐groups enables the formation of isolated active metal sites embedded in a chemically robust and highly inert environment. The catalyst maintained high porosity and without prior activation exhibited efficacy in the gas phase hydrogenation of ethene and propene at room temperature and low pressure. The catalyst can be recycled for at least four times.
An iridium pincer complex, immobilized in a microporous polymer network, has been used as an efficient and recyclable catalyst for the gas phase hydrogenation of ethene and propene at room temperature and low pressure.
Poly(heptazine imides) hosting cobalt ions as countercations are presented as promising electrocatalysts for the oxygen evolution reaction (OER). A facile mixed-salt melt-assisted condensation is ...developed to prepare such cobalt poly(heptazine imides) (PHI-Co). The Co ions can be introduced in well-controlled amounts using this method, and are shown to be atomically dispersed within the imide-linked heptazine matrix. When applied to electrocatalytic OER, PHI-Co shows a remarkable activity with an overpotential of 324 mV and Tafel slope of 44 mV dec
in 1 m KOH.
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