Acridine functionalized covalent organic frameworks (COFs) as photocatalysts for metallaphotocatalytic C–N cross-coupling

Covalent organic frameworks (COFs) are structurally tuneable, porous and crystalline polymers constructed through the covalent attachment of small organic building blocks as elementary units. Using the myriad of such building blocks, a broad spectrum of functionalities has been applied for COF syntheses for broad applications, including heterogeneous catalysis. Herein, we report the synthesis of a new family of porous and crystalline COFs using a novel acridine linker and benzene-1,3,5-tricarbaldehyde derivatives bearing a variable number of hydroxy groups. With the broad absorption in the visible light region the COFs were applied as photocatalysts in metallaphotocatalytic C–N cross coupling. The fully β-ketoenamine linked COF showed the highest activity, due to the increased charge separation upon irradiation. The COF showed good to excellent yields for several aryl bromides, good recyclability and even catalysed the organic transformation in presence of green light as energy source

Covalent Organic Framework (COF) derived Ni-N-C Catalysts for Electrochemical CO₂ Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites

Electrochemical CO2 reduction is a potential approach to convert CO2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO2 electro-reduction to CO, and the single-site Ni-Nx motif is believed as the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-Nx content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency

Covalent Organic Framework (COF) derived Ni-N-C Catalysts for Electrochemical CO₂ Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites

Electrochemical CO2 reduction is a potential approach to convert CO2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO2 electro-reduction to CO, and the single-site Ni-Nx motif is believed as the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-Nx content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency

Magnetic and Photoluminescent Sensors Based on Metal-Organic Frameworks Built up from 2-aminoisonicotinate

Red Guipuzcoana de Ciencia, Tecnologia e Innovacion OF218/2018 University of Basque Country GIU 17/13 Basque Government IT1005-16 IT1291-19 IT1310-19 Junta de Andalucia FQM-394 Spanish Ministry of Science, Innovation and Universities (MCIU/AEI/FEDER, UE) PGC2018-102052-A-C22 PGC2018-102052-B-C21 MAT2016-75883-C2-1-P European Union (EU) ESFIn this work, three isostructural metal-organic frameworks based on frst row transition metal ions and 2-aminoisonicotinate (2ain) ligands, namely, {[M(μ-2ain)2]·DMF}n [MII=Co (1), Ni (2), Zn (3)], are evaluated for their sensing capacity of various solvents and metal ions by monitoring the modulation of their magnetic and photoluminescence properties. The crystal structure consists of an open diamond-like topological 3D framework that leaves huge voids, which allows crystallizing two-fold interpenetrated architecture that still retains large porosity. Magnetic measurements performed on 1 reveal the occurrence of feld-induced spin-glass behaviour characterized by a frequency-independent relaxation. Solvent-exchange experiments lead successfully to the replacement of lattice molecules by DMSO and MeOH, which, on its part, show dominating SIM behaviour with low blocking temperatures but substantially high energy barriers for the reversal of the magnetization. Photoluminescence studied at variable temperature on compound 3 show its capacity to provide bright blue emission under UV excitation, which proceeds through a ligand-centred charge transfer mechanism as confrmed by timedependent DFT calculations. Turn-of and/or shift of the emission is observed for suspensions of 3 in diferent solvents and aqueous solutions containing metal ions

Metal-assisted and solvent-mediated synthesis of two-dimensional triazine structures on gram scale

We thank the German Science Foundation (DFG) for financial support within the grants SFB 765 and SFB 658. M.F.G. and J.P.R. also acknowledge the support of the Cluster of Excellence “Matters of Activity. Image Space Material” funded by the DFG under Germany’s Excellence Strategy EXC 2025-390648296. Furthermore, A.T. acknowledges the DFG for funding within the project TH 1463/12-1. We thank Dr. Andreas Schäfer and Maiko Schulze for solid NMR experiments and we appreciate the effort of Vahid Ahmadi Soureshjani in MALDI-TOF experiments. We acknowledge M. Eng. Jörg M. Stockmann for operating the XPS instrument at the BAM and Prof. Stephanie Reich and Dr. Antonio Setaro for fruitful discussions. 2DTs-HRTEM and -EELS studies were conducted at the Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Spain. R.A. gratefully acknowledges the support from the Spanish Ministry of Economy and Competitiveness (MINECO) through project grant MAT2016-79776-P (AEI/FEDER, UE) and from the European Union H2020 programs ETN projects “Graphene Flagship” (785219 and 881603), FLAG-ERA - Graphene (MICINN) GATES (PCI2018-093137) and “ESTEEM3” (823717).Peer reviewe

Three-dimensional nitrogen-doped graphene supported molybdenum disulfide nanoparticles as an advanced catalyst for hydrogen evolution reaction

An efficient three-dimensional (3D) hybrid material of nitrogen-doped graphene sheets (N-RGO) supporting molybdenum disulfide (MoS2) nanoparticles with high-performance electrocatalytic activity for hydrogen evolution reaction (HER) is fabricated by using a facile hydrothermal route. Comprehensive microscopic and spectroscopic characterizations confirm the resulting hybrid material possesses a 3D crumpled few-layered graphene network structure decorated with MoS2 nanoparticles. Electrochemical characterization analysis reveals that the resulting hybrid material exhibits efficient electrocatalytic activity toward HER under acidic conditions with a low onset potential of 112 mV and a small Tafel slope of 44 mV per decade. The enhanced mechanism of electrocatalytic activity has been investigated in detail by controlling the elemental composition, electrical conductance and surface morphology of the 3D hybrid as well as Density Functional Theory (DFT) calculations. This demonstrates that the abundance of exposed active sulfur edge sites in the MoS2 and nitrogen active functional moieties in N-RGO are synergistically responsible for the catalytic activity, whilst the distinguished and coherent interface in MoS 2 /N-RGO facilitates the electron transfer during electrocatalysis. Our study gives insights into the physical/chemical mechanism of enhanced HER performance in MoS2/N-RGO hybrids and illustrates how to design and construct a 3D hybrid to maximize the catalytic efficiency

Experimental and computational approach of understanding the gas adsorption in amino functionalized interpenetrated metal organic frameworks (MOFs)

10.1039/c1jm13762jJournal of Materials Chemistry214417737-17745JMAC

Amino functionalized zeolitic tetrazolate framework (ZTF) with high capacity for storage of carbon dioxide

10.1039/c0cc04169fChemical Communications4772011-2013CHCO

Donor–acceptor covalent organic frameworks for visible light induced free radical polymerization

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 thieno[3,2-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.DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat