Preparation of Versatile, Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

10.26434/chemrxiv.14075390.v1 ◽

2021 ◽

Author(s):

Miguel A. Rivero-Crespo ◽

Georgios Toupalas ◽

Bill Morandi

Keyword(s):

High Surface ◽

Building Blocks ◽

Polyphenylene Sulfide ◽

Extreme Resistance ◽

Surface Areas ◽

Metal Capture ◽

2D And 3D ◽

Metal Sensing ◽

Single Material ◽

Porous Poly

Porous organic frameworks have shown a number of promising properties; however, their industrial application is usually hampered due to the lability of their linkages (imine, boroxine, etc.). Inspired by the outstanding chemical, mechanical and thermal resistance of the 1D polymer polyphenylene sulfide (PPS), we hypothesized that 2D and 3D poly-arylthioether frameworks would merge the attractive features common to porous frameworks and PPS in a single material. Herein, we report a Pd-catalysed C–S/C–S metathesis-based method to prepare new porous poly-arylthioether frameworks in good yields. The self-correcting nature of the process has enabled the synthesis of new, robust materials with high surface areas. Despite the frameworks’ extreme resistance to harsh chemicals, they can be fully recycled to recover the original building blocks using the same catalytic reaction. In addition, we demonstrate preliminary results showing that these materials have great potential in several environmentally relevant applications including metal capture, metal sensing and heterogeneous catalysis. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new materials.

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A Highly Crystalline Anthracene-Based MOF-74 Series Featuring Electrical Conductivity and Luminescence

10.26434/chemrxiv.8222492 ◽

2019 ◽

Author(s):

Patricia Scheurle ◽

Andre Mähringer ◽

Andreas Jakowetz ◽

Pouya Hosseini ◽

Alexander Richter ◽

...

Keyword(s):

Electrical Conductivity ◽

Metal Ions ◽

Light Emission ◽

Block Design ◽

High Surface ◽

Visible Spectrum ◽

Building Blocks ◽

Divalent Metal Ions ◽

Conductivity Enhancement ◽

Surface Areas

Recently, a small group of metal-organic frameworks (MOFs) has been discovered featuring substantial charge transport properties and electrical conductivity, hence promising to broaden the scope of potential MOF applications in fields such as batteries, fuel cells and supercapacitors. In combination with light emission, electroactive MOFs are intriguing candidates for chemical sensing and optoelectronic applications. Here, we incorporated anthracene-based building blocks into the MOF-74 topology with five different divalent metal ions, that is, Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, resulting in a series of highly crystalline MOFs, coined ANMOF-74(M). This series of MOFs features substantial photoluminescence, with ANMOF-74(Zn) emitting across the whole visible spectrum. The materials moreover combine this photoluminescence with high surface areas and electrical conductivity. Compared to the original MOF-74 materials constructed from 2,5-dihydroxy terephthalic acid and the same metal ions Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, we observed a conductivity enhancement of up to six orders of magnitude. Our results point towards the importance of building block design and the careful choice of the embedded MOF topology for obtaining materials with desired properties such as photoluminescence and electrical conductivity.

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Metal Nanotube/Nanowire-Based Unsupported Network Electrocatalysts

Catalysts ◽

10.3390/catal8120597 ◽

2018 ◽

Vol 8 (12) ◽

pp. 597 ◽

Cited By ~ 8

Author(s):

Falk Muench

Keyword(s):

Network Architecture ◽

High Surface ◽

High Surface Area ◽

Building Blocks ◽

Free Standing ◽

Additional Processing ◽

Metal Nanotubes ◽

The Stability ◽

Synthetic Approaches ◽

2D And 3D

Combining 1D metal nanotubes and nanowires into cross-linked 2D and 3D architectures represents an attractive design strategy for creating tailored unsupported catalysts. Such materials complement the functionality and high surface area of the nanoscale building blocks with the stability, continuous conduction pathways, efficient mass transfer, and convenient handling of a free-standing, interconnected, open-porous superstructure. This review summarizes synthetic approaches toward metal nano-networks of varying dimensionality, including the assembly of colloidal 1D nanostructures, the buildup of nanofibrous networks by electrospinning, and direct, template-assisted deposition methods. It is outlined how the nanostructure, porosity, network architecture, and composition of such materials can be tuned by the fabrication conditions and additional processing steps. Finally, it is shown how these synthetic tools can be employed for designing and optimizing self-supported metal nano-networks for application in electrocatalysis and related fields.

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Competitive formation between 2D and 3D metal-organic frameworks: insights into the selective formation and lamination of a 2D MOF

IUCrJ ◽

10.1107/s2052252519007760 ◽

2019 ◽

Vol 6 (4) ◽

pp. 681-687 ◽

Cited By ~ 1

Author(s):

Sojin Oh ◽

Jeehyun Park ◽

Moonhyun Oh

Keyword(s):

Active Sites ◽

High Surface ◽

Metal Organic Frameworks ◽

Building Blocks ◽

Structural Features ◽

Ultrasonic Dispersion ◽

Surface Areas ◽

Metal Organic ◽

Physical Stimuli ◽

Selective Formation

The structural dimension of metal–organic frameworks (MOFs) is of great importance in defining their properties and thus applications. In particular, 2D layered MOFs are of considerable interest because of their useful applications, which are facilitated by unique structural features of 2D materials, such as a large number of open active sites and high surface areas. Herein, this work demonstrates a methodology for the selective synthesis of a 2D layered MOF in the presence of the competitive formation of a 3D MOF. The ratio of the reactants, metal ions and organic building blocks used during the reaction is found to be critical for the selective formation of a 2D MOF, and is associated with its chemical composition. In addition, the well defined and uniform micro-sized 2D MOF particles are successfully synthesized in the presence of an ultrasonic dispersion. Moreover, the laminated 2D MOF layers are directly synthesized via a modified bottom-up lamination method, a combination of chemical and physical stimuli, in the presence of surfactant and ultrasonication.

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Multifunctional Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Porous Materials for CO2 Uptake and Iodine Adsorption

Polymers ◽

10.3390/polym13020221 ◽

2021 ◽

Vol 13 (2) ◽

pp. 221

Author(s):

Mohamed Gamal Mohamed ◽

Mei-Yin Tsai ◽

Chih-Feng Wang ◽

Chih-Feng Huang ◽

Martin Danko ◽

...

Keyword(s):

Porous Materials ◽

High Surface ◽

Polyhedral Oligomeric Silsesquioxane ◽

Building Blocks ◽

Co2 Uptake ◽

Thermal Stabilities ◽

Surface Areas ◽

Different Types ◽

Oligomeric Silsesquioxane ◽

High Carbon Dioxide

In this study, two different types of hybrid porous organic polymers (POPs), polyhedral oligomeric silsesquioxane tetraphenylpyrazine (POSS-TPP) and tetraphenylethene (POSS-TPE), were successfully synthesized through the Friedel−Crafts polymerization of tetraphenylpyrazine (TPP) and tetraphenylethene (TPE), respectively, with octavinylsilsesquioxane (OVS) as node building blocks, in the presence of anhydrous FeCl3 as a catalyst and 1,2-dichloroethane at 60 °C. Based on N2 adsorption and thermogravimetric analyses, the resulting hybrid porous materials displayed high surface areas (270 m2/g for POSS-TPP and 741 m2/g for POSS-TPE) and outstanding thermal stabilities. Furthermore, as-prepared POSS-TPP exhibited a high carbon dioxide capacity (1.63 mmol/g at 298 K and 2.88 mmol/g at 273 K) with an excellent high adsorption capacity for iodine, reaching up to 363 mg/g, compared with the POSS-TPE (309 mg/g).

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A Highly Crystalline Anthracene-Based MOF-74 Series Featuring Electrical Conductivity and Luminescence

10.26434/chemrxiv.8222492.v1 ◽

2019 ◽

Author(s):

Patricia Scheurle ◽

Andre Mähringer ◽

Andreas Jakowetz ◽

Pouya Hosseini ◽

Alexander Richter ◽

...

Keyword(s):

Electrical Conductivity ◽

Metal Ions ◽

Light Emission ◽

Block Design ◽

High Surface ◽

Visible Spectrum ◽

Building Blocks ◽

Divalent Metal Ions ◽

Conductivity Enhancement ◽

Surface Areas

Recently, a small group of metal-organic frameworks (MOFs) has been discovered featuring substantial charge transport properties and electrical conductivity, hence promising to broaden the scope of potential MOF applications in fields such as batteries, fuel cells and supercapacitors. In combination with light emission, electroactive MOFs are intriguing candidates for chemical sensing and optoelectronic applications. Here, we incorporated anthracene-based building blocks into the MOF-74 topology with five different divalent metal ions, that is, Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, resulting in a series of highly crystalline MOFs, coined ANMOF-74(M). This series of MOFs features substantial photoluminescence, with ANMOF-74(Zn) emitting across the whole visible spectrum. The materials moreover combine this photoluminescence with high surface areas and electrical conductivity. Compared to the original MOF-74 materials constructed from 2,5-dihydroxy terephthalic acid and the same metal ions Zn2+, Mg2+, Ni2+, Co2+ and Mn2+, we observed a conductivity enhancement of up to six orders of magnitude. Our results point towards the importance of building block design and the careful choice of the embedded MOF topology for obtaining materials with desired properties such as photoluminescence and electrical conductivity.

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Synthesis of Vinylene-Linked Covalent Organic Frameworks by Monomer-Self-Catalyzed Activation of Knoevenagel Condensation

10.26434/chemrxiv-2021-4sxn0 ◽

2021 ◽

Author(s):

Shuai Bi ◽

Fancheng Meng ◽

Dongqing Wu ◽

Fan Zhang

Keyword(s):

Mixed Solvent ◽

Molecular Level ◽

Knoevenagel Condensation ◽

High Surface ◽

Building Blocks ◽

Surface Areas ◽

Benzoic Anhydride ◽

Semiconducting Properties ◽

Vertically Aligned ◽

Solvent Molecules

Reticular chemistry on the basis of thermodynamically controlled linking modes and numerous organic building blocks has constituted versatile crystalline frameworks in molecular-level precision. However, vinylene-linked organic frameworks (COFs) are still quite far from flexible tailoring either in their structures or topologies, due to the lack of monomers with sufficient activities. Herein, we established a strategy to synthesize vinylene-linked COFs via Knoevenagel condensation of a tetratopic monomer 2,2’,6,6’-tetramethyl-4,4’-bipyridine (TMBP) with linear aromatic dialdehydes in a mixed solvent of benzoic anhydride and benzoic acid. Mechanism investigation suggested that the condensation was promoted by a pyridine-self-catalyzed benzoylation upon the cleavage of benzoic anhydride solvent molecules. The layered structures of the resultant COFs were highly crystallized into orthorhombic lattice with vertically aligned AA stacking mode, delivering high surface areas up to 1560 m2 g-1. The pi-extended conjugated skeletons comprising para-bipyridyl units and vinylene linkages endow these COFs with substantial semiconducting properties, releasing visible light-stimulated catalytic activity in water-splitting hydrogen evolution with a rate as high as 3300 μmol g-1 h-1.

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Mitigating the Agglomeration of Nanofiller in a Mixed Matrix Membrane by Incorporating an Interface Agent

Membranes ◽

10.3390/membranes11050328 ◽

2021 ◽

Vol 11 (5) ◽

pp. 328

Author(s):

Manh-Tuan Vu ◽

Gloria M. Monsalve-Bravo ◽

Rijia Lin ◽

Mengran Li ◽

Suresh K. Bhatia ◽

...

Keyword(s):

Gas Separation ◽

Polymer Matrix ◽

Ion Beam ◽

High Surface ◽

Mixed Matrix Membrane ◽

Mechanical And Thermal Properties ◽

Separation Membranes ◽

Surface Areas ◽

Separation Membrane ◽

Focus Ion Beam

Nanodiamonds (ND) have recently emerged as excellent candidates for various applications including membrane technology due to their nanoscale size, non-toxic nature, excellent mechanical and thermal properties, high surface areas and tuneable surface structures with functional groups. However, their non-porous structure and strong tendency to aggregate are hindering their potential in gas separation membrane applications. To overcome those issues, this study proposes an efficient approach by decorating the ND surface with polyethyleneimine (PEI) before embedding it into the polymer matrix to fabricate MMMs for CO2/N2 separation. Acting as both interfacial binder and gas carrier agent, the PEI layer enhances the polymer/filler interfacial interaction, minimising the agglomeration of ND in the polymer matrix, which is evidenced by the focus ion beam scanning electron microscopy (FIB-SEM). The incorporation of PEI into the membrane matrix effectively improves the CO2/N2 selectivity compared to the pristine polymer membranes. The improvement in CO2/N2 selectivity is also modelled by calculating the interfacial permeabilities with the Felske model using the gas permeabilities in the MMM. This study proposes a simple and effective modification method to address both the interface and gas selectivity in the application of nanoscale and non-porous fillers in gas separation membranes.

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A simple one-step electrochemical deposition of bioinspired nanocomposite for the non-enzymatic detection of dopamine

Journal of Analytical Science & Technology ◽

10.1186/s40543-021-00260-y ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Vijayaraj Kathiresan ◽

Dinakaran Thirumalai ◽

Thenmozhi Rajarathinam ◽

Miri Yeom ◽

Jaewon Lee ◽

...

Keyword(s):

Electrochemical Deposition ◽

Electrochemical Impedance ◽

High Surface ◽

Electrochemical Characteristics ◽

Surface Areas ◽

Electrochemically Reduced Graphene Oxide ◽

Sensitivity And Selectivity ◽

Controlled Deposition ◽

Enzymatic Detection ◽

Walled Carbon Nanotubes

AbstractA simple and cost-effective electrochemical synthesis of carbon-based nanomaterials for electrochemical biosensor is of great challenge these days. Our study describes a single-step electrochemical deposition strategy to prepare a nanocomposite of electrochemically reduced graphene oxide (ErGO), multi-walled carbon nanotubes (MWCNTs), and polypyrrole (PPy) in an aqueous solution of pH 7.0 for dopamine (DA) detection. The ErGO/MWCNTs/PPy nanocomposites show enhanced electrochemical performance due to the strong π–π* stacking interactions among ErGO, MWCNTs, and PPy. The efficient interaction of the nanocomposites is confirmed by evaluating its physical and electrochemical characteristics using field-emission scanning electron microscopy, Raman spectroscopy, electrochemical impedance spectroscopy, cyclic voltammetry, and amperometry. The deposited nanocomposites are highly stable on the substrates and possess high surface areas, which is vital to improve the sensitivity and selectivity for DA detection. The controlled deposition of the ErGO/MWCNTs/PPy nanocomposites can provide enhanced electrochemical detection of DA. The sensor demonstrates a short time response within 2 s and is a highly sensitive approach for DA detection with a dynamic linear range of 25–1000 nM (R2 = 0.999). The detection limit is estimated to be 2.3 nM, and the sensor sensitivity is calculated to be 8.96 μA μM−1 cm−2, with no distinct responses observed for other biological molecules.

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