Covalent organic frameworks (COFs) have emerged as promising electrode materials in supercapacitors (SCs). However, their insoluble powder-like nature, poor capacitive performance in pristine form, integrated with inferior electrochemical stability is a primary concern for their long-term use in electrochemical devices. Keeping this in perspective, herein we report a redox active and hydrogen bonded COF with ultrahigh stability in conc. HSO (18 M), conc. HCl (12 M) and NaOH (9 M). The as-synthesized COF fabricated as thin sheets were efficiently employed as a free-standing supercapacitor electrode material using 3 M aq. HSO as an electrolyte. Moreover, the pristine COF sheet showcased outstanding areal capacitance 1600 mF cm (gravimetric 169 F g) and excellent cyclic stability (>100 000) without compromising its capacitive performance or Coulombic efficiency. Moreover, as a proof-of-concept, a solid-state supercapacitor device was also assembled and subsequently tested.
A rapid and scalable synthesis of six new imine-linked highly porous and crystalline COFs is presented that feature exceptionally high chemical stability in harsh environments including conc. H SO (18 m), conc. HCl (12 m), and NaOH (9 m). This is because of the presence of strong interlayer C-H⋅⋅⋅N hydrogen bonding among the individual layers, which provides significant steric hindrance and a hydrophobic environment around the imine (-C=N-) bonds, thus preventing their hydrolysis in such an abrasive environment. These COFs were further converted into porous, crystalline, self-standing, and crack-free COF membranes (COFMs) with extremely high chemical stability for their potential applications for sulfuric acid recovery. The as-synthesized COFMs exhibit unprecedented permeance for acetonitrile (280 Lm h bar ) and acetone (260 Lm h bar ).
The key factor responsible for fast diffusion and mass transfer through a porous material is the availability of a widely open pore interior having complete accessibility from their surface. However, because of their highly stacked nature, ordered two-dimensional (2D) materials fail to find real-world applicability, as it is difficult to take advantage of their complete structure, especially the inner cores. In this regard, three-dimensional (3D) nanostructures constructed from layered two-dimensional crystallites could prove to be advantageous. However, the real challenge is to cultivate a porous nanostructure with ordered pores where the pores are surrounded by crystalline walls. Herein, a simple yet versatile in situ gas-phase foaming technique has been employed to address these cardinal issues. The use of baking soda leads to the continuous effervescence of CO2 during the crystallization of foam, which creates ripples and fluctuations on the surface of the 2D crystallites. The induction of ordered micropores within the disordered 3D architecture synergistically renders fast diffusion of various guests through the interconnected pore network. The high-density defects in the hierarchically porous structure help in ultrafast adsorption (<10 s) of various pollutants (removal efficiency of 99%) from water, all of which would lead to significant environmental benefit. The pseudo-second-order rate constant for the BPA pollutant is 182.3 g mg–1 min–1, which is the highest among all the literature reports to date. The high removal efficiency (highest efficiency of 94% and average efficiency of 70%) of a persistent organic pollutant has been attended for the first time.
In this investigation, we have explored the possibility of a class of chemically stable covalent organic frameworks (COFs) as water adsorbing materials through pore surface engineering.
A strategy based on tandem alkynylation of o-hydroxyarylenaminones followed by intramolecular cyclization has been developed to generate a diverse array of 3-alkynyl chromones. The functionality embedded in these key intermediates enables their facile elaboration into more diverse structures by a variety of functionalizations and ring-forming processes.
Amine-linked (C-NH) porous organic cages (POCs) are preferred over the imine-linked (C=N) POCs owing to their enhanced chemical stability. In general, amine-linked cages, obtained by the reduction of corresponding imines, are not shape-persistent in the crystalline form. Moreover, they require multistep synthesis. Herein, a one-pot synthesis of four new amine-linked organic cages by the reaction of 1,3,5-triformylphloroglucinol (Tp) with different analogues of alkanediamine is reported. The POCs resulting from the odd diamine (having an odd number of -CH groups) is conformationally eclipsed, while the POCs constructed from even diamines adopt a gauche conformation. This odd-even alternation in the conformation of POCs has been supported by computational calculations. The synthetic strategy hinges on the concept of Schiff base condensation reaction followed by keto-enol tautomerization. This mechanism is the key for the exceptional chemical stability of cages and facilitates their resistance towards acids and bases.
Porous solids that can be switched between different forms with distinct physical properties are appealing candidates for separation, catalysis, and host–guest chemistry. In this regard, porous organic cages (POCs) are of profound interest because of their solution‐state accessibility. However, the application of POCs is limited by poor chemical stability. Synthesis of an exceptionally stable imine‐linked (4+6) porous organic cage (TpOMe‐CDA) is reported using 2,4,6‐trimethoxy‐1,3,5‐triformyl benzene (TpOMe) as a precursor aldehyde. Introduction of the ‐OMe functional group to the aldehyde creates significant steric and hydrophobic characteristics in the environment around the imine bonds that protects the cage molecules from hydrolysis in the presence of acids or bases. The electronic effect of the ‐OMe group also plays an important role in enhancing the stability of the reported POCs. As a consequence, TpOMe‐CDA reveals exceptional chemical stability in neutral, acidic and basic conditions, even in 12 m NaOH. Interestingly, TpOMe‐CDA exists in three different porous and non‐porous polymorphic forms (α, β, and γ) with respect to differences in crystallographic packing and the orientation of the flexible methoxy groups. All of the polymorphs retain their crystallinity even after treatment with acids and bases. All the polymorphs of TpOMe‐CDA differ significantly in their properties as well as morphology and could be reversibly switched in the presence of an external stimulus.
Covalent Organic Frameworks (COFs) have convened inordinate scientific attention from last few years because of their unique tunable porosity and long range ordered structures with high atomic precisions. Although the high crystalline nature with considerable porosity fashioned these novel materials as an eligible candidate for diverse applications, the ordered nanochannels with controllable pore aperture, especially regarding membrane separations in extreme conditions, have been poorly explored. Herein, we have demonstrated rapid and scalable synthesis of six new imine-linked highly crystalline and porous COFs via salt (p-toluenesulfonic acid) mediated solid state crystallization approach. These as-synthesized materials show exceptionally high chemical stability in harsh environments including conc. H2SO4 (36 N), conc. HCl (12 N) and NaOH (9N). This is exclusivly because of the presence of strong interlayer C-H•••N H-bonding interactions among the individual layers. This H-bonding reinforce interlayer stacking interaction and provides a steric hindrance and hydrophobic environment around the imine (-C=N) bonds making it safe from hydrolysis, as confirmed by the Density Functional Theory (DFT) calculations. By taking advantage of processability of COF powders in salt mediated synthesis approach, the continuous, porous, crystalline, self-standing and crack-free COF membranes (COFMs) with high chemical stability have been transmuted, for their potential applications to separate various environmentally toxic materials from drinking water with high water flux. Moreover, owing to its highly robust backbone, the COFM have showed the unprecedented Sulfuric acid (12 N) permeance reflecting its potential applications for sulfuric acid purification. Also, the as-synthesized COFMs exhibit exceptionally high permeance of acetonitrile (380 Lm -2 h -1 bar -1 ) and acetone (340 Lm -2 h -1 bar -1 ).
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