@article {48070,
	title = {Covalent organic framework with electrodeposited copper nanoparticles - a desirable catalyst for the Ullmann coupling reaction},
	journal = {Journal of Materials Chemistry A},
	volume = {10},
	year = {2022},
	month = {JUL},
	pages = {15647-15656},
	type = {Article},
	abstract = {<p>
	A covalent organic framework is a porous covalently-linked polymeric assembly built from molecular lego blocks, the monomers. A COF{\textquoteright}s high surface area, ordered pores, and intrinsic low density makes it a perfect heterogeneous catalyst component. Dispersing catalytic metal nanoparticles into the porous COF matrix in a {\textquoteleft}capping-agent-free{\textquoteright} manner can aid the maximal utilization of the active sites. To generate single-site catalysts, metals have been anchored to dense supports, or metal ions have been coordinated to the porous organic framework. The latter has superior atom efficiency and a substrate diffusion advantage. Stably nestling neutral metallic clusters into open-framework supports with no specifically strong binding groups requires a different approach. If infused from extremely dilute electrolytes, metal clusters can be nanoconfined into electrically activated COFs. At low-loadings, it can resemble a single-site catalyst with high atom efficiency. Herein, we report the larger scale synthesis of IISERP-COF15 and electrochemical loading of copper nanoparticles into its pores at loadings as low as 3.34 wt\%. We employed classical Ullmann reactions to adjudge its activity. Typical turnover numbers for the catalysts reported in the literature are approximately 50-100. A Cu@COF shows high activity with a very low catalyst loading of 0.25 mol\% (TON around similar to 300-350 vs. 4 for neat CuCl2 center dot 2H(2)O (homogeneous catalyst) and turnover frequency (similar to 15-17 h(-1))). We recycled it for up to 3 cycles. Furthermore, we report a multi-fold Ullmann reaction producing an unreported hexaaldehyde to demonstrate the latitude of the catalyst. Our work points to the potential of a dilutely loaded metal@COF as a mimic of the single-site catalyst for synthesizing valuable C-O linked molecules. Our findings from computational modeling shed light on the role of the COF as an active nanoporous support for Ullmann C-O coupling.</p>
},
	issn = {2050-7488},
	doi = {10.1039/d2ta01326f},
	author = {Chandran, Chandana and Singh, Himan Dev and Leo, Liya S. and Shekhar, Pragalbh and Rase, Deepak and Chakraborty, Debanjan and Vinod, Chathakudath P. and Vaidhyanathan, Ramanathan}
}
@article {48448,
	title = {Hydroxide ion-conducting viologen-bakelite organic frameworks for flexible solid-state zinc-air battery applications},
	journal = {Nanoscale Horizons},
	volume = {8},
	year = {2023},
	month = {JAN },
	pages = {224-234},
	type = {Article},
	abstract = {<p>
	Adaptable polymer-based solid-state electrolytes can be a game-changer toward safe, lightweight flexible batteries. We present a robust Bakelite-type organic polymer covalently decked with viologen, triazine, and phenolic moieties. Its flexible structure with cationic viologen centers incorporates counter-balancing free hydroxide ions into the polymeric framework. By design, the aromatic groups and heteroatoms in the framework can be activated under an applied potential to prompt a push-pull drive, setting off the towing of hydroxide ions via weak electrostatic, van der Waals, and hydrogen-bond interactions. The frontier orbitals from a DFT-modeled structure certify this. The hydroxyl-polymer requires minimal KOH wetting to maintain a humid environment for Grotthuss-type transport. The hydroxide ion conductivity reaches a value of 1.4 x 10(-2) S cm(-1) at 80 degrees C and 95\% RH, which is retained for over 15 h. We enhanced its practical utility by coating it as a thin solid-state separator-cum-electrolyte on readily available filter paper. The composite exhibits a conductivity of 4.5 x 10(-3) S cm(-1) at 80 degrees C and 95\% RH. A zinc-air battery (ZAB) constructed using this polymer-coated paper as electrolyte yields a maximum power density of 115 mW cm(-2) and high specific capacitance of 435 mA h g(-1). The power density recorded for our ZAB is among the best reported for polymer electrolyte-based batteries. Subsequently, the flexible battery fabricated with IISERP-POF11_OH@FilterPaper exhibits an OCV of 1.44 V, and three batteries in series power a demo traffic signal. To underscore the efficiency of hydroxide ion transport through the complex multifunctional backbone of the polymer, we calculated the diffusion coefficient for OH- (Exp: 2.9 x 10(-5) cm(2) s(-1); Comp. 5.2 x 10(-6) cm(2) s(-1)) using electrochemical methods and MD simulations. Climbing-edge NEB calculations reveal a large energy barrier of 2.11 eV for Zn2+ to penetrate the polymer and identify hydroxide ions within the polymer, suggesting no undesirable Zn2+ crossover. Our findings assert the readily accessible C-C-linked cationic polymer{\textquoteright}s capacity as a solid-state electrolyte for ZABs and any anion-conducting membrane.</p>
},
	issn = {2055-6756},
	doi = {10.1039/d2nh00455k},
	author = {Rase, Deepak and Illathvalappil, Rajith and Singh, Himan Dev and Shekhar, Pragalbh and Leo, Liya S. and Chakraborty, Debanjan and Haldar, Sattwick and Shelke, Ankita and Ajithkumar, Thalasseril G. and Vaidhyanathan, Ramanathan}
}
