02149nas a2200217 4500008004100000245017900041210006900220260000800289300001600297490000600313520130400319100002001623700001801643700001701661700002201678700003001700700001601730700002901746700002901775856012701804 2016 eng d00aCO2 Laser direct written MOF-based metal-decorated and heteroatom-doped porous graphene for flexible all-solid-state microsupercapacitor with extremely high cycling stability0 aCO2 Laser direct written MOFbased metaldecorated and heteroatomd cNOV a31841-318480 v83 aOver the past decade, flexible and wearable microelectronic devices and systems have gained significant importance. Because portable power source is an essential need of such wearable devices, currently there is considerable research emphasis on the development of planar interdigitated micro energy-torage devices by employing diverse precursor materials to obtain functional materials (functional carbon, oxides, etc.) with the desirable set of properties. Herein we report for the first time the use of metal organic framework (MOF) and zeolitic imidazolate framework (ZIF-67) for high-wavelength photothermal laser direct writing of metal-decorated, heteroatom-doped, porous few-layer graphene electrodes for microsupercapacitor application. We argue that the specific attributes of MOF as a precursor and the high-wavelength laser writing approach (which creates extremely high localized and transient temperature (>2500 degrees C) due to strong absorption by lattice vibrations) are together responsible for the peculiar interesting properties of the carbon material thus synthesized, thereby rendering extremely high cycling stability to the corresponding microsupercapacitor device. Our device exhibits near 100% retention after 200 000 cycles as well as stability under 150 degrees bending.1 aBasu, Aniruddha1 aRoy, Kingshuk1 aSharma, Neha1 aNandi, Shyamapada1 aVaidhyanathan, Ramanathan1 aRane, Sunit1 aRode, Chandrashekhar, V.1 aOgale, Satishchandra, B. uhttps://library.ncl.res.in/content/co2-laser-direct-written-mof-based-metal-decorated-and-heteroatom-doped-porous-graphene02337nas a2200253 4500008004100000022001400041245017500055210006900230260000800299300001600307490000600323520138600329100002601715700002201741700002701763700002101790700001701811700002301828700002101851700002801872700002401900700003001924856012901954 2019 eng d a2470-134300aCarbon derived from soft pyrolysis of a covalent organic framework as a support for small-sized RuO2 showing exceptionally low overpotential for oxygen evolution reaction0 aCarbon derived from soft pyrolysis of a covalent organic framewo cAUG a13465-134730 v43 a

Electrochemical water splitting is the most energy-efficient technique for producing hydrogen and oxygen, the two valuable gases. However, it is limited by the slow kinetics of the anodic oxygen evolution reaction (OER), which can be improved using catalysts. Covalent organic framework (COF)-derived porous carbon can serve as an excellent catalyst support. Here, we report high electrocatalytic activity of two composites, formed by supporting RuO2 on carbon derived from two COFs with closely related structures. These composites catalyze oxygen evolution from alkaline media with overpotentials as low as 210 and 217 mV at 10 mA/cm(2), respectively. The Tafel slopes of these catalysts (65 and 67 mV/dec) indicate fast kinetics compared to commercial RuO2. The observed activity is the highest among all RuO2-based heterogeneous OER catalysts-a touted benchmark OER catalyst. The high catalytic activity arises from the extremely small-sized (similar to 3-4 nm) RuO2 nanoparticles homogeneously dispersed in a micro-mesoporous (BET = 517 m(2)/g) COF-derived carbon. The porous graphenic carbon favors mass transfer, while its N-rich framework anchors the catalytic nanoparticles, making it highly stable and recyclable. Crucially, the soft pyrolysis of the COF enables the formation of porous carbon and simultaneous growth of small RuO2 particles without aggregation.

1 aChakraborty, Debanjan1 aNandi, Shyamapada1 aIllathvalappil, Rajith1 aMullangi, Dinesh1 aMaity, Rahul1 aSingh, Santosh, K.1 aHaldar, Sattwick1 aVinod, Chathakudath, P.1 aKurungot, Sreekumar1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/carbon-derived-soft-pyrolysis-covalent-organic-framework-support-small-sized-ruo2-showing02868nas a2200265 4500008004100000022001400041245015400055210006900209260000900278300001600287490000700303520188300310653002502193653003102218653003002249653002802279653002502307100002602332700002202358700002102380700002102401700002802422700003002450856012202480 2019 eng d a1944-824400aCu/Cu2O nanoparticles supported on a phenol-pyridyl COF as a heterogeneous catalyst for the synthesis of unsymmetrical diynes via glaser-hay coupling0 aCuCu2O nanoparticles supported on a phenolpyridyl COF as a heter cMAY  a15670-156790 v113 a

Covalent organic frameworks (COFs) are a new class of porous crystalline polymers with a modular construct that favors fiinctionalization. COF pores can be used to grow nanoparticles (nPs) with dramatic size reduction, stabilize them as dispersions, and provide excellent nP access. Embedding substrate binding sites in COFs can generate host-guest synergy, leading to enhanced catalytic activity. In this report, Cu/Cu2O nPs (2-3 nm) are grown on a COF, which is built by linking a phenolic trialdehyde and a triamine through Schiff bonds. Their micropores restrict the nP to exceptionally small sizes (similar to 2-3 nm), and the pore walls decorated with strategically positioned hydrogen-bonding phenolic groups anchor the substrates via hydrogen-bonding, whereas the basic pyridyl sites serve as cationic species to stabilize the [CuclusterCl2](2-) type reactive intermediates. This composite catalyst shows high activity for Glaser-Hay heterocoupling reactions, an essential 1,3-diyne yielding reaction with widespread applicability in organic synthesis and material science. Despite their broad successes in homocoupled products, preparation of unsymmetrical 1,3-diynes is challenging due to poor selectivity. Here, our COF-based Cu catalyst shows elevated selectivity toward heterocoupling product(s) (Cu nP loading 0.0992 mol %; turn over frequency: similar to 4S-50; turn over number: similar to 17S-190). The reversible redox activity at the Cu centers has been demonstrated by carrying out X-ray photoelectron spectroscopy on the frozen reactions, whereas the crucial interactions between the substrates and the binding sites in their optimized configurations have been modeled using density functional theory methods. This report emphasizes the utility of COFs in developing a heterogeneous catalyst for a truly challenging organic heterocoupling reaction.

10aCopper nanoparticles10aCovalent organic framework10aGlaser-Hay heterocoupling10aheterogeneous catalysis10aunsymmetrical diynes1 aChakraborty, Debanjan1 aNandi, Shyamapada1 aMullangi, Dinesh1 aHaldar, Sattwick1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/cucu2o-nanoparticles-supported-phenol-pyridyl-cof-heterogeneous-catalyst-synthesis02165nas a2200253 4500008004100000022001400041245008400055210006900139260000800208300001500216490000700231520135000238653001601588653001701604653001101621653001701632100002201649700002201671700002601693700002101719700002801740700003001768856011301798 2022 eng d a1861-472800aCoordination flexibility aided CO2-specific gating in an iron isonicotinate MOF0 aCoordination flexibility aided CO2specific gating in an iron iso cFEB ae2021013050 v173 a

Coordination flexibility assisted porosity has been introduced into an Iron-isonicotinate metal-organic framework (MOF), (Fe(4-PyC)(2) . (OH). The framework showed CO2-specific gate opening behavior, which gets tuned as a function of temperature and pressure. The MOF ` s physisorptive porosity towards CO2, CH4, and N-2 was investigated; it adsorbed only CO2 via a gate opening phenomenon. The isonicotinate, representing a borderline soft base, is bound to the hard Fe3+ centre through monodentate carboxylate and pyridyl nitrogen. This moderately weak binding enables isonicotinate to spin like a spindle under the CO2 pressure opening the gate for a sharp increase in CO2 uptake at 333 mmHg (At 298 K, the CO2 uptake increases from 0.70 to 1.57 mmol/g). We investigated the MOF ` s potential for CO2/N-2 and CO2/CH4 gas separation aided by this gating. IAST model reveals that the CO2/N-2 selectivity jumps from 325 to 3131 when the gate opens, while the CO2/CH4 selectivity increases three times. Interestingly, this Fe-isonicotinate MOF did not follow the trend set by our earlier reported Hard-Soft Gate Control (established for isostructural M2+-isonicotinate MOFs (M=Mg, Mn)). However, we account for this discrepancy using the different oxidation state of metals confirmed by X-ray photoelectron spectroscopy and magnetism.

10aCO2 capture10aflexible MOF10agating10aIsonicotinic1 aSingh, Himan, Dev1 aNandi, Shyamapada1 aChakraborty, Debanjan1 aSingh, Kirandeep1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/coordination-flexibility-aided-co2-specific-gating-iron-isonicotinate-mof02813nas a2200229 4500008004100000022001400041245013100055210006900186260000800255300001600263490000700279520198000286100002302266700002202289700001802311700002202329700001702351700002602368700002802394700003002422856013102452 2022 eng d a2050-748800aCovalent organic framework with electrodeposited copper nanoparticles - a desirable catalyst for the Ullmann coupling reaction0 aCovalent organic framework with electrodeposited copper nanopart cJUL a15647-156560 v103 a

A covalent organic framework is a porous covalently-linked polymeric assembly built from molecular lego blocks, the monomers. A COF'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 `capping-agent-free' 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.

1 aChandran, Chandana1 aSingh, Himan, Dev1 aLeo, Liya, S.1 aShekhar, Pragalbh1 aRase, Deepak1 aChakraborty, Debanjan1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/covalent-organic-framework-electrodeposited-copper-nanoparticles-desirable-catalyst-ullmann02092nas a2200277 4500008004100000245013500041210006900176260000800245300001100253490000700264520112600271100002201397700003701419700001701456700002201473700001701495700001801512700001701530700002701547700002501574700002001599700002601619700001801645700003001663856012101693 2023 eng d00aCOF-supported zirconium oxyhydroxide as a versatile heterogeneous catalyst for Knoevenagel condensation and nerve agent hydrolysis0 aCOFsupported zirconium oxyhydroxide as a versatile heterogeneous cNOV a1080880 v263 a

A composite of catalytic Lewis acidic zirconium oxyhydroxides (8 wt %) and a covalent organic framework (COF) was synthesized. X-ray diffraction and infrared (IR) spectroscopy reveal that COF's structure is pre-served after loading with zirconium oxyhydroxides. Electron microscopy confirms a homogeneous distri-bution of nano-to sub-micron-sized zirconium clusters in the COF. 3D X-ray tomography captures the micron-sized channels connecting the well-dispersed zirconium clusters on the COF. The crystalline ZrOx(OH)(y)@COF's nanostructure was model-optimized via simulated annealing methods. Using 0.8 mol % of the catalyst yielded a turnover number of 100-120 and a turnover frequency of 160-360 h(-1) for Knoevenagel condensation in aqueous medium. Additionally, 2.2 mol % of catalyst catalyzes the hy-drolysis of dimethyl nitrophenyl phosphate, a simulant of nerve agent Soman, with a conversion rate of 37% in 180 min. The hydrolytic detoxification of the live agent Soman is also achieved. Our study unveils COF-stabilized ZrOx(OH)(y) as a new class of zirconium-based Lewis + Bronsted-acid catalysts.

1 aShekhar, Pragalbh1 aDevulapalli, Venkata, Swaroopa D1 aReji, Reshma1 aSingh, Himan, Dev1 aJose, Aleena1 aSingh, Piyush1 aTorris, Arun1 aVinod, Chatakudath, P.1 aIII, John, A. Tokarz1 aMahle, John, J.1 aPeterson, Gregory, W.1 aBorguet, Eric1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/cof-supported-zirconium-oxyhydroxide-versatile-heterogeneous-catalyst-knoevenagel