01806nas a2200205 4500008004100000022001400041245010400055210006900159260000900228300001000237490000600247520107000253100002101323700002201344700002001366700002501386700002801411700003001439856013101469 2015 eng d a2045-232200aPd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation0 aPd loaded amphiphilic COF as catalyst for multifold Heck reactio cJUN  a108760 v53 a

COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd-0 nanoparticles into it. An 18-20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) < 0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using `non-boronic acid' substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 degrees C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable.

1 aMullangi, Dinesh1 aNandi, Shyamapada1 aShalini, Sorout1 aSreedhala, Sheshadri1 aVinod, Chathakudath, P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/pd-loaded-amphiphilic-cof-catalyst-multi-fold-heck-reactions-c-c-couplings-and-co-oxidation02113nas a2200229 4500008004100000022001400041245008000055210006900135260000900204300002300213490000600236520133300242100002201575700002601597700002101623700002701644700001801671700002801689700002401717700003001741856011201771 2016 eng d a1614-683200aLow band gap benzimidazole COF supported Ni3N as highly active OER catalyst0 aLow band gap benzimidazole COF supported Ni3N as highly active O cDEC  aArticle No:16011890 v63 a

Covalent organic frameworks (COFs) have structures and morphologies closely resembling graphenes, whose modular construction permits atomiclevel manipulations. This, combined with their porous structure, makes them excellent catalyst supports. Here, the high electrocatalytic activity of a composite, formed by supporting Ni3N nanoparticles on a benzimidazole COF, for oxygen evolution reaction is shown. The composite oxidizes alkaline water with a near-record low overpotential of 230 mV @ 10 mA cm(-2) (eta(10)). This high activity is attributed to the ability of the COF to confine the Ni3N nanoparticles to size regimes otherwise difficult to obtain and to its low band gap character (1.49 eV) arising from the synergy between the conducting Ni3N nanoparticles and the pi-conjugated COF. The COF itself, as a metalfree self-standing framework, has an oxygen evolution reaction activity with 10 of 400 mV. The periodic structure of the COF makes it serve as a matrix to disperse the catalytically active Ni3N nanoparticles favoring their high accessibility and thereby good charge-transport within the composite. This is evident from the amount of O-2 evolved (230 mmol h(-1) g(-1)), which, to the best of our knowledge, is the highest reported. The work reveals the emergence of COF as supports for electrocatalysts.

1 aNandi, Shyamapada1 aSingh, Santosh, Kumar1 aMullangi, Dinesh1 aIllathvalappil, Rajith1 aGeorge, Leena1 aVinod, Chathakudath, P.1 aKurungot, Sreekumar1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/low-band-gap-benzimidazole-cof-supported-ni3n-highly-active-oer-catalyst02259nas a2200229 4500008004100000022001400041245013200055210006900187260007500256300002400331490000600355520136500361100002101726700002401747700002001771700002201791700001801813700001301831700002401844700003001868856013101898 2016 eng d a1614-683200aLow-overpotential electrocatalytic water splitting with noble-metal-free nanoparticles supported in a sp(3) n-rich flexible COF0 aLowoverpotential electrocatalytic water splitting with noblemeta aPOSTFACH 101161, 69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcJUL aArticle No. 16001100 v63 a

Covalent organic frameworks (COFs) are crystalline organic polymers with tunable structures. Here, a COF is prepared using building units with highly flexible tetrahedral sp(3) nitrogens. This flexibility gives rise to structural changes which generate mesopores capable of confining very small (<2 nm sized) non-noble-metal-based nanoparticles (NPs). This nanocomposite shows exceptional activity toward the oxygen-evolution reaction from alkaline water with an overpotential of 258 mV at a current density of 10 mA cm(-2). The overpotential observed in the COF-nanoparticle system is the best in class, and is close to the current record of approximate to 200 mV for any noble-metalfree electrocatalytic water splitting system-the Fe-Co-Ni metal-oxide-film system. Also, it possesses outstanding kinetics (Tafel slope of 38.9 mV dec(-1)) for the reaction. The COF is able to stabilize such small-sized NP in the absence of any capping agent because of the COF-Ni(OH)(2) interactions arising from the N-rich backbone of the COF. Density-functional-theory modeling of the interaction between the hexagonal Ni(OH)(2) nanosheets and the COF shows that in the most favorable configuration the Ni(OH)(2) nanosheets are sandwiched between the sp(3) nitrogens of the adjacent COF layers and this can be crucial to maximizing their synergistic interactions.

1 aMullangi, Dinesh1 aDhavale, Vishal, M.1 aShalini, Sorout1 aNandi, Shyamapada1 aCollins, Sean1 aWoo, Tom1 aKurungot, Sreekumar1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/low-overpotential-electrocatalytic-water-splitting-noble-metal-free-nanoparticles-supported01827nas a2200253 4500008004100000245013400041210006900175260000800244300001600252490000700268520093800275100002201213700002301235700001801258700002001276700002101296700001801317700002101335700002501356700002101381700002101402700002101423856012901444 2016 eng d00aUltrahydrophobic fluorous metal-organic framework derived recyclable composite as apromising platform to tackle marine oil spills0 aUltrahydrophobic fluorous metalorganic framework derived recycla cJUL a10937-109430 v223 aDerived from a strategically chosen hexafluorinated dicarboxylate linker aimed at the designed synthesis of a superhydrophobic metal-organic framework (MOF), the fluorine-rich nanospace of a water-stable MOF (UHMOF-100) exhibits excellent water-repellent features. It registered the highest water contact angle (approximate to 176 degrees) in the MOF domain, marking the first example of an ultrahydrophobic MOF. Various experimental and theoretical studies reinforce its distinc-tive water-repellent characteristics, and the conjugation of superoleophilicity and unparalleled hydrophobicity of a MOF material has been coherently exploited to achieve real-time oil/water separation in recyclable membrane form, with significant absorption capacity performance. This is also the first report of an oil/water separating fluorinated ultrahydrophobic MOF-based membrane material, with potential promise for tackling marine oil spillages.1 aMukherjee, Soumya1 aKansara, Ankit, M.1 aSaha, Debasis1 aGonnade, Rajesh1 aMullangi, Dinesh1 aManna, Biplab1 aDesai, Aamod, V.1 aThorat, Shridhar, H.1 aSingh, Puyam, S.1 aMukherjee, Arnab1 aGhosh, Sujit, K. uhttps://library.ncl.res.in/content/ultrahydrophobic-fluorous-metal-organic-framework-derived-recyclable-composite-apromising02314nas a2200205 4500008004100000245014500041210006900186260000800255490000700263520153500270100002101805700002601826700001701852700001801869700002801887700002501915700001601940700003001956856012201986 2018 eng d00aHighly stable COF-supported Co/Co(OH)(2) nanoparticles heterogeneous catalyst for reduction of nitrile/nitro compounds under mild conditions0 aHighly stable COFsupported CoCoOH2 nanoparticles heterogeneous c cSEP0 v143 aOrdered nanoporosity in covalent organic framework (COF) offers excellent opportunity for property development. Loading nanoparticles (nPs) onto them is one approach to introducing tailor-made properties into a COF. Here, a COF-Co/Co(OH)(2) composite containing about 16 wt% of <6 nm sized Co/Co(OH)(2) nPs is prepared on a N-rich COF support that catalyzes the release of theoretical equivalence of H-2 from readily available, safe, and cheap NaBH4. Furthermore, the released H-2 is utilized for the hydrogenation of nitrile and nitro compounds to amines under ambient conditions in a facile one-pot reaction. The COF "by choice" is built from "methoxy" functionalized dialdehydes which is crucial in enabling the complete retention of the COF structure under the conditions of the catalysis, where the regular Schiff bonds would have hydrolyzed. The N-rich binding pockets in the COF ensure strong nP-COF interactions, which provides stability and enables catalyst recycling. Modeling studies reveal the crucial role played by the COF in exposing the active facets and thereby in controlling the activation of the reducing agent. Additionally, via density functional theory, we provide a rational explanation for how these COFs can stabilize nanoparticles which grow beyond the limiting pore size of the COF and yet result in a truly stable heterogeneous catalyst - a ubiquitous observation. The study underscores the versatility of COF as a heterogeneous support for developing cheap and highly active nonnoble metal catalysts.1 aMullangi, Dinesh1 aChakraborty, Debanjan1 aPradeep, Anu1 aKoshti, Vijay1 aVinod, Chathakudath, P.1 aPanja, Soumendranath1 aNair, Sunil1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/highly-stable-cof-supported-cocooh2-nanoparticles-heterogeneous-catalyst-reduction02516nas a2200289 4500008004100000022001400041245014300055210006900198260000800267300001400275490000600289520149400295653004001789653002001829653002001849653002001869653002801889653001901917100001701936700002601953700002201979700002402001700002102025700001802046700003002064856013202094 2019 eng d a2574-097000aAqueous-phase differentiation and speciation of Fe3+ and Fe2+ using water-stable photoluminescent lanthanide-based metal-organic framework0 aAqueousphase differentiation and speciation of Fe3 and Fe2 using cAUG a5169-51780 v23 a

Fe2+ is vital to O-2 transportation and photosynthesis regulated by oxidases and reductases. On the other hand, Fe3+ is detrimental due to its irreversible binding to O-2. Hence there is a need for selective identification of Fe3+ from aqueous systems in the presence of Fe2+. However, given their close chemical nature, it is not straightforward to differentiate them. Fe2+ and Fe3+ are typically sensed and differentiated using magnetic measurements, Mossbauer, X-ray absorption spectroscopy, or EXAFS, which are complex and equipment intensive techniques. In comparison, the fluorescence technique is advantageous in terms of time and accessibility. Although readily available lanthanide salts exhibit fluorescence, they are weak, and to serve as an optical probe, their luminescence has to be enhanced via ligand design. Hence we have designed a chromophoric ligand that can covalently bind to lanthanides and enhance its fluorescence intensity, and it binds selectively to Fe3+ through its nitrogen centers. It detects Fe3+ from low concentration (similar to 100 mu M) aqueous solutions, with fast response time (<1 min) and with a detection limit of 3.6 ppm. Importantly, the Fe3+ adsorbed MOF can be readily reactivated for the next cycle by merely washing with an aqueous ascorbic acid solution and can be used for multiple cycles without any appreciable loss in activity. This makes the Ln-MOF an environmentally benign, cost-effective, scalable, and recyclable probe.

10aFe3+ differentiation and speciation10aflexible ligand10afluorescent MOF10airon speciation10aMetal-organic framework10awater sorption1 aMaity, Rahul1 aChakraborty, Debanjan1 aNandi, Shyamapada1 aYadav, Ankit, Kumar1 aMullangi, Dinesh1 aVinod, C., P.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/aqueous-phase-differentiation-and-speciation-fe3-and-fe2-using-water-stable-photoluminescent02337nas 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-synthesis02285nas a2200313 4500008004100000022001400041245011700055210006900172260000900241300001400250490000600264520120100270653002701471653003101498653002701529653002801556653001901584653001901603100002001622700002901642700002101671700002601692700002101718700001801739700002801757700002501785700003001810856013101840 2020 eng d a2574-097000aNanoporous covalent organic framework embedded with Fe/Fe3O4 nanoparticles as air-stable low-density nanomagnets0 aNanoporous covalent organic framework embedded with FeFe3O4 nano cSEP  a9088-90960 v33 a

Covalent organic frameworks (COFs) made of light atoms such as H, C, N, and O with a significant void-to-framework ratio are excellent low-density supports for nanoparticles (nPs). Their framework can be precoded with heteroatoms to ensure binding with metallic nanoclusters. With these advantages, if controlled amounts of magnetic nPs are anchored to them, they can yield low-density organic-inorganic nanomagnets. Their organic nature facilitates fusion with bulk materials such as paper/textile to enable bulk composites with well-dispersed low-density magnets, which have potential for defense and next-generation aviation applications. Herein, we have grown small Fe/Fe3O4 nPs (5-18 wt %) inside a COF. Interestingly, 300 mg of this organic-inorganic framework material (containing 50 mg of nPs) can lift a vial of similar to 15,000 mg (300 times heavier). Also, the hydrophobic COF wraps around the Fe/Fe3O4 nanocluster retaining its room-temperature magnetic character even after 1 year, while the naked nPs lose it within a few days because of air oxidation. Bulk composites with paper and polymers have been made using this low-density Fe-COF to demonstrate their processability.

10aair-stable nanomagnets10aCovalent organic framework10aFe/Fe3O4 nanoparticles10alow-density nanomagnets10amagnetic rayon10ananoporous COF1 aKushwaha, Rinku1 aKaleeswaran, Dhananjayan1 aHaldar, Sattwick1 aChakraborty, Debanjan1 aMullangi, Dinesh1 aBorah, Aditya1 aVinod, Chathakudath, P.1 aMurugavel, Ramaswamy1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/nanoporous-covalent-organic-framework-embedded-fefe3o4-nanoparticles-air-stable-low-density