02617nas a2200169   4500008004100000022001400041245012800055210006900183260011000252300001600362490000700378520184900385100002902234700003102263700002402294856012902318       2012                        eng d  a0959-942800aEfficient oxygen reduction electrocatalyst from graphene by simultaneously generating pores and nitrogen doped active sites0 aEfficient oxygen reduction electrocatalyst from graphene by simu  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcDEC  a23799-238050 v223 a<p>A simple way to simultaneously create pores and nitrogen doped active sites on graphene for the electrochemical oxygen reduction reaction (ORR) is developed. The key aspect of the process is the in-situ generation of Fe2O3 nanoparticles and their concomitant dispersion on graphene by pyrolyzing graphene oxide (GO) with the iron phenanthroline complex. Thus the deposited Fe2O3 nanoparticles act as the seeds for pore generation by etching the carbon layer along the graphene-Fe2O3 interface. Detection of the presence of Fe3C along with Fe2O3 confirms carbon spill-over from graphene as a plausible step involved in the pore engraving process. Since the process offers a good control on the size and dispersion of the Fe2O3 nanoparticles, the pore size and distribution also could be managed very effectively in this process. As the phenanthroline complex decomposes and gives Fe2O3 nanoparticles and subsequently the pores on graphene, the unsaturated carbons along the pore openings simultaneously capture nitrogen of the phenanthroline complex and provide very efficient active sites for ORR under alkaline conditions. The degree of nitrogen doping and hence the ORR activity could be further improved by subjecting the porous material for a second round of nitrogen doping using iron-free phenanthroline. This porous graphene enriched with the N-doped active sites effectively reduces oxygen molecule through a 3e(-) pathway, suggesting a preferential shift towards the more favourable 4e(-) route compared to the 2e(-) reaction as reported for many N-doped carbon nano-morphologies. The 90 mV onset potential difference for oxygen reduction as compared to the state-of-the art 20 wt% Pt/C catalyst is significantly low compared to the overpotentials in the range of 120-200 mV reported in the literature for few N-doped graphenes.</p>1 aPalaniselvam, Thangavelu1 aAiyappa, Harshitha, Barike1 aKurungot, Sreekumar  uhttps://library.ncl.res.in/content/efficient-oxygen-reduction-electrocatalyst-graphene-simultaneously-generating-pores-and-001783nas a2200181   4500008004100000022001400041245011400055210006900169260007100238300001400309490000700323520104600330100003101376700002101407700002001428700002401448856012901472       2013                        eng d  a1528-748300aPorous carbons from nonporous MOFs: influence of ligand characteristics on intrinsic properties of end carbon0 aPorous carbons from nonporous MOFs influence of ligand character  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcOCT  a4195-41990 v133 a<p>Synthesis of porous carbons on direct carbonization of nonporous Zn-based MOFs has been achieved without using any additional carbon precursor. The effect of ligand nature on the resulting carbon porosity has been studied systematically using the MOFs synthesized from rigid and flexible ligands. The linear relations between Zn/C ratio of the MOF versus surface area of the resulting carbon, micro-porosity versus H-2 uptake achieved in these carbons, and surface area versus specific capacitance of the end carbons have been verified from the gas adsorption, molecular composition, and electrochemical studies, respectively. Cyclic voltammetry and charge-discharge cycling have been carried out to study the capacitive behavior of the carbons. The interdependence of capacitive behavior on the surface area has been analyzed using data derived from N-2 adsorption isotherms and charge-discharge curves. Among the carbons synthesized, C-MOF-2 shows maximal surface area of 1378 m(2)/g with a specific capacitance of 170 F/g at 1 A/g.</p>1 aAiyappa, Harshitha, Barike1 aPachfule, Pradip1 aBanerjee, Rahul1 aKurungot, Sreekumar  uhttps://library.ncl.res.in/content/porous-carbons-nonporous-mofs-influence-ligand-characteristics-intrinsic-properties-end-001926nas a2200265   4500008004100000022001400041245012800055210006900183260007700252300001600329490000700345520092500352653002001277653003201297653002101329653002401350653001901374100001901393700003101412700002201443700002201465700002401487700002001511856012901531       2014                        eng d  a0947-653900aCovalent organic framework-cadmium sulfide hybrid as a prototype photocatalyst for visible-light-driven hydrogen production0 aCovalent organic frameworkcadmium sulfide hybrid as a prototype   aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcNOV  a15961-159650 v203 a<p>CdS nanoparticles were deposited on a highly stable, two-dimensional (2D) covalent organic framework (COF) matrix and the hybrid was tested for photocatalytic hydrogen production. The efficiency of CdS-COF hybrid was investigated by varying the COF content. On the introduction of just 1 wt% of COF, a dramatic tenfold increase in the overall photocatalytic activity of the hybrid was observed. Among the various hybrids synthesized, that with 10 wt% COF, named CdS-COF (90: 10), was found to exhibit a steep H2 production amounting to 3678 mmolh(-1) g(-1), which is significantly higher than that of bulk CdS particles (124 mmolh(-1)g(-1)). The presence of a p-conjugated backbone, high surface area, and occurrence of abundant 2D hetero-interface highlight the usage of COF as an effective support for stabilizing the generated photoelectrons, thereby resulting in an efficient and high photocatalytic activity.</p>10acharge transfer10acovalent organic frameworks10ahybrid materials10ahydrogen production10aPhotocatalysis1 aThote, Jayshri1 aAiyappa, Harshitha, Barike1 aDeshpande, Aparna1 aDiaz, David, Diaz1 aKurungot, Sreekumar1 aBanerjee, Rahul  uhttps://library.ncl.res.in/content/covalent-organic-framework-cadmium-sulfide-hybrid-prototype-photocatalyst-visible-light-001073nas a2200205   4500008004100000022001400041245010000055210006900155260007100224300001400295490000700309520029000316100003100606700002000637700001800657700001900675700002400694700002000718856012900738       2014                        eng d  a1528-748300aDistinctive PdCl2-mediated transformation of Fe-based metallogels into metal-organic frameworks0 aDistinctive PdCl2mediated transformation of Febased metallogels   a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL  a3434-34370 v143 a<p>Simple, efficient conversion of viable Fe3+-based metallogels into Fe-metal-organic frameworks (MOFs) has been achieved by PdCl2-mediated gel degradation. The metallogels and the resulting MOFs have been characterized, and a probable mechanism for the event has been elucidated.</p>1 aAiyappa, Harshitha, Barike1 aSaha, Subhadeep1 aGarai, Bikash1 aThote, Jayshri1 aKurungot, Sreekumar1 aBanerjee, Rahul  uhttps://library.ncl.res.in/content/distinctive-pdcl2-mediated-transformation-fe-based-metallogels-metal-organic-frameworks-001085nas a2200181   4500008004100000022001400041245012000055210006900175260011000244300001400354490000700368520030800375100002100683700003100704700002000735700002400755856012400779       2014                        eng d  a1359-734500aPost modification of MOF derived carbon via g-C3N4 entrapment for an efficient metal-free oxygen reduction reaction0 aPost modification of MOF derived carbon via gC3N4 entrapment for  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcFEB  a3363-33660 v503 a<p>High surface area carbon with a nitrogen content of 7.0% is derived from MOF via in situ g-C3N4 formation. The material shows excellent ORR activity with an onset potential of 0.035 V (vs. Hg/HgO) in alkaline medium apart from high durability and strong disinclination towards methanol crossover.</p>1 aPandiaraj, Sekar1 aAiyappa, Harshitha, Barike1 aBanerjee, Rahul1 aKurungot, Sreekumar  uhttps://library.ncl.res.in/content/post-modification-mof-derived-carbon-g-c3n4-entrapment-efficient-metal-free-oxygen-001278nas a2200193   4500008004100000022001400041245009900055210006900154260011000223300001200333490000600345520049100351100003100842700002000873700001900893700002000912700002400932856012800956       2015                        eng d  a2041-652000aFe(III) phytate metallogel as a prototype anhydrous, intermediate temperature proton conductor0 aFeIII phytate metallogel as a prototype anhydrous intermediate t  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcOCT  a603-6070 v63 a<p>A proton conducting metallogel [FNPA; ferric nitrate (FN)-phytic acid (PA)] is synthesized by immobilizing a protogenic ligand (phytic acid) using iron(III) nitrate in DMF. The xerogel shows high proton conductivity of 2.4 x 10(-2) S cm(-1) at 120 degrees C, the best value known among all metal organic materials (MOMs). Marking the first such attempt in MOMs, an electrode made using the xerogel showed a power density of 0.94 mW cm(-2) at 0.6 V under dry fuel cell conditions.</p>1 aAiyappa, Harshitha, Barike1 aSaha, Subhadeep1 aWadge, Pritish1 aBanerjee, Rahul1 aKurungot, Sreekumar  uhttps://library.ncl.res.in/content/feiii-phytate-metallogel-prototype-anhydrous-intermediate-temperature-proton-conductor-000964nas a2200181   4500008004100000022001400041245007900055210006900134260011000203300001400313490000600327520025200333100001700585700001700602700003100619700002000650856011200670       2015                        eng d  a2046-206900aPhosphate enriched polyoxometalate based ionic salts for proton conduction0 aPhosphate enriched polyoxometalate based ionic salts for proton   aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcDEC  a2333-23370 v53 a<p>A series of [NiMo12O30(PO4)(8)](n-) POM anion and organic cation based ionic composites have been prepared in hydrothermal conditions. The ionic composites with protonated ethylene diamine molecules have been tested for proton conductivity.</p>1 aDey, Chandan1 aKundu, Tanay1 aAiyappa, Harshitha, Barike1 aBanerjee, Rahul  uhttps://library.ncl.res.in/content/phosphate-enriched-polyoxometalate-based-ionic-salts-proton-conduction-001574nas a2200193   4500008004100000022001400041245009000055210006900145260007100214300001400285490000700299520083100306100003101137700001901168700002901187700002001216700002401236856012001260       2016                        eng d  a0897-475600aCobalt-modified covalent organic framework as a robust wateroxidation electrocatalyst0 aCobaltmodified covalent organic framework as a robust wateroxida  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUN  a4375-43790 v283 a<p>The development of stable, efficient oxygen evolution reaction (OER) catalyst capable of oxidizing water is one of the premier challenges in the conversion of solar energy to electrical energy, because of its poor kinetics. Herein, a bipyridine-containing covalent organic framework (TpBpy) is utilized as an OER catalyst by way of engineering active Co(II) ions into its porous framework. The as-obtained Co-TpBpy retains a highly accessible surface area (450 m(2)/g) with exceptional stability, even after 1000 cycles and 24 h of OER activity in phosphate buffer under neutral pH conditions with an overpotential of 400 mV at a current density of 1 mA/cm(2). The unusual catalytic stability of Co-TpBpy arises from the synergetic effect of the inherent porosity and presence of coordinating units in the COF skeleton.</p>1 aAiyappa, Harshitha, Barike1 aThote, Jayshri1 aShinde, Digambar, Balaji1 aBanerjee, Rahul1 aKurungot, Sreekumar  uhttps://library.ncl.res.in/content/cobalt-modified-covalent-organic-framework-robust-wateroxidation-electrocatalyst01626nas a2200217   4500008004100000245008300041210006900124260000800193300001200201490000600213520088800219100001901107700003101126700002301157700002401180700002301204700002901227700002101256700002001277856011101297       2016                        eng d00aConstructing covalent organic frameworks in water via dynamic covalent bonding0 aConstructing covalent organic frameworks in water via dynamic co  cNOV  a402-4070 v33 aThe formation of keto-enamine based crystalline, porous polymers in water is investigated for the first time. Facile access to the Schiff base reaction in water has been exploited to synthesize stable porous structures using the principles of Dynamic Covalent Chemistry (DCC). Most credibly, the water-based Covalent Organic Frameworks (COFs) possess chemical as well as physical properties such as crystallinity, surface area and porosity, which is comparable to their solvothermal counterparts. The formation of COFs in water is further investigated by understanding the nature of the monomers formed using hydroxy and non-hydroxy analogues of the aldehyde. This synthetic route paves a new way to synthesize COFs using a viable, greener route by utilization of the DCC principles in conjunction with the keto-enol tautomerism to synthesize useful, stable and porous COFs in water.1 aThote, Jayshri1 aAiyappa, Harshitha, Barike1 aKumar, Raya, Rahul1 aKandambeth, Sharath1 aBiswal, Bishnu, P.1 aShinde, Digambar, Balaji1 aRoy, Neha, Chaki1 aBanerjee, Rahul  uhttps://library.ncl.res.in/content/constructing-covalent-organic-frameworks-water-dynamic-covalent-bonding01987nas a2200253   4500008004100000022001400041245010200055210006900157260011000226300001400336490000600350520102900356100002901385700003101414700002101445700002301466700001901489700002401508700001801532700001701550700002401567700002001591856012201611       2016                        eng d  a2050-748800aMechanochemically synthesized covalent organic framework as a proton-conducting solid electrolyte0 aMechanochemically synthesized covalent organic framework as a pr  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN  a2682-26900 v43 a<p>Mechanochemistry has become an increasingly important synthetic tool for a waste-free environment. However, the poor quality of the so-derived materials in terms of their crystallinity and porosity has been their major drawback for any practical applications. In this report, we have for the first time successfully leveraged such characteristics to show that the mechanochemically synthesized bipyridine based covalent organic framework (COF) outperforms its conventional solvothermal counterpart as an efficient solid-state electrolyte in PEM fuel cells. Marking the first such attempt in COFs, a Membrane Electrode Assembly (MEA) fabricated using the mechanochemically synthesized COF was observed to inhibit the fuel crossover and build up a stable Open Circuit Voltage (OCV = 0.93 V at 50 degrees C), thereby establishing itself as an effective solid electrolyte material (with a proton conductivity of 1.4 x 10(-2) S cm(-1)), while the solvothermally synthesized COF proved ineffective under similar conditions.</p>1 aShinde, Digambar, Balaji1 aAiyappa, Harshitha, Barike1 aBhadra, Mohitosh1 aBiswal, Bishnu, P.1 aWadge, Pritish1 aKandambeth, Sharath1 aGarai, Bikash1 aKundu, Tanay1 aKurungot, Sreekumar1 aBanerjee, Rahul  uhttps://library.ncl.res.in/content/mechanochemically-synthesized-covalent-organic-framework-proton-conducting-solid-001216nas a2200205   4500008004100000245009200041210006900133260000800202300001400210490000700224520050100231100002100732700001900753700003100772700002400803700002500827700001700852700002000869856012100889       2017                        eng d00aPorous porphyrin organic polymer (PPOP) for visible light triggered hydrogen production0 aPorous porphyrin organic polymer PPOP for visible light triggere  cAPR  a4461-44640 v533 aA visible light active porphyrin-based porous organic polymer having high chemical stability and surface area has been synthesized and its ability to influence the photocatalytic activity of large band gap-TiO2 nanoparticles has been tested. The resultant composite shows improved photocatalytic activity as compared to the parent precursors. This study provides insights into the photosensitizing ability of the polymer in addition to its ability to firmly harbor nanoparticles onto its surface.1 aMukherjee, Gargi1 aThote, Jayshri1 aAiyappa, Harshitha, Barike1 aKandambeth, Sharath1 aBanerjee, Subhrashis1 aVanka, Kumar1 aBanerjee, Rahul  uhttps://library.ncl.res.in/content/porous-porphyrin-organic-polymer-ppop-visible-light-triggered-hydrogen-production02103nas a2200241   4500008004100000022001400041245017400055210006900229260000800298300001400306490000600320520118800326653001401514653002101528653002401549653001501573653002901588100003101617700002801648700003001676700002401706856013101730       2017                        eng d  a2196-021600aSingle cell fabrication towards the realistic evaluation of a CNT-strung ZIF-derived electrocatalyst as a cathode material in alkaline fuel cells and metal-air batteries0 aSingle cell fabrication towards the realistic evaluation of a CN  cNOV  a2928-29330 v43 a<p>The development of an electrocatalyst possessing all the vital requisites of an ideal electrode material, such as high porosity, high conductivity, and high intrinsic electrochemical activity, holds a decisive key in determining the activity of the triplephase boundary in many energy devices like fuel cells and metal-air battery systems. In the present work, highly porous cobalt-based ZIFs are strung along the highly conducive CNT backbone by using a simple one-pot technique at room temperature, which is then utilized to derive a porous, corrosion-resistant, Co nanoparticle-embedded electrocatalyst. Herein, for the first time, the single cell performance of the Co-ZIF-67-derived electrocatalyst has been evaluated by fabricating membrane electrode assemblies of alkaline exchange membrane fuel cell (AEMFC) and zinc-air battery (ZAB) systems. A maximum power density of 296 mW/cm(2) (vs. 317 mW/cm(2) for 40 wt.% Pt/C) and 60 mW/cm(2) (vs. 64 mW/cm(2) for 40 wt.% Pt/C) in the single cells of ZAB and AEMFC systems, respectively, establishes the practical proficiency of the homemade electrocatalyst for cathode applications during realistic system-level validations.</p>10aBatteries10aCarbon nanotubes10aComposite materials10afuel cells10ametal-organic frameworks1 aAiyappa, Harshitha, Barike1 aBhange, Siddheshwar, N.1 aSivasankaran, Vijitha, P.1 aKurungot, Sreekumar  uhttps://library.ncl.res.in/content/single-cell-fabrication-towards-realistic-evaluation-cnt-strung-zif-derived-electrocatalyst