01599nas a2200253 4500008004100000022001400041245014700055210006900202260007100271300001600342490000600358520064800364653002001012653001401032653002501046653001901071100002201090700002001112700002701132700002101159700002101180700001801201856012601219 2013 eng d a1944-824400aSelective imaging of quorum sensing receptors in bacteria using fluorescent Au nanocluster probes surface functionalized with signal molecules0 aSelective imaging of quorum sensing receptors in bacteria using  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcDEC a13076-130810 v53 a

Fluorescent ultrasmall gold clusters decorated with bacterial quorum sensing signal molecules, acyl homoserine lactone, are synthesized. These fluorescent probes are found to have emission in the near-infrared spectral region advantageous for bioimaging. Imaging studies using different. strains of bacteria with and without acyl homoserine lactone receptors with the aid of confocal microscopy have shown that the probe interacts preferentially with cells possessing these receptors. This indicates that, with appropriate surface functionalization, the Au clusters can be used for receptor specific detection with enhanced selectivity.

10aAu nanoclusters10aBiosensor10afluorescence imaging10aquorum sensing1 aMukherji, Ruchira1 aSamanta, Anupam1 aIllathvalappil, Rajith1 aChowdhury, Somak1 aPrabhune, Asmita1 aDevi, Nandini uhttps://library.ncl.res.in/content/selective-imaging-quorum-sensing-receptors-bacteria-using-fluorescent-au-nanocluster-001137nas a2200193 4500008004100000022001400041245015700055210006900212260011000281300001600391490000700407520026900414100002500683700002700708700002800735700002800763700002400791856012800815 2014 eng d a1359-734500aLayer-separated distribution of nitrogen doped graphene by wrapping on carbon nitride tetrapods for enhanced oxygen reduction reactions in acidic medium0 aLayerseparated distribution of nitrogen doped graphene by wrappi aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a13769-137720 v503 a

Layer-separated 3D nitrogen doped graphene (NG) with an accessible interstitial surface and modulated activity characteristics for oxygen reduction in acidic medium could be prepared by wrapping NG sheets on in situ generated carbon nitride (CNx) tetrapods.

1 aUnni, SreeKuttan, M.1 aIllathvalappil, Rajith1 aGangadharan, Pranav, K.1 aBhange, Siddheshwar, N.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/layer-separated-distribution-nitrogen-doped-graphene-wrapping-carbon-nitride-tetrapods-003237nas a2200181 4500008004100000022001400041245014900055210006900204260011000273300001400383490000600397520241500403100002902818700003002847700002702877700002402904856012702928 2014 eng d a1754-569200aNanoporous graphene by quantum dots removal from graphene and its conversion to a potential oxygen reduction electrocatalyst via nitrogen doping0 aNanoporous graphene by quantum dots removal from graphene and it aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a1059-10670 v73 a

A simple way to produce an efficient metal-free oxygen reduction electrocatalyst from graphene by generating nanopores in the matrix and subsequently establishing nitrogen-doped active sites along the pore openings is demonstrated. Well-structured nanoporous graphene (pGr) and photoluminescent graphene quantum dots (GQDs) could be simultaneously generated by a chemically assisted oxidative treatment of graphene. The process helped to knock out small pieces of Gr through epoxide formation, which subsequently resulted in the generation of GQD and pGr simultaneously. A longer oxidation time increased the quantity of GQDs and also resulted in a higher photoluminescent (PL) quantum yield. The PL quantum yield of GQD formed after 72 h of the oxidative treatment (GQD-72) was 15.8%, which is greater than the previous reported values. The TEM images showed matching sizes for GQDs and the pores present in pGr, implying that the pores are generated by the removal of GQDs from graphene during the oxidative treatment. Since pore openings are expected to give higher levels of unsaturation and defect sites in the system and are thus being treated as fertile regions for heteroatom doping, pGr-72 was further subjected to nitrogen (NpGr-72). NpGr-72 displayed excellent activity towards the electrochemical oxygen reduction reaction (ORR) compared to nitrogen-doped non-porous graphene (NGr) and many other reported nitrogen-doped carbon materials. A distinct 50 mV gain in the overpotential and 2.5 times increment in the kinetic current density (j(k)) have been achieved in the case of NpGr-72 compared to NGr. Interestingly, unlike NGr, NpGr-72 effectively reduced the oxygen molecule with a greater involvement of the preferred four-electron pathway. Additionally, the overpotential difference of NpGr-72 with respect to 20 wt% Pt/C is only 60 mV. Additionally, in a single cell evaluation under anion exchange membrane fuel cell (AEMFC) conditions, NpGr-72 exhibited a maximum power density of 27 mW cm(-2), which is significantly higher than the corresponding value of 10 mW cm(-2) obtained for NGr. Thus, the overall enhancement in the performance characteristics of NpGr-72 is attributed to the higher content of nitrogen (7.8 wt%) and its large proportion of desired chemical environment, which could be established by utilizing the high level of carbon unsaturation around the pore openings.

1 aPalaniselvam, Thangavelu1 aValappil, Manila, Ozhukil1 aIllathvalappil, Rajith1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/nanoporous-graphene-quantum-dots-removal-graphene-and-its-conversion-potential-oxygen-002350nas a2200193 4500008004100000022001400041245013500055210006900190260011000259300001600369490000600385520151900391100002101910700002701931700002701958700001801985700002202003856013102025 2014 eng d a2050-748800aNew approach of blending polymeric ionic liquid with polybenzimidazole (PBI) for enhancing physical and electrochemical properties0 aNew approach of blending polymeric ionic liquid with polybenzimi aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN a14449-144580 v23 a

Although the use of ionic liquids (IL) in polymeric membranes is known to elevate the electrochemical performance for proton exchange membrane-based fuel cells (PEMFC), they suffer from drawbacks such as IL drain and lowering in mechanical properties that lead to deterioration in PEMFC performance. To mitigate these issues, we report, for the first time, the use of polymeric ionic liquid (PIL), namely, poly(diallyl dimethyl ammonium trifluoride methane sulphonate) (P[DADMA][TFMS]) to be blended with polybenzimidazole (PBI-I) as a membrane material for PEMFC. PBI-I and (P[DADMA][TFMS]) were chosen because they form miscible blends and are suitable for acid doping as a matrix, which can eventually be used as proton conductor. The structure, miscibility and inter-polymer interactions were studied by infrared (IR) spectroscopy and differential scanning calorimetry (DSC). The increase in proton conduction in comparison to the PBI membranes was observed due to the presence of ionic groups of PILs in blend membranes. With the increase in PIL content, the proton conductivity of the composite membranes gradually increased from 0.04 S cm(-1) for PBI to 0.07 S cm(-1) for the blend membrane at 150 degrees C. The MEAs were fabricated with PBI-I, PBI-PIL15, PBI-PIL25 and PBI-PIL35. Corresponding single cells were successfully tested at temperatures of 160 degrees C. The maximum power density and current density obtained were 515 mW cm(-2) and 1632 mA cm(-2), respectively, for PBI-PIL25-based MEA.

1 aRewar, Anita, S.1 aChaudhari, Harshal, D.1 aIllathvalappil, Rajith1 aSreekumar, K.1 aKharul, Ulhas, K. uhttps://library.ncl.res.in/content/new-approach-blending-polymeric-ionic-liquid-polybenzimidazole-pbi-enhancing-physical-and-002386nas a2200253 4500008004100000022001400041245008400055210006900139260007100208300001600279490000600295520147900301653002101780653002001801653002001821653001401841653003001855100002501885700002701910700002801937700002701965700002401992856011602016 2015 eng d a1944-824400aCarbon nanohorn-derived graphene nanotubes as a platinum-free fuel cell cathode0 aCarbon nanohornderived graphene nanotubes as a platinumfree fuel a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcNOV a24256-242640 v73 a

Current low-temperature fuel cell research mainly focuses on the development of efficient nonprecious electrocatalysts for the reduction of dioxygen molecule due to the reasons like exorbitant cost and scarcity of the current state-of-the-art Pt-based catalysts. As a potential alternative to such costly electrocatalysts, we report here the preparation of an efficient graphene nanotube based oxygen reduction electrocatalyst which has been derived from single walled nanohorns, comprising a thin layer of graphene nanotubes and encapsulated iron oxide nanopartides (FeGNT). FeGNT shows a surface area of 750 m(2)/g, which is the highest ever reported among the metal encapsulated nanotubes. Moreover, the graphene protected iron oxide nanoparticles assist the system to attain efficient distribution of Fe-N-x and quaternary nitrogen based active reaction centers, which provides better activity and stability toward the oxygen reduction reaction (ORR) in acidic as well as alkaline conditions. Single cell performance of a proton exchange membrane fuel cell by using FeGNT as the cathode catalyst delivered a maximum power density of 200 mW cm(-2) with Nafion as the proton exchange membrane at 60 degrees C. The facile synthesis strategy with iron oxide encapsulated graphitic carbon morphology opens up a new horizon of hope toward developing Pt-free fuel cells and metal-air batteries along with its applicability in other energy conversion and storage devices.

10acarbon nanohorns10acarbon nanotube10aelectrocatalyst10afuel cell10aoxygen reduction reaction1 aUnni, SreeKuttan, M.1 aIllathvalappil, Rajith1 aBhange, Siddheshwar, N.1 aPuthenpediakkal, Hasna1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/carbon-nanohorn-derived-graphene-nanotubes-platinum-free-fuel-cell-cathode-002551nas a2200169 4500008004100000022001400041245018300055210006900238260011000307300001600417490000600433520174300439100002702182700002502209700002402234856012302258 2015 eng d a2040-336400aLayer-separated MoS2 bearing reduced graphene oxide formed by an in situ intercalation-cum-anchoring route mediated by Co(OH)(2) as a Pt-free electrocatalyst for oxygen reduction0 aLayerseparated MoS2 bearing reduced graphene oxide formed by an  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a16729-167360 v73 a

A significant improvement in the electrochemical oxygen reduction reaction (ORR) activity of molybdenum sulphide (MoS2) could be accomplished by its layer separated dispersion on graphene mediated by cobalt hydroxide (Co(OH)(2)) through a hydrothermal process (Co(OH)(2)-MoS2/rGO). The activity make-over in this case is found to be originated from a controlled interplay of the favourable modulations achieved in terms of electrical conductivity, more exposure of the edge planes of MoS2 and a promotional role played by the coexistence of Co(OH)(2) in the proximity of MoS2. Co(OH)(2)-MoS2/rGO displays an oxygen reduction onset potential of 0.855 V and a half wave potential (E-1/2) of 0.731 V vs. RHE in 0.1 M KOH solution, which are much higher than those of the corresponding values (0.708 and 0.349 V, respectively) displayed by the as synthesized pristine MoS2 (P-MoS2) under identical experimental conditions. The Tafel slope corresponding to oxygen reduction for Co(OH)(2)-MoS2/rGO is estimated to be 63 mV dec(-1) compared to 68 mV dec(-1) displayed by the state-of-the-art Pt/C catalyst. The estimated number of electrons transferred during oxygen reduction for Co(OH)(2)-MoS2/rGO is in the range of 3.2-3.6 in the potential range of 0.77 V to 0.07 V, which again stands out as valid evidence on the much favourable mode of oxygen reduction accomplished by the system compared to its pristine counterpart. Overall, the present study, thus, demonstrates a viable strategy of tackling the inherent limitations, such as low electrical conductivity and limited access to the active sites, faced by the layered structures like MoS2 to position them among the group of potential Pt-free electrocatalysts for oxygen reduction.

1 aIllathvalappil, Rajith1 aUnni, SreeKuttan, M.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/layer-separated-mos2-bearing-reduced-graphene-oxide-formed-situ-intercalation-cum-002284nas a2200205 4500008004100000022001400041245019700055210006900252260000900321300001200330490000700342520145200349100002501801700002801826700002701854700001901881700002401900700002401924856013001948 2015 eng d a1613-681000aNitrogen-induced surface area and conductivity modulation of carbon nanohorn and its function as an efficient metal-free oxygen reduction electrocatalyst for anion-exchange membrane fuel cells0 aNitrogeninduced surface area and conductivity modulation of carb cJAN  a352-3600 v113 a

Nitrogen-doped carbon morphologies have been proven to be better alternatives to Pt in polymer-electrolyte membrane (PEM) fuel cells. However, efficient modulation of the active sites by the simultaneous escalation of the porosity and nitrogen doping, without affecting the intrinsic electrical conductivity, still remains to be solved. Here, a simple strategy is reported to solve this issue by treating single-walled carbon nanohorn (SWCNH) with urea at 800 degrees C. The resulting nitrogen-doped carbon nanohorn shows a high surface area of 1836 m(2) g(-1) along with an increased electron conductivity, which are the pre-requisites of an electro catalyst. The nitrogen-doped nanohorn annealed at 800 degrees C (N-800) also shows a high oxygen reduction activity (ORR). Because of the high weight percentage of pyridinic nitrogen coordination in N-800, the present catalyst shows a clear 4-electron reduction pathway at only 50 mV overpotential and 16 mV negative shift in the half-wave potential for ORR compared to Pt/C along with a high fuel selectivity and electrochemical stability. More importantly, a membrane electrode assembly (MEA) based on N-800 provides a maximum power density of 30 mW cm(-2) under anion-exchange membrane fuel cell (AEMFC) testing conditions. Thus, with its remarkable set of physical and electrochemical properties, this material has the potential to perform as an efficient Pt-free electrode for AEMFCs.

1 aUnni, SreeKuttan, M.1 aBhange, Siddheshwar, N.1 aIllathvalappil, Rajith1 aMutneja, Nisha1 aPatil, Kasinath, R.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/nitrogen-induced-surface-area-and-conductivity-modulation-carbon-nanohorn-and-its-function02123nas a2200193 4500008004100000022001400041245011800055210006900173260011000242300001400352490000600366520130200372100002501674700002001699700002701719700002801746700002401774856013101798 2015 eng d a2050-748800aSurface-modified single wall carbon nanohorn as an effective electrocatalyst for platinum-free fuel cell cathodes0 aSurfacemodified single wall carbon nanohorn as an effective elec aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a4361-43670 v33 a

Platinum (Pt) and its alloys are routinely used in the cathodes of polymer electrolyte membrane fuel cells (PEMFCs) due to their high electrocatalytic activity in oxygen reduction reactions (ORRs). A variety of alternative materials have been examined as alternatives to Pt, but most of these had low activity and their performance deteriorated even further in use. In the present study an alternate electrocatalyst has been examined, obtained by a simple surface modification of single-walled carbon nanohorns by simultaneous doping with Fe and N at 900 degrees C (FeNCNH-900). This had an ORR activity superior to that of 40 wt% Pt on carbon (Pt/C). Compared to Pt/C, FeNCNH-900 gave a 30 mV improvement in onset potential and a 20 mV gain in half-wave potential in an ORR. Its high activity is the result of the simultaneous modulation achieved by the high surface area and the microporosity of carbon nanohorns, together with the establishment of the desired nitrogen-iron coordinated pyrrolic active centres. The catalyst showed excellent electrochemical stability and, most notably, its ORR activity was still increasing after 1000 cycles. Single-cell fuel cell performance using FeNCNH-900 as cathode catalyst showed a maximum power density of 35 mW cm(-2) under alkaline conditions.

1 aUnni, SreeKuttan, M.1 aRamadas, Sarath1 aIllathvalappil, Rajith1 aBhange, Siddheshwar, N.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/surface-modified-single-wall-carbon-nanohorn-effective-electrocatalyst-platinum-free-fuel-000941nas a2200181 4500008004100000022001400041245009800055210006900153260011000222300001200332490000700344520017600351100002300527700002700550700002400577700003000601856012800631 2016 eng d a1359-734500aConjugated porous polymers as precursors for electrocatalysts and storage electrode materials0 aConjugated porous polymers as precursors for electrocatalysts an aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcOCT a316-3180 v523 a

Conjugated porous polymers were used as precursors to prepare nitrogen and sulphur doped carbon atoms, which were then used for oxygen reduction and energy storage.

1 aBhosale, Manik, E.1 aIllathvalappil, Rajith1 aKurungot, Sreekumar1 aKrishnamoorthy, Kothandam uhttps://library.ncl.res.in/content/conjugated-porous-polymers-precursors-electrocatalysts-and-storage-electrode-materials-001952nas a2200289 4500008004100000022001400041245010900055210006900164260000900233300001600242490000700258520096700265653001601232653003901248653003401287653002201321653001501343100002201358700002701380700002501407700001801432700002001450700002101470700002401491700002101515856012601536 2016 eng d a1433-785100aHydrogen-bonded organic frameworks (HOFs): a new class of porous crystalline proton-conducting materials0 aHydrogenbonded organic frameworks HOFs a new class of porous cry cAUG  a10667-106710 v553 a

Two porous hydrogen-bonded organic frameworks (HOFs) based on arene sulfonates and guanidinium ions are reported. As a result of the presence of ionic backbones appended with protonic source, the compounds exhibit ultra-high proton conduction values (sigma) 0.75x 10(-2)Scm(-1) and 1.8x10(-2)Scm(-1) under humidified conditions. Also, they have very low activation energy values and the highest proton conductivity at ambient conditions (low humidity and at moderate temperature) among porous crystalline materials, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). These values are not only comparable to the conventionally used proton exchange membranes, such as Nafion used in fuel cell technologies, but is also the highest value reported in organic-based porous architectures. Notably, this report inaugurates the usage of crystalline hydrogen-bonded porous organic frameworks as solid-state proton conducting materials.

10aguanidinium10ahydrogen-bonded organic frameworks10aporous crystalline frameworks10aproton conduction10asulfonates1 aKarmakar, Avishek1 aIllathvalappil, Rajith1 aAnothumakkool, Bihag1 aSen, Arunabha1 aSamanta, Partha1 aDesai, Aamod, V.1 aKurungot, Sreekumar1 aGhosh, Sujit, K. uhttps://library.ncl.res.in/content/hydrogen-bonded-organic-frameworks-hofs-new-class-porous-crystalline-proton-conducting02113nas 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-catalyst01808nas a2200205 4500008004100000022001400041245012700055210006900182260011000251300001600361490000700377520096600384100001801350700002801368700002701396700001801423700002401441700001801465856011901483 2016 eng d a1463-907600aUnderstanding the electron transfer process in ZnO-naphthol azobenzoic acid composites from photophysical characterisation0 aUnderstanding the electron transfer process in ZnOnaphthol azobe aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcAUG a22179-221870 v183 a

Semiconductor nanoparticles surface modified with organic molecules capable of visible light absorption and effectively transferring the electrons to the catalytic sites have the potential to be good photocatalysts. ZnO nanoparticles of size similar to 3 nm are grafted with two azonaphthols, one conjugated and the other non-conjugated. The photophysical properties of modified ZnO indicate an effective electron transfer from the conjugated azonaphthol to ZnO but not in the case of the non-conjugated molecule. It is also observed from lifetime studies that the conjugated molecule stabilises the defect sites on ZnO nanoparticles. It is possible that excited electrons from the conjugated molecule are transferred to specific defect sites in ZnO. This apparently does not occur in the non-conjugated molecule, bringing to focus the importance of the photophysical characteristics of organic modifiers in designing visible light active photocatalysts.

1 aGeorge, Leena1 aKunhikannan, Athira, K.1 aIllathvalappil, Rajith1 aOttoor, Divya1 aKurungot, Sreekumar1 aDevi, Nandini uhttps://library.ncl.res.in/content/understanding-electron-transfer-process-zno-naphthol-azobenzoic-acid-composites02503nas a2200289 4500008004100000022001400041245016700055210006900222260000800291300001400299490000600313520146900319653002001788653001401808653002201822653003001844100002501874700002701899700002401926700002401950700001801974700002101992700003002013700002002043700002002063856013002083 2017 eng d a2365-654900aChitosan intercalated metal organic gel as a green precursor of fe entrenched and fe distributed N-doped mesoporous graphitic carbon for oxygen reduction reaction0 aChitosan intercalated metal organic gel as a green precursor of  cSEP a8762-87700 v23 a

Herein, we present Metal-Organic Gel intercalated with chitosan, a `green'' precursor for the synthesis of intrinsic N-doped Fe entrenched (CHI-TMA-Fe-CW) and Fe distributed mesoporous graphitic carbon structures (CHI-TMA-Fe-CW-M1) with appreciable Oxygen Reduction Reaction (ORR) activity in alkaline medium. Modulation of the synthetic protocol as a function of reaction kinetics and gelation time while maintaining identical pyrolysis conditions (900 degrees C, flowing N-2 atmosphere) improves the microstructure, surface area and Fe distribution of the graphitic structures (CHI-TMA-Fe-CW-M1). CHI-TMA-Fe-CW has a Fe entrenched graphitic nanocapsule like morphology while Fe distributed mesoporous graphitic carbon sheets, with a specific surface area value of 565 m(2) g(-1) obtained by modulating the synthesis chemistry in CHI-TMA-Fe-CW-M1. The higher percentage of graphitic N in CHI-TMA-Fe-CW-M1 apparent from the XPS data validate that the modified synthetic method favours creation of more graphitic N sites contributing for better catalytic performance. CHI-TMA-Fe-CW-M1 catalyst exhibited comparable electrocatalytic activity with that of the commercially available Pt/C via an efficient four-electron-dominant ORR pathway with a positive onset potential value of 0.925 V vs RHE. Good durability of CHI-TMA-Fe-CW-M1 after 5000 cycles further confirm the prospects of MOG-chitosan and the feasibility to be used as a potential catalyst for ORR.

10aelectrocatalyst10afuel cell10aMetal-Organic-Gel10aoxygen reduction reaction1 aShijina, Kottarathil1 aIllathvalappil, Rajith1 aKurungot, Sreekumar1 aNair, Balagopal, N.1 aMohamed, Peer1 aYamaguchi, Takeo1 aAnilkumar, Gopinathan, M.1 aHareesh, U., S.1 aSailaja, G., S. uhttps://library.ncl.res.in/content/chitosan-intercalated-metal-organic-gel-green-precursor-fe-entrenched-and-fe-distributed-n02740nas a2200169 4500008004100000245019800041210006900239260000800308300001400316490000600330520200500336100002702341700002402368700002802392700002402420856012602444 2017 eng d00aNitrogen-doped graphene anchored with mixed growth patterns of CuPt alloy nanoparticles as a highly efficient and durable electrocatalyst for the oxygen reduction reaction in an alkaline medium0 aNitrogendoped graphene anchored with mixed growth patterns of Cu cJUL a9009-90170 v93 a

A highly active and durable CuPt alloy catalyst with trigonal bipyramidal and truncated cube-type mixed morphologies, anchored on the nitrogen-doped graphene (NGr) surface (CuPt-TBTC/NGr), was prepared by a simple and fast method. The obtained CuPt alloy showed improved oxygen reduction reaction (ORR) activity, with a 30 mV positive shift in the half-wave potential value, as compared to the state-of-the-art Pt/C catalyst in a 0.1 M KOH solution. The CuPt alloy with the trigonal bipyramidal morphology possesses porous type inter-connected sides, which help to achieve improved mass transport of oxygen during the ORR. The exposure of the (111) plane of the CuPt alloy further improved the catalytic activity towards the dioxygen reduction in alkaline media. The ORR activity of the NGr-supported CuPt alloy was found to be dependent on the reaction time, and improved activity was obtained on the material derived at a reaction time of 90 min (CuPt-TBTC/NGr-90). The material synthesized at a lower or higher reaction time than 90 min resulted in a partially formed trigonal bipyramidal morphology with more truncated cubes or agglomerated trigonal bipyramidal and truncated cubes with closed type structures, respectively. Along with the high intrinsic ORR activity, CuPt-TBTC/NGr-90 displayed excellent electrochemical stability. Even after repeated 1000 potential cycling in a window ranging from 0.10 to 1.0 V (vs. RHE), the system clearly outperformed the state-of-the-art Pt/C catalyst with 15 and 60 mV positive shifts in the onset and half-wave potentials, respectively. CuPt-TBTC/NGr-90 also exhibited 2.1 times higher mass activity and 2.2 times higher specific activity, compared to Pt/C at 0.90 V (vs. RHE). Finally, a zinc-air battery fabricated with the alloy catalyst as the air electrode displayed a peak power density of 300 mW cm(-2), which is much higher than the peak power density of 253 mW cm(-2) obtained for the state-of-the-art Pt/C catalyst as the air electrode.

1 aIllathvalappil, Rajith1 aDhavale, Vishal, M.1 aBhange, Siddheshwar, N.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/nitrogen-doped-graphene-anchored-mixed-growth-patterns-cupt-alloy-nanoparticles-highly01579nas a2200205 4500008004100000245008700041210006900128260000800197300001400205490000700219520088200226100001801108700002101126700002701147700001701174700001801191700002401209700002101233856011901254 2017 eng d00aUltrahigh ionic conduction in water-stable close-packed metal-carbonate frameworks0 aUltrahigh ionic conduction in waterstable closepacked metalcarbo cAUG a9710-97150 v563 aUtilization of the robust metal-carbonate backbone in a series of water-stable, anionic frameworks has been harnessed for the function of highly efficient solid-state ion conduction. The compact organization of hydrophilic guest ions facilitates water-assisted ion-conduction in all the compounds. The dense packing of the compounds imparts high ion-conducting ability and minimizes the possibility of fuel crossover, making this approach promising for design and development of compounds as potential components of energy devices. This work presents the first report of evaluating ion-conduction in a purely metal-carbonate framework, which exhibits high ion-conductivity on the order of 10(-2) S cm(-1) along with very low activation energy, which is comparable to highly conducting well-known crystalline coordination polymers or commercialized organic polymers like Nafion.1 aManna, Biplab1 aDesai, Aamod, V.1 aIllathvalappil, Rajith1 aGupta, Kriti1 aSen, Arunabha1 aKurungot, Sreekumar1 aGhosh, Sujit, K. uhttps://library.ncl.res.in/content/ultrahigh-ionic-conduction-water-stable-close-packed-metal-carbonate-frameworks02277nas a2200289 4500008004100000022001400041245014000055210006900195260000800264300001400272490000600286520128800292653002001580653001401600653002601614653003001640653001001670100001801680700002701698700002401725700002401749700001801773700003001791700002101821700002001842856012501862 2018 eng d a2365-654900aMorphological ensembles of N-doped porous carbon derived from ZIF-8/Fe-graphene nanocomposites: processing and electrocatalytic studies0 aMorphological ensembles of Ndoped porous carbon derived from ZIF cAUG a8688-86970 v33 a

Engineering the active site density of porous carbon catalysts for enhanced electrocatalytic activity is the current focus in the quest for economically viable fuel cells. Herein, we synthesise ZIF-8/Fe-graphene composites for the formation of N and Fe co-doped carbon with diverse morphologies ranging from tubes and sheets to frameworks of carbon. A synthetic strategy involving the one pot synthesis of ZIF-8 based composites is accomplished by the reaction of 2-methylimidazole with mixed Zn/Fe salt solution containing graphene dispersions. The high temperature heat treatment of this precursor mix yielded micro-meso porous architectures of N, Fe co-doped carbon with dispersions of Fe/Fe3C. An onset potential value of 0.95 V and a half-wave potential of 0.82 V coupled with excellent durability and stability in alkaline medium indicated improved electrocatalytic performances over its commercial Pt/C counterpart. The appreciable electrocatalytic properties of the synthesized carbon are attributed to its morphological diversity, hybrid structure, high N doping and its heteroporous characteristics. The dispersed Fe/Fe3C and FeNx sites facilitated enhanced oxygen adsorption and the graphene inclusions in the composite provided retention of high nitrogen contents.

10aelectrocatalyst10afuel cell10aN- Fe co-doped carbon10aoxygen reduction reaction10aZIF-81 aThomas, Minju1 aIllathvalappil, Rajith1 aKurungot, Sreekumar1 aNair, Balagopal, N.1 aMohamed, Peer1 aAnilkumar, Gopinathan, M.1 aYamaguchi, Takeo1 aHareesh, U., S. uhttps://library.ncl.res.in/content/morphological-ensembles-n-doped-porous-carbon-derived-zif-8fe-graphene-nanocomposites01865nas a2200181 4500008004100000022001500041245010000056210006900156260000800225300001200233490000800245520120500253100002701458700002701485700002401512700002201536856012501558 2018 eng d a 0376-738800aPreparation and investigations of ABPBI membrane for HT-PEMFC by immersion precipitation method0 aPreparation and investigations of ABPBI membrane for HTPEMFC by  cOCT a211-2170 v5643 aPoly(2,5-benzimidazole) (ABPBI) membranes were prepared by an easy and benign 'immersion precipitation' method; alleviating drawbacks of conventional solution casting method involving evaporation of the corrosive solvent. The importance of varying inherent viscosity on the properties of resulting membranes was investigated. The porous membranes formed by immersion precipitation method were analyzed for basic properties (water flux, porosity and dimensional analysis). Since the dense structure is required for their applicability for a fuel cell, through-porosity of the formed membranes was successfully eliminated using a unique shrinkage (similar to 50%) property of ABPBI, initially, at 60 degrees C followed by at higher temperature. The correlation of membranes annealing temperature with the mechanical properties, phosphoric acid doping and proton conductivity was established. The present membranes exhibited high doping level (5.1 mol/RU), proton conductivity (0.083 S cm(-1)) and fuel cell performance. For comparison, solution casted membranes were prepared and analyzed. The OCP (0.91 V) and max power density (766mWcm(-2)) are quite promising features of this new type of membranes.1 aChaudhari, Harshal, D.1 aIllathvalappil, Rajith1 aKurungot, Sreekumar1 aKharul, Ulhas, K. uhttps://library.ncl.res.in/content/preparation-and-investigations-abpbi-membrane-ht-pemfc-immersion-precipitation-method02273nas a2200229 4500008004100000022001300041245012200054210006900176260000800245300001400253490000700267520144600274100002501720700002101745700002701766700002401793700002401817700002501841700002401866700002301890856013001913 2018 eng d a1466803300aWater mediated proton conductance in a hydrogen-bonded Ni(II)-bipyridine-glycoluril chloride self-assembled framework0 aWater mediated proton conductance in a hydrogenbonded NiIIbipyri cJAN a1094-11000 v203 a

Proton conducting properties have been investigated in a new Ni(II)-based hydrogen-bonded porous framework synthesized using a urea-fused bipyridine-glycoluril (BPG) tecton. This hydrogen-bonded self-assembled structure encapsulates water molecules in the channels with hydrogen-bonding networks which exhibits a significant temperature dependent proton conductance of 1.5 × 10−4 S cm−1 at 95 °C and 95% RH with a low activation energy (Ea) of 0.54 eV, implying a Grotthuss proton hopping mechanism mediated by hydrogen-bonded water molecules in the channels. In addition, this framework exhibited a very high water uptake under humid conditions. A continuous array of water molecules and chloride ions embedded in the highly hydrophilic porous channels of the hydrogen-bonded framework acts as the proton conducting medium.

 

 

1 aTayade, Sakharam, B.1 aBhat, Satish, S.1 aIllathvalappil, Rajith1 aDhavale, Vishal, M.1 aKawade, Vitthal, A.1 aKumbhar, Avinash, S.1 aKurungot, Sreekumar1 aNäther, Christian uhttps://library.ncl.res.in/content/water-mediated-proton-conductance-hydrogen-bonded-niii-bipyridine-glycoluril-chloride-self02337nas 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-showing02899nas a2200205 4500008004100000245012800041210006900169260000800238300001600246490000700262520213600269100002502405700002702430700002302457700001802480700002402498700002402522700002502546856012202571 2019 eng d00aA copper(ii)-coordination polymer based on a sulfonic-carboxylic ligand exhibits high water-facilitated proton conductivity0 acopperiicoordination polymer based on a sulfoniccarboxylic ligan cAUG a11034-110440 v483 a

Proton conduction ability has been investigated in a new Cu(ii) based coordination polymer (CP), {[Cu-2(sba)(2)(bpg)(2)(H2O)(3)]center dot 5H(2)O}(n) (1), synthesized using the combination of 4-sulfobenzoic acid (4-Hsba) and bipyridine-glycoluril (BPG) ligands. Single crystal X-ray structure determination revealed that 1 features 1D porous channels encapsulating a continuous array of water molecules. Proton conductivity measurements reveal a high conductivity value of 0.94 x 10(-2) S cm(-1) at 80 degrees C and 95% RH. The activation energy (E-a) of 0.64 eV demonstrates that the solvate water, coordinated water and hydrophilic groups in the channels promote the mobility of protons in the framework. Water sorption measurements exhibited hysterical behaviour with a high uptake value of 379.07 cm(3) g(-1). Time-dependent measurements revealed that the proton conductivity is retained even after 12 h of measurements. The proton conduction mechanism was validated by ab initio electronic structure calculations using the Nudged Elastic Band (NEB) method with molecular dynamics (MD) simulation studies. The theoretical activation energy is calculated to be 0.54 eV which is in accordance with the experimental value.

1 aTayade, Sakharam, B.1 aIllathvalappil, Rajith1 aLapalikar, Vaidehi1 aMarkad, Datta1 aKurungot, Sreekumar1 aPujari, Bhatchandra1 aKumbhar, Avinash, S. uhttps://library.ncl.res.in/content/copperii-coordination-polymer-based-sulfonic-carboxylic-ligand-exhibits-high-water02253nas a2200253 4500008004100000022001400041245011800055210006900173260000900242300001200251490000800263520137900271653002701650653002301677653001401700653002401714653002401738100001901762700002101781700002701802700002401829700001401853856013201867 2019 eng d a0013-468600aStudies on nano composites of SPEEK/ethylene glycol/cellulose nanocrystals as promising proton exchange membranes0 aStudies on nano composites of SPEEKethylene glycolcellulose nano cJAN  a260-2720 v2933 a

The present work deals with fabrication and characterisations of nano-composite membranes composed of sulfonated poly (ether ether ketone) (SPEEK) cross-linked and reinforced with ethylene glycol (EG) and cellulose nanocrystals (CNCs) respectively. The thin films of cross-linked composite membranes were prepared by solvent casting method and further analysed for physicochemical and electrochemical properties to execute their applicability as promising proton exchange membrane (PEM) in fuel cells. The process of cross-linking helps to improve the strength and dimensional stability of bare SPEEK membranes without compromising with conductivity. However, presence of CNCs further improves the strength and provides an effective pathway for the conduction of protons in membranes by interacting through their surface hydroxyl and sulfonic acid groups with ionic moieties of polymer matrix. All prepared composite membranes showed good oxidative and thermal stability along with good proton conductivity. The cross-linked SPEEK membranes with 4 wt% loading of CNCs possess an appreciable proton conductivity of 0.186 S/cm at 95 degrees C and 95% RH which is comparable to Nafion 117. From the view point of above studies, the prepared nano-composite can be described as promising proton exchange membrane for fuel cells. (c) 2018 Elsevier Ltd. All rights reserved.

10aCellulose nanocrystals10aCross-linked SPEEK10afuel cell10aoxidative stability10aproton conductivity1 aBano, Saleheen1 aNegi, Yuvraj, S.1 aIllathvalappil, Rajith1 aKurungot, Sreekumar1 aRamya, K. uhttps://library.ncl.res.in/content/studies-nano-composites-speekethylene-glycolcellulose-nanocrystals-promising-proton-exchange02390nas a2200217 4500008004100000022001400041245015200055210006900207260000800276300001400284490000600298520158300304653001901887653001501906653001801921653002601939653003001965100002701995700002402022856012602046 2020 eng d a2196-021600aCo (9) S (8) nanoparticle-supported nitrogen-doped carbon as a robust catalyst for oxygen reduction reaction in both acidic and alkaline conditions0 aCo 9 S 8 nanoparticlesupported nitrogendoped carbon as a robust  cJUL a3123-31340 v73 a

The present work illustrates the synthesis of an efficient and durable catalyst for electrochemical oxygen reduction reaction (ORR) which is active both in the alkaline and acidic conditions by dispersing few-layer graphitic carbon coated Co(9)S(8)nanoparticles on the nitrogen-doped carbon (NVC-G) support (Co9S8/NVC-G). The size of the Co(9)S(8)nanoparticles is nearly 7-8 nm and the particles are found to be dispersed homogeneously on the NVC-G support. The few-layer graphitic carbon formed on the surface of Co(9)S(8)nanoparticles is assisting to accomplish their small size and it also prevents agglomeration of the nanoparticles. The ORR activity of the obtained material was analyzed in both 0.1 M KOH and 0.5 M H(2)SO(4)solutions. Co9S8/NVC-G displays nearly 70 mV overpotential compared to thestate-of-the-artPt/C in 0.1 M KOH solution. The half-wave potential (E-1/2) difference of the present system is nearly 75 mV with the commercial Pt/C. Co9S8/NVC-G displays promising ORR activity in the acidic conditions as well with nearly 140 mV overpotential compared to its Pt/C counterpart. The system shows about 170 mV lowerE(1/2)value with Pt/C. The system shows good stability both in acidic and basic conditions compared to the Pt/C system. Finally, testing of a single cell of a polymer electrolyte membrane fuel cell (PEMFC) was performed by employing Co9S8/NVC-G as the cathode catalyst and Nafion-212 as the proton exchange membrane. The system displays a maximum power density of 245 mW cm(-2)in H-2-O(2)and 115 mW cm(-2)in H-2-air feeding conditions.

10acobalt sulfide10afuel cells10aNanoparticles10anitrogen-doped carbon10aoxygen reduction reaction1 aIllathvalappil, Rajith1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/co-9-s-8-nanoparticle-supported-nitrogen-doped-carbon-robust-catalyst-oxygen-reduction01677nas a2200301 4500008004100000022001400041245015300055210006900208260001000277300001100287490000800298520065100306653001400957653002700971653001700998653000801015100002501023700002701048700001301075700002001088700002201108700002401130700003001154700002401184700002101208700002001229856012601249 2020 eng d a0167-577X00aFe3+ stabilized 3D cross-linked glycine-melamine formaldehyde networks as precursor for highly efficient oxygen reduction catalyst in alkaline media0 aFe3 stabilized 3D crosslinked glycinemelamine formaldehyde netwo cAPR 1 a1273650 v2643 a

Development of inexpensive oxygen reduction electrocatalyst with high activity and durability is very important. Herein, iron carbide encapsulated pod-like graphitic carbon structures were prepared by simple pyrolysis involving Fe-glycine complex integrated melamine-formaldehyde resin precursor. The best catalyst among those studied, Fe-Gly 2 MF-C, possessing high degree of graphitization (I-D /I-G = 0.99) and enhanced specific surface area (205 m(2)/g) exhibited the highest ORR activity with a half-wave potential of 0.80 V in alkaline medium through the four-electron reduction pathway. (C) 2020 Elsevier B.V. All rights reserved.

10afuel cell10aGraphitic carbon alloy10aIron carbide10aORR1 aKottarathil, Shijina1 aIllathvalappil, Rajith1 aNisa, S.1 aSailaja, G., S.1 aMohamed, Peer, A.1 aNair, Balagopal, N.1 aGopinathan, Anilkumar, M.1 aKurungot, Sreekumar1 aYamaguchi, Takeo1 aHareesh, U., S. uhttps://library.ncl.res.in/content/fe3-stabilized-3d-cross-linked-glycine-melamine-formaldehyde-networks-precursor-highly02910nas a2200265 4500008004100000022001400041245014100055210006900196260000900265300001400274490000700288520197300295653001902268653002102287653002302308653002802331653002102359100002702380700002402407700002702431700002102458700001802479700002402497856012302521 2020 eng d a0947-653900aHierarchical nanoflower arrays of Co9S8-Ni3S2 on nickel foam: a highly efficient binder-free electrocatalyst for overall water splitting0 aHierarchical nanoflower arrays of Co9S8Ni3S2 on nickel foam a hi cJUN  a7900-79110 v263 a

Hydrogen production is vital for meeting future energy demands and managing environmental sustainability. Electrolysis of water is considered as the suitable method for H-2 generation in a carbon-free pathway. Herein, the synthesis of highly efficient Co9S8-Ni3S2 based hierarchical nanoflower arrays on nickel foam (NF) is explored through the one-pot hydrothermal method (Co9S8-Ni3S2/NF) for overall water splitting applications. The nanoflower arrays are self-supported on the NF without any binder, possessing the required porosity and structural characteristics. The obtained Co9S8-Ni3S2/NF displays high hydrogen evolution reaction (HER), as well as oxygen evolution reaction (OER), activities in 1 m KOH solution. The overpotentials exhibited by this system at 25 mA cm(-2) are nearly 277 and 102 mV for HER and OER, respectively, in 1 m KOH solution. Subsequently, the overall water splitting was performed in 1 m KOH solution by employing Co9S8-Ni3S2/NF as both the anode and cathode, where the system required only 1.49, 1.60, and 1.69 V to deliver the current densities of 10, 25, and 50 mA cm(-2), respectively. Comparison of the activity of Co9S8-Ni3S2/NF with the state-of-the-art Pt/C and RuO2 coated on NF displays an enhanced performance for Co9S8-Ni3S2/NF both in the half-cell as well as in the full cell, emphasizing the significance of the present work. The post analysis of the material after water electrolysis confirms that the surface Co(OH)(2) formed during the course of the reaction serves as the favorable active sites. Overall, the activity modulation achieved in the present case is attributed to the presence of the open-pore morphology of the as formed nanoflowers of Co9S8-Ni3S2 on NF and the simultaneous presence of the surface Co(OH)(2) along with the highly conducting Co9S8-Ni3S2 core, which facilitates the adsorption of the reactants and subsequently its conversion into the gaseous products during water electrolysis.

10acobalt sulfide10aelectrocatalysts10aHydrogen evolution10aoverall water splitting10aoxygen evolution1 aIllathvalappil, Rajith1 aWalko, Priyanka, S.1 aKanheerampockil, Fayis1 aBhat, Suresh, K.1 aDevi, Nandini1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/hierarchical-nanoflower-arrays-co9s8-ni3s2-nickel-foam-highly-efficient-binder-free02343nas a2200253 4500008004100000022001400041245014800055210006900203260000900272300001600281490000700297520143700304100002301741700001801764700002701782700001601809700002401825700002401849700001801873700003001891700002101921700002001942856012701962 2020 eng d a1144-054600aTemplate assisted synthesis of Ni,N co-doped porous carbon from Ni incorporated ZIF-8 frameworks for electrocatalytic oxygen reduction reaction0 aTemplate assisted synthesis of NiN codoped porous carbon from Ni cJUL  a12343-123540 v443 a

A heteroatom doped porous carbon electrocatalyst with enhanced oxygen reduction reaction (ORR) performance in alkaline medium was obtained by high temperature treatment of Ni incorporated ZIF-8 frameworks and its composite with g-C(3)N(4)as a supporting matrix template. The morphology and porosity of this heteroatom containing carbon were tuned by varying the Ni : Zn molar ratio in Ni/Zn ZIF-8 and Ni/Zn ZIF-8@g-C(3)N(4)composites. The template aided synthetic strategy using g-C(3)N(4)helped in the controlled decomposition of composites leading to a heteroporous sheet like architecture with increased nitrogen content. The Ni/Zn ZIF-8 sample on heat treatment in the 800-1000 degrees C temperature range led to the formation of Ni,N co-doped porous carbon (Ni-NPC) with Ni-C active sites. The defective sites induced by nickel carbide along with the distributed N atoms on the carbon surface enabled active O(2)adsorption sites. The high surface area, high degree of graphitisation as well as the defects created by well dispersed N and Ni on porous carbon matrices favoured charge separation leading to higher electrochemical ORR activity. The Ni,N co-doped carbon catalyst in alkaline medium exhibited a limiting current density of 5.2 mA cm(-2)with a half-wave potential of 0.76 Vvs.RHE in 0.1 M KOH. The catalyst also showed improved methanol tolerance and better stability compared to the standard Pt/C catalyst.

1 aK., Vaishna, Priya1 aThomas, Minju1 aIllathvalappil, Rajith1 aK., Shijina1 aKurungot, Sreekumar1 aNair, Balagopal, N.1 aMohamed, Peer1 aAnilkumar, Gopinathan, M.1 aYamaguchi, Takeo1 aHareesh, U., S. uhttps://library.ncl.res.in/content/template-assisted-synthesis-nin-co-doped-porous-carbon-ni-incorporated-zif-8-frameworks01684nas a2200205 4500008004100000022001400041245011400055210006900169260000800238300001400246490000700260520095000267100002001217700001801237700002401255700002701279700002401306700002101330856012701351 2022 eng d a1359-734500aEnhanced proton conductivity in amino acid based self-assembled non-porous hydrogen-bonded organic frameworks0 aEnhanced proton conductivity in amino acid based selfassembled n cMAY a5972-59750 v583 a

beta-Alaninium oxalate hemihydrate, glycinium oxalate, and L-leucinium oxalate salt-cocrystals as non-porous self-assembled hydrogen-bonded organic frameworks afforded proton conductivity of 2.43 x 10(-2) S cm(-1) (60 degrees C, 95% RH), 3.03 x 10(-2) S cm(-1) (60 degrees C, 95% RH), and 1.19 x 10(-2) S cm(-1) (80 degrees C, 95% RH), respectively. These materials possess an extensive 3-dimensional network of hydrogen bonds in their crystal structures, making them efficient proton conducting membranes. The reduction in conductivity values over 10(-1) S cm(-1) order upon exposure of the samples to a D2O atmosphere in extreme conditions ratified the role of humidity for the conduction of protons. This work explores the relationship between structural features and proton conductivity for the design of proton conducting membranes that are easy to synthesize, eco-friendly, and cheap with potential for futuristic applications.

1 aPramanik, Titas1 aAnand, Ashish1 aPandikassala, Ajmal1 aIllathvalappil, Rajith1 aKurungot, Sreekumar1 aRow, T., N. Guru uhttps://library.ncl.res.in/content/enhanced-proton-conductivity-amino-acid-based-self-assembled-non-porous-hydrogen-bonded01378nas a2200217 4500008004100000022001400041245012800055210006900183260001100252300001400263490000700277520059000284100001800874700002700892700001900919700001800938700002400956700002400980700002501004856013101029 2022 eng d a1523-706000aSynthesis of a highly electron-deficient, water-stable, large ionic box: multielectron accumulation and proton conductivity0 aSynthesis of a highly electrondeficient waterstable large ionic  cAPR 19 a3038-30420 v243 a

pi-acidic boxes exhibiting electron reservoir and proton conduction are unprecedented because of their instability in water. We present the synthesis of one of the strongest electron-deficient ionic boxes showing e(-) uptake as well as proton conductivity. Two large anions fit in the box to form anion-pi interactions and form infinite anion-solvent wires. The box with NO3-center dot center dot center dot water wires confers high proton conductivity and presents the first example that manifests redox and ionic functionality in an organic electron-deficient macrocycle.

1 aShukla, Jyoti1 aIllathvalappil, Rajith1 aKumar, Sharvan1 aChorol, Sonam1 aPandikassala, Ajmal1 aKurungot, Sreekumar1 aMukhopadhyay, Pritam uhttps://library.ncl.res.in/content/synthesis-highly-electron-deficient-water-stable-large-ionic-box-multielectron-accumulation02689nas a2200337 4500008004100000022001400041245014200055210006900197260000800266490000700274520145100281653004201732653003801774653002701812653003601839653003601875653002801911653002301939100002001962700003001982700002702012700003002039700002702069700002402096700002102120700001802141700001802159700002602177700002402203856012402227 2023 eng d a1613-681000aActive site engineering and theoretical aspects of ``Superhydrophilic'' nanostructure array enabling efficient overall water electrolysis0 aActive site engineering and theoretical aspects of Superhydrophi cDEC0 v193 a

The rational design of noble metal-free electrocatalysts holds great promise for cost-effective green hydrogen generation through water electrolysis. In this context, here, the development of a superhydrophilic bifunctional electrocatalyst that facilitates both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline conditions is demonstrated. This is achieved through the in situ growth of hierarchical NiMoO4@CoMoO4 center dot xH(2)O nanostructure on nickel foam (NF) via a two-step hydrothermal synthesis method. NiMoO4@CoMoO4 center dot xH(2)O/NF facilitates OER and HER at the overpotentials of 180 and 220 mV, respectively, at the current density of 10 mA cm(-2). The NiMoO4@CoMoO4 center dot xH(2)O/NF parallel to NiMoO4@CoMoO4 center dot xH(2)O/NF cell can be operated at a potential of 1.60 V compared to 1.63 V displayed by the system based on the Pt/C@NF parallel to RuO2@NF standard electrode pair configuration at 10 mA cm(-2) for overall water splitting. The density functional theory calculations for the OER process elucidate that the lowest Delta G of NiMoO4@CoMoO4 compared to both Ni and NiMoO4 is due to the presence of Co in the OER catalytic site and its synergistic interaction with NiMoO4. The preparative strategy and mechanistic understanding make the windows open for the large-scale production of the robust and less expensive electrode material for the overall water electrolysis.

10adensity functional theory (DFT) study10ahydrogen evolution reaction (HER)10aHydrothermal synthesis10aoxygen evolution reaction (OER)10asuperhydrophilic nanostructures10asynergistic interaction10awater electrolysis1 aBarik, Sidharth1 aKharabe, Geeta, Pandurang1 aIllathvalappil, Rajith1 aSingh, Chandrodai, Pratap1 aKanheerampockil, Fayis1 aWalko, Priyanka, S.1 aBhat, Suresh, K.1 aDevi, Nandini1 aVinod, C., P.1 aKrishnamurty, Sailaja1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/active-site-engineering-and-theoretical-aspects-superhydrophilic-nanostructure-array02763nas a2200229 4500008004100000022001400041245017600055210006900231260000800300300001400308490000600322520188200328100003002210700002702240700002002267700002702287700002402314700002102338700001802359700002402377856013202401 2023 eng d a2398-490200aCobalt-manganese modified theophrastite phase of nickel hydroxide nanoflower arrays on nickel foam as a self-standing bifunctional electrode for overall water electrolysis0 aCobaltmanganese modified theophrastite phase of nickel hydroxide cMAY a2428-24400 v73 a

Designing and developing self-supported electrodes for water electrolysis is attractive as compared to conventional catalyst-coated electrodes. Herein, a (Co0.3Mn0.1Ni0.6)(OH)(2)/NF nanocomposite is prepared by anchoring (Co0.3Mn0.1Ni0.6)(OH)(2)via simple one-pot hydrothermal synthesis on nickel foam. The presence of Mn induces the external electronic structure of Co(OH)(2), and this also improves the electrochemically active surface area (ECSA). These favor better accessibility of active sites and increased intrinsic activity for the OER and HER. (Co0.3Mn0.1Ni0.6)(OH)(2)/NF has shown promising electrochemical activity toward the OER and HER in a 1 M KOH electrolyte, with an overpotential of 270 mV for the OER and 163 mV for the HER to deliver 10 mA cm(-2) current density. The overall water splitting was performed by employing (Co0.3Mn0.1Ni0.6)(OH)(2)/NF as both the cathode and anode by displaying a voltage of 1.62 V at 10 mA cm(-2), which is comparable to that extracted from a similar system based on the state-of-the-art Pt/C@NF cathode and RuO2@NF anode (1.60 V at 10 mA cm(-2)) standard electrode pair. Interestingly, at high current densities, the (Co0.3Mn0.1Ni0.6)(OH)(2)/NF//(Co0.3Mn0.1Ni0.6)(OH)(2)/NF system displayed better overall water splitting performance (1.78 V at 100 mA cm(-2)) compared to its Pt/C@NF//RuO2@NF (1.89 V at 100 mA cm(-2)) counterpart while displaying a stable output during the evolution period that lasted for 24 h. The amounts of H-2 and O-2 produced are estimated to be 701.2 and 358.6 mmol, respectively, at a time interval of 1 h; these amounts correspond to an similar to 1 : 2 ratio of O-2 and H-2, respectively. This study confirms the capability for employing (Co0.3Mn0.1Ni0.6)(OH)(2)/NF as a bi-functional and self-standing electrode for the realistic demonstrations of overall water splitting applications.

1 aKharabe, Geeta, Pandurang1 aIllathvalappil, Rajith1 aBarik, Sidharth1 aKanheerampockil, Fayis1 aWalko, Priyanka, S.1 aBhat, Suresh, K.1 aDevi, Nandini1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/cobalt-manganese-modified-theophrastite-phase-nickel-hydroxide-nanoflower-arrays-nickel-foam03138nas a2200253 4500008004100000022001400041245012100055210006900176260000900245300001200254490000600266520224700272100001702519700002702536700002202563700002202585700001802607700002602625700002102651700001902672700003202691700003002723856013102753 2023 eng d a2055-675600aHydroxide ion-conducting viologen-bakelite organic frameworks for flexible solid-state zinc-air battery applications0 aHydroxide ionconducting viologenbakelite organic frameworks for  cJAN  a224-2340 v83 a

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's capacity as a solid-state electrolyte for ZABs and any anion-conducting membrane.

1 aRase, Deepak1 aIllathvalappil, Rajith1 aSingh, Himan, Dev1 aShekhar, Pragalbh1 aLeo, Liya, S.1 aChakraborty, Debanjan1 aHaldar, Sattwick1 aShelke, Ankita1 aAjithkumar, Thalasseril, G.1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/hydroxide-ion-conducting-viologen-bakelite-organic-frameworks-flexible-solid-state-zinc-air02409nas a2200289 4500008004100000022001400041245011300055210006900168260000800237490000700245520141200252653003201664653002301696653001501719653002301734653002101757100002001778700001801798700002201816700001701838700002701855700001601882700002301898700003601921700003001957856013201987 2023 eng d a1614-683200aMade to measure squaramide COF cathode for zinc dual-ion battery with enriched storage via redox electrolyte0 aMade to measure squaramide COF cathode for zinc dualion battery  cSEP0 v133 a

Aqueous rechargeable batteries are promising grid-scale energy storage devices because of their affordability, operational safety, and environmental benignity. Among these, Zn-ion batteries (ZIBs) have unfolded new horizons. Designing superior cathodes for ZIBs is crucial. Covalent organic frameworks (COFs) can be made redox active with a high storage surface. Here, for the first time, a chelating COF with redox-active ZnI2 in a ZnSO4(aq) electrolyte is combined. Including iodide harvests an approximately threefold enhancement in capacity from 208 to 690 mAh g(-1) at 1.5 A g(-1), the highest among all the COF-derived ZIBs. Remarkably, a charge-discharge curve at 1.3 V exhibits very limited dropout voltage and super-flat platform, with a remarkable capacity of 600 mAh g(-1) at 5 A g(-1) stable up to 6000 cycles, confirming that the polyiodide generation and storage are sustainable. The COF's dual-ion storage (Zn2+ and polyidode) delivers a ZIB with the highest energy density. Spectro-electrochemical measurements coupled with X-ray photoelectron spectroscopy unambiguously unveil the existence of multiple polyiodide species, with I-3(-) and IO3- ions as the prominent species. The latter gets reduced at the COF electrode under an applied potential, leaving I-3(-) as the major species stored on the COF. The prospect of COF-polyiodide((aq)) is a windfall for metal-ion batteries.

10acovalent organic frameworks10aflexible batteries10apolyiodide10aredox electrolytes10aZn ion batteries1 aKushwaha, Rinku1 aJain, Chitvan1 aShekhar, Pragalbh1 aRase, Deepak1 aIllathvalappil, Rajith1 aMekan, Deep1 aCamellus, Augastus1 aVinod, Chathakudath, Prabhakara1 aVaidhyanathan, Ramanathan uhttps://library.ncl.res.in/content/made-measure-squaramide-cof-cathode-zinc-dual-ion-battery-enriched-storage-redox-electrolyte03376nas a2200337 4500008004100000022001400041245023000055210006900285260000800354490000700362520209900369653000702468653002602475653001402501653002702515653001802542653003002560653003002590653003402620653003402654100003002688700002002718700003302738700001802771700002702789700002002816700001802836700003602854700002402890856012402914 2024 eng d a1613-681000aAluminium, nitrogen-dual-doped reduced graphene oxide Co-existing with cobalt-encapsulated graphitic carbon nanotube as an activity modulated electrocatalyst for oxygen electrocatalyst for oxygen electrochemistry applications0 aAluminium nitrogendualdoped reduced graphene oxide Coexisting wi cAUG0 v203 a

There is a rising need to create high-performing, affordable electrocatalysts in the new field of oxygen electrochemistry. Here, a cost-effective, activity-modulated electrocatalyst with the capacity to trigger both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in an alkaline environment is presented. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with cobalt-encapsulated carbon nanotube units. Based on X-ray Absorption Spectroscopy (XAS) studies, it is established that the superior reaction kinetics in Al, Co/N-rGCNT over their bulk counterparts can be attributed to their electronic regulation. The Al, Co/N-rGCNT performs as a versatile bifunctional electrocatalyst for zinc-air battery (ZAB), delivering an open circuit potential approximate to 1.35 V and peak power density of 106.3 mW cm-2, which are comparable to the system based on Pt/C. The Al, Co/N-rGCNT-based system showed a specific capacity of 737 mAh gZn-1 compared to 696 mAh gZn-1 delivered by the system based on Pt/C. The DFT calculations indicate that the adsorption of Co in the presence of Al doping in NGr improves the electronic properties favoring ORR. Thus, the Al, Co/N-rGCNT-based rechargeable ZAB (RZAB) emerges as a highly viable and affordable option for the development of RZAB for practical applications. This manuscript reports the development of a new bifunctional catalyst that exhibits high activity and stability under practical operating conditions. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with the in situ formed cobalt-encapsulated CNT units is synthesized by a scalable pyrolysis method in an inert Ar atmosphere. The developed electrocatalyst achieved enhanced the oxygen reduction reaction (ORR) and the oxygen evolution reaction OER activity as a result of the favorable synergistic modulations and the system can serve as a process-friendly air-electrode for rechargeable zinc-air battery (RZAB). image

10aAl10aBifunctional catalyst10aDFT study10aencapsulated structure10aN-dual doping10aOxygen Evolution Reaction10aoxygen reduction reaction10arechargeable zinc-air battery10aX-ray absorption spectroscopy1 aKharabe, Geeta, Pandurang1 aBarik, Sidharth1 aVeeranmaril, Sudheesh, Kumar1 aNair, Aathira1 aIllathvalappil, Rajith1 aYoyakki, Athira1 aJoshi, Kavita1 aVinod, Chathakudath, Prabhakara1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/aluminium-nitrogen-dual-doped-reduced-graphene-oxide-co-existing-cobalt-encapsulated02205nas a2200253 4500008004100000022001400041245009700055210006900152260000800221490000800229520133700237653002901574653003401603653000901637653001401646653002101660100002801681700002701709700001701736700002201753700002401775700002501799856012701824 2026 eng d a0021-899500aHigh-performance sultone-modified PVA/PAMPS semi-IPN hydrogels for proton exchange membranes0 aHighperformance sultonemodified PVAPAMPS semiIPN hydrogels for p cAPR0 v1433 a

Hydrogel membranes composed of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) and sultone-modified poly(vinyl alcohol) (PVA) were successfully synthesized and evaluated as promising proton-conducting materials. A key advantage involves the premodification of PVA with 1,3-propane sultone to introduce sulfonic acid groups, thereby imparting proton conductivity to the PVA backbone. This sultone-modified PVA was then physically entangled within a PAMPS cross-linked network to form novel semi-interpenetrating network (semi-IPN) hydrogels. This synergistic design leverages the excellent film-forming and mechanical properties of PVA with the high proton conductivity inherent to PAMPS. The synthesized membranes exhibited robust mechanical properties, with tensile strengths ranging from 5 to 30 MPa and percentage elongations between 200% and 400%, depending on their humidity content. These hydrogel membranes demonstrated proton conductivities ranging from 0.6 to 4.3 x 10-2 S cm-1. The activation energy for proton conduction was found to be as low as 3.5 kJ mol-1, significantly lower than that of the commercial benchmark membrane, Nafion 117 (12 kJ mol-1). These findings underscore the potential of these novel PAMPS/sultone-modified PVA semi-IPN hydrogel membranes for advanced fuel cell applications.

10abatteries and fuel cells10afunctionalization of polymers10aGels10amembranes10apolyelectrolytes1 aPatwadkar, Manjusha, V.1 aIllathvalappil, Rajith1 aTorris, Arun1 aFrancis, Sifa, C.1 aKurungot, Sreekumar1 aBadiger, Manohar, V. uhttps://library.ncl.res.in/content/high-performance-sultone-modified-pvapamps-semi-ipn-hydrogels-proton-exchange-membranes