01137nas 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-001077nas a2200193 4500008004100000022001400041245011400055210006900169260000800238300001600246490000600262520037200268100002300640700002800663700002200691700002400713700002100737856012500758 2016 eng d a2040-336400aHigh-index faceted Au nanocrystals with highly controllable optical properties and electro-catalytic activity0 aHighindex faceted Au nanocrystals with highly controllable optic cNOV a19224-192280 v83 a

We introduce a new and naturally abundant mild reducing agent, tannic acid, to improve the seed-mediated growth method for the synthesis of elongated tetrahexahedral Au nanocrystals enclosed with high-index (730) planes, at room-temperature. The control of the dimensions, plasmonics and electro-catalysis of such high-index faceted nanocrystals is remarkable.

1 aRajendra, Ranguwar1 aGangadharan, Pranav, K.1 aTripathi, Shalini1 aKurungot, Sreekumar1 aBallav, Nirmalya uhttps://library.ncl.res.in/content/high-index-faceted-au-nanocrystals-highly-controllable-optical-properties-and-electro02139nas a2200253 4500008004100000022001400041245016900055210006900224260000800293300001400301490000600315520119100321653001901512653003001531653002001561653003201581653002801613100002801641700002501669700001801694700002101712700002401733856012801757 2017 eng d a2196-021600aNitrogen-doped graphene with a three-dimensional architecture assisted by carbon nitride tetrapods as an efficient metal-free electrocatalyst for hydrogen evolution0 aNitrogendoped graphene with a threedimensional architecture assi cOCT a2643-26520 v43 aCurrent polymer membrane-based electrolyzers use Pt as a cathode catalyst for efficient reduction of water. The high cost of Pt-based catalysts forces researchers to develop alternative electrocatalysts. Here, a simple strategy has been proposed to synthesize a metal-free electrocatalyst for the hydrogen evolution reaction (HER) by high-temperature annealing of graphene oxide-coated melamine foam. The prepared catalyst possesses both structural and functional advantages with its three-dimensional (3D) interconnected arms of carbon nitride (CNx) backbone wrapped with nitrogen-doped graphene (N-RGO) sheets (CNx@N-RGO). CNx@N-RGO faces only a 193 mV overpotential to achieve a current density of 10mAcm(-2), which is far superior to the previously reported Pt-free systems. Along with the high exchange current density 34.7 x 10(-6)A cm(-2) and low Tafel slope of 54 mV dec(-1), CNx@N-RGO follows a Volmer-Heyrovsky mechanism for the HER. DFT calculations show that the synergy between CNx and N-RGO facilitates good electrical coupling between the two moieties and provides optimal binding to H+ ions on the catalyst that, in turn, results in efficient reduction of hydrogen ions.10acarbon nitride10aDensity functional theory10aelectrocatalyst10ahydrogen evolution reaction10anitrogen doped graphene1 aGangadharan, Pranav, K.1 aUnni, SreeKuttan, M.1 aKumar, Nandha1 aGhosh, Prasenjit1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/nitrogen-doped-graphene-three-dimensional-architecture-assisted-carbon-nitride-tetrapods01991nas a2200265 4500008004100000022001400041245012300055210006900178260000900247300001400256490000700270520109400277653004101371653002101412653001601433653000801449653002001457100001601477700001101493700002801504700002001532700002401552700001801576856013101594 2019 eng d a1867-388000aCubic palladium nanorattles with solid octahedron gold core for catalysis and alkaline membrane fuel cell applications0 aCubic palladium nanorattles with solid octahedron gold core for  cSEP  a4383-43920 v113 a

Herein, we report the synthesis of palladium nanorattles (Au-Pd NRTs) comprising of a gold octahedral core caged within a thin porous cubic palladium shell. The introduction of core-shell and porous architecture was realized by combining seed mediated and galvanic replacement reaction techniques. Next, we examined the catalytic efficiency of the nanocatalyst in comparison with solid palladium nanocube (Pd-NC) of similar size for the degradation of p-nitrophenol and organic dyes. The rate constant of Au-Pd NRTs was found nearly 12 times higher than the Pd-NCs. Further, we exploited our catalyst for electrochemical oxygen reduction reaction (ORR) and observed its high intrinsic ORR activity. Compared with commercialized Pt/C, the Au-Pd NRT displayed nearly comparable onset and half-wave potential values and excellent durability upon potential cycling. The system level validation in a single-cell mode of alkaline exchange membrane fuel cell also confirms the efficiency of the present catalyst to serve as a potential cathode catalyst for realistic device applications.

10aalkaline exchange membrane fuel cell10aelectrocatalysis10ananorattles10aORR10aPd nanoparticle1 aSingh, Prem1 aSonika1 aGangadharan, Pranav, K.1 aKhan, Ziyauddin1 aKurungot, Sreekumar1 aJaiswal, Amit uhttps://library.ncl.res.in/content/cubic-palladium-nanorattles-solid-octahedron-gold-core-catalysis-and-alkaline-membrane-fuel02183nas a2200253 4500008004100000022001400041245012000055210006900175260000800244300001200252490000600264520129000270653002101560653001501581653001301596653003001609100002801639700002701667700002901694700002901723700002501752700002401777856012801801 2021 eng d a2366-748600aIn situ preparation of ionomer as a tool for triple-phase boundary enhancement in 3D graphene supported Pt catalyst0 aIn situ preparation of ionomer as a tool for triplephase boundar cJAN a20001250 v53 a

For improving the performance of platinum electrocatalysts in polymer electrolyte membrane fuel cells (PEMFCs), it is important to enhance the Pt utilization level in the catalyst systems. A high performing electrocatalyst (Pt/3DNG) is developed for PEMFC applications by using nitrogen-doped 3D graphene (3DNG) as the support material and an in situ grafted active ``triple-phase boundary'' to more precisely control the formation of the proton conducting ionomer interface at the active sites. Considering the 3D morphology of the system, during the electrode fabrication for realistic single-cell evaluation, the concept of in situ generation of the proton conducting-ionomer based ``active triple-phase boundary'' is introduced, which could potentially replace the conventional method of using Nafion ionomer for the electrode preparation. The monomers owing to their small-size can access the pores and inner regions of the 3DNG support, which on UV-curing, undergo polymerization and transform into an ionomer with an extended interfacial network into the nanoregimes of 3DNG. Single cell evaluation of the membrane electrode assembly in a high-temperature PEMFC by using phosphoric acid doped polybenzimidazole membrane demonstrates the utility of the present strategy.

10aelectrocatalysts10afuel cells10agraphene10aoxygen reduction reaction1 aGangadharan, Pranav, K.1 aVijayakumar, Vidyanand1 aNediyirakkal, Shijil, A.1 aFernandez, Roshni, Tresa1 aSiddharthan, Adhrika1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/situ-preparation-ionomer-tool-triple-phase-boundary-enhancement-3d-graphene-supported-pt02644nas a2200265 4500008004100000245012200041210006900163260000900232300001400241490000600255520168400261653002901945653003401974653002102008653003002029653002502059653003002084100001902114700002302133700002802156700002402184700002402208700002102232856012502253 2021 eng d00aSeed-mediated growth of Pt on high-index faceted Au nanocrystals: the ag lining and implications for electrocatalysis0 aSeedmediated growth of Pt on highindex faceted Au nanocrystals t cSEP  a9155-91660 v43 aBimetallic Au@Pt nanocrystals (NCs) offer a unique combination of plasmonic and catalytic properties and are a growing field of research. Herein, we report an unusual observation in the behavior of silver ions (Ag+) which was found to play a dominant role in dictating the Pt deposition in a seed-mediated growth method. `While the literature is replete with various instances of Ag-assisted Pt deposition whereby higher concentration of Ag+ translates into a thicker Pt shell, in the present study, contradictory observations were made. In the presence of lower amounts of Ag+, thick Pt shells were visualized, while at higher concentrations of Ag+, the extent of Pt deposition via the galvanic replacement reaction was reduced. Additionally, the presence of Ag was deemed necessary for the Pt deposition to take place, either in the form of an underpotential deposition layer on the Au NCs or by introducing Ag+ in the growth solution. We have demonstrated our findings on two different Au NCs enclosed with high-index facets, concave cuboid, and elongated tetrahexahedra, which mirror similar observations and provide generality to our claim. To the best of our knowledge, the time required for Pt deposition on the Au core in the present work is the least among the reported seed-mediated routes. Furthermore, this work, besides presenting a facile and general route for the amalgamation of catalytic and plasmonic properties in hybrid Pt-Au NCs, sheds light on the mechanistic aspects of Ag-assisted wet-chemical generation of bimetallic Au@Pt NCs. The overall electrocatalytic performance of our Au@Pt NCs toward the oxygen reduction reaction was realized to be impressive.10abimetallic nanostructure10agalvanic replacement reaction10ahigh-index facet10aoxygen reduction reaction10aseed-mediated growth10aunderpotential deposition1 aRoy, Debashree1 aRajendra, Ranguwar1 aGangadharan, Pranav, K.1 aPandikassala, Ajmal1 aKurungot, Sreekumar1 aBallav, Nirmalya uhttps://library.ncl.res.in/content/seed-mediated-growth-pt-high-index-faceted-au-nanocrystals-ag-lining-and-implications02706nas a2200265 4500008004100000022001400041245013400055210006900189260000900258300001400267490000700281520178300288653001802071653002002089653001402109653002102123653001702144653002002161653002202181653003002203100002802233700002402261700002402285856013102309 2021 eng d a1944-824400aToward pH independent oxygen reduction reaction by polydopamine derived 3D interconnected, iron carbide embedded graphitic carbon0 aToward pH independent oxygen reduction reaction by polydopamine  cFEB  a8147-81580 v133 a

Recent advancements on the development of nonprecious electrocatalysts with iron (Fe) incorporated active centers have generated confidence on realizing cost-effective proton exchange membrane fuel cells (PEMFCs). However, most of these catalysts that emerged as a substitution for the platinum supported on carbon (Pt/C) catalysts in oxygen reduction reaction (ORR) are active under basic conditions, and their feasibility in PEMFCs remains as a challenge. In this scenario, this work reports the synthesis of a Pt-free oxygen reduction electrocatalyst prepared by the annealing of polydopamine grown melamine foam. The prepared catalyst has a three-dimensional (3D) interconnected bilayer network structure possessing the carbon nitride backbone wrapped by graphitic carbon layer bearing iron carbides and nitrides as the active centers (3DFePDC). Interestingly, the 3D-FePDC catalyst displayed an ORR activity both under acidic and basic conditions. Whereas the ORR performance of 3D-FePDC closely matches that of the commercial Pt/C in the basic medium, it displays only a low overpotential value of 60 mV under acidic conditions compared to its Pt counterpart. The kinetics of ORR on 3DFePDC is found to be similar to the four-electron (4e) reduction pathway displayed by Pt/C. Testing of a PEMFC in a single cell mode by using 3D-FePDC as the cathode catalyst and Nafion membrane delivered a maximum power density of 278 mW cm(-2), which is a promising value expected from a system based on the nonprecious metal cathode. Ultimately, as a cost-effective catalyst that can effectively perform irrespective of the pH conditions, 3D-FePDC offers significant prospects in the areas like fuel cells and metal-air batteries which work in acidic and/or basic conditions.

10aacidic medium10aelectrocatalyst10afuel cell10agraphitic carbon10aIron carbide10anitrogen doping10anonprecious metal10aoxygen reduction reaction1 aGangadharan, Pranav, K.1 aPandikassala, Ajmal1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/toward-ph-independent-oxygen-reduction-reaction-polydopamine-derived-3d-interconnected-iron02683nas a2200217 4500008004100000022001400041245012900055210006900184260000800253490000600261520186200267653003002129653003002159653004302189100002402232700001802256700002802274700001702302700002402319856012202343 2024 eng d a2366-748600aAdvanced 3D network of N-doped graphitic carbon with FeNi alloy embedding for high-performance rechargeable Zn-air batteries0 aAdvanced 3D network of Ndoped graphitic carbon with FeNi alloy e cJUL0 v83 a

Despite the significant progress in Zn-air batteries (ZABs), their widespread use in the rechargeable sector is hindered due to the scarcity of efficient bifunctional oxygen catalysts that can catalyze both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). To address this, an ORR/OER bifunctional electrocatalyst is designed with ultrafine alloyed FeNi nanoparticles encapsulated in a 3D interconnected N- doped carbon network structure, featuring a carbon nitride backbone enclosed in graphitic carbon. The FeNi electrocatalyst (3DFeNiPDC) showed good bifunctional activity toward both ORR and OER in the basic medium with a low overpotential value of 30 mV for ORR and 6 mV for OER compared to its state-of-the-art counterparts Pt/C, and RuO2, respectively. Utilizing 3DFeNiPDC in a rechargeable Zn-air battery (RZAB) yields an open circuit voltage (OCV) of 1.35 V, a maximum power density of 232 mW cm-2, and an energy density of 707 W h kg-1. Additionally, a flexible RZAB employing 3DFeNiPDC demonstrates an OCV of 1.4 V with various bending angles. These finding suggest 3DFeNiPDC as a viable alternative to noble metal-based RZABs, offering superior bifunctional electrocatalytic activity and stability, particularly with its enhanced air-breathing properties facilitating improved operability under practical conditions. The bifunctional electrocatalytic activity of FeNi alloy nanoparticles embedded in a 3D- interconnected N-doped graphitic carbon (3DFeNiPDC) for both oxygen reduction and oxygen evolution is studied. The 3D architecture and core-shell characteristics of FeNi alloy nanoparticles provide better activity and stability for oxygen electrocatalysis. The electrocatalytic activity of 3DFeNiPDC has been exploited for liquid-state and solid-state flexible rechargeable zinc-air batteries. image

10aOxygen Evolution Reaction10aoxygen reduction reaction10arechargeable flexible zinc-air battery1 aPandikassala, Ajmal1 aKurian, Maria1 aGangadharan, Pranav, K.1 aTorris, Arun1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/advanced-3d-network-n-doped-graphitic-carbon-feni-alloy-embedding-high-performance