02350nas a2200193 4500008004100000022001400041245011700055210006900172260011000241300001600351490000600367520155200373100002401925700002401949700001801973700001801991700002402009856012302033 2014 eng d a2040-336400aNitrogen-doped graphene interpenetrated 3D Ni-nanocages: efficient and stable water-to-dioxygen electrocatalysts0 aNitrogendoped graphene interpenetrated 3D Ninanocages efficient  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a13179-131870 v63 a

Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of similar to 290 mV at a practical current density of 20 mA cm(-2) in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of similar to 570 and similar to 370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm(-2) was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm(-2), which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h(-1) g(-1) of oxygen, which is constant in the second cycle as well.

1 aDhavale, Vishal, M.1 aGaikwad, Sachin, S.1 aGeorge, Leena1 aDevi, Nandini1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/nitrogen-doped-graphene-interpenetrated-3d-ni-nanocages-efficient-and-stable-water-003100nas a2200193 4500008004100000022001400041245014400055210006900199260011000268300001600378490000600394520226300400100002402663700002302687700002002710700002402730700002402754856012802778 2015 eng d a2040-336400aNanocrystalline Fe-Fe2O3 particle-deposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction0 aNanocrystalline FeFe2O3 particledeposited Ndoped graphene as an  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcOCT a20117-201250 v73 a

The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E-1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E-1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open circuit voltage (OCV) of 0.73 V and maximum power and current densities of 54.40 mW cm(-2) and 200 mA cm(-2), respectively, which are comparable to the performance characteristics of a similar system derived by using 40 wt% Pt/C as the cathode electrode.

1 aDhavale, Vishal, M.1 aSingh, Santosh, K.1 aNadeema, Ayasha1 aGaikwad, Sachin, S.1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/nanocrystalline-fe-fe2o3-particle-deposited-n-doped-graphene-activity-modulated-pt-free-000720nas a2200181 4500008004100000022001500041245014300056210006900199260000800268300001600276490000600292100002400298700002300322700002000345700002400365700002400389856012500413 2017 eng d a 2040-336400aNanocrystalline Fe-Fe2O3 particledeposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction0 aNanocrystalline FeFe2O3 particledeposited Ndoped graphene as an  cSEP a13341-133420 v91 aDhavale, Vishal, M.1 aSingh, Santosh, K.1 aNadeema, Ayasha1 aGaikwad, Sachin, S.1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/nanocrystalline-fe-fe2o3-particledeposited-n-doped-graphene-activity-modulated-pt-free02739nas a2200169 4500008004100000245019800041210006900239260000800308300001400316490000600330520200500336100002702341700002402368700002802392700002402420856012502444 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 uhttp://library.ncl.res.in/content/nitrogen-doped-graphene-anchored-mixed-growth-patterns-cupt-alloy-nanoparticles-highly02138nas a2200289 4500008004100000022001400041245016200055210006900217260000800286300001600294490000600310520116500316653001401481653003001495653001301525653001001538653002101548653001001569653003001579653001601609653001601625653000901641100002001650700002401670700002401694856013001718 2017 eng d a2040-336400aNiZn double hydroxide nanosheet-anchored nitrogen-doped graphene enriched with the gamma-NiOOH phase as an activity modulated water oxidation electrocatalyst0 aNiZn double hydroxide nanosheetanchored nitrogendoped graphene e cSEP a12590-126000 v93 a

Herein, we report a facile solvothermal process to synthesize an active electrocatalyst for the oxygen evolution reaction (OER) in an alkaline medium by anchoring nanosheets of a NiZn double hydroxide over nitrogen doped reduced graphene oxide after enriching the system with the γ-NiOOH phase. This catalyst possesses a thin, porous and open layered structure, which makes the system more efficient and accessible for a better electrochemical water oxidation reaction. Moreover, we experimentally demonstrated that incorporation of Zn via a single-step solvothermal method provides an easy approach to obtain plenty of exposed γ-NiOOH phases to make the system more viable for OER with a small overpotential of 290 mV at 10 mA cm−2 and a Tafel slope of 44 mV per decade. In addition to this, the oxophilic nature of Zn in the (Zn)Ni-LDH/N-rGO catalyst helps to improve the long-term stability of the whole system. The obtained results open up possibilities for the design of future robust OER electrocatalysts by the use of very cheap and abundant materials like Ni and Zn in place of expensive Ir and Ru in the present commercial electrocatalysts.

10acatalysis10aEfficient Electrocatalyst10akinetics10aMetal10aNickel-Hydroxide10aoxide10aOxygen Evolution Reaction10aperformance10aXPS Spectra10azinc1 aNadeema, Ayasha1 aDhavale, Vishal, M.1 aKurungot, Sreekumar uhttp://library.ncl.res.in/content/nizn-double-hydroxide-nanosheet-anchored-nitrogen-doped-graphene-enriched-gamma-niooh-phase