02901nas a2200301 4500008004100000022001400041245013800055210006900193260000800262300001400270490000600284520183300290653003802123653002502161653002402186653003002210653002802240653001902268100002302287700002402310700002102334700002802355700001502383700002302398700002202421700002502443856013102468 2017 eng d a2155-543500aEfficient and durable oxygen reduction electrocatalyst based on CoMn alloy oxide nanoparticles supported over N-doped porous graphene0 aEfficient and durable oxygen reduction electrocatalyst based on  cOCT a6700-67100 v73 aTransition metal oxide derived materials are very important for various applications, such as electronics, magnetism, catalysis, electrochemical energy conversion, and storage. Development of efficient and durable catalysts for the oxygen reduction reaction (ORR), an important reaction in fuel cells and metal air batteries, is highly desirable. Moreover, the futuristic catalysts for these applications need to be costeffective in order to ensure a competitive edge for these devices in the energy market. This article describes the synthesis of a cost-effective and efficient electrocatalyst for ORR It is based on supporting CoMn alloy oxide nano particles on N-doped porous graphene through a simple and scalable microwave irradiation method. Microwave irradiation was found to be very crucial for the fast creation of pores in the graphene framework with a concomitant formation of the CoMn alloy oxide nanoparticles. A series of catalysts have been synthesized by varying the Co:Mn ratio, among which, the one with the Co:Mn ratio of 2:1 [designated as CoMn/pNGr(2:1)] displayed remarkably higher ORR activity in 0.1 M KOH solution. It showed a similar to 60 mV potential shift with a low Tafel slope of 74 mV/decade, which is comparable to that derived from the commercial Pt/C catalyst. This high activity of CoMn/pNGr(2:1) has been credited to the cooperative effect arising from the metal entities and the defects present in the N-doped porous graphene. Finally, real system-level validations of the use of CoMn/pNGr(2:1) as cathode catalyst could be performed by fabricating and testing single-cells of an anion-exchange membrane fuel cell (AEMFC) and a primary Zn-air battery, which successfully demonstrated the efficiency of the catalyst to facilitate ORR in real integrated systems of the single-cell assemblies.10aanion-exchange membrane fuel cell10acooperativity effect10amicrowave synthesis10aoxygen reduction reaction10aporous N-doped graphene10aZn-air battery1 aSingh, Santosh, K.1 aKashyap, Varchaswal1 aManna, Narugopal1 aBhange, Siddheshwar, N.1 aSoni, Roby1 aBoukherroub, Rabah1 aSzunerits, Sabine1 aKurungot, Sreekurnar uhttps://library.ncl.res.in/content/efficient-and-durable-oxygen-reduction-electrocatalyst-based-comn-alloy-oxide-nanoparticles02395nas a2200241 4500008004100000022001400041245009700055210006900152260000900221300001400230490000600244520158800250653001901838653002401857653001401881653003001895653002101925100002401946700001601970700001501986700002402001856012802025 2019 eng d a2196-021600aMedium modulated oxygen reduction activity of Fe/Co active centre-engrafted electrocatalysts0 aMedium modulated oxygen reduction activity of FeCo active centre cJUN  a2956-29640 v63 a

Iron and cobalt metal atoms are effective active centers for the synthesis of carbon-based noble-metal-free catalysts for the oxygen reduction reaction (ORR) owing to their cost-effective intrinsic activity and tunable properties. Annealing of the active center with the conducting carbon enhances the ORR activity significantly. Herein, we have engrafted Fe and Co active centers in the homemade conducting carbon and the ORR performance has been closely observed under acidic and basic pH conditions to understand the influence of the medium and participating moieties towards the performance. In the half-cell reaction, the onset potential and half-wave potential for ORR are governed by the surface intermediates and concomitantly driven by the adsorption energies of the intermediates over the active centers. The iron and cobalt active center-engrafted carbon catalyst behaves differently in acidic and basic electrolytes owing to the dissociation of the surface intermediates. The iron-based catalyst shows improved onset potential against the cobalt-based one. Similarly, the cobalt-based catalyst shows improved half-wave potential against the iron active-center-grafted catalyst. The combined synergistic effect of the two catalysts is realized in the composition represented as Fe/2Co-N-GVC, where improved onset and half-wave potentials are noted in basic medium. A significant variation in the activity of the catalyst is observed as the medium changes from acidic to basic and the effect is directly associated with the surface adsorption of the intermediates.

10aactive centers10ahalf-wave potential10aMechanism10aoxygen reduction reaction10atransition state1 aKashyap, Varchaswal1 aAnand, Aljo1 aSoni, Roby1 aSreekumar, Kurungot uhttps://library.ncl.res.in/content/medium-modulated-oxygen-reduction-activity-feco-active-centre-engrafted-electrocatalysts02872nas a2200253 4500008004100000022001400041245010000055210006900155260000800224300001400232490000600246520202700252653002002279653002002299653001402319653003002333653001602363100002802379700001502407700001902422700002302441700002402464856013002488 2020 eng d a2574-097000aFeNx/FeSx-anchored carbon sheet-carbon nanotube composite electrocatalysts for oxygen reduction0 aFeNxFeSxanchored carbon sheetcarbon nanotube composite electroca cMAR a2234-22450 v33 a

Even though various Pt-free electrocatalysts for oxygen reduction reaction (ORR) have been introduced, many of them are found to be active only in alkaline conditions. Considering Nafion, phosphoric acid-doped polybenzimidazole (PBI), and so on as the prominent ionomer membranes, used in the commercially available polymer electrolyte membrane fuel cells (PEMFCs), it becomes important that any development on the Pt-free catalysts should ensure the better ORR performance under acidic conditions. The present work effectively tackles this issue, where an ORR-based catalyst could be prepared with simultaneous incorporation of both Fe-N and Fe-S active sites on in situ generated carbon sheets which are spatially separated by the carbon nanotube (CNT) network. This catalyst shows ability to perform under both acidic and basic conditions. This has been achieved by growing a polyethylenedioxythiophene polymer network in the presence of CNT and melamine followed by its pyrolysis under an inert atmosphere. The catalyst formed at 900 degrees C (PMCNT-900) displays 0.94 V onset potential for ORR under acidic electrolyte conditions, which corresponds to 60 mV overpotential compared to its 40 wt % Pt/C counterpart. Interestingly, in single cell demonstration of Nafion-based PEMFC with PMCNT-900 as the cathode catalyst, the system delivered a maximum power density (PD) of 500 and 275 mW/cm(2) at 60 degrees C under H-2-O-2 and H-2-air feed conditions, respectively. On the other hand, in a single cell test in the anion exchange membrane fuel cell (AEMFC) mode, a maximum power density of 65 mW/cm(2) at 50 degrees C could be achieved with the same cathode catalyst, which is a comparable value obtained while employing Pt/C as the cathode. These results, thus, infer to the efficiency of the catalyst to facilitate ORR under the extreme pH conditions, and particularly its performance under acidic condition reveals its prospect as a potential Pt-free electrocatalyst to serve in the Nafion-based systems.

10acarbon nanotube10aelectrocatalyst10afuel cell10aoxygen reduction reaction10aPt-free ORR1 aBhange, Siddheshwar, N.1 aSoni, Roby1 aSingla, Gourav1 aAjithkumar, T., G.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/fenxfesx-anchored-carbon-sheet-carbon-nanotube-composite-electrocatalysts-oxygen-reduction02844nas a2200241 4500008004100000022001400041245017400055210006900229260000800298300001400306490000600320520196200326653001602288653002002304653001402324653003002338653001902368100001802387700002802405700001502433700002402448856013002472 2020 eng d a2574-096200aWO3 nanorods bearing interconnected Pt nanoparticle units as an activity-modulated and corrosion-resistant carbon-free system for polymer electrolyte membrane fuel cells0 aWO3 nanorods bearing interconnected Pt nanoparticle units as an  cFEB a1908-19210 v33 a

Commercial platinum-supported carbon (Pt/C) catalyst is the most widely used oxygen reduction reaction (ORR) electrocatalyst in polymer electrolyte membrane fuel cells (PEMFCs). However, carbon oxidation in Pt/C during the operation of PEMFCs poses serious issues, particularly in meeting long-term durability of the cells. Although carbon-free Pt-based catalysts are considered to be the best alternatives, the single-cell performances reported for many such systems are found to be inferior to that of the carbon-based systems. As a practical way to realize a carbon-free electrocatalyst, we have developed a system by dispersing an interconnected Pt nanoparticle network on the nanorods of tungsten oxide (WO3). Uniform dispersion of the WO3 nanorods by fine and more or less interconnected Pt nanoparticles (20 wt %) is a key feature of the electrocatalyst. This has helped the system to achieve an intrinsic ORR characteristics which is very similar to that of Pt/C, as reflected from the comparative analysis of the onset potential, half-wave potential, limiting current density, and the number of electrons transferred in the ORR process. Pt/WO3 also shows better stability under start-stop accelerated potential cycling after 10 000 cycles, compared to Pt/C. The relative decrement in the electrochemically active surface area (ECSA) for Pt/WO3 nanorods was negligible, compared to the similar to 26% decrement registered by Pt/C under the identical testing conditions. Finally, a system-level validation in a single-cell model of PEMFC by fabricating a membrane electrode assembly (MEA) with Pt/WO3 as both the anode and cathode catalyst delivered comparable output power density as that of a similar system fabricated by using Pt/C. ECSA comparison in MEA shows the potential use of Pt/WO3-400 as the catalyst for the fuel cells, since it is exhibiting an ECSA value that is 3.4 greater than that of Pt/C at a Pt loading of 0.5 mg cm(-2).

10aCarbon-free10aelectrocatalyst10afuel cell10aoxygen reduction reaction10atungsten oxide1 aKumar, Sachin1 aBhange, Siddheshwar, N.1 aSoni, Roby1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/wo3-nanorods-bearing-interconnected-pt-nanoparticle-units-activity-modulated-and-corrosion02156nas a2200229 4500008004100000022001400041245014800055210006900203260000800272490000600280520131300286653003301599653001501632653003001647653002401677100001801701700002001719700002401739700001501763700002401778856012401802 2023 eng d a2366-748600aPt-anchored-zirconium phosphate nanoplates as high-durable carbon-free oxygen reduction reaction electrocatalyst for PEM fuel cell applications0 aPtanchoredzirconium phosphate nanoplates as highdurable carbonfr cFEB0 v73 a

Commercially available platinum-supported carbon (Pt/C) catalysts are the most widely used oxygen reduction reaction (ORR) electrocatalysts in polymer electrolyte membrane fuel cells (PEMFCs). However, inadequate active triple-phase boundary formation and carbon oxidation in Pt/C during PEMFC operation shorten its lifetime and efficiency. In this direction, a new class of carbon-free electrocatalysts for ORR is prepared by dispersing Pt nanoparticles on ZrP (Zirconium phosphates) nanoplates. In one case (ZrP@Pt), the Pt nanoparticles are found to be closely distributed and completely covering the ZrP nanoplates, whereas in the second case (Pt/ZrP), the Pt nanoparticles selectively restrict dispersion along the edges of the support. ZrP as the support displays an intrinsic proton conductivity of approximate to 0.5 x 10(-4) S cm(-1) at 70 degrees C, with an activation energy (E-a) of 0.19 eV. Pt/ZrP shows better durability after 3000 start-stop cycles. The mass activity of Pt/ZrP is increased by 4.6 times compared to Pt/C, which exhibits a loss in mass activity by 1.37 times. The single-cell level validation of ZrP@Pt, Pt/ZrP, and Pt/C as the electrocatalysts in PEMFC at an operating potential of 0.60 V shows the achievable current densities of 0.600, 0.890, and 0.890 A cm(-2).

10acarbon-free electrocatalysts10afuel cells10aoxygen reduction reaction10azirconium phosphate1 aKumar, Sachin1 aYoyakki, Athira1 aPandikassala, Ajmal1 aSoni, Roby1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/pt-anchored-zirconium-phosphate-nanoplates-high-durable-carbon-free-oxygen-reduction