01718nas a2200169 4500008004100000022001400041245010300055210006900158260011000227300001600337490000600353520100600359100001401365700001801379700002301397856012801420 2015 eng d a2046-206900aPreparation of mesoporous titanosilicate with isolated Ti active centers for cyclohexene oxidation0 aPreparation of mesoporous titanosilicate with isolated Ti active aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcOCT a92371-923770 v53 a

We report the preparation of mesoporous titanosilicate with active Ti centres using CTAB as the structure directing agent and ethylenediamine as the complexing agent (TSC-ED). The finalmaterial contained isolated Ti4+ centres substituting Si4+ in the mesoporous silica framework. The crucial role played by ethylenediamine in complexing with Ti4+ during the sol-gel process and preventing the phase segregation of TiO2 was studied systematically. The textural parameters, structural order, morphology, nature and co-ordination of Ti species were analyzed using various techniques such as X-ray diffraction (XRD), UV-vis diffused reflectance spectroscopy (UV-vis DRS), UV resonance Raman spectroscopy, Fourier transformed Infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transition electron microscopy (TEM), and X-ray photoelectron spectroscopy. Finally, the catalysts were tested for catalytic activity in the oxidation of cyclohexene using various oxidants.

1 aGupta, S.1 aVinod, C., P.1 aJagadeesan, Dinesh uhttps://library.ncl.res.in/content/preparation-mesoporous-titanosilicate-isolated-ti-active-centers-cyclohexene-oxidation-001197nas a2200193 4500008004100000022001400041245011300055210006900168260011000237300001200347490000600359520041800365100001900783700001700802700001800819700001800837700001800855856013000873 2016 eng d a2044-475300aPhenylacetylene hydrogenation on Au@Ni bimetallic core-shell nanoparticles synthesized under mild conditions0 aPhenylacetylene hydrogenation on AuNi bimetallic coreshell nanop aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a708-7120 v63 a

The synthesis of Au@Ni bimetallic core-shell nanoparticles through an energy efficient (lower temperature) route in oleylamine following a sequential reduction strategy is reported. The method is found to be useful for the synthesis of a very thin nickel shell (2 nm) over a gold core (15 nm). Synergistic effects are observed in catalyzing phenylacetylene hydrogenation under different solvent conditions.

1 aVysakh, A., B.1 aLazar, Anish1 aYadukiran, V.1 aSingh, A., P.1 aVinod, C., P. uhttps://library.ncl.res.in/content/phenylacetylene-hydrogenation-auni-bimetallic-core-shell-nanoparticles-synthesized-under-002106nas a2200193 4500008004100000245008300041210006900124260000800193300000900201490000600210520145500216100001801671700002301689700002601712700001501738700001801753700003001771856011101801 2016 eng d00aPorous thin films towards bridging the material gap in heterogeneous catalysis0 aPorous thin films towards bridging the material gap in heterogen cMAR a1-120 v23 a

An attempt has been made to bridge the material gap, existing between ideal single crystals and real-world powder nanocatalyst employed in surface science and heterogeneous catalysis, respectively. Simple wet chemical method (sol–gel and spin-coating deposition) has been applied to make continuous Ce1 − xZrxO2 (x = 0–1) (CZ) thin films with uniform thickness (~40 nm) and smooth surface characteristics. Uniform thickness and surface smoothness of the films over a large area was supported by a variety of measurements. Molecular beam (MB) studies of O2 adsorption on CZ surfaces reveals the oxygen storage capacity (OSC), and sticking coefficient increases from 400 to 800 K. Porous nature of Ce-rich CZ compositions enhances O2 adsorption and OSC, predominantly due to O-diffusion and redox nature, even at 400 K. A good correlation exists between MB measurements made on CZ films for oxygen adsorption, and OSC, and ambient pressure CO oxidation on powder form of CZ; this demonstrates the large potential to bridge the material gap. CZ was particularly chosen as a model system for the present studies, since it has been well-studied and a correlation between surface science properties made on thin films and catalysis on powder CZ materials could be a litmus test. Ambient catalysis on ceria-zirconia nanocatalyst correlates well with surface properties measured through molecular beam on thinfilm and close the material gap.

1 aDubey, Anjani1 aKolekar, Sadhu, K.1 aGnanakumar, Edwin, S.1 aRoy, Kanak1 aVinod, C., P.1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/porous-thin-films-towards-bridging-material-gap-heterogeneous-catalysis01974nas a2200241 4500008004100000245014200041210006900183260000800252300001600260490000600276520110900282653001801391653001801409653002801427653003701455653002501492100001801517700001901535700001701554700001701571700001801588856012601606 2023 eng d00aPd nanoparticles supported on N-incorporated hybrid organosilica as an active and selective low-temperature phenol hydrogenation catalyst0 aPd nanoparticles supported on Nincorporated hybrid organosilica  cJUN a11500-115120 v63 a

A heterogeneous Pd-NPMO hybrid-silicacatalyst is synthesized andits application for aqueous phase selective hydrogenation of phenolto cyclohexanone at near ambient temperature (40 degrees C) and underatmospheric hydrogen pressure is demonstrated. The homogeneously distributedPd nanoparticles on N-bridged hybrid mesoporous organosilica showedremarkable activity and selectivity for cyclohexanone compared tothe unmodified Pd-SBA-15 catalyst. Control experiments strongly claimthe role of nitrogen domains in the organic framework of hybrid silicasupport in stabilizing small Pd nanoparticles and possibly modifyingthe Pd sites responsible for catalysis to activate the substrate moleculesin water. The hybrid silica catalyst was stable and reused severaltimes without any significant drop-in activity, proving the heterogeneityof the bifunctional Pd catalyst. Based on the density functional theorystudy and experimental interventions, a possible reaction mechanismfor the low-temperature phenol hydrogenation explaining the role oforganic domains in the hybrid-silica framework is proposed.

10acyclohexanone10aHybrid silica10apalladium nanoparticles10aPeriodic mesoporous organosilica10aphenol hydrogenation1 aBetsy, K., J.1 aBajpai, Priyam1 aLazar, Anish1 aVanka, Kumar1 aVinod, C., P. uhttps://library.ncl.res.in/content/pd-nanoparticles-supported-n-incorporated-hybrid-organosilica-active-and-selective-low02981nas a2200277 4500008004100000022001400041245015800055210006900213260000800282300001600290490000700306520197400313653002102287653003202308653002102340653002902361653002202390653003802412100002002450700001802470700002402488700002402512700001802536700002402554856012502578 2025 eng d a2155-543500aA Pt-Based Carbon-Free Cathode with Embedded Oxygen Nanoreservoirs: A Promising Approach for Oxygen Buffering to Aid Oxygen Reduction Reactions of PEMFCs0 aPtBased CarbonFree Cathode with Embedded Oxygen Nanoreservoirs A cNOV a19677-196940 v153 a

For practical applications of proton exchange membrane fuel cells (PEMFCs), the system needs to be operated by employing air in the cathode instead of pure oxygen (O2). This makes it necessary to develop innovative electrode engineering solutions so that the system can function well even in oxygen-lean environments under the realistic working conditions of PEMFCs. Taking this into account, we introduce Pt/SiO2@CeO2-30%, an engineered electrocatalyst with potentially generated oxygen vacancies (Ov), which can immensely contribute toward the enhancement in the O2 availability in oxygen-lean conditions like the air feed conditions, allowing an effective control of the overpotential related to the oxygen reduction reactions (ORRs) at the electrode level. The meticulously crafted Pt-CeO2 interface serves as one of the appreciable structural attributes of the present catalyst, facilitating oxygen spillover toward the Pt environment, aided by the creation of the immense Ov along the nano CeO2 phase of the catalyst. In addition to the benefit of addressing the oxygen-lean conditions and overcoming the limitations of the state-of-the-art catalysts, usage of a noncarbonaceous support like SiO2 to house the Pt and CeO2 nanoparticles has been anticipated to lessen the corrosion problems, a major drawback associated with the carbon-based ORR catalysts. Apart from this, a significant contribution of SiO2 to the self-humidification of the ionomer interface plays a crucial role in enabling the MEA to work under low relative humidity conditions, which can be attributed to an additional benefit of the current composition of the catalyst. The catalyst demonstrated a promising ORR performance with a substantial improvement in H2-air feed circumstances and better corrosion resistance when tested with a membrane electrode assembly (MEA) in a single-cell configuration, illustrating the practical feasibility in a realistic system-level validation.

10acarbon corrosion10acarbon-free electrocatalyst10aoxygen buffering10aoxygen reductionreaction10aoxygen spill over10aprotonexchange membrane fuel cell1 aYoyakki, Athira1 aKumar, Sachin1 aPandikassala, Ajmal1 aJadhav, Swapnil, D.1 aVinod, C., P.1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/pt-based-carbon-free-cathode-embedded-oxygen-nanoreservoirs-promising-approach-oxygen