01895nas a2200157 4500008004100000022001400041245004600055210004300101260000800144300001400152490000700166520144700173100001701620700002601637856007401663 2018 eng d a1463-907600aAu26: a case of fluxionality/co-existence0 aAu26 a case of fluxionalitycoexistence cAPR a8616-86230 v203 a

The Au26 cluster is one of the widely studied gold clusters in the size range of n = 21–30. It has been proposed in a more recent combined experimental and theoretical study that the neutral Au26 cluster is fluxional. The fluxionality of a cluster is relevant to its catalytic applications. In this context, to explore the extent of fluxionality, Born Oppenheimer Molecular Dynamical (BOMD) simulations are carried out on experimentally and theoretically proposed fluxional Au26 conformations (three compact or core–shell structures and a high symmetry cage structure). The simulations reveal that the high energy golden tube outperforms the ground state structure (compact C2v conformation) as well as the other two low-symmetry compact conformations in terms of thermal stability. The enhancement in the thermal stability is explained on the basis of structural integrity imposed by the open skeleton of shortest bond distances within Au26-Tube. In addition to this, the homogeneous distribution of charges and the strong s–d hybridization exhibited by FMOs are seen to play a pivotal role in increasing the stability of Au26-Tube. The present investigation also reveals that the characteristic fluxionality proposed to exist in the Au26 system is noted only above 400 K and it is missing at room temperature. The simulations also bring forth the question of how relevant a ground state conformation is at working temperatures.

1 aJoshi, Krati1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/au26-case-fluxionalityco-existence02689nas 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-array02596nas a2200253 4500008004100000022001400041245011300055210006900168260000800237490000600245520168400251653002101935653003001956653002601986653002402012653001802036100002402054700002702078700002202105700002602127700003002153700002702183856013202210 2024 eng d a2367-093200aAniline and indoline donors based far-red active unsymmetrical squaraine dyes for dye sensitized solar cells0 aAniline and indoline donors based farred active unsymmetrical sq cFEB0 v83 a

In dye-sensitized solar cells (DSSC), controlling the dye-aggregation on the metal-oxide surface by appending the alkyl groups around the donor or pi-spacer unit of the dye is a potential approach to enhance DSSC efficiency. Further, rigidification of the dye structures by cyclization modulates the photophysical properties of the sensitizer. Here a series of donor-acceptor-donor (D-A-D) type far-red active unsymmetrical squaraine dyes (SQA) have been designed and synthesized, where N,N-dimethylaniline, methylated- and branched-indoline have been used as donor units. These dyes showed absorption between 629-654 nm (lambda max) with the molar extinction coefficient of 1.49-1.94x105 M-1 cm-1. Systematic enhancements in DSSC device efficiency have been observed due to the cyclization and alkyl-groups incorporation in this set of dyes which were further enhanced with the addition of chenodeoxycholic acid (CDCA). The highest DSSC device efficiency of 4.78 % (Jsc of 8.77 mA/cm2 and Voc of 692 mV) has been achieved for SQA3. The IPCE profile of SQA dyes indicates the contribution of aggregated structures for the photocurrent generation. Further, co-sensitization of SQA3 dye with a complementary visible light active dye AK4 showed the enhanced device efficiency of 6.27 % with panchromatic IPCE response. Dye rigidification, and controlled aggregation of dyes on TiO2 by means of cyclization of donor unit and introducing the alkyl groups in the dye structure synergistically improve the dye-sensitized solar cell (DSSC) device performance. Donor-Acceptor-Donor (D-A-D) based unsymmetrical squaraine dye SQA3 showed the DSSC device performance of 4.78 %.image

10aco-sensitization10adye-sensitized solar cell10aeffect of alkyl chain10amolecular planarity10asquaraine dye1 aJadhav, Avinash, P.1 aSingh, Ambarish, Kumar1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj uhttps://library.ncl.res.in/content/aniline-and-indoline-donors-based-far-red-active-unsymmetrical-squaraine-dyes-dye-sensitized