02009nas a2200241   4500008004100000022001400041245006900055210006900124260000800193300001100201490000800212520131900220653001201539653001201551653000801563653001601571653002501587653000801612100001801620700002001638700001801658856009101676       2022                        eng d  a0039-602800aRole of facet in the competitive pathway of ethylene epoxidation0 aRole of facet in the competitive pathway of ethylene epoxidation  cFEB  a1219540 v7163 aEthylene epoxide (EtO) is used as raw material for a broad range of products from pharmaceuticals and plastics to paints and adhesives. Although the reaction of ethylene interacting with preadsorbed oxygen on Ag surface is known for decades, the underlying mechanism of EtO formation is not completely understood. Successful investigation of oxametallacycle (OMC) intermediate common to selective as well as non-selective pathways has ensured at least 50% selectivity. The current study brings out the electronic signatures of distinct conformers of OMC stabilised on two different facets of Ag viz. (100) and (111). There are subtle differences between OMC conformers observed on these two facets with near-eclipsed on Ag(100) and near-staggered on Ag(111). A detailed analysis of Ag-O, C-O, C-C, and Ag-C interactions along with projected Density of States (pDOS) and projected Crystal Orbital Hamilton Population (pCOHP) imply towards ring closure on Ag(100) and hydrogen transfer on Ag(111). Finally, our understanding based on electronic and structural signatures are backed up by activation barriers computed through NEB calculations. Activation barrier for EtO is lower on (100) as compared to (111) facet. Thus, our study sheds light on how these differences between OMC affect the selectivity towards EtO.10aAg(100)10aAg(111)10aDFT10aepoxidation10aEthylene Oxide (EtO)10aOMC1 aNair, Aathira1 aKenge, Nivedita1 aJoshi, Kavita  uhttps://library.ncl.res.in/content/role-facet-competitive-pathway-ethylene-epoxidation02221nas a2200241   4500008004100000022001400041245015300055210006900208260000800277520129500285653004401580653000801624653002401632653002701656653002901683100004001712700001801752700001901770700001801789700001801807700002401825856013001849       2024                        eng d  a1613-681000aInsights on prussian blue analogue cathode material engineered with polypyrrole surface protection layer for aqueous rechargeable zinc metal battery0 aInsights on prussian blue analogue cathode material engineered w  cNOV3 a<p>
	One of the key intricacies against using Prussian blue analogues (PBAs) in aqueous batteries is their gradual dissolution in aqueous electrolytes, resulting in inadequate cycling stability. Besides, the rate capability of PBAs is limited due to their poor electrical conductivity. To overcome these challenges, it is essential to tune the physical and chemical properties of PBAs at the nano regime without affecting the inherent charge storage properties, especially at high-voltage operating conditions. Through this work, a strategy is demonstrated to enhance the electrochemical performance of vanadium-based PBA (V-PBA) by surface engineering using a conducting polymer nano-skin (V-PBA/PPy) for aqueous zinc metal batteries. The polypyrrole (PPy) nano-skin over the V-PBA nanoparticles acts as an electron percolation path to ameliorate the poor electronic conductivity of the otherwise pristine V-PBA. Interestingly, the V-PBA with an optimized polypyrrole coating (V-PBA/PPy-2) exhibits an enhanced specific capacity (173 mAh g-1 at 0.10 A g-1) than the pristine V-PBA counterpart (80 mAh g-1) and 85% capacity retention up to 500 cycles. The DFT calculation confirms the synergistic interaction between PPy and V-PBA and the presence of PPy favors the adsorption of Zn.</p>
10aaqueous rechargeable zinc metal battery10aDFT10apolypyrrole coating10aPrussian blue analogue10asurface protection layer1 aPuthiyaveetil, Priyanka, Pandinhare1 aNair, Aathira1 aDilwale, Swati1 aKurian, Maria1 aJoshi, Kavita1 aKurungot, Sreekumar  uhttps://library.ncl.res.in/content/insights-prussian-blue-analogue-cathode-material-engineered-polypyrrole-surface-protection01990nas a2200217   4500008004100000022001400041245013800055210006900193260000800262490000800270520122900278653001201507653000801519653002301527653002501550653002501575653000801600100001801608700001801626856012801644       2024                        eng d  a0927-025600aWhat leads to direct epoxidation? an exhaustive DFT investigation of electrophilic oxygen mediated epoxidation of ethylene on Ag(100)0 aWhat leads to direct epoxidation an exhaustive DFT investigation  cAPR0 v2393 a<p>
	Extensive research has contributed to a better understanding of the commercially important epoxidation reaction. Selectivity, a crucial aspect of this reaction, has received significant attention in both experimental and theoretical investigations. However, a consensus regarding the role of electrophilic oxygen in epoxidation is yet to be reached. The present study is a theoretical examination of the prerequisites necessary for direct epoxidation to occur on the Ag(100) surface, at varied monolayer concentrations. Additionally, the study investigates the characteristics of various oxygen species interacting with ethylene to promote the direct epoxidation pathway. Based on the effective charges and projected density of states (pDOS) analysis, three oxygen variants were identified on the Ag(100) surface: atomic oxygen, dissociatively adsorbed molecular oxygen, and O 3 . The investigation reveals that all oxygen species, despite their physical and electronic differences, are electrophilic and undergo direct epoxidation. This work provides insights into the complex nature of epoxidation reaction and discusses electronic factors influencing the selective oxidation route on different Ag-O complexes.</p>
10aAg(100)10aDFT10aDirect epoxidation10aElectrophilic oxygen10aEthylene Oxide (EtO)10aOMC1 aNair, Aathira1 aJoshi, Kavita  uhttps://library.ncl.res.in/content/what-leads-direct-epoxidation-exhaustive-dft-investigation-electrophilic-oxygen-mediated