02219nas a2200229 4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520137100266653001501637653003101652653003001683653003001713653003101743100002701774700003001801700002601831856013201857 2023 eng d a0169-433200aChemically modified graphene sheets as potential sensors for organophosphate compounds(pesticide): A DFT study0 aChemically modified graphene sheets as potential sensors for org cMAY a1567450 v6193 a

Owing to the extensive use of pesticides in agriculture and the threat posed to the environment and humankind, attention is drawn toward the need for its remediation from various sources, in particular from water. The adsorption characteristics of hydrophobic graphene and its BN doped counterparts are evaluated using DFT methodology, to assess their sensing potential towards notable pesticide molecules (Organophosphate pesticides (OPs) such as chlorpyriphos, parathion, methyl-parathion, and fenitrothion). To accomplish this, various elec-tronic properties such as band structure, DOS, Bader charge analysis, and CDD have been calculated. Interest-ingly, exothermic interactions (-0.1 eV to-2 eV) have been noted for all the OPs with NB doped single vacancy defect induced graphene surfaces. With an exception of FTN, all the other OPs showed significant changes in the electronic properties of surfaces as apparent from the change in band gap and nature of the band from indirect to direct. The appreciable adsorption energy, higher charge transfer, and notable variation in the band gap are the decisive factors behind the strong interaction exhibited by NB doped surfaces especially dg-(NB-2)2 (except FTN). These findings demonstrate the suitability of NB doped single vacancy defect induced graphene sheets for the detection of the studied OPs.

10aAdsorption10aBN doped graphene surfaces10aCharge density difference10aDensity functional theory10aOrganophosphate pesticides1 aShivankar, Bhavana, R.1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/chemically-modified-graphene-sheets-potential-sensors-organophosphate-compoundspesticide-dft02215nas a2200253 4500008004100000022001400041245013200055210006900187260000800256300001100264490000900275520129000284653001501574653004001589653002501629653003001654653002501684100002901709700003001738700002001768700001901788700002601807856012801833 2024 eng d a2210-271X00aIndazole-5-amine (AIA) as competing corrosion coating to Benzotriazole (BTAH) at the interface of Cu: A DFT and BOMD case study0 aIndazole5amine AIA as competing corrosion coating to Benzotriazo cSEP a1147620 v12393 a

This study compares three organic compounds-benzotriazole (BTAH), imidazole (IM), and indazole-5-amine (AIA)-as corrosion inhibitors for copper substrates. Using Density Functional Theory (DFT) and Born-Oppenheimer Molecular Dynamics (BOMD) calculations, it identifies AIA as a promising and cost-effective alternative to the toxic BTAH. The adsorption strength on Cu(1 0 0) surfaces is ranked AIA>BTAH>IM for both neutral and deprotonated forms. These findings are supported by electronic parameter studies, including Bader charge analysis, density of states (DOS), charge density differences (CDD), and frontier molecular orbital analysis. AIA shows the best adsorption in a parallel orientation at the top site. Packing studies reveal that hydrogen bonding stabilizes the interaction energies within self-assembled AIA aggregates. Organometallic complexation studies reveal that deprotonated BTAH exhibits higher interaction energy with a single Cu atom compared to AIA when bonded through the carbon end, consistent with the findings from BOMD studies. However, on periodic Cu surfaces, AIA outperforms BTAH molecules as seen from adsorption energies. This investigation highlights AIA's potential as a superior and more economical corrosion inhibitor for copper.

10aAdsorption10aBorn-Oppenheimer molecular dynamics10aCorrosion inhibition10aDensity functional theory10aIndazole derivatives1 aSamal, Pragnya, Paramita1 aSingh, Chandrodai, Pratap1 aTiwari, Shivani1 aShah, Vaishali1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/indazole-5-amine-aia-competing-corrosion-coating-benzotriazole-btah-interface-cu-dft-and02223nas a2200241 4500008004100000022001400041245009300055210006900148260000800217300001400225490000700239520137500246653001501621653001601636653002101652653003201673653004501705653003101750100002401781700002901805700002601834856012101860 2026 eng d a2168-048500aSilico imine-based ligand engineering of CALF-20 for electrocatalytic ammonia production0 aSilico iminebased ligand engineering of CALF20 for electrocataly cAPR a7217-72280 v143 a

Electrocatalytic ammonia synthesis is emerging as a globally compelling, sustainable alternative to the Haber-Bosch process under ambient conditions. As a result, active-site engineering has taken center stage in the development of stable and effective electrocatalysts. In this work, we report how the introduction of an imine group in the ligand backbone of CALF-20, a Zn-based, moisture-stable MOF with high surface area, results in the formation of an N-4 macrocycle for transition-metal anchoring. PBE + D3 calculations, supported by spectroscopic, ab initio molecular dynamics, and electronic analyses, identify Fe-bound modified CALF-20 as the most stable configuration among the Mn-, Fe-, Co-, Ni-, Cu-, Ru-, Rh-, Ag-, and Au-anchored within the modified CALF-20 framework. Upon modification, the d-band center shifts from -5.08 to -4.44 eV in M-Fe-CALF-20. Adsorption studies confirm activation of both N-2 and NO2, reflected by bond elongation and red-shifted IR peaks. Mechanistic studies show that M-Fe-CALF-20 selectively facilitates NH3 formation, exhibiting PDS values of 0.69 and 0.62 eV for the NRR and NO2RR, respectively, while a competitive adsorption shows a clear preference over HER. Our study illustrates how functionalization tunes CALF-20 for dual application as an adsorbent and as an electrocatalyst for NH3 synthesis and storage.

10aAdsorption10aCALF-20 MOF10aelectrocatalysis10ahydrogen evolution reaction10anitrogen oxide reductionreaction (NO2RR)10anitrogen reductionreaction1 aSamudre, Nikhil, S.1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/silico-imine-based-ligand-engineering-calf-20-electrocatalytic-ammonia-production