03453nas a2200253   4500008004100000022001400041245009600055210006900151260000800220300001600228490000800244520261200252653001102864653001002875653001302885653001702898100002802915700002702943700002202970700002602992700003003018700002703048856012403075       2023                        eng d  a1932-744700aSteric and electronic effect in unsymmetrical squaraine dyes for dye-sensitized solar cells0 aSteric and electronic effect in unsymmetrical squaraine dyes for  cNOV  a22473-224880 v1273 a<p>Functionalizing the light harvesting sensitizers with additional electron-donating or -withdrawing groups is a potential approach to modulate the photophysical and electrochemical properties which in-turn optimizes the driving force associated with the charge injection and dye-regeneration processes at the dye-TiO2/electrolyte interface and the photovoltaic device performance in dye-sensitized solar cells (DSSCs). Furthermore, modulated electronic levels of the dyes provide an opportunity to reduce the overpotential associated with the dye-regeneration process and make the dye-TiO2 interface compatible with various electrolytes. Furthermore, an in-built steric feature by means of introducing linear/branched alkyl groups in the sensitizer is important in controlling the aggregation of dyes on the TiO2 surface. Hence, to integrate both steric and electronic properties, a series of alkyl group-wrapped unsymmetrical squaraine dyes (SQ-X) with electron-donating and -withdrawing groups have been designed, synthesized, and utilized for DSSC device fabrication. These dyes are functionalized with alkyl groups at both sp(3)-C and N-atoms of the indoline donor moiety at the nonanchoring side to have a similar steric feature. Photophysical and electrochemical studies revealed that the HOMO and LUMO energy levels of the SQ-X series of dyes have been modulated systematically with sufficient driving forces for both charge injection and dye-regeneration processes with iodolyte (I-/I-3(-)) electrolyte. In the presence of electron-donating groups in SQ-X (where X = -NPh2 and -OMe), the HOMO energy levels are less positive than SQ-H, whereas the presence of electron-withdrawing groups such as -CO2Me, -CN, and -NO2 pushed the HOMO energy levels toward more positive potentials. Enhanced photovoltaic performances have been obtained for the dyes containing electron-donating groups, where the dye with the -NPh2 group showed a maximum of eta 7.03% (V-OC 708 mV, J(SC) 13.16 mA cm(-2), and ff 78%). The dye with the strong electron-withdrawing group -NO2 showed an efficiency of 1.49% (V-OC = 634 mV, J(SC) = 3.13 mA cm(-2), and ff 75%). As the dyes with the electron-withdrawing group possess deep positive HOMO energy levels, the DSSC device characterization has been investigated with the Cu+/2+ redox shuttle. The reduced device performance of electron-withdrawing-group-containing dyes is due to the unfavored charge distribution in the LUMO compared to the presence of electron-donating-group-containing dyes, and it was supported by the difference in the charge injection efficiency.</p>
10acobalt10aDonor10aDynamics10aOrganic dyes1 aNawghare, Indrajeet, S.1 aSingh, Ambarish, Kumar1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aKrishnamoorthy, Kothandam1 aNithyanandhan, Jayaraj  uhttps://library.ncl.res.in/content/steric-and-electronic-effect-unsymmetrical-squaraine-dyes-dye-sensitized-solar-cells02159nas a2200265   4500008004100000022001400041245011500055210006900170260000900239300001400248490000700262520120400269653003601473653004801509653002701557653002201584653002101606653002001627100002201647700002301669700002601692700002101718700002501739856012901764       2024                        eng d  a1944-824400aSurface electronic properties-driven electrocatalytic nitrogen reduction on metal-conjugated porphyrin 2D-MOFs0 aSurface electronic propertiesdriven electrocatalytic nitrogen re  cFEB   a8707-87160 v163 a<p>
	Two-dimensional (2D) metal organic framework (MOF) or metalloporphyrin nanosheets with a stable metal-N-4 complex unit present the metal as a single-atom catalyst dispersed in the 2D porphyrin framework. First-principles calculations on the 3d-transition metals in M-TCPP are investigated in this study for their surface-dependent electronic properties including work function and d-band center. Crystal orbital Hamiltonian population (-pCOHP) analysis highlights a higher contribution of the bonding state in the M-N bond and antibonding state in the N-N bond to be essential for N-N bond activation. A linear relationship between Delta G(max) and surface electronic properties, N-N bond strength, and Bader charge has been found to influence the rate-determining potential for nitrogen reduction reaction (NRR) in M-TCPP MOFs. 2D Ti-TCPP MOF, with a kinetic energy barrier of 1.43 eV in the final protonation step of enzymatic NRR, shows exclusive NRR selectivity over competing hydrogen reduction (HER) and nitrogenous compounds (NO and NO2). Thus, Ti-TCPP MOF with an NRR limiting potential of -0.35 V in water solvent is proposed as an attractive candidate for electrocatalytic NRR.</p>
10aDensity Functional Theory (DFT)10aelectrocatalytic nitrogen reductionreaction10akinetic energy barrier10alimitingpotential10aMetalloporphyrin10aNRR selectivity1 aMaibam, Ashakiran1 aOrhan, Ibrahim, B.1 aKrishnamurty, Sailaja1 aRusso, Salvy, P.1 aBabaRao, Ravichandar  uhttps://library.ncl.res.in/content/surface-electronic-properties-driven-electrocatalytic-nitrogen-reduction-metal-conjugated00993nas a2200289   4500008004100000022001400041245012000055210006900175260001100244300001600255490000700271653001400278653001300292653000700305653001700312653002800329100002500357700002800382700002000410700002600430700002700456700002200483700002500505700002200530700002100552856013000573       2024                        eng d  a2050-748800aSynthesis of Hofmann-based metal-organic frameworks incorporating a bis-pyrazole linker for various gas separations0 aSynthesis of Hofmannbased metalorganic frameworks incorporating   cJUN 25  a15106-151140 v1210aacetylene10aC2H2/CH410aNi10aPurification10aSPIN-CROSSOVER BEHAVIOR1 aMatthews, Brooke, L.1 aHarvey-Reid, Nathan, C.1 aJangodaz, Elnaz1 aScott, Victoria-Jayne1 aPolson, Matthew, I. J.1 aMaibam, Ashakiran1 aBabaRao, Ravichandar1 aTelfer, Shane, G.1 aKruger, Paul, E.  uhttps://library.ncl.res.in/content/synthesis-hofmann-based-metal-organic-frameworks-incorporating-bis-pyrazole-linker-various