Single B-vacancy enriched α1-borophene sheet: an efficient metal-free electrocatalyst for CO2 reduction.

By employing first principles calculations, we have studied the electronic structures of pristine (α1) and different defective (α1-t1, α1-t2) borophene sheets to understand the efficacy of such systems as metal-free electrocatalysts for the CO2 reduction reaction. Among the three studied systems, only α1-t1, the defective borophene sheet created by removal of a 5-coordinated boron atom, can chemisorb and activate a CO2 molecule for its subsequent reduction processes, leading to different C1 chemicals, followed by selective conversion into C2 products by multiple proton coupled electron transfer steps. The computed onset potentials for the C1 chemicals such as CH3OH and CH4 are low enough. On the other hand, in the case of the C2 reduction process, the C-C coupling barrier is only 0.80 eV in the solvent phase which produces CH3CHO and CH3CH2OH with very low onset potential values of -0.21 and -0.24 V, respectively, suppressing the competing hydrogen evolution reaction.

Polaron Induced Conductance Switching in Conjugated Oligophenylene: A First-Principles Analysis.

For π-conjugated systems, polaron formation has a major impact on their optoelectronic properties. In fact, for such systems, an exquisite interplay between electron delocalization and the steric effect determines their ground state properties. However, an excess charge (positive or negative) injection causes structural reorientation because of extended conjugation. Herein, we investigate the effect of such an excess charge in an individual polyphenylene on its quantum conductance behavior. By combining the DFT and NEGF formalisms, we characterize both structural and electronic changes occurring upon electron and hole injection. We demonstrate that for both the cationic and anionic radicals, the excess charge is observed to be localized, inducing a partial planarization of the molecule and forming cationic and anionic polarons, respectively. The calculated low-bias conductance values determine the polaronic effect and could be implemented for easy determination and measurement of polaron formation. In fact, cationic and anionic polarons induce a large degree of conductance switching, involving a decrease and increase of conductance, respectively.

Dual-Silicon-Doped Graphitic Carbon Nitride Sheet: An Efficient Metal-Free Electrocatalyst for Urea Synthesis.

Searching for an alternative nonhazardous catalyst for direct urea synthesis that avoids the traditional route of NH3 synthesis followed by CO2 addition is a challenging field of research nowadays. Based on first-principles calculations, we herein propose a novel electrocatalyst comprising of totally nonmetal earth abundant elements (dual-Si doped g-C6N6 sheet) which is capable of activating N2 and making it susceptible toward direct insertion of CO into the N-N bond, producing *NCON* which is the precursor for urea production by direct coupling of N2 and CO2 followed by multiple proton coupled electron transfer processes. Remarkably, the calculated onset potential for urea production is much less than that of NH3 synthesis and hydrogen evolution reactions, and also the faradaic efficiency is nearly 100% for production urea over ammonia, which promotes exclusive electrocatalytic urea synthesis by suppressing the NH3 synthesis as well as hydrogen evolution reactions.

Graphitic Carbon Nitride Sheet Supported Single-Atom Metal-Free Photocatalyst for Oxygen Reduction Reaction: A First-Principles Analysis.

Designing metal-free photocatalysts for oxygen reduction reaction (ORR) is an important step toward the development of sustainable and alternative energy resources because ORR plays a key role in fuel cell reactions. An efficient photocatalyst for ORR must possess suitable band positions with respect to electrochemical potentials of ORR, minimize energy losses due to charge transport and electron-hole recombination, and have kinetically suitable electron transfer properties. Using first-principles theoretical studies, we herein demonstrate that a single Si atom doped on the alternative pores of the porous graphitic carbon nitride (g-C6N6) surface has satisfied the above criteria and has the potential to be an efficient photocatalyst for ORR. Our study reveals that molecular oxygen, chemisorbed on the dopant atom of the doped surface via an end-on fashion, is activated and readily reduced with a very low onset potential (-0.07 V) via a four-electron transfer pathway. Thus, the doped system can act as an efficient metal-free photocathode in fuel cells.

Computational studies on the hydride transfer barrier for the catalytic hydrogenation of CO2 by different Ni(II) complexes.

Hydride transfer is the most crucial step for the catalytic hydrogenation of CO2 in homogeneous condition. Here, we perform state-of-the-art calculations to show the effect of geometry and spin states of Ni-hydride complexes containing different types of multidentate phosphine ligands on their hydride transfer barrier. For doing this, we first choose Ni-bis(diphosphine) complexes of the type NiP4, which have been synthesized recently and then by extrapolating the idea we propose a new type of NiP2N2 complex showing much lower hydride transfer barrier. We also compute the hydricities of the Ni-hydride complexes in aqueous medium and try to correlate these thermodynamic quantities with the kinetic barrier of hydride transfer. Graphical Abstract NiP2N2 complex can efficiently hydrogenage CO2 with a quite low hydride transfer barrier.