PH3 and AsH3 Adsorption Through Pristine and Stone-Wales Defected Zinc Oxide Nanosheets: A Density Functional Theory Study

The adsorption of the XH3 (X = As or P) molecules were explored onto a pure and Stone-wales defected ZnONS (SW ZnONS) through density functional theory computations. As XH3 approaches the pure ZnONS their adsorption releases -3.7 to -7.6 kcal/mol, indicating a physisorption. Also, the electronic properties of the nanosheet do not change significantly. But when AsH3 approaches SW ZnONS, its adsorption releases -23.3 kcal/mol, and electronic analysis showed that the SW ZnONS HOMO/LUMO gap reduces about ~ -27.1% and the electrical conductivity increases significantly. Therefore, the SW ZnONS can generate electrical signals when the AsH3 molecule approaches, being a hopeful sensor. τ value which calculated for the desorption of AsH3 from the surface of the SW ZnONS is 9.5 s. This indicates that the SW ZnONS has the advantage of having a short τ as a sensor for AsH3 detection.

BCl3 Adsorption on Pristine, S-Doped, and Cr-Doped Graphynes: A DFT Study

The adsorption of boron trichloride (BCl3) was explored onto pristine, S-doped, and Cr-doped graphyne through density functional theory computations. The interaction of BCl3 with pristine graphyne was weak and, thus, this sheet cannot be used as a sensor. Although S-doping strengthens the interaction, the S-doped sheet cannot still be used as a sensor. However, the reactivity and sensitivity of the sheet are significantly increased toward BCl3 by replacing the C atom of graphyne with the transition metal Cr. The HOMO-LUMO gap of Cr-doped graphyne reduces from 2.18 to 1.38 eV following the adsorption of BCl3, which significantly increases the electrical conductivity. Thus, the great change in the conductivity can be converted into an electronic signal, indicating that Cr-doped graphyne may be a promising sensor for BCl3. Also, its work function is considerably decreased by the adsorption process, indicating that it can also work as a work function-type sensor for BCl3 detection.

Electrocatalytic synthesis of heterocycles from biomass-derived furfuryl alcohols

It is very attractive yet underexplored to synthesize heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds. Herein, we report an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from furfuryl alcohols, which can be readily produced from biomass-derived and industrially available furfural. Taking advantage of photo-induced polymerization of a bipyridyl ligand, we demonstrate the facile preparation of a heterogenized nickel electrocatalyst, which effectively drives the Achmatowicz reaction electrochemically. A suite of characterization techniques and density functional theory computations were performed to aid the understanding of the reaction mechanism. It is rationalized that the unsaturated coordination sphere of nickel sites in our electrocatalyst plays an important role at low applied potential, not only allowing the intimate interaction between the nickel center and furfuryl alcohol but also enabling the transfer of hydroxide from nickel to the bound furfuryl alcohol.

Mechanistic insights into α-branched amines formation with pivalic acid assisted C−H bond activation catalysed by Cp*Rh complexes

Density functional theory computations revealed a pivalic acid assisted C−H bond activation mechanism for rhodium catalyzed formation of α-branched amines with C−C and C−N bond couplings. The reaction energies of...