Adsorption and destruction of the nerve agent sarin (GB) on the pristine and hydroxylated/water surfaces of copper oxides have been investigated by extensive first-principles calculations, and the unsaturated Cu site in both CuO(111) and Cu 2 O(111) surfaces was predicted to have strong GB-adsorption ability through its bonding interaction with the phosphoryl oxygen of sarin. Decomposition of GB on the surface mainly proceeds through the fission of the P−F bond, and the predicted energy spans are 106.3 and 109.5 kJ/mol on the pristine and hydroxylated CuO(111) surfaces, respectively. In comparison with CuO(111), the pristine Cu 2 O(111) surface has a relatively strong binding interaction with GB, and the wet Cu 2 O(111) surface can effectively degrade GB under mild conditions with the energy span of 77.0 kJ/mol. The Cu 2 O(111) surface has more exposed and unsaturated Cu sites, compared to CuO(111), and their different electronic and surface structures are responsible for their distinct activities toward the decontamination of GB. Overall, both copper oxides may be used as the very promising protective materials to decontaminate GB, and the molecular-level knowledge about adsorption and decomposition of nerve agents (NAs) on related decontamination materials is essential for development of chemical protection strategies.
The visible-light-driven switchable phosphorylation of cyanoaromatics with the 1,6-enyne moiety for the diverse and selective synthesis of phosphorylated polyheterocycles, including phosphorylated aminophosphonates, iminophosphonates, and ketones, has been described. Importantly, these photocatalytic transformations feature good functional group tolerance and high regio-and chemoselectivities under mild reaction conditions. These findings might stimulate the exploration of new photocatalytic utilizations of P(O)−H compounds by employing CN-containing substrates as the radical acceptors.
The leading edge of biocatalysis is human intervention to expand the specificity of the reactions, so that enzymes can catalyze an impressive range of challenging chemical reactions. Here density functional theory (DFT) calculations were used to explore the catalytic coupling of CH 4 with CO 2 and CO into value-added chemicals by a rhodium(I)-substituted human carbonic anhydrase [Rh(hCAII)] under the oriented external electric fields (OEEFs), and possible mechanisms and OEEF effects have been discussed. The DFT calculations show that the rate-determining step for the catalytic coupling of CH 4 and CO 2 into acetic acid is CO 2 insertion and the formation of a C−C bond, and the application of OEEF (F x = +0.0075 au) can remarkably reduce the free energy span from 37.4 to 19.3 kcal/mol. The coupling of CH 4 with CO into acetaldehyde has a barrier requirement of below 28.0 kcal/mol. On the basis of the present results, the artificial carbonic anhydrase is very promising for the conversion of carbon-based small molecules with the judicious use of OEEFs.
The production of acetic acid and acetone from the direct coupling of CO2 and CH4 on the doped In2O3(110) surface has been studied by extensive first‐principles calculations, and the Ga or Al substitution for the single In atom at the active oxygen vacancy of In2O3(110) can stabilize the reaction species and reduce the free energy barrier of the rate‐limiting C−H activation for the conversion of CO2 and CH4 to acetic acid. Herein, the metal doping lowers the energy level of partially empty s and p orbitals of In1 at the oxygen vacancy site and manipulates its electronic properties, resulting in the activity improvement. The stable intermediate with the newly‐formed CH3COO* has the available In1 site for subsequent CH4 activation, which may initiate the direct C−C coupling of CH3COO* and CH3* to yield C3 species on the doped In2O3(110). These findings suggest that the metal doping of the active oxygen vacancy opens an avenue for the carbon‐chain growth through heterogeneously catalytic coupling of CO2 and CH4.
Hexanuclear polyoxomolybdenum-based discrete supermolecules Nax[MoV6O6(μ2-O)9(Htrz)6-x(trz)x]·nH2O (x = 0, n = 15, 1; x = 1, n = 12, 2; x = 2, n = 10, 3; x = 2, n...
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