Carbon dioxide hydrogenation over the carbon-terminated niobium carbide (111) surface: a density functional theory study.

Carbon dioxide (CO2) hydrogenation is an energetic process which could be made more efficient through the use of effective catalysts, for example transition metal carbides. Here, we have employed calculations based on the density functional theory (DFT) to evaluate the reaction processes of CO2 hydrogenation to methane (CH4), carbon monoxide (CO), methanol (CH3OH), formaldehyde (CH2O), and formic acid (HCOOH) over the carbon-terminated niobium carbide (111) surface. First, we have studied the adsorption geometries and energies of 25 different surface-adsorbed species, followed by calculations of all of the elementary steps in the CO2 hydrogenation process. The theoretical findings indicate that the NbC (111) surface has higher catalytic activity towards CO2 methanation, releasing 4.902 eV in energy. CO represents the second-most preferred product, followed by CH3OH, CH2O, and HCOOH, all of which have exothermic reaction energies of 4.107, 2.435, 1.090, and 0.163 eV, respectively. Except for the mechanism that goes through HCOOH to produce CH2O, all favourable hydrogenation reactions lead to desired compounds through the creation of the dihydroxycarbene (HOCOH) intermediate. Along these routes, CH3* hydrogenation to CH4* has the highest endothermic reaction energy of 3.105 eV, while CO production from HCO dehydrogenation causes the highest exothermic reaction energy of -3.049 eV. The surface-adsorbed CO2 hydrogenation intermediates have minimal effect on the electronic structure and interact only weakly with the surface. Our results are consistent with experimental observations.

A First-Principles Study of CO2 Hydrogenation on a Niobium-Terminated NbC (111) Surface.

As promising materials for the reduction of greenhouse gases, transition-metal carbides, which are highly active in the hydrogenation of CO2 , are mainly considered. In this regard, the reaction mechanism of CO2 hydrogenation to useful products on the Nb-terminated NbC (111) surface is investigated by applying density functional theory calculations. The computational results display that the formation of CH4 , CH3 OH, and CO are more favored than other compounds, where CH4 is the dominant product. In addition, the findings from reaction energies reveal that the preferred mechanism for CO2 hydrogenation is thorough HCOOH* , where the largest exothermic reaction energy releases during the HCOOH* dissociation reaction (2.004 eV). The preferred mechanism of CO2 hydrogenation towards CH4 production is CO2 * →t,c-COOH* →HCOOH* →HCO* →CH2 O* →CH2 OH* →CH2 * →CH3 * →CH4 * , where CO2 * →t,c-COOH* →HCOOH* →HCO* →CH2 O* →CH2 OH* →CH3 OH* and CO2 * →t,c-COOH* →CO* are also found as the favored mechanisms for CH3 OH and CO productions thermodynamically, respectively. During the mentioned mechanisms, the hydrogenation of CH2 O* to CH2 OH* has the largest endothermic reaction energy of 1.344 eV.

Electron transport in polycyclic aromatic hydrocarbons/boron nitride hybrid structures: density functional theory combined with the nonequilibrium Green's function.

We investigate the electronic transport properties of two types of junction based on single polyaromatic hydrocarbons (PAHs) and PAHs embedded in boron nitride (h-BN) nanoribbons, using nonequilibrium Green's functions (NEGF) and density functional theory (DFT). In the PAH junctions, a Fano resonance line shape at the Fermi energy in the transport feature can be clearly seen. In hybrid junctions, structural asymmetries enable interactions between the electronic states, leading to observation of interface-based transport. Our findings reveal that the interface of PAH/h-BN strongly affects the transport properties of the structures.