A DFT Study on the Adsorption of CO_2 Molecules on CaO(001) Surface at Different Coverages

The CO_2 adsorption on CaO(001) surface at different coverages from 1/9 monolayer(ML) to 1 ML has been investigated using density functional theory calculations. With the analysis of the most stable adsorption structures at different coverages, the mechanism of CaO(001)surface carbonating into CaCO_3 has been explored. At low coverages(≤1/3 ML), CO_2 molecule prefers sitting in parallel pattern on the CaO(001) surface, while the structure of the CaO(001)surface remains unchanged. At medium coverage(4/9 ～ 2/3 ML), the repulsive interactions between oxygen atoms of CO_2 become stronger, and the calcium carbonation structure appears on the CaO(001) surface. At high coverage( ≥ 7/9 ML), the structure of the CaO(001) surface is deeply damaged, and a few CO_2 molecules have penetrated into the surface and bound to the O atom of the second layer(sub-surface), eventually forming the layered structure of CaCO_3.Additionally, herein has discussed the simulation of HREELS and thermodynamical stability of these structures at different coverages.

A First-principles Study on the Gas Sensitivity of Metal-loaded Graphene with an Atomic Vacancy to O_2

In this work, adsorption energies, geometrical and electronic structures for adsorption systems of O_2 at metal-loaded graphene(M-Gra) and metal-loaded defective graphene(M-D-Gra)(M = Ni, Pd, Pt and Al) surfaces are studied using a GGA-PW91 method. Calculated results show that loaded M make the interaction between O_2 and the graphene surface change from physical to chemical adsorptions, band gaps of M-Gra systems after the O_2 adsorption change, and the Ni-loaded Gra has the highest sensitivity to O_2. For O_2-M-D-Gra systems, interactions between O_2 and the M-D-Gra surfaces are chemical, similar to the O_2-M-Gra systems, and loaded Pt and Al have the strongest effect on the sensitivity of D-Gra to O_2. The M loads at the perfect Gra and D-Gra surfaces make the interactions between O_2 and the surfaces have obvious charge transfer. This work would provide a valuable guidance on the gas sensitivity study of graphene to O_2.

Adsorption of NO on the M/c-ZrO_2(110)(M=Ru,Rh)Surface:A Density Functional Theory Study

The adsorption of NO on the M/c-ZrOu（110） （M = Ru, Rh） surface has been studied with periodic slab model by PWgl approach of GGA within the framework of density functional theory. The results of geometry optimization indicated that the hollow site is energetically stable for Ru and Rh atoms＇ adsorption on the c-ZrO2（110） surface with adsorption energies of 207.4 and 106.3 kJ/mol, respectively. When NO is adsorbed on the M/ZrO2（110） surface, the N-down adsorption is the most stable. We also studied the adsorption of double NO on the M/c-ZrOu（110） surface. Complete linear synchronous transit and quadratic synchronous transit approaches were used to search the transition state for dissociation reaction. NO has two possible dissociation passways： （1） 2NO → N2 （g） ＋ 20 （ads）, （2） 2NO→ N20 （g） ＋ O （ads）, and the former is easier than the latter based on the calculation results.

Density Functional Theory for the Investigation of Catalytic Activity of X@Cu_(12)(X = Cu, Ni, Co, or Fe) for N_2O Decomposition

We have investigated the reaction mechanism for N20 decomposition on Cu13 via density functional theory. It is found that N20 decomposition on the cluster is more prone to be along the Eley-Rideal （ER） pathway in comparison with the Langmuir-Hinshelwood （LH） channel. There exists structural relaxation for Cu13 cluster in the reaction, which may influence the catalytic activity of cluster for the subsequent N2O decomposition. The core atom in the Cu13 cluster is substituted with the Fe, Co, or Ni to enhance structural stability and prevent from the obvious configuration relaxation in the reaction. Note that these bimetallic clusters are of icosahedra as the Cu13. They have activities for N2O dissociation along ER pathway and the heteroatorn in the cluster can prevent configuration from relaxation. Finally, the Ni@Cu12 cluster can be as a superior catalyst in a complete catalytic cycle via comparison in this study.

Electronic Structures and Chemical Bonding of NbS6^(-/0)Clusters

Density functional theory（DFT） and coupled cluster theory（CCSD（T）） calculations were employed to investigate the structural and electronic properties of Nb S6^- and Nb S6 clusters. Generalized Koopmans＇ theorem was applied to predict the vertical detachment energies and simulate the photoelectron spectra（PES）. The current study indicated that various types of sulfur ligands（i.e., S^（2-）, S^（2-）, S2^（2-） and S3^（2-）） were presented in the lowest-energy structures of Nb S6^（-/0）. The ground-state structure of Nb S6^- is shown to be Cs（~1A＇） symmetry with a terminal S^（2-）, a side-on bound S2^（2-） and a S3^（2-） ligands. Molecular orbital analyses were performed to analyze the chemical bonding in NbS6^（-/0） clusters and elucidate their structural and electronic properties.

Adsorption and Reaction of CN +O→OCN on Cu(100) Surface: A Density Functional Theory Study

The adsorption and reaction of O ＋ CN → OCN on Cu（100） are studied by using density functional theory and cluster model. Cu14 cluster model is used to simulate the surface. The calculated results show that the OCN species with the molecule perpendicular to the surface via N atom （N-down） is more favorable than other adsorption models, and the N-down at the bridge site is the most favorable. For N-down, calculated OCN symmetric and asymmetric stretching frequencies are all blue-shifted compared with the calculated values of free and in good agreement with the experiments. The charge transfer from the surface to the OCN species leads to that the bonding of OCN to the metal surface is largely ionic. The present studies also show that CN with the molecule perpendicular to the surface via C atom （NC-down） at the top site is the most stable. Except NC-down at the top site, the calculated CN stretching frequencies are all red-shifted. With O coadsorbed at the hollow site, the adsorption of NC-down at the next nearest bridge or top site is energetically more favorable than that at the adjacent hollow site. The reaction of O ＋ CN → OCN on Cu（100） has no energy barrier via both Eley-Rideal and Langmuir-Hinshelwood processes.

Nanoclusters Au19Pd and Au19Pt Catalyzing CO Oxidation: a Density Functional Study

The gold atoms on the Au20 cluster had been substituted by the palladium and platinum atoms to obtain the doped clusters with more stable geometries as a function of the bind energy and interaction energy in the previous study. Therefore, we investigated the catalytic activities of the AuPd and AuPt clusters for CO oxidation along the Langmuir-Hinshelwood mechanism. It is found that the coadsorption of CO and O2 on the doped clusters is obviously stronger than on the Au20 cluster, especially on the doped atom, which makes potential energy of the transition state lower than the total energy of the reactants so that it can promote CO oxidation. The reaction on these doped clusters with the heteroatom on the vertex is more difficult. However, the AuPd(S) is more prone to catalyzing the CO oxidation, in which the rate-limiting step has the lower energy barrier of 38.84 kJ/mol for this study. Therefore, the single atom can be modified to change the catalytic activity of the cluster for the CO oxidation. Meanwhile, the different sites on the clusters have different strengths of activity for the reaction.

Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO2 Photoreduction

Defect engineering has being regarded as one of the effective ways to regulate chemical and electronic structure of semiconductors.Recently,our collaborative work has shown experimentally that carbon vacancy on polymeric carbon nitride(CV)can greatly improve the CO2 to CO conversion with a 45-fold improvement over the polymeric carbon nitride(Angew.Chem.Int.Ed.,2019,58,1134).In order to clarify the detailed mechanism of promotion,we have systematically studied the electronic properties of CV and hydrogenated CV(CV+H)as well as the effective CO2 reduction reaction through density functional theory calculations.We found that it is the synergistic effect for the CO2 reduction reaction in the CV systems,as the onset potentials of several CVs are much lower than that of the polymeric carbon nitride.In particular,the onset potentials of CV1,CV2,and CV2+H are around 0.9~1.5 eV with a strong chemisorbed CO2 on them.Combined with the analysis of the electronic properties,our results confirm that defect engineering increases the lifetime of photo-generated charges,improves photocatalytic activity,and promotes the CO2 reduction reaction on the defected polymeric carbon nitrides.