Activation mechanisms of silver toward CO oxidation by tungsten carbide substrate: A density functional theory study

The development of efficient catalysts for low temperature CO oxidation is important to the application of fuel cells. In this work, we report that the Ag monolayer on WC (0001) surface (Ag_ML/WC) could effectively catalyze CO oxidation through the L-H mechanism (CO + O₂ → OOCO → CO₂ + O). The most sluggish reaction step is suggested to be CO + O → CO₂ with a barrier of 0.48 eV, which is 1.21 eV lower than the barrier of O₂ dissociation. The electronic structure and d-band center analyses demonstrate that the promoted activity may originate from the synergistic effect between Ag monolayer and WC. The present study is conducive to design new efficient and cost-effective catalysts for CO oxidation without using of the noble platinum.     

Interaction mechanism among CO,H2S and CuO oxygen carrier in chemical looping combustion: A density functional theory calculation study

When using coal-derived syngas or coal as fuel in chemical looping combustion (CLC), CO as a representative pyrolysis/gasification product and H₂S as the main sulfurous gas coexist in fuel reactor. Either CO or H₂S can absorb on the surface of CuO (the active component of Cu-based oxygen carriers), and reactions will occur among them. In this study, density functional theory (DFT) calculations are conducted to investigate the interaction among H₂S, CO, and CuO, including: the reaction between CO and H₂S over CuO particle, the influence of CO on the H₂S dissociation and further reaction process, and the impact of H₂S dissociation products on CO oxidation. Firstly, the co-adsorption results suggest that H₂S might directly react with CO to produce COS via the Eley–Rideal mechanism, while CO prefers to react with HS* or S* via the Langmuir–Hinshelwood mechanism. This means that the reaction mechanisms between CO and H₂S will change as the H₂S dissociation proceeds, which has already been forecasted by the co-adsorption energies and verified by all of potential Eley–Rideal and Langmuir–Hinshelwood reaction pathways. Then, the influence of CO on the H₂S dissociation process is examined, and it is noted that the presence of CO greatly limits the dissociation of H₂S due to the increased energy barrier of the rate-determining dehydrogenation step. Furthermore, the impact of H₂S dissociation products on CO oxidation by CuO is also investigated. The presence of H₂S and S* significantly supresses the CO oxidation activity, while the presence of HS* slightly promotes the CO oxidation activity. Finally, the complete interaction mechanisms among H₂S, CO, and CuO are concluded. It should be noted that COS will be inevitably produced via the Langmuir–Hinshelwood reaction between surface S* and CO*, which is prior to H₂O generation and subsequent sulfidation reaction.     

Catalytic activity of Pd ensembles incorporated into Au nanocluster for CO oxidation: A first-principles study

We investigated the catalytic activity of Pd atoms incorporated into Au(111) facet through first-principles calculations, and found that the Pd monomer, dimer, and trimer are highly reactive for the reaction of CO+O₂→CO₂+Ovia association mechanism, in which an intermediate state (OOCO) is formed. Significantly, a low energy barrier (0.19-0.32 eV) was found for the formation of OOCO. The atomic oxygen left by CO+O₂→CO₂+O reaction can be removed by another CO on Pd-decorated Au cluster via Langmuir-Hinshelwood or Eley-Rideal mechanism. Our studies indicate Pd ensembles incorporated into Au(111) facet markedly improve the catalytic activity of gold nanocluster.     

CO oxidation over BC3 nanosheet: a theoretical study

ABSTRACT

Metal-free catalysts have attracted more attention due to their highly active in catalytic oxidation reactions. The electronic structure and catalytic property of BC₃ sheet are investigated by using first-principles calculations. It is found that the BC₃ sheet as the active surface can effectively regulate the adsorptive stability of reactive gases. Besides, the possible reaction processes for CO oxidation on the BC₃ sheet are comparably analysed through different reaction mechanisms, which include the Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and termolecular Eley–Rideal (TER). In the CO oxidation reactions, the decomposition of O₂ molecule as the starting state (0.40?eV) is an energetically more favourable process than those of other processes, the Eley–Rideal (ER) reactions (2O_ads+2CO→CO₂) are more prone to take place with lower energy barriers (3 sheet. These results provide an important guidance on exploring the highly efficiency metal-free catalyst for CO oxidation.     

Electric field gradients of 111Cd in the copper oxides CuO and Cu2O

Perturbed angular correlation measurements were performed after ¹¹¹In implantation into CuO and Cu₂O powder samples and 1 μm thick Cu₂O surface layers. The quadrupole hyperfine interaction of ¹¹¹Cd was studied in isochronal annealing cycles at 370–1170 K covering the CuO→Cu₂O phase transition. The electric field gradients obtained for ¹¹¹Cd on substitutional Cu lattice sites were associated with the repective oxygen coordinations. Annealing of Cu₂O surface layers on copper foils resulted in a texture with the efg pointing preferentially out of the surface plane.     

C20 fullerene and its boron- and nitrogen-doped counterparts as an efficient catalyst for CO oxidation

DFT calculations are utilised to investigate the CO oxidation on the C₂₀, BC₁₉, and NC₁₉ clusters. For CO oxidation over considered clusters, two continuous steps are proposed that in each step one CO₂ molecule is released from clusters surface. The calculations demonstrate that in the case of the C₂₀ cluster, the first step of CO oxidation takes place through the ER mechanism on two routes with a barrier height of 1.06?eV and 2.57?eV for the rate-limiting step. Also, in the cases of BC₁₉ and NC₁₉ clusters, both reaction paths occur via the ER mechanism. The activation energy of the first reaction step is about 0.53 and 0.46?eV, while it is negligible for the second step that is 0.04 and 0.18?eV for BC₁₉ and NC₁₉ clusters, respectively. Based on the present theoretical results, the catalytic activity of BC₁₉ and NC₁₉ clusters toward the CO oxidation is more than that of the C₂₀ cluster. These results show that the BC₁₉ and NC₁₉ clusters can be recommended as an efficient and metal-free catalyst for CO oxidation at near ambient temperatures.

Research Highlights

• CO oxidation over C₂₀ fullerene has been investigated.

• The effect of N/B-doing on the CO oxidation reaction is also studied.

• The N/B-doping increases the catalytic activity of C₂₀ fullerene.

• Boron/Nitrogen-doped C₂₀ fullerene can be applied as an efficient catalyst for CO oxidation.

     

Performance improvement of Cu x O resistive switching memory by surface modification

The Cu _x O films grown by plasma oxidation are composed of an insulating CuO layer and a conductive gradient Cu _x O layer. We found that the surface CuO layer influenced the switching behaviors greatly. Giant improvement of reliable endurance was achieved after annealing the device in the N₂ atmosphere, resulting from the transition of CuO to Cu₂O. The possible mechanism for this improvement is attributed to the alleviation of over-programming during forming process. The result shows that for resistance switching Cu₂O is much more preferred than CuO. After further reducing the thickness of Cu₂O layer, the forming voltage can be totally eliminated.     

Molecular orbital study of co chemisorption and oxidation on a Pt(111) surface

A molecular orbital study was made, using an atom superposition and electron delocalization (ASED) technique, of the structures and energy levels of CO on Pt(111) surface. CO is predicted to be preferentially adsorbed at a height of 2.05 Å from the surface at a 1-fold position with the carbon end down. The calculated binding energy (1.7 eV) is in good agreement with the recent experimental result (1.5 eV) of Campbell et al. Calculated binding energies for bridging (1.3 eV) and high coordinate (1.1 eV) sites are predicted to be smaller in magnitude. Calculated results are used to discuss the ordering of energy levels of adsorbed CO. The interaction between CO (adsorbed) and O (adsorbed) has been studied to estimate the energy of activation for the oxidation of CO on Pt(111) surface. The calculated activation energy (1.6 eV) is in reasonable agreement with the recent experimental result (1 eV) of Campbell et al. The Langmuir-Hinshelwood mechanism is found to be favored. We predict CO₂ bonds vertically.     

Identification of Cu(I) and Cu(II) oxides by electron spectroscopic methods: AES,ELS and UPS investigations

The externally prepared black-coloured copper oxide (T? 700 K, P_O2 ? 100 torr) on a Cu(100) surface is identified by electron spectroscopy as CuO. Compared to the red-coloured Cu(I) oxide (in situ oxidation at T ? 400 K, P_O2 ? 0.5 torr, ～ 10⁹ L), the He(I)- excited photoemisson from CuO reveals characteristic shake-up satellites 10–12 eV below E_F and a broadened emission from overlapping oxygen-induced 2p and Cu 3d states. From the AES and ELS results, in correlation with the data from core electron spectroscopy, chemical shifts of Cu 2p, Cu 3s and Cu 3p in CuO to higher binding energy and decreases in binding energy of the oxygen-induced states were deduced. The unoccupied electron states of Cu at 5 and 7.5 eV above E_F — postulated from the ELS results — are preserved in Cu₂O and CuO compounds. Annealing of the Cu(II) oxide at 670 K is accompanied by decomposition into Cu₂O due to the solid-state reaction following the scheme: 2CuO → 1/2 O₂ + Cu₂O.     

A density functional theory study on the adsorption of CO and O2 on Cu-terminated Cu2O （111） surface

The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.     

Fabrication of cuprous and cupric oxide thin films by heat treatment

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were prepared by thermal oxidation of copper films coated on indium tin oxide (ITO) glass and non-alkaline glass substrates. The formation of Cu₂O and CuO was controlled by varying oxidation conditions such as, oxygen partial pressure, heat treatment temperature, and oxidation time. The microstructure, crystal direction, and optical properties of copper oxide films were measured with X-ray diffraction, atomic force microscopy, and optical spectroscopy. The results indicated that the phase-pure Cu₂O and CuO films were produced in the oxidation process. Optical transmittance and reflectance spectra of Cu₂O and CuO clearly exhibited distinct characteristics related to their phases. The electrical properties indicated that these films formed ohmic contacts with Cu and ITO electrode materials. Multilayers of Cu₂O/CuO were fabricated by choosing the oxidation sequence. The experimental results in this paper suggest that the thermal oxidation method can be employed to fabricate device quality Cu₂O and CuO films that are up to 200–300 nm thick.     

Nano-scale copper oxidation on leadframe surface

Copper oxidation studies were carried out by means of field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) techniques. The growth of copper oxide occurs as a copper surface comes in an oxygen containing environment. The reaction sequence leading to oxidation of the copper surface is generally accepted to be oxygen chemisorption, nucleation and growth of the surface oxide and bulk oxide growth. HRTEM examination of the cross section of the oxidized copper sample revealed the interface region in between the copper and copper oxide. At high oxidation temperature, formation of micro-voids and separations were observed along this interface region. Poor adhesion at this interface region due to micro-voids and separation were found to be the root cause of delamination issue. EELS analysis determined that for regions with intact interface the oxidation system is Cu/CuO/Cu₂O/CuO, however, in regions containing micro-voids or separation it is found to be Cu/Cu₂O/CuO.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Reaction mechanism for CO oxidation on Cu(3 1 1): A density functional theory study

The microscopic reaction mechanism for CO oxidation on Cu(3 1 1) surface has been investigated by means of comprehensive density functional theory (DFT) calculations. The elementary steps studied include O₂ adsorption and dissociation, dissociated O atom adsorption and diffusion, as well as CO adsorption and oxidation on the metal. Our results reveal that O₂ is considerably reactive on the Cu(3 1 1) surface and will spontaneously dissociate at several adsorption states, which process are highly dependent on the orientation and site of the adsorbed oxygen molecule. The dissociated O atom may likely diffuse via inner terrace sites or from a terrace site to a step site due to the low barriers. Furthermore, we find that the energetically most favorable site for CO molecule on Cu(3 1 1) is the step edge site. According to our calculations, the reaction barrier of CO + O → CO₂ is about 0.3 eV lower in energy than that of CO + O₂ → CO₂ + O, suggesting the former mechanism play a main role in CO oxidation on the Cu(3 1 1) surface.     

Fabrication of Cu2O nanocrystalline thin films photosensor prepared by RF sputtering technique

Cuprous oxide (Cu₂O) nanocrystalline thin films were prepared on two types of substrates known as crystalline silicon and amorphous glass, by radio frequency reactive magnetron sputtering method. Scanning electron microscopy images confirmed that Cu₂O particles covered the entire surface of both substrates with smoothing distribution. The root mean square surface roughness for the prepared Cu₂O thin films on glass and Si (111) substrates is 4.16, and 3.36 nm, respectively. Meanwhile, X-ray diffraction results demonstrated that the two phases of Cu₂O and CuO were produced on Si (111) and glass substrates. The optical bandgap of Cu₂O thin films synthesised on glass substrate is 2.42 eV. Furthermore, the prepared Cu₂O nanocrystalline thin films have showed low reflectance value in the visible spectrum. Metal-Semiconductor-Metal photodetector based Cu₂O nanocrystalline thin films deposited onto Si (111) was fabricated using aluminium and platinum, with the current-voltage and photoresponse characteristic investigated under various applied bias voltages. The fabricated Metal-Semiconductor-Metal (M-S-M) photodetector had shown 126% sensitivity in the presence of 10 mW/cm² of 490 nm light with 1.0 V bias, displaying 90 and 100 ms response and recovery times, respectively. These findings have demonstrated the suitability of M-S-M Cu₂O photodetector as an affordable photosensor in the future.     

Photoemission valence band spectra and electronic density of states in copper oxides and copper based ceramic super-conductors

Photoemission valence band spectra with three different photon energies (21.2 eV, 40.8 eV, 1253.6 eV) for Cu₂O and CuO and a number of copper oxide based superconducting ceramics are investigated, namely La₂CuO₄ (LCO), Y₁Ba₂Cu₃O₇ (YBCO), Bi₂Sr₂CaCu₂O₈ (BSCCO) and Tl₂Ba₂Ca₂Cu₃O₁₀ (TBCCO). From the Cu₂O data it can be infered, that the He-II (40.8 eV) spectra give a fair representation of the density of states (DOS). In addition the agreement between the calculated density of states (DOS) and the He-II photoemission spectrum is almost perfect for Cu₂O. This agreement is worse for CuO and the other materials which all have a Cu groundstate close to a 3d ⁹ configuration indicating a large contribution of thed-d correlation energy to the excitation spectra which is absent in Cu₂O because of the filled 3d-shell. In all cases the experimental DOS atE _F is very small and only the spectra of BSCCO show a well defined Fermi edge. The relevance of these findings with respect to the theoretical local functional density DOS calculations is discussed.     

Mechanism and kinetics of Cu2O oxidation in chemical looping with oxygen uncoupling

In chemical looping with oxygen uncoupling, oxygen carrier (OC) circulates between the fuel and air reactors to release and absorb O₂ repeatedly. In order to assess the re-oxidation characteristic of Cu-based OC in the air reactor from the microscopic mechanism and macroscopic kinetics perspective, DFT calculations and isothermal oxidation experiments were conducted. In DFT calculations, Cu₂O(111) surface was chosen as the objective surface to explore the oxygen uptake as well as the atomic transportation pathways, and to determine the rate-limiting steps basing on the energy barrier analyses. It was found that the energy barrier of the surface reaction step (0.96?eV) is smaller than that of the ions diffusion step (1.61?eV). Moreover, the Cu cations outward diffusion occurs more easily than O anions inward diffusion, which confirmed the epitaxial growth characteristic of Cu₂O oxidation. The isothermal oxidation experiments were conducted in a thermogravimetric analyzer (TGA), and about 3.5?mg CuO@TiO₂-Al₂O₃ particles within the diameter range of 75–110?µm were tested between 540 and 600 °C, where the internal and external gas diffusion effects were eliminated. Mixtures of 5.2-21.0?vol.% O₂ in N₂ were adopted as the gas agent for oxidation. Based on the understandings obtained from DFT calculations, a simple mathematical model with unknown parameters of the surface reaction process (mainly the activation energy, E_k) and ions diffusion process (mainly the activation energy, E_D) was established to describe the overall oxidation process in TGA experiments. Eventually, these unknown parameters were determined as E_k=?50.5?kJ/mol and E_k=?79.2?kJ/mol via global optimization. With the attained parameters, simulations reproduced the experimental results very well, which demonstrated that this simplification model, where grain is converted almost layer by layer but different from the feature of the shrinking core model is able to accurately describe the overall oxidation process of Cu₂O.     

Oxide films of copper prepared by the oxidation of copper sulphide films

Copper sulphide films prepared by reactive evaporation, when heated in air at 500 K, oxidized to Cu₂O after a series of intermediate chemical transitions. Golden yellow coloured Cu₂O films showed a large absorption before the fundamental absorption edge. The optical band gap was found to be (2.29±0.02)eV. When these Cu₂O films were further heated they got converted to CuO and the optical band gap was found to be (2.17±0.02)eV.     

Structural,electronic and catalytic performance of single-atom Fe anchored 3Si-doped graphene

By density functional theory (DFT) calculations, it is found that the single-atom Fe anchored three Si modified defective graphene (3Si-graphene-Fe) exhibits the high stability, and this system is semiconducting property and has non-magnetic moment. Besides the most stable configurations, electronic structures and magnetic properties of adsorbed species (O₂, CO, 2CO and CO/O₂) on 3Si-graphene-Fe systems are comparably discussed. The adsorption of O₂ is more stable than that of CO molecule and the coadsorption of 2CO and CO/O₂ has the larger adsorption energy than that of the isolated one. The adsorbed O₂, CO and CO/O₂ can induce the change in magnetic properties of 3Si-graphene-Fe system, and the coadsorbed CO/O₂ on system exhibits the metallic property. Among the reaction mechanisms, the CO oxidation reactions through Eley–Rideal (ER) reactions have lower energy barriers (<0.5?eV) than those of the Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms, indicating that the ER reaction as starting step is an energetically favourable process. These results provide an important guidance on validating the catalytic activity of single atom on graphene-based materials.     

Preparation of Cu2O nanowires by thermal oxidation-plasma reduction method

Facial synthesis of cuprous oxide (Cu₂O) nanowires by directly heating copper substrates is difficult; however, in this study, it was successfully done by thermal oxidation followed by a plasma reduction process. The preparation of CuO nanowires with an average diameter of 76.2?nm supported on the surface of copper substrate was conducted first in air at 500?°C for 3?hrs, and then the CuO nanowires were reduced into Cu₂O in 15?min using either radio frequency (RF) N₂ plasma or microwave (MW) N₂ plasma. The characteristics of CuO and Cu₂O nanowires were analyzed using XRD, FE-SEM, and TEM. The results showed that Cu₂O nanowires can be successfully reduced from CuO nanowires by a simple, promising, and fast nitrogen plasma process. Moreover, in RF plasma, narrower and longer Cu₂O nanowires can be produced as compared to MW plasma, because energetic N-containing species can reduce the nanowires at a relatively lower temperature.