Mechanism of CO Oxidation on Cu<sub>2</sub>O (111) Surface: A DFT and Microkinetic Study

Wu, Lingnan; Tian, Zhen‐Yu; Wu, Qin

doi:10.1002/kin.21176

Cited by 29 publications

(21 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Adsorption energy ( E ad ) is calculated to characterize the magnitude of interaction between CO and the surface, which is defined as E ad = E sys – E sur – E ads , where E sys is the energy of the total adsorption system after adsorption, E sur is the energy of the bare surface before adsorption, and E ads is the energy of the adsorbate before adsorption. The basis set superposition error of DNP basis set is smaller than that of 6-311+G(3df,2pd) basis set, and it is not considered in the current study, which is consistent with previous works using DNP basis set to study CO adsorption and oxidation mechanism , on the periodic Cu 2 O slab surface.…”

Section: Methodssupporting

confidence: 90%

“…The CO oxidation mechanism on the perfect nonpolar Cu 2 O(111) surface has already been studied in our previous work, and the Cu I site was found to play an important role during the adsorption and subsequent oxidation processes. It is therefore of interest to investigate the surface activity without the presence of Cu I .…”

Section: Results and Discussionmentioning

confidence: 85%

“…The CO oxidation mechanism on the perfect nonpolar Cu 2 O(111) surface has already been studied in our previous work, 25 8 Under different preparation conditions, the ratio of surface Cu/O varied a lot, and it was found that the surface activity for CO oxidation increased with the increase of the amount of adsorbed O atoms on the surface. Therefore, the adsorbed O could originate from the growth and synthesis process of the Cu 2 O samples.…”

Section: Methodsmentioning

confidence: 96%

“…Several works have attempted to study the CO adsorption and oxidation mechanism on the Cu 2 O surface on the basis of density functional theory (DFT) calculations, ,,− but most of these studies used the nonpolar Cu 2 O(111) surface as the model surface. In such an ideal surface model, the effect of surface defects was not incorporated or it was considered within a limited level.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu₂O(111) Surface

Tian

2018

J. Phys. Chem. C

Self Cite

View full text Add to dashboard Cite

Understanding the role of surface defects on the catalyst performance is of great significance for a good command of the catalytic mechanism on the real catalyst surface. This work reports the mechanistic study of CO oxidation on the defective Cu 2 O(111) surface using density functional theory calculations. The effect of surface defects on surface catalytic activity was investigated by creating surface-adsorbed O atoms and Cu vacancies on the perfect Cu 2 O(111) surface. Possible defective surface structures were found, and calculated results showed that Cu vacancy on the Cu 2 O(111) surface could promote CO oxidation in two ways by (I) promoting the reaction between CO and lattice O with the energy barrier of 1.316 eV following the Mars−van− Krevelen mechanism; (II) promoting the reaction between CO and adsorbed O atoms below 575 K. For the perfect Cu 2 O(111) surface, adding adsorbed O to the surface could either cause a strong surface reconstruction with the adsorbed O evolving into a lattice O or stay in the active state. The obtained results could explain the experimental observations that a higher O/Cu ratio on the Cu 2 O surface can improve the activity of Cu 2 O toward CO oxidation. Rate constants were provided according to harmonic transition state theory, which would be helpful for the kinetic modeling of CO catalytic oxidation on the real Cu 2 O surface.

show abstract

Section: Methodssupporting

confidence: 90%

Section: Results and Discussionmentioning

confidence: 85%

Section: Methodsmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu₂O(111) Surface

Tian

2018

J. Phys. Chem. C

Self Cite

View full text Add to dashboard Cite

show abstract

“…DFT computations were used here to further investigate the catalytic cycles and understand the enhanced catalytic performance of Cu–Cu 2 O (111). Very recently, Wu et al only compared Langmuir–Hinshelwood (LH) mechanism and Mars‐van‐Krevelen (MvK) mechanism of CO oxidation on the Cu 2 O (111) surface and proposed that the former is more favorable 33. On the other hand, Sun et al suggested that CO oxidation on the Cu 2 O(111) surface adopts the ER mechanism, in which the adsorbed O 2 reacts with the CO from gas directly 34.…”

Section: Resultsmentioning

confidence: 99%

Cu–Cu₂O Heterogeneous Architecture for the Enhanced CO Catalytic Oxidation

Kong

et al. 2020

Adv Materials Inter

View full text Add to dashboard Cite

surface of metal-metal oxidation can be oxidized. [12][13][14] Experimentally, relatively limited amount of group metals attached on catalyst surface present a tremendous potential in determining the active structure and composition during the CO oxidation. [15,16] Although noble metals (such as Au, Ag, and Ru) exhibit highly CO oxidation activities, [17][18][19] the rare quantity and high cost restrict their application. In contrast, transition metal oxides are of interest as the most suitable substitutes owing to the low cost and abundance. Among them, copper (Cu) and Cu-based materials are basically featured for CO oxidation, owning to the multiple oxidation states, such as cuprous oxide (Cu 2 O) and copper oxide (CuO). [20][21][22] Huang et al. have separately studied the CO oxidation activities over Cu, Cu 2 O, and CuO, and found that Cu 2 O exhibits higher activities than the other two copper species due to the propensity of Cu 2 O toward valence variations is easy to release or seize oxygen molecule. [23] Penkala et al. have prepared CuO-Ca 2 Fe 2 O 5 catalysts and studied the enhanced CO oxidation performance. [24] However, few appeared reports have concerned about the CO catalytic activity of Cu-Cu 2 O interface in oxygen atmospheres. From the previous theoretical perspective, the role of the loading particles focuses on the variations in work functions, the polarization at the interface of hybrid material, and the regulating and controlling of oxygen vacancy. [17,25] The lack of Cu-Cu 2 O heterogeneous interface and molecular understanding during the catalytic process remain unclear.Herein, we report a facile two-step synthesis approach for monodispersed Cu-Cu 2 O heterogeneous particles (HPs), where Cu nanoparticles on the surface were in situ reduced from octahedral Cu 2 O particles. Cu-Cu 2 O HPs were found to exhibit better catalytic performance than pure Cu 2 O particles during the first cycle of CO oxidation. In addition, after the first run of CO catalytic reaction, composite CuO-Cu 2 O interfaces are formed on the surface of Cu-Cu 2 O HPs, which further increased the conversion of CO oxidation efficiencies. The density functional theory (DFT) simulations indicate that due to loaded Cu nanoparticles, the heterogeneous architecture promotes the catalytic reaction under both the Eley-Rideal mechanism (key step: O 2 dissociation) as well as Langmuir-Hinshelwood mechanism. In Heterogeneous architecture of Cu 2 O-based composite has exhibited beneficial effort in the CO oxidation, due to the low cost and the multiple oxidation states. In this work, Cu-Cu 2 O heterogeneous particles (HPs) comprising uniformly distributed Cu nanoparticles anchored on the Cu 2 O surface are synthesized by in situ reduction reaction. Comparing with the pure Cu 2 O particles, Cu-Cu 2 O HPs exhibit enhanced and stable catalytic performance during CO oxidation. Moreover, both the transformation of interface and the role of loaded Cu nanoparticle at a molecular level are investigated to analyze the promotion, suggesting that ...

show abstract

Al‐Decorated C₂₀ Fullerene as a Promising Noble Metal‐Free Catalyst for CO Oxidation: A DFT Study

Ragab,

Hassan,

Khan

2024

ChemistrySelect

View full text Add to dashboard Cite

To remove the toxic carbon monoxide (CO) gas from the environment, recently, researchers have taken great interest in single‐atom catalysts (SACs). In this study, we investigated various reaction pathways and barrier energies for the CO oxidation process onto Al‐decorated C20 fullerene (Al@C20) employing density functional theory (DFT). The outcomes validate that Al decoration on C20 is energetically stable while the corresponding electronic properties show that the Al atom acts as the reactive site for catalytic activity. The bond distances and larger negative adsorption energies (−0.65 and −2.53 eV) evince that CO and O2 species adsorbed strongly to the Al atom. For the oxidation of CO, two popular mechanisms are examined: Eley Rideal (ER) and Langmuir Hinshelwood (LH). The assessment of energy barriers discloses that the CO oxidation reaction progresses via the LH mechanism. Additionally, the CO + O* → CO2 reaction proceeds very quickly onto the Al@C20 catalyst, with a very small energy barrier (0.13 eV), indicating the excellent catalytic reactivity of the studied catalyst. These results propose that the designed catalyst can be valuable in the progress of novel noble metal‐free catalysts for harmful CO elimination from the environment.

show abstract

Mechanism of CO Oxidation on Cu₂O (111) Surface: A DFT and Microkinetic Study

Cited by 29 publications

References 36 publications

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu₂O(111) Surface

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu₂O(111) Surface

Cu–Cu₂O Heterogeneous Architecture for the Enhanced CO Catalytic Oxidation

Al‐Decorated C₂₀ Fullerene as a Promising Noble Metal‐Free Catalyst for CO Oxidation: A DFT Study

Contact Info

Product

Resources

About

Mechanism of CO Oxidation on Cu2O (111) Surface: A DFT and Microkinetic Study

Cited by 29 publications

References 36 publications

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu2O(111) Surface

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu2O(111) Surface

Cu–Cu2O Heterogeneous Architecture for the Enhanced CO Catalytic Oxidation

Al‐Decorated C20 Fullerene as a Promising Noble Metal‐Free Catalyst for CO Oxidation: A DFT Study

Contact Info

Product

Resources

About

Mechanism of CO Oxidation on Cu₂O (111) Surface: A DFT and Microkinetic Study

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu₂O(111) Surface

DFT Study on CO Catalytic Oxidation Mechanism on the Defective Cu₂O(111) Surface

Cu–Cu₂O Heterogeneous Architecture for the Enhanced CO Catalytic Oxidation

Al‐Decorated C₂₀ Fullerene as a Promising Noble Metal‐Free Catalyst for CO Oxidation: A DFT Study