Coverage-dependent structure and reactivity of vanadia clusters supported on anatase TiO2(1 0 1) surface

Ma, Shanshan; Huang, Zequan; Qu, Bingyan; Li, Dongdong; Zhou, Rulong

doi:10.1016/j.apsusc.2020.148774

Cited by 5 publications

(3 citation statements)

References 38 publications

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“…The evolutionary algorithm-based USPEX package has shown great success in predicting the most stable structures of various materials. − Therefore, in this work, we performed an extensive search for the most stable structures of various-sized Ni clusters supported on the anatase TiO 2 (101) [denoted as A(101)] surface by using the surface structure prediction module implemented in the USPEX package. The details of our structural search have been described clearly in our previous work. − Briefly, the whole structure model is divided into three regions, that is, the vacuum region, the surface region, and the substrate region. The substrate is simulated by a slab with two TiO 2 layers within a 1 × 3 surface supercell, whose lattice constants are a = 10.38 Å and b = 11.41 Å. Ni cluster structures are generated within the surface region.…”

Section: Computational Detailsmentioning

confidence: 99%

Size-Dependent Atomic and Electronic Structures of Small-Sized Ni_n (n = 2–10) Clusters Supported on the Anatase TiO₂(101) Surface: A Density Functional Theory Study

et al. 2022

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The atomic and electronic structures of small-sized Ni n (n = 2−10) clusters supported on the anatase TiO 2 (101) surface [denoted as A(101)] are systematically investigated by an extensive evolutionary structural search and density functional theory calculations. The predicted low-energy structures show that 3D geometries are more favored for most supported Ni n clusters. Thermodynamic stability analysis indicates that the cluster−substrate interaction plays a critical role in stabilizing the Ni n /A(101) system. Ni 4 /A(101), Ni 6 /A(101), and Ni 8 /A(101) are more stable compared to their neighbors and may be easily formed experimentally. Electrons transfer from the supported Ni n clusters to the TiO 2 substrate and mostly accumulate at the Ti 5c sites just below the Ni n cluster. These extra electrons may easily transfer to other surface sites, enhancing the reactivity of the TiO 2 surface, and can also transfer back to the Ni n cluster, providing additional active sites besides the metallic Ni atoms. Moreover, the introduction of Ni n clusters can enhance the visible light response of the system. The results of this work indicate that Ni n /TiO 2 systems are promising high-performance photocatalysts or electrocatalysts for efficient N 2 reduction reactions and NH 3 synthesis.

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Section: Computational Detailsmentioning

confidence: 99%

Size-Dependent Atomic and Electronic Structures of Small-Sized Ni_n (n = 2–10) Clusters Supported on the Anatase TiO₂(101) Surface: A Density Functional Theory Study

et al. 2022

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“…Integrated areal analysis of the spin–orbit doublets fitted to each state allows for quantitative comparison of the prevalence of each state and gives a ratio of 4.6:1 for the relative amount of Pt 2+ to Pt 4+ . Notably, there is no detectable presence of the Pt 0 state, indicating that all the Pt atoms in the sample are oxygen-bound, and there is no feature corresponding to metallic Pt, excluding the presence of Pt nanoparticles − which could form via cluster fragmentation and subsequent agglomeration in a deposition process. − This supports the successful soft landing of cluster ions at the substrate surface with low kinetic energies. The Zr 3d spectrum acquired for as-prepared Zr 2 O 7 /HOPG shows a Zr 3d 5/2 binding energy of 182.1 eV, which is consistent with a Zr 4+ state. − By comparison, the Zr 3d 5/2 feature for the Pt 1 Zr 2 O 7 /HOPG sample is shifted to a higher binding energy of 182.7 eV, comprising a 0.6 eV binding energy shift.…”

Section: Resultsmentioning

confidence: 80%

Ultrasmall Cluster Model for Investigating Single Atom Catalysis: Dehydrogenation of 1-Propanamine by Size-Selected Pt₁Zr₂O₇ Clusters Supported on HOPG

et al. 2022

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The selective dehydrogenation of hydrocarbons and their functionalized derivatives is a promising pathway in the realization of endothermic fuel systems for powering important technologies such as hypersonic aircraft. The recent surge in interest in single atom catalysts (SACs) over the past decade offers the opportunity to achieve the ultimate levels of selectivity through the subnanoscale design tailoring of novel catalysts. Experimental techniques capable of investigating the fundamental nature of the active sites of novel SACs in well-controlled model studies offer the chance to reveal promising insights. We report here an approach to accomplish this through the soft landing of mass-selected, ultrasmall metal oxide cluster ions, in which a single noble metal atom bound to a metal oxide moiety serves as a model SAC active site. This method allows the preparation of model catalysts in which monodispersed neutral SAC model active sites are decorated across an inert electrically conductive support at submonolayer surface coverage, in this case, Pt 1 Zr 2 O 7 clusters supported on highly oriented pyrolytic graphite (HOPG). The results contained herein show the characterization of the Pt 1 Zr 2 O 7 /HOPG model catalyst by X-ray photoelectron spectroscopy (XPS), along with an investigation of its reactivity toward the functionalized hydrocarbon molecule, 1-propanamine. Through temperature-programmed desorption/reaction (TPD/R) experiments it was shown that Pt 1 Zr 2 O 7 /HOPG decomposes 1-propanamine exclusively into propionitrile and H 2 , which desorb at 425 and 550 K, respectively. Conversely, clusters without the single platinum atom, that is, Zr 2 O 7 /HOPG, exhibited no reactivity toward 1propanamine. Hence, the single platinum atom in Pt 1 Zr 2 O 7 /HOPG was found to play a critical role in the observed reactivity.

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“…Subsequently, the lower-energy structures are selected for high-level structural optimization. For more details on structure search, please refer to our previous works. − …”

Section: Methodsmentioning

confidence: 99%

Small-Sized Fe_n Clusters Supported on the Anatase TiO₂(101) Surface as a Promising High-Performance Catalyst for the N₂ Reduction Reaction

Jin,

Feng,

et al. 2024

J. Phys. Chem. C

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Based on an extensive structural search and firstprinciples calculations, the structural evolution, electronic properties, and catalytic properties for the nitrogen reduction reaction (NRR) of TiO 2 (101) surface supported Fe n clusters are systematically investigated. Much difference from those of Ni n /TiO 2 and Cu n /TiO 2 is observed. The growth pattern of Fe n /TiO 2 is similar to that of Ni n /TiO 2 for n ≤ 7 but different for n ≥ 8. The stronger Fe−Fe and Fe−TiO 2 interactions lead to different size-dependent behaviors of thermodynamic stabilities of Fe n /TiO 2 compared to Ni

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Coverage-dependent structure and reactivity of vanadia clusters supported on anatase TiO2(1 0 1) surface

Cited by 5 publications

References 38 publications

Size-Dependent Atomic and Electronic Structures of Small-Sized Ni_n (n = 2–10) Clusters Supported on the Anatase TiO₂(101) Surface: A Density Functional Theory Study

Size-Dependent Atomic and Electronic Structures of Small-Sized Ni_n (n = 2–10) Clusters Supported on the Anatase TiO₂(101) Surface: A Density Functional Theory Study

Ultrasmall Cluster Model for Investigating Single Atom Catalysis: Dehydrogenation of 1-Propanamine by Size-Selected Pt₁Zr₂O₇ Clusters Supported on HOPG

Small-Sized Fe_n Clusters Supported on the Anatase TiO₂(101) Surface as a Promising High-Performance Catalyst for the N₂ Reduction Reaction

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Coverage-dependent structure and reactivity of vanadia clusters supported on anatase TiO2(1 0 1) surface

Cited by 5 publications

References 38 publications

Size-Dependent Atomic and Electronic Structures of Small-Sized Nin (n = 2–10) Clusters Supported on the Anatase TiO2(101) Surface: A Density Functional Theory Study

Size-Dependent Atomic and Electronic Structures of Small-Sized Nin (n = 2–10) Clusters Supported on the Anatase TiO2(101) Surface: A Density Functional Theory Study

Ultrasmall Cluster Model for Investigating Single Atom Catalysis: Dehydrogenation of 1-Propanamine by Size-Selected Pt1Zr2O7 Clusters Supported on HOPG

Small-Sized Fen Clusters Supported on the Anatase TiO2(101) Surface as a Promising High-Performance Catalyst for the N2 Reduction Reaction

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Size-Dependent Atomic and Electronic Structures of Small-Sized Ni_n (n = 2–10) Clusters Supported on the Anatase TiO₂(101) Surface: A Density Functional Theory Study

Size-Dependent Atomic and Electronic Structures of Small-Sized Ni_n (n = 2–10) Clusters Supported on the Anatase TiO₂(101) Surface: A Density Functional Theory Study

Ultrasmall Cluster Model for Investigating Single Atom Catalysis: Dehydrogenation of 1-Propanamine by Size-Selected Pt₁Zr₂O₇ Clusters Supported on HOPG

Small-Sized Fe_n Clusters Supported on the Anatase TiO₂(101) Surface as a Promising High-Performance Catalyst for the N₂ Reduction Reaction