Study on the Reaction of Nanosized Yttrium Oxide Cluster Anions with n-Butane in the Gas Phase

doi:10.6023/A20110511

Abstract

Investigation on the reactions of atomically precise transition metal oxide nanoparticles with small molecules can not only identify the property evolution of nanoparticles with respect to the continuum change of size and composition, but also improve our understanding of the formation mechanism of reactive oxygen species [e.g., atomic oxygen radical anions (O^-• radicals)] over oxide surface. Yttrium oxide cluster anions Y_xO_y^- (x≤50,y≤76) with different oxygen deficiencies (Δ≡2y–1–3x, Δ=0~5) and Y _xO_yF^- (x≤49,y≤74) with Δ=1 [Δ≡(2y+1)–1–3x] have been prepared by laser ablation in an O₂ background and reacted with alkane molecules (n-butane) in a fast flow reactor. The reactions of mass-selected small-sized Y_xO_y^- (x≤8) clusters withn-butane were investigated in a linear ion trap reactor. Time-of-flight mass spectrometer was used to detect the cluster distribution before and after the reactions. The observation of (Y₂O₃)_NOH^- (N=1~25), (Y₂O₃)_NYO₄H^- (N=1, 3~24), and (Y₂O₃)_NYO₂FH^- (N=1~24) products suggest that (Y₂O₃)_NO^- (∆=1;N=1~25), (Y₂O₃)_NYO₄^- (∆=4;N=1, 3~24) and (Y₂O₃)_NYO₂F^- (Δ=1;N=1~24) can bring about hydrogen-atom abstraction (HAA) from n-butane. The reactivity of (Y₂O₃)_NO^-, (Y₂O₃)_NYO₂F^- and (Y₂O₃)_NYO₄^- clusters are significantly size-dependent and the highest reactivity was observed for N=3 (Y₆O₁₀^-, Y₇O₁₁F^-, and Y₇O₁₃^-). Density functional theory (DFT) calculations were performed to study the geometrical structures and unpaired spin densities of (Y₂O₃)_NO^- (N=1~4), (Y₂O₃)_NYO₂F^- (N=1~3), and (Y₂O₃)_NYO₄^- (N=1, 3, 4) clusters that were found to contain O^-• radicals as active centers to abstract hydrogen atoms from n-butane, in agreement with the experiments. The results imply that the O^-• radicals which had been proved to be present in the small yttrium oxide clusters with Δ=1 or 4 are well preserved in the yttrium oxide nanoparticles. (Y ₂O₃)_NYO₄^- (∆=4;N=1, 3~24) and (Y₂O₃)_NYO₂F^- (∆=1;N=1~24) can be considered to be generated by the adsorption of an O₂ molecule or F onto the unreactive singlet (Y₂O₃)_NYO₂^- (∆=0;N=1~24). The studies on gas-phase clusters suggest that adsorption of O₂ molecule or F atom onto unreactive metal oxide clusters will result in the generation of O^-• radical (O^2-+O₂→O^-•+O₂^-• and O^2-+F^•→O^-•+F^-). This work not only reveals the new mechanisms of the formation of O^-• radical on metal oxide surfaces, but also provides new insights into the design of novel transition metal oxide-based catalysts.

Key words: yttrium oxide cluster, nanosize, reactivity, atomic oxygen radical anion, time-of-flight mass spectrometer

Cite this article

Man Ruan, Yan-Xia Zhao, Sheng-Gui He. Study on the Reaction of Nanosized Yttrium Oxide Cluster Anions with n-Butane in the Gas Phase[J]. Acta Chimica Sinica, 2021, 79(4): 490-499.

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Fig. & Tab. 6

Figure 1. TOF mass spectra for the reactions of mass-selected YxOy- with n-C4H10 and n-C4D10. The n-C4H10 partial pressures were 9.0 mPa (b1), 17 mPa (b2), 13 mPa (b3), 9.4 mPa (b4) and 9.0 mPa (b5). The n-C4D10 partial pressures were 12 mPa (c1), 36 mPa (c2), 31 mPa (c3), 17 mPa (c4) and 15 mPa (c5). The times for the reactions in panels (b) and (c) were about 1.5 ms. Panels (a) show the corresponding background spectra with He. YxOy- are labeled as x, y. The product peaks YxOyH- and YxOyD- are labeled with +H and +D, respectively. Peaks marked with circle originate from the reaction with water impurity (Y3O7-+H2O→Y3O5H2O-+O2).

Figure 2. TOF mass spectra for the reactions of YxOyF0,1- (Δ=0~5) with n-C4H10. The n-C4H10 partial pressures were 0.30 Pa n-C4H10 (b), 0.34 Pa n-C4H10 (d), 0.34 Pa n-C4H10 (f) and 0.32 Pa n-C4H10 (h). Panels (a), (c), (e) and (g) show the corresponding background spectra with He. YxOy- and YxOyF- are labeled as x, y and x, y, F, respectively. The product peaks YxOyH- and YxOyFH- are labeled with +H.

Figure 3. Relative rate constants for the reactions of (Y2O3)NYxOyF0,1- (x≤1; ∆=1, 4) with n-C4H10.

Figure 4. DFT calculated structures and profiles for unpaired spin density distributions of YxOyF0,1-. Mulliken atomic spin densities over O-• radicals are given (in μ B). The local charge (e) around the Y-O-• are given in the parentheses. The symmetry, electronic state and energy (in eV) with respect to the most stable isomer are given below each structure. The relative energies at the B3LYP/Def2-TZVP (E1) and CCSD(T)/Def2-TZVP//B3LYP/Def2-TZVP (E2) levels are given as E1/[E2]. Superscripts number denotes the spin multiplicity.

Figure 5. DFT calculated potential energy profiles for Y2O4-+n-C4H10 →Y 2O4H-+C4H9 (a), Y6O10-+n-C4H10→Y6O10H-+C4H9 (b). The ΔH 0 energies in eV with respect to the separated reactants are given in parentheses. Some bond lengths in pm are shown.

Figure 6. Changes of the angle (θ) between H-O and Y-O with respect to the distance of H-O bond for the reactions Y2O4- with n-C4H10 (a) and Y6O10- with n-C4H10(b).

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