Chem. J. Chinese Universities ›› 2019, Vol. 40 ›› Issue (5): 940.doi: 10.7503/cjcu20190063
• Physical Chemistry • Previous Articles Next Articles
CHENG Wenmin, XIA Wensheng*(), WAN Huilin
Received:
2019-01-23
Online:
2019-05-06
Published:
2019-03-27
Contact:
XIA Wensheng
E-mail:wsxia@xmu.edu.cn
Supported by:
CLC Number:
TrendMD:
CHENG Wenmin,XIA Wensheng,WAN Huilin. Influence of Surface Reactivity of Lanthanum Oxide on the Activation of Methane and Oxygen†[J]. Chem. J. Chinese Universities, 2019, 40(5): 940.
Fig.1 Structures for bulk La2O3 and the experimental and calculated(in parentheses) values for the three unique La-O bond lengths in nmO4c and O6 crepresent 4- and 6-coordinated oxygen atoms, respectively.
Fig.2 Side(A1—D1) and top(A2—D2) views of La2O3 surfaces(A1, A2)(2×2)(001);(B1, B2)(1×1)(110);(C1, C2)(2×2)(100), before dipole correction;(D1, D2)(2×2)(100), after dipole correction; O4c and O6c represent 4- and 6-coordinated oxygen atoms, respectively.
Fig.3 Density of states(DOS) of La2O3 surfaces (001)(A), (110)(B) and (100)(C)The densities of states above 0 are for orbitals with spin up, and those below 0 are for orbitals with spin down.
Fig.4 Structures, energies and related bond length of associative(vdw) and dissociative(dis) adsorption states and corresponding transition states(TS) for CH4 on La2O3 surfaces(001), (110) and (100)
Fig.5 Diagram of potential energy surface for methane C—H activation on La2O3 surfaces(A) (001), H is bound to O4c; (B) (110), H is bound to O6c; (C) (100), H is bound to O6c; (D) (100), H is bound to O4c.The energy is in eV.
Fig.6 Structures, energies and related bond length of O2 associative adsorption(vdw), dissociative(dis) adsorption modes and corresponding transition states(TS) on La2O3 surfaces (001), (110) and (100)
Fig.7 Diagram of potential energy surface for O—O activation on La2O3 surfaces(A) (001), O is bound to two O4c; (B) (110), O is bound to two O4c; (C) (110), O is bound to O6c/O4c;(D) (100), O is bound to O6c/O4c. The energy is in eV.
Crystal plane of La2O3 | Ead(AB)/eV | Ead(A-B)/eV | ETS(A-B)/eV | qAB/e | qTS(A-B)/e | qA-B/e | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
CH4 | O2 | H—CH3 | O—O | H—CH3 | O—O | CH4 | O2 | H—CH3 | O—O | H—CH3 | O—O | |
(001) | -0.03 | -0.04 | 1.56 | 0.57 | 2.16 | 1.22 | -0.01 | -0.02 | -0.03 | -1.02 | -0.10 | -1.19 |
(110) | -0.04 | -0.31 | 0.45 | -0.43 | 0.68 | 0.53 | -0.02 | -0.24 | -0.10 | -1.05 | -0.10 | -1.34 |
(100) | -0.03 | -0.12 | -0.22 | -0.13 | 0.90 | 1.52 | -0.02 | -0.10 | -0.09 | -1.04 | -0.12 | -1.30 |
Table 1 Energy of the preferred associative adsorption states, dissociative adsorption states and transition states relative to reactants(Ead(AB), Ead(A-B), ETS(A-B)) for CH4 and O2 on La2O3 surfaces, and an analysis on Bader charges(qAB, qTS(A-B), qA-B) of the corresponding species
Crystal plane of La2O3 | Ead(AB)/eV | Ead(A-B)/eV | ETS(A-B)/eV | qAB/e | qTS(A-B)/e | qA-B/e | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
CH4 | O2 | H—CH3 | O—O | H—CH3 | O—O | CH4 | O2 | H—CH3 | O—O | H—CH3 | O—O | |
(001) | -0.03 | -0.04 | 1.56 | 0.57 | 2.16 | 1.22 | -0.01 | -0.02 | -0.03 | -1.02 | -0.10 | -1.19 |
(110) | -0.04 | -0.31 | 0.45 | -0.43 | 0.68 | 0.53 | -0.02 | -0.24 | -0.10 | -1.05 | -0.10 | -1.34 |
(100) | -0.03 | -0.12 | -0.22 | -0.13 | 0.90 | 1.52 | -0.02 | -0.10 | -0.09 | -1.04 | -0.12 | -1.30 |
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