Mechanistic Complexity of Methane Oxidation with H2O2 by Single-Site Fe/ZSM-5 Catalyst

被引:111
作者
Szecsenyi, Agnes [1 ,2 ,3 ]
Li, Guanna [1 ,2 ]
Gascon, Jorge [3 ]
Pidko, Evgeny A. [2 ,4 ]
机构
[1] Delft Univ Technol, Dept Chem Engn, Catalysis Engn Grp, Van der Maasweg 9, NL-2629 HZ Delft, Netherlands
[2] Delft Univ Technol, Dept Chem Engn, Inorgan Syst Engn Grp, Van der Maasweg 9, NL-2629 HZ Delft, Netherlands
[3] King Abdullah Univ Sci & Technol, Catalysis Ctr, Adv Catalyt Mat, Thuwal 23955, Saudi Arabia
[4] ITMO Univ, TheoMAT Grp, Lomonosova St 9, St Petersburg 191002, Russia
关键词
selective oxidation; catalytic reaction networks; DFT calculations; zeolites; heterogeneous catalysis; computational chemistry; selectivity control; H BOND ACTIVATION; INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; SELECTIVE OXIDATION; ZSM-5; ZEOLITE; NITROUS-OXIDE; ATOM TRANSFER; ACTIVE-SITE; CONVERSION; FE;
D O I
10.1021/acscatal.8b01672
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Periodic density functional theory (DFT) calculations were carried out to investigate the mechanism of methane oxidation with H2O2 over the defined Fe sites in Fe/ZSM-5 zeolite. The initial Fe site is modeled as a [(H2O)(2)-Fe(III)- (mu O)(2)-Fe(III)-(H2O)(2)](2+) extraframework cluster deposited in the zeolite pore and charge-compensated by two anionic lattice sites. The activation of this cluster with H2O2 gives rise to the formation of a variety of Fe(III)-oxo and Fe(IV)-oxo complexes potentially reactive toward methane dissociation. These sites are all able to promote the first C-H bond cleavage in methane by following three possible reaction mechanisms: namely, (a) heterolytic and (b) homolytic methane dissociation as well as (c) Fenton-type reaction involving free OH radicals as the catalytic species. The C-H activation step is followed by formation of MeOH and MeOOH and regeneration of the active site. The Fenton-type path is found to proceed with the lowest activation barrier. Although the barriers for the alternative heterolytic and homolytic pathways are found to be somewhat higher, they are still quite favorable and are expected to be feasible under reaction conditions, resulting ultimately in MeOH and MeOOH products. H2O2 oxidant competes with CH4 substrate for the same sites. Since the oxidation of H2O2 to O-2 and two [H+] is energetically more favorable than the C-H oxofunctionalization, the overall efficiency of the latter target process remains low.
引用
收藏
页码:7961 / 7972
页数:23
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