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1

Sugiyama, Shigeru, Yasunori Hayashi, Ikumi Okitsu, Naohiro Shimoda, Masahiro Katoh, Akihiro Furube, Yuki Kato, and Wataru Ninomiya. "Oxidative Dehydrogenation of Methane When Using TiO2- or WO3-Doped Sm2O3 in the Presence of Active Oxygen Excited with UV-LED." Catalysts 10, no. 5 (May 18, 2020): 559. http://dx.doi.org/10.3390/catal10050559.

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There are active oxygen species that contribute to oxidative coupling or the partial oxidation during the oxidative dehydrogenation of methane when using solid oxide catalysts, and those species have not been definitively identified. In the present study, we clarify which of the active oxygen species affect the oxidative dehydrogenation of methane by employing photo-catalysts such as TiO2 or WO3, which generate active oxygen from UV-LED irradiation conditions under an oxygen flow. These photo-catalysts were studied in combination with Sm2O3, which is a methane oxidation coupling catalyst. For this purpose, we constructed a reaction system that could directly irradiate UV-LED to a solid catalyst via a normal fixed-bed continuous-flow reactor operated at atmospheric pressure. Binary catalysts prepared from TiO2 or WO3 were either supported on or kneaded with Sm2O3 in the present study. UV-LED irradiation clearly improved the partial oxidation from methane to CO and/or slightly improved the oxidative coupling route from methane to ethylene when binary catalysts consisting of Sm2O3 and TiO2 are used, while negligible UV-LED effects were detected when using Sm2O3 and WO3. These results indicate that with UV-LED irradiation the active oxygen of O2− from TiO2 certainly contributes to the activation of methane during the oxidative dehydrogenation of methane when using Sm2O3, while the active oxygen of H2O2 from WO3 under the same conditions afforded only negligible effects on the activation of methane.
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2

ZANTHOFF, H., Z. ZHANG, T. GRZYBEK, L. LEHMANN, and M. BAERNS. "ChemInform Abstract: Oxidative Coupling and Partial Oxidation of Methane." ChemInform 23, no. 38 (August 21, 2010): no. http://dx.doi.org/10.1002/chin.199238105.

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3

Siritanaratkul, Bhavin, Sean-Thomas B. Lundin, and Kazuhiro Takanabe. "Oxidative coupling of methane over sodium zirconate catalyst." Catalysis Science & Technology 11, no. 14 (2021): 4803–11. http://dx.doi.org/10.1039/d1cy00741f.

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Previously only known for CO2 absorption and CO oxidation, Na2ZrO3 is shown to be a selective catalyst for the oxidative coupling of methane (OCM) by detailed kinetic measurements and kinetic analysis.
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4

Mackie, John C., Julie G. Smith, Peter F. Nelson, and Ralph J. Tyler. "Inhibition of C2 oxidation by methane under oxidative coupling conditions." Energy & Fuels 4, no. 3 (May 1990): 277–85. http://dx.doi.org/10.1021/ef00021a011.

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5

Lomonosov, V. I., T. R. Usmanov, M. Yu Sinev, and V. Yu Bychkov. "Ethylene oxidation under conditions of the oxidative coupling of methane." Kinetics and Catalysis 55, no. 4 (July 2014): 474–80. http://dx.doi.org/10.1134/s0023158414030070.

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6

Delparish, Amin, Shamayita Kanungo, John van der Schaaf, and M. Fernanda Neira d'Angelo. "Towards coupling direct activation of methane with in situ generation of H2O2." Catalysis Science & Technology 9, no. 18 (2019): 5142–49. http://dx.doi.org/10.1039/c9cy01304k.

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7

Simon, Yves, and Paul-Marie Marquaire. "A unified mechanism for oxidative coupling and partial oxidation of methane." Fuel 297 (August 2021): 120683. http://dx.doi.org/10.1016/j.fuel.2021.120683.

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8

Wang, Shibin, Shenggang Li, and David A. Dixon. "Mechanism of selective and complete oxidation in La2O3-catalyzed oxidative coupling of methane." Catalysis Science & Technology 10, no. 8 (2020): 2602–14. http://dx.doi.org/10.1039/d0cy00141d.

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9

Liu, Shanfu, Sagar Udyavara, Chi Zhang, Matthias Peter, Tracy L. Lohr, Vinayak P. Dravid, Matthew Neurock, and Tobin J. Marks. "“Soft” oxidative coupling of methane to ethylene: Mechanistic insights from combined experiment and theory." Proceedings of the National Academy of Sciences 118, no. 23 (June 1, 2021): e2012666118. http://dx.doi.org/10.1073/pnas.2012666118.

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The oxidative coupling of methane to ethylene using gaseous disulfur (2CH4 + S2 → C2H4 + 2H2S) as an oxidant (SOCM) proceeds with promising selectivity. Here, we report detailed experimental and theoretical studies that examine the mechanism for the conversion of CH4 to C2H4 over an Fe3O4-derived FeS2 catalyst achieving a promising ethylene selectivity of 33%. We compare and contrast these results with those for the highly exothermic oxidative coupling of methane (OCM) using O2 (2CH4 + O2 → C2H4 + 2H2O). SOCM kinetic/mechanistic analysis, along with density functional theory results, indicate that ethylene is produced as a primary product of methane activation, proceeding predominantly via CH2 coupling over dimeric S–S moieties that bridge Fe surface sites, and to a lesser degree, on heavily sulfided mononuclear sites. In contrast to and unlike OCM, the overoxidized CS2 by-product forms predominantly via CH4 oxidation, rather than from C2 products, through a series of C–H activation and S-addition steps at adsorbed sulfur sites on the FeS2 surface. The experimental rates for methane conversion are first order in both CH4 and S2, consistent with the involvement of two S sites in the rate-determining methane C–H activation step, with a CD4/CH4 kinetic isotope effect of 1.78. The experimental apparent activation energy for methane conversion is 66 ± 8 kJ/mol, significantly lower than for CH4 oxidative coupling with O2. The computed methane activation barrier, rate orders, and kinetic isotope values are consistent with experiment. All evidence indicates that SOCM proceeds via a very different pathway than that of OCM.
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10

Lacombe, S., J. G. Sanchez, M. P. Delichere, H. Mozzanega, J. M. Tatibouet, and C. Mirodatos. "Total oxidation pathways in oxidative coupling of methane over lanthanum oxide catalysts." Catalysis Today 13, no. 2-3 (March 1992): 273–82. http://dx.doi.org/10.1016/0920-5861(92)80151-c.

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11

Fan, Zhi Hua, Yu Tian, Jing Wang, and Qian Zhang. "The Study of the Methane Oxidation in Soil Cover under Extraction Condition." Advanced Materials Research 512-515 (May 2012): 2277–80. http://dx.doi.org/10.4028/www.scientific.net/amr.512-515.2277.

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The methane transport was effected by the oxygen reaction across the cover soil. The air flow into the cover could be contribute to methane oxidation, when the extraction working. The gas flow and transport were the coupling process, which must be considered to evaluate the methane reaction in landfill cover. Both of the maximum oxidation rate and permeability of the soil was the critical index for assessing the methane outflow the cover from the landfill. It will provide technological support and theoretical evidence for the evaluation of the methane removal under the gas extraction system in landfill cover.
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12

Miyazaki, T., K. Michitani, M. Ookawa, and T. Yamaguchi. "On the behavior of the selective oxidation by LiNiO2: Oxidative coupling of methane." Research on Chemical Intermediates 28, no. 5 (July 2002): 479–84. http://dx.doi.org/10.1163/156856702760346897.

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13

IKARIYA, Takao, and Yo OSADA. "Oxidative Coupling Reaction of Methane." Journal of Japan Oil Chemists' Society 39, no. 12 (1990): 1014–21. http://dx.doi.org/10.5650/jos1956.39.12_1014.

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14

SUN, J., J. THYBAUT, and G. MARIN. "Microkinetics of methane oxidative coupling." Catalysis Today 137, no. 1 (August 30, 2008): 90–102. http://dx.doi.org/10.1016/j.cattod.2008.02.026.

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15

Kaiji, Zhen, Bi Yingli, and Yang Xiangguang. "Catalytic oxidative coupling of methane." Reaction Kinetics and Catalysis Letters 37, no. 1 (March 1988): 133–38. http://dx.doi.org/10.1007/bf02061722.

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16

Keulks, George W., and Min Yu. "The oxidative coupling of methane." Reaction Kinetics and Catalysis Letters 35, no. 1-2 (March 1987): 361–68. http://dx.doi.org/10.1007/bf02062171.

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17

Du, Jin, Wei Chen, Gangfeng Wu, Yanfang Song, Xiao Dong, Guihua Li, Jianhui Fang, Wei Wei, and Yuhan Sun. "Evoked Methane Photocatalytic Conversion to C2 Oxygenates over Ceria with Oxygen Vacancy." Catalysts 10, no. 2 (February 6, 2020): 196. http://dx.doi.org/10.3390/catal10020196.

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Direct conversion of methane to its oxygenate derivatives remains highly attractive while challenging owing to the intrinsic chemical inertness of CH4. Photocatalysis arises as a promising green strategy which could stimulate water splitting to produce oxidative radicals for methane C–H activation and subsequent C–C coupling. However, synthesis of a photocatalyst with an appropriate capability of methane oxidation by water remains a challenge using an effective and viable approach. Herein, ceria nanoparticles with abundant oxygen vacancies prepared by calcinating commercial CeO2 powder at high temperatures in argon are reported to capably produce ethanol and aldehyde from CH4 photocatalytic oxidation under ambient conditions. Although high-temperature calcinations lead to lower light adsorptions and increased band gaps to some extent, deficient CeO2 nanoparticles with oxygen vacancies and surface CeIII species are formed, which are crucial for methane photocatalytic conversion. The ceria catalyst as-calcinated at 1100 °C had the highest oxygen vacancy concentration and CeIII content, achieving an ethanol production rate of 11.4 µmol·gcat−1·h−1 with a selectivity of 91.5%. Additional experimental results suggested that the product aldehyde was from the oxidation of ethanol during the photocatalytic conversion of CH4.
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18

Bannert, A., C. Bogen, J. Esperschütz, A. Koubová, F. Buegger, D. Fischer, V. Radl, et al. "Anaerobic oxidation of methane in grassland soils used for cattle husbandry." Biogeosciences 9, no. 10 (October 10, 2012): 3891–99. http://dx.doi.org/10.5194/bg-9-3891-2012.

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Abstract. While the importance of anaerobic methane oxidation has been reported for marine ecosystems, the role of this process in soils is still questionable. Grasslands used as pastures for cattle overwintering show an increase in anaerobic soil micro-sites caused by animal treading and excrement deposition. Therefore, anaerobic potential methane oxidation activity of severely impacted soil from a cattle winter pasture was investigated in an incubation experiment under anaerobic conditions using 13C-labelled methane. We were able to detect a high microbial activity utilizing CH4 as nutrient source shown by the respiration of 13CO2. Measurements of possible terminal electron acceptors for anaerobic oxidation of methane were carried out. Soil sulfate concentrations were too low to explain the oxidation of the amount of methane added, but enough nitrate and iron(III) were detected. However, only nitrate was consumed during the experiment. 13C-PLFA analyses clearly showed the utilization of CH4 as nutrient source mainly by organisms harbouring 16:1ω7 PLFAs. These lipids were also found as most 13C-enriched fatty acids by Raghoebarsing et al. (2006) after addition of 13CH4 to an enrichment culture coupling denitrification of nitrate to anaerobic oxidation of methane. This might be an indication for anaerobic oxidation of methane by relatives of "Candidatus Methylomirabilis oxyfera" in the investigated grassland soil under the conditions of the incubation experiment.
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19

Lomonosov, V., Yu Gordienko, and M. Sinev. "Effect of Water on Methane and Ethane Oxidation in the Conditions of Oxidative Coupling of Methane Over Model Catalysts." Topics in Catalysis 56, no. 18-20 (July 9, 2013): 1858–66. http://dx.doi.org/10.1007/s11244-013-0122-2.

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20

Einsiedl, Florian, Anja Wunderlich, Mathieu Sebilo, Ömer K. Coskun, William D. Orsi, and Bernhard Mayer. "Biogeochemical evidence of anaerobic methane oxidation and anaerobic ammonium oxidation in a stratified lake using stable isotopes." Biogeosciences 17, no. 20 (October 23, 2020): 5149–61. http://dx.doi.org/10.5194/bg-17-5149-2020.

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Abstract. Nitrate pollution of freshwaters and methane emissions into the atmosphere are crucial factors in deteriorating the quality of drinking water and in contributing to global climate change. The n-damo (nitrite-dependent anaerobic methane oxidation), nitrate-dependent anaerobic methane oxidation and the anaerobic oxidation of ammonium (anammox) represent two microbially mediated processes that can reduce nitrogen loading of aquatic ecosystems and associated methane emissions to the atmosphere. Here, we report vertical concentration and stable-isotope profiles of CH4, NO3-, NO2-, and NH4+ in the water column of Fohnsee (lake in southern Bavaria, Germany) that may indicate linkages between denitrification, anaerobic oxidation of methane (AOM), and anammox. At a water depth from 12 to 20 m, a methane–nitrate transition zone (NMTZ) was observed, where δ13C values of methane and δ15N and δ18O of dissolved nitrate markedly increased in concert with decreasing concentrations of methane and nitrate. These data patterns, together with the results of a simple 1-D diffusion model linked with a degradation term, show that the nonlinear methane concentration profile cannot be explained by diffusion and that microbial oxidation of methane coupled with denitrification under anaerobic conditions is the most parsimonious explanation for these data trends. In the methane zone at the bottom of the NMTZ (20 to 22 m) δ15N of ammonium increased by 4 ‰, while ammonium concentrations decreased. In addition, a strong 15N enrichment of dissolved nitrate was observed at a water depth of 20 m, suggesting that anammox is occurring together with denitrification. The conversion of nitrite to N2 and nitrate during anammox is associated with an inverse N isotope fractionation and may explain the observed increasing offset (Δδ15N) of 26 ‰ between δ15N values of dissolved nitrate and nitrite at a water depth of 20 m compared to the Δδ15Nnitrate-nitrite of 11 ‰ obtained in the NMTZ at a water depth between 16 and 18 m. The associated methane concentration and stable-isotope profiles indicate that some of the denitrification may be coupled to AOM, an observation supported by an increased concentration of bacteria known to be involved in n-damo/denitrification with AOM (NC10 and Crenothrix) and anammox (“Candidatus Anammoximicrobium”) whose concentrations were highest in the methane and ammonium oxidation zones, respectively. This study shows the potential for a coupling of microbially mediated nitrate-dependent methane oxidation with anammox in stratified freshwater ecosystems, which may be important for affecting both methane emissions and nitrogen concentrations in lakes.
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21

Burch, R., and S. C. Tsang. "Investigation of the partial oxidation of hydrocarbons on methane coupling catalysts." Applied Catalysis 65, no. 2 (October 1990): 259–80. http://dx.doi.org/10.1016/s0166-9834(00)81602-4.

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22

Lane, G. S., Z. Kalenik, and E. E. Wolf. "Methane oxidative coupling over titanate catalysts." Applied Catalysis 53, no. 2-3 (September 1989): 183–95. http://dx.doi.org/10.1016/s0166-9834(00)80020-2.

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23

Lunsford, Jack H. "The Catalytic Oxidative Coupling of Methane." Angewandte Chemie International Edition in English 34, no. 9 (May 15, 1995): 970–80. http://dx.doi.org/10.1002/anie.199509701.

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24

PARIDA, K. M., R. S. THAKUR, J. R. RAO, S. N. DAS, and S. B. RAO. "ChemInform Abstract: Oxidative Coupling of Methane." ChemInform 22, no. 43 (August 22, 2010): no. http://dx.doi.org/10.1002/chin.199143255.

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25

Imai, Hisao, and Tomohiko Tagawa. "Oxidative coupling of methane over LaAlO3." Journal of the Chemical Society, Chemical Communications, no. 1 (1986): 52. http://dx.doi.org/10.1039/c39860000052.

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26

Amenomiya, Yoshimitsu, Viola I. Birss, Maciej Goledzinowski, Jan Galuszka, and Alan R. Sanger. "Conversion of Methane by Oxidative Coupling." Catalysis Reviews 32, no. 3 (August 1990): 163–227. http://dx.doi.org/10.1080/01614949009351351.

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27

Yan, Q. J., Y. Wang, Y. S. Jin, and Y. Chen. "Methane oxidative coupling over Na2WO4/SiO2." Catalysis Letters 13, no. 3 (September 1992): 221–28. http://dx.doi.org/10.1007/bf00770994.

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28

Golpasha, R. D., D. Karami, R. Ahmadi, and E. Bagherzadeh. "Heterogeneous methane oxidative coupling using perovskites." Reaction Kinetics & Catalysis Letters 51, no. 2 (December 1993): 393–400. http://dx.doi.org/10.1007/bf02069083.

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29

Bartsch, S., J. Falkowski, and H. Hofmann. "Catalyst development for oxidative methane coupling." Catalysis Today 4, no. 3-4 (February 1989): 421–31. http://dx.doi.org/10.1016/0920-5861(89)85038-2.

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30

Chao, Zi Sheng, Xiao Ping Zhou, Hui Lin Wan, and Khi Rui Tsai. "Methane oxidative coupling on BaF2LaOF catalyst." Applied Catalysis A: General 130, no. 2 (September 1995): 127–33. http://dx.doi.org/10.1016/0926-860x(95)00116-6.

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31

Martinez-Cruz, K., A. Sepulveda-Jauregui, K. Walter Anthony, and F. Thalasso. "Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes." Biogeosciences 12, no. 15 (August 4, 2015): 4595–606. http://dx.doi.org/10.5194/bg-12-4595-2015.

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Abstract. Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH4) produced in lakes. Aerobic CH4 oxidation depends mainly on lake CH4 and oxygen (O2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcely reported in the literature. In the present study, we measured CH4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH4 and O2 concentrations. We found that in the winter, aerobic CH4 oxidation was mainly controlled by the dissolved O2 concentration, while in the summer it was controlled primarily by the CH4 concentration, which was scarce compared to dissolved O2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH4 cycling.
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32

Xie, Rui, Daidai Wu, Jie Liu, Guangrong Jin, Tiantian Sun, Lihua Liu, and Nengyou Wu. "The influence of coupling mode of methane leakage and debris input on anaerobic oxidation of methane." Acta Oceanologica Sinica 40, no. 8 (August 2021): 78–88. http://dx.doi.org/10.1007/s13131-021-1803-5.

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33

Fowles, E. H., J. A. Labinger, J. L. Beauchamp, and B. Fultz. "Fast ion conductors as oxidation catalysts: oxidative coupling and deep oxidation of methane over transition-metal-exchanged .beta."-aluminas." Journal of Physical Chemistry 95, no. 19 (September 1991): 7393–400. http://dx.doi.org/10.1021/j100172a052.

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34

Campbell, Kenneth D., and Jack H. Lunsford. "Contribution of gas-phase radical coupling in the catalytic oxidation of methane." Journal of Physical Chemistry 92, no. 20 (October 1988): 5792–96. http://dx.doi.org/10.1021/j100331a049.

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35

Sugiyama, Shigeru, Yoshiharu Fujii, Keiichi Abe, Hiromu Hayashi, and John B. Moffat. "Facile Formation of the Partial Oxidation and Oxidative-Coupling Products from the Oxidation of Methane on Barium Hydroxyapatites with Tetrachloromethane." Energy & Fuels 13, no. 3 (May 1999): 637–40. http://dx.doi.org/10.1021/ef980191f.

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36

Osada, Y., S. Koike, T. Fukushima, S. Ogasawara, T. Shikada, and T. Ikariya. "Oxidative coupling of methane over Y2O3CaO catalysts." Applied Catalysis 59, no. 1 (March 1990): 59–74. http://dx.doi.org/10.1016/s0166-9834(00)82187-9.

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37

Long, R. Q., and H. L. Wan. "Oxidative coupling of methane overSrF2/Y2O3 catalyst." Applied Catalysis A: General 159, no. 1-2 (October 1997): 45–58. http://dx.doi.org/10.1016/s0926-860x(97)00047-1.

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38

HAGGIN, JOSEPH. "Insight gained to oxidative coupling of methane." Chemical & Engineering News 68, no. 4 (January 22, 1990): 23–24. http://dx.doi.org/10.1021/cen-v068n004.p023.

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39

Hutchings, G. J., M. S. Scurrell, and J. R. Woodhouse. "Oxidative coupling of methane using oxide catalysts." Chemical Society Reviews 18 (1989): 251. http://dx.doi.org/10.1039/cs9891800251.

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40

Baldwin, T. R., R. Burch, E. M. Crabb, G. D. Squire, and S. C. Tsang. "Oxidative coupling of methane over chloride catalysts." Applied Catalysis 56, no. 1 (January 1989): 219–29. http://dx.doi.org/10.1016/s0166-9834(00)80171-2.

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41

Lacombe, S., C. Geantet, and C. Mirodatos. "Oxidative Coupling of Methane over Lanthana Catalysts." Journal of Catalysis 151, no. 2 (February 1995): 439–52. http://dx.doi.org/10.1006/jcat.1995.1046.

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42

Lacombe, S., H. Zanthoff, and C. Mirodatos. "Oxidative Coupling of Methane over Lanthana Catalysts." Journal of Catalysis 155, no. 1 (August 1995): 106–16. http://dx.doi.org/10.1006/jcat.1995.1192.

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43

Fleischer, V., R. Steuer, and R. Schomäcker. "Pulse Experiments in Oxidative Coupling of Methane." Chemie Ingenieur Technik 86, no. 9 (August 28, 2014): 1540. http://dx.doi.org/10.1002/cite.201450680.

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44

Zhou, Xiaoping, Weide Zhang, Huilin Wan, and Khirui Tsai. "Methane oxidative coupling over fluoro-oxide catalysts." Catalysis Letters 21, no. 1-2 (1993): 113–22. http://dx.doi.org/10.1007/bf00767376.

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45

Lee, J. S., and S. T. Oyama. "Oxidative Coupling of Methane to Higher Hydrocarbons." Catalysis Reviews 30, no. 2 (June 1988): 249–80. http://dx.doi.org/10.1080/01614948808078620.

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46

Otsuka, Kiyoshi, and Takayuki Komatsu. "Active catalysts in oxidative coupling of methane." Journal of the Chemical Society, Chemical Communications, no. 5 (1987): 388. http://dx.doi.org/10.1039/c39870000388.

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47

Lomonosov, V. I., and M. Yu Sinev. "Oxidative coupling of methane: Mechanism and kinetics." Kinetics and Catalysis 57, no. 5 (September 2016): 647–76. http://dx.doi.org/10.1134/s0023158416050128.

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48

Bao, X., M. Muhler, R. Schl�gl, and G. Ertl. "Oxidative coupling of methane on silver catalysts." Catalysis Letters 32, no. 1-2 (1995): 185–94. http://dx.doi.org/10.1007/bf00806113.

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49

Bistolfi, M., G. Fornasari, M. Molinari, S. Palmery, M. Dente, and E. Ranzi. "Kinetic model for methane oxidative coupling reactors." Chemical Engineering Science 47, no. 9-11 (June 1992): 2647–52. http://dx.doi.org/10.1016/0009-2509(92)87107-2.

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50

Noon, Daniel, Anusorn Seubsai, and Selim Senkan. "Oxidative Coupling of Methane by Nanofiber Catalysts." ChemCatChem 5, no. 1 (December 3, 2012): 146–49. http://dx.doi.org/10.1002/cctc.201200408.

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