Recent trends, current challenges and future prospects for syngas-free methane partial oxidation

Andrea Blankenship; Mikalai Artsiusheuski; Vitaly Sushkevich; Jeroen A. van Bokhoven

doi:10.1038/s41929-023-01000-8

journal article Sep 21, 2023

Recent trends, current challenges and future prospects for syngas-free methane partial oxidation

Andrea Blankenship

Mikalai Artsiusheuski

Vitaly Sushkevich Jeroen A. van Bokhoven

Nature Catalysis Vol. 6 No. 9 pp. 748-762 · Springer Science and Business Media LLC

View at Publisher Save 10.1038/s41929-023-01000-8

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References

87

[1]

Vogel, F. Chasing after methane’s ultra-emitters. Science 375, 490–491 (2022). 10.1126/science.abm1676

[2]

The Direct Catalytic Oxidation of Methane to Methanol—A Critical Assessment

Manoj Ravi, Marco Ranocchiari, Jeroen A. van Bokhoven

Angewandte Chemie International Edition 2017 10.1002/anie.201702550

[3]

Lawton, T. J. & Rosenzweig, A. C. Methane-oxidizing enzymes: an upstream problem in biological gas-to-liquids conversion. J. Am. Chem. Soc. 138, 9327–9340 (2016). 10.1021/jacs.6b04568

[4]

Wang, V. C. C. et al. Alkane oxidation: methane monooxygenases, related enzymes, and their biomimetics. Chem. Rev. 117, 8574–8621 (2017). 10.1021/acs.chemrev.6b00624

[5]

Latimer, A. A., Kakekhani, A., Kulkarni, A. R. & Norskov, J. K. Direct methane to methanol: the selectivity-conversion limit and design strategies. ACS Catal. 8, 6894–6907 (2018). 10.1021/acscatal.8b00220

[6]

Ahlquist, M., Nielsen, R. J., Periana, R. A. & Goddard Iii, W. A. Product protection, the key to developing high performance methane selective oxidation catalysts. J. Am. Chem. Soc. 131, 17110–17115 (2009). 10.1021/ja903930e

[7]

Mlekodaj, K., Lemishka, M., Sklenak, S., Dedecek, J. & Tabor, E. Dioxygen splitting at room temperature over distant binuclear transition metal centers in zeolites for direct oxidation of methane to methanol. Chem. Commun. 57, 3472–3475 (2021). 10.1039/d1cc00909e

[8]

Tabor, E. et al. Dioxygen dissociation over man-made system at room temperature to form the active alpha-oxygen for methane oxidation. Sci. Adv. 6, eaaz9776 (2020). 10.1126/sciadv.aaz9776

[9]

Sushkevich, V. L., Palagin, D., Ranocchiari, M. & van Bokhoven, J. A. Selective anaerobic oxidation of methane enables direct synthesis of methanol. Science 356, 523–527 (2017). 10.1126/science.aam9035

[10]

Lee, S. H., Kang, J. K. & Park, E. D. Continuous methanol synthesis directly from methane and steam over Cu(II)-exchanged mordenite. Korean J. Chem. Eng. 35, 2145–2149 (2018). 10.1007/s11814-018-0150-5

[11]

Jovanovic, Z. R. et al. Oxidation of methane to methanol over Cu-exchanged zeolites: Scientia gratia scientiae or paradigm shift in natural gas valorization? J. Catal. 385, 238–245 (2020). 10.1016/j.jcat.2020.02.001

[12]

Jocz, J. N., Medford, A. J. & Sievers, C. Thermodynamic limitations of the catalyst design space for methanol production from methane. ChemCatChem 11, 593–600 (2019). 10.1002/cctc.201801438

[13]

Artsiusheuski, M. A., Verel, R., van Bokhoven, J. A. & Sushkevich, V. L. Methane transformation over copper-exchanged zeolites: from partial oxidation to C–C coupling and formation of hydrocarbons. ACS Catal. 11, 12543–12556 (2021). 10.1021/acscatal.1c02547

[14]

Sushkevich, V. L. & van Bokhoven, J. A. Effect of Brønsted acid sites on the direct conversion of methane into methanol over copper-exchanged mordenite. Catal. Sci. Technol. 8, 4141–4150 (2018). 10.1039/c8cy01055b

[15]

Dyballa, M. et al. Zeolite surface methoxy groups as key intermediates in the stepwise conversion of methane to methanol. ChemCatChem 11, 5022–5026 (2019). 10.1002/cctc.201901315

[16]

Yamasaki, T. et al. Low-temperature activation of methane with nitric oxide and formation of hydrogen cyanide over an alumina-supported platinum catalyst. ACS Catal. 11, 14660–14668 (2021). 10.1021/acscatal.1c04548

[17]

Pappas, D. K. et al. Methane to methanol: structure activity relationships for Cu-CHA. J. Am. Chem. Soc. 139, 14961–14975 (2017). 10.1021/jacs.7b06472

[18]

Narsimhan, K., Iyoki, K., Dinh, K. & Roman-Leshkov, Y. Catalytic oxidation of methane into methanol over copper-exchanged zeolites with oxygen at low temperature. ACS Cent. Sci. 2, 424–429 (2016). Demonstration of the catalytic conversion of methane to methanol in a gas–solid mode enabled by co-feeding water along with methane and oxygen over copper-exchanged zeolites. 10.1021/acscentsci.6b00139

[19]

Hirayama, A. et al. Catalytic oxidation of methane to methanol over Cu-CHA with molecular oxygen. Catal. Sci. Technol. 11, 6217–6224 (2021). 10.1039/d1cy00676b

[20]

Vargheese, V., Kobayashi, Y. & Oyama, S. T. The direct partial oxidation of methane to dimethyl ether over Pt/Y2O3catalysts using an NO/O2 shuttle. Angew. Chem. Int. Ed. 59, 16644–16650 (2020). 10.1002/anie.202006020

[21]

Vargheese, V. et al. The direct molecular oxygen partial oxidation of CH4 to dimethyl ether without methanol formation over a Pt/Y2O3 catalyst using an NO/NO2 oxygen atom shuttle. J. Catal. 389, 352–365 (2020). 10.1016/j.jcat.2020.05.021

[22]

Ghampson, I. T. et al. Methane selective oxidation on metal oxide catalysts at low temperatures with O2 using an NO/NO2 oxygen atom shuttle. J. Catal. 408, 401–412 (2022). 10.1016/j.jcat.2021.07.014

[23]

Dinh, K. T., Sullivan, M. M., Serna, P., Meyer, R. J. & Roman-Leshkov, Y. Breaking the selectivity-conversion limit of partial methane oxidation with tandem heterogeneous catalysts. ACS Catal. 11, 9262–9270 (2021). A concept for the tandem catalytic conversion of methane to methanol with subsequent alkylation of benzene to toluene using a mixture of small-pore copper-exchanged zeolites and larger-pore zeolite. 10.1021/acscatal.1c02187

[24]

Lange, J. P. In Sustainable Strategies for the Upgrading of Natural Gas: Fundamentals, Challenges, and Opportunities (eds. Derouane, E. G. et al.) 51–83 (NATO Science Series II: Mathematics, Physics and Chemistry, Vol. 191, 2005).

[25]

Periana, R. A. et al. Perspectives on some challenges and approaches for developing the next generation of selective, low temperature, oxidation catalysts for alkane hydroxylation based on the CH activation reaction. J. Mol. Catal. A 220, 7–25 (2004). 10.1016/j.molcata.2004.05.036

[26]

Bunting, R. J., Rice, P. S., Thompson, J. & Hu, P. Investigating the innate selectivity issues of methane to methanol: consideration of an aqueous environment. Chem. Sci. 12, 4443–4449 (2021). 10.1039/d0sc05402j

[27]

Jin, Z. et al. Hydrophobic zeolite modification for in situ peroxide formation in methane oxidation to methanol. Science 367, 193–197 (2020). A nanoreactor concept involving zeolite-encapsulated AuPd nanoparticles with a hydrophobic coating generating hydrogen peroxide in situ near methane activation sites, allowing high methanol selectivity at larger extents of methane conversion. 10.1126/science.aaw1108

[28]

Periana, R. A. et al. Amercury-catalyzed, high-yield system for the oxidation of methane to methanol. Science 259, 340–343 (1993). 10.1126/science.259.5093.340

[29]

Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative

Roy A. Periana, Douglas J. Taube, Scott Gamble et al.

Science 1998 10.1126/science.280.5363.560

[30]

Michalkiewicz, B. Methane conversion to methanol in condensed phase. Kinet. Catal. 44, 801–805 (2003). 10.1023/b:kica.0000009057.79026.0b

[31]

Gang, X., Zhu, Y. M., Birch, H., Hjuler, H. A. & Bjerrum, N. J. Iodine as catalyst for the direct oxidation of methane to methyl sulfates in oleum. Appl Catal. A 261, 91–98 (2004). 10.1016/j.apcata.2003.10.039

[32]

Zimmermann, T., Soorholtz, M., Bilke, M. & Schüth, F. Selective methane oxidation catalyzed by platinum salts in oleum at turnover frequencies of large-scale industrial processes. J. Am. Chem. Soc. 138, 12395–12400 (2016). 10.1021/jacs.6b05167

[33]

Conley, B. L. et al. Design and study of homogeneous catalysts for the selective, low temperature oxidation of hydrocarbons. J. Mol. Catal. A 251, 8–23 (2006). 10.1016/j.molcata.2006.02.035

[34]

Blankenship, A. N., Ravi, M. & van Bokhoven, J. A. Esterification product protection strategies for direct and selective methane conversion. Chimia 75, 305–310 (2021). 10.2533/chimia.2021.305

[35]

Noceti, R. P., Taylor, C. E. & D’Este, J. R. Photocatalytic conversion of methane. Catal. Today 33, 199–204 (1997). 10.1016/s0920-5861(96)00155-1

[36]

Li, X. Y., Wang, C. & Tang, J. W. Methane transformation by photocatalysis. Nat. Rev. Mater. 7, 617–632 (2022). 10.1038/s41578-022-00422-3

[37]

Li, Q., Ouyang, Y. X., Li, H. L., Wang, L. B. & Zeng, J. Photocatalytic conversion of methane: recent advancements and prospects. Angew. Chem. Int. Ed. 61, e202108069 (2022). 10.1002/anie.202108069

[38]

Ohkubo, K. & Hirose, K. Light-driven C–H oxygenation of methane into methanol and formic acid by molecular oxygen using a perfluorinated solvent. Angew. Chem. Int Ed. 57, 2126–2129 (2018). The photochemical conversion of methane with a high product yield enabled by a biphasic solvent system, in which the product is sequestered into an oxidant-poor phase to prevent overoxidation. 10.1002/anie.201710945

[39]

Liebov, N. S. et al. Selective photo-oxygenation of light alkanes using iodine oxides and chloride. ChemCatChem 11, 5045–5054 (2019). 10.1002/cctc.201901175

[40]

Sun, H. L. et al. Ultra-stable molecular interface SiW12Ox/TiO2 catalyst derived from keggin-type polyoxometalates for photocatalytic conversion of methane to oxygenates. ChemCatChem 14, e202200001 (2022). 10.1002/cctc.202200001

[41]

Wu, X. Y. et al. Noble-metal-free dye-sensitized selective oxidation of methane to methanol with green light (550 nm). Nano Res. 14, 4584–4590 (2021). 10.1007/s12274-021-3380-5

[42]

An, B. et al. Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site. Nat. Mater. 21, 932–938 (2022). A flow reaction concept for photocatalytic methane conversion using iron-containing MOFs with relatively high product concentrations and activity using a molecular oxygen oxidant. 10.1038/s41563-022-01279-1

[43]

Feng, G. H. et al. Solar driven efficient direct conversion of methane to multicarbon oxygenates. J. Mater. Chem. A 10, 7856–7868 (2022). 10.1039/d1ta10846h

[44]

Luo, L. et al. Binary Au-Cu reaction sites decorated ZnO for selective methane oxidation to C1 oxygenates with nearly 100% selectivity at room temperature. J. Am. Chem. Soc. 144, 740–750 (2022). 10.1021/jacs.1c09141

[45]

Sakata, Y., Hayashi, T., Yasunaga, R., Yanaga, N. & Imamura, H. Remarkably high apparent quantum yield of the overall photocatalytic H2O splitting achieved by utilizing Zn ion added Ga2O3 prepared using dilute CaCl2 solution. Chem. Commun. 51, 12935–12938 (2015). 10.1039/c5cc03483c

[46]

Takata, T. et al. Photocatalytic water splitting with a quantum efficiency of almost unity. Nature 581, 411–414 (2020). 10.1038/s41586-020-2278-9

[47]

Zhao, Y. et al. A hydrogen farm strategy for scalable solar hydrogen production with particulate photocatalysts. Angew. Chem. Int. Ed. 59, 9653–9658 (2020). 10.1002/anie.202001438

[48]

Han, B., Wei, W., Li, M. J., Sun, K. & Hu, Y. H. A thermo-photo hybrid process for steam reforming of methane: highly efficient visible light photocatalysis. Chem. Commun. 55, 7816–7819 (2019). 10.1039/c9cc04193a

[49]

Lopez-Martin, A., Caballero, A. & Colon, G. Photochemical methane partial oxidation to methanol assisted by H2O2. J. Photochem. Photobiol. A 349, 216–223 (2017). 10.1016/j.jphotochem.2017.09.039

[50]

Indarto, A. A review of direct methane conversion to methano by dielectric barrier discharge. IEEE Trans. Dielectr. Electr. Insul. 15, 1038–1043 (2008). 10.1109/tdei.2008.4591225

Showing 50 of 87 references

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Details

Published: Sep 21, 2023
Vol/Issue: 6(9)
Pages: 748-762
License: View

Authors

A

Andrea Blankenship

M

Mikalai Artsiusheuski

V

Vitaly Sushkevich

J

Jeroen A. van Bokhoven

Department of Energy and Environment Paul Scherrer Institut Forschungsstrasse 111 5232 Villigen PSI Switzerland; Department of Chemistry and Applied Biosciences ETH Zurich Vladimir-Prelog-Weg 1–5/10 8093 Zürich Switzerland

Cite This Article

Andrea Blankenship, Mikalai Artsiusheuski, Vitaly Sushkevich, et al. (2023). Recent trends, current challenges and future prospects for syngas-free methane partial oxidation. Nature Catalysis, 6(9), 748-762. https://doi.org/10.1038/s41929-023-01000-8

Recent trends, current challenges and future prospects for syngas-free methane partial oxidation

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