Low-temperature conversion of methane to oxygenates by supported metal catalysts: From nanoparticles to single atoms

doi:10.1016/j.cjche.2021.04.034

Abstract

Abstract: Direct cost-effective conversion of abundant methane to high value-added oxygenates (methanol, formic acid, acetic acid, etc.) under mild conditions is prospective for optimizing the structure of energy resources. However, the CH bond of products is more reactive than that of high thermodynamic stable methane. Exploring an appropriate approach to eliminate the “seesaw effect” between methane conversion and oxygenate selectivity is significant. In this review, we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal (Fe, Cu, Rh, Pd, AuPd, etc.) based nanoparticle or single-atom catalyst. Furthermore, the prospects of catalyst design and catalysis process are also discussed.

Key words: Methane, Oxygenates, Supported metal catalysts, Nanoparticle, Single-atom catalysts

摘要： Direct cost-effective conversion of abundant methane to high value-added oxygenates (methanol, formic acid, acetic acid, etc.) under mild conditions is prospective for optimizing the structure of energy resources. However, the CH bond of products is more reactive than that of high thermodynamic stable methane. Exploring an appropriate approach to eliminate the “seesaw effect” between methane conversion and oxygenate selectivity is significant. In this review, we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal (Fe, Cu, Rh, Pd, AuPd, etc.) based nanoparticle or single-atom catalyst. Furthermore, the prospects of catalyst design and catalysis process are also discussed.

关键词: Methane, Oxygenates, Supported metal catalysts, Nanoparticle, Single-atom catalysts

Geqian Fang, Jian Lin, Xiaodong Wang. Low-temperature conversion of methane to oxygenates by supported metal catalysts: From nanoparticles to single atoms[J]. Chinese Journal of Chemical Engineering, 2021, 38(10): 18-29.

Geqian Fang, Jian Lin, Xiaodong Wang. Low-temperature conversion of methane to oxygenates by supported metal catalysts: From nanoparticles to single atoms[J]. 中国化学工程学报, 2021, 38(10): 18-29.

References

[1] P. Schwach, X.L. Pan, X.H. Bao, Direct conversion of methane to value-added chemicals over heterogeneous catalysts: Challenges and prospects, Chem. Rev. 117 (13) (2017) 8497-8520
[2] W. Taifan, J. Baltrusaitis, CH₄ conversion to value added products: Potential, limitations and extensions of a single step heterogeneous catalysis, Appl. Catal. B: Environ. 198 (2016) 525-547
[3] T. Zhang, A.Q. Wang, H. Liu, X.Y. Liu, Direct conversion of methane on single-atom catalysts, Sci. Sin.-Chim. 51 (2) (2021) 175-187
[4] Z.J. Yang, F. Wang, Differentiation of alkane isomers through binding energy spectra and total momentum cross sections, New J. Chem. 38 (3) (2014) 1031
[5] J. Berkowitz, J.P. Greene, H. Cho, B. Ruščić, Photoionization mass spectrometric studies of SiHnull (n=1-4), J. Chem. Phys. 86 (3) (1987) 1235-1248
[6] R. Horn, R. Schlogl, Methane activation by heterogeneous catalysis, Catal. Lett. 145 (1) (2015) 23-39
[7] M. Ravi, M. Ranocchiari, J.A. Van Bokhoven, The direct catalytic oxidation of methane to methanol-A critical assessment, Angew. Chem. Int. Ed. 56 (52) (2017) 16464-16483
[8] P. Tomkins, M. Ranocchiari, J.A. van Bokhoven, Direct conversion of methane to methanol under mild conditions over Cu-zeolites and beyond, Acc. Chem. Res. 50 (2) (2017) 418-425
[9] J. Xie, R. Jin, A. Li, Y. Bi, Q. Ruan, Y. Deng, Y. Zhang, S. Yao, G. Sankar, D. Ma, J. Tang, Highly selective oxidation of methane to methanol at ambient conditions by titanium dioxide-supported iron species, Nature Catal. 1 (11) (2018) 889-896
[10] H. Schulz, Short history and present trends of Fischer-Tropsch synthesis, Appl. Catal. A: Gen. 186 (1-2) (1999) 3-12
[11] V.L. Sushkevich, D. Palagin, M. Ranocchiari, J.A. van Bokhoven, Selective anaerobic oxidation of methane enables direct synthesis of methanol, Science 356 (6337) (2017) 523-527
[12] B.W. Wang, S. Albarracín-Suazo, Y. Pagán-Torres, E. Nikolla, Advances in methane conversion processes, Catal. Today 285 (2017) 147-158
[13] O.A. Mironov, S.M. Bischof, M.M. Konnick, B.G. Hashiguchi, V.R. Ziatdinov, W. A. Goddard 3rd, M. Ahlquist, R.A. Periana, Using reduced catalysts for oxidation reactions: Mechanistic studies of the “Periana-Catalytica” system for CH₄ oxidation, J. Am. Chem. Soc. 135 (39) (2013) 14644-14658
[14] R.A. Periana, O. Mironov, D. Taube, G. Bhalla, C.J. Jones, Catalytic, oxidative condensation of CH₄ to CH₃COOH in one step via CH activation, Science 301 (5634) (2003) 814-818
[15] V.L. Sushkevich, J.A. van Bokhoven, Methane-to-methanol: Activity descriptors in copper-exchanged zeolites for the rational design of materials, ACS Catal. 9 (7) (2019) 6293-6304
[16] S.E. Bozbag, P. Sot, M. Nachtegaal, M. Ranocchiari, J.A. van Bokhoven, C. Mesters, Direct stepwise oxidation of methane to methanol over Cu-SiO₂, ACS Catal. 8 (7) (2018) 5721-5731
[17] C.Y. Ruan, Z.Q. Huang, J. Lin, L. Li, X.Y. Liu, M. Tian, C.D. Huang, C.R. Chang, J. Li, X.D. Wang, Synergy of the catalytic activation on Ni and the CeO₂-TiO₂/Ce₂Ti₂O₇ stoichiometric redox cycle for dramatically enhanced solar fuel production, Energy Environ. Sci. 12 (2) (2019) 767-779
[18] L. Zhang, W. Xu, J. Wu, Y. Hu, C. Huang, Y. Zhu, M. Tian, Y. Kang, X. Pan, Y. Su, J. Wang, X. Wang, Identifying the role of A-site cations in modulating oxygen capacity of iron-based perovskite for enhanced chemical looping methane-to-syngas conversion, ACS Catal. 10 (16) (2020) 9420-9430
[19] M. Tian, X.D. Wang, T. Zhang, Hexaaluminates: A review of the structure, synthesis and catalytic performance, Catal. Sci. Technol. 6 (7) (2016) 1984-2004
[20] X.G. Meng, X.J. Cui, N.P. Rajan, L. Yu, D.H. Deng, X.H. Bao, Direct methane conversion under mild condition by thermo-, electro-, or photocatalysis, Chem 5 (9) (2019) 2296-2325
[21] Y.T. Liu, D.H. Deng, X.H. Bao, Catalysis for selected C1 chemistry, Chem 6 (10) (2020) 2497-2514
[22] Q.H. Yang, Q. Xu, H.L. Jiang, Metal-organic frameworks meet metal nanoparticles: Synergistic effect for enhanced catalysis, Chem. Soc. Rev. 46 (15) (2017) 4774-4808
[23] J.L. Shi, On the synergetic catalytic effect in heterogeneous nanocomposite catalysts, Chem. Rev. 113 (3) (2013) 2139-2181
[24] Z. Li, S. Ji, Y. Liu, X. Cao, S. Tian, Y. Chen, Z. Niu, Y. Li, Well-defined materials for heterogeneous catalysis: From nanoparticles to isolated single-atom sites, Chem. Rev. 120 (2) (2020) 623-682
[25] K.J. Zhen, M.M. Khan, C.H. Mak, K.B. Lewis, G.A. Somorjai, Partial oxidation of methane with nitrous oxide over V₂O₅-SiO₂ catalyst, J. Catal. 94 (1985) 501-507
[26] S.H. Taylor, J.S.J. Hargreaves, G.J. Hutchings, R.W. Joyner, C.W. Lembacher, The partial oxidation of methane to methanol: An approach to catalyst design, Catal. Today 42 (3) (1998) 217-224
[27] G.O. Alptekin, A.M. Herring, D.L. Williamson, T.R. Ohno, R.L. McCormick, Methane partial oxidation by unsupported and silica supported iron phosphate catalysts, J. Catal. 181 (1) (1999) 104-112
[28] B.T. Qiao, A.Q. Wang, X.F. Yang, L.F. Allard, Z. Jiang, Y.T. Cui, J.Y. Liu, J. Li, T. Zhang, Single-atom catalysis of CO oxidation using Pt1/FeOnull, Nat. Chem. 3 (8) (2011) 634-641
[29] J. Lin, A.Q. Wang, B.T. Qiao, X.Y. Liu, X.F. Yang, X.D. Wang, J.X. Liang, J. Li, J.Y. Liu, T. Zhang, Remarkable performance of Ir1/FeO(x) single-atom catalyst in water gas shift reaction, J. Am. Chem. Soc. 135 (41) (2013) 15314-15317
[30] J.X. Liang, J. Lin, J.Y. Liu, X.D. Wang, T. Zhang, J. Li, Dual metal active sites in an Ir1 /FeOnull single-atom catalyst: A redox mechanism for the water-gas shift reaction, Angew. Chem. Int. Ed. Engl. 59 (31) (2020) 12868-12875
[31] Y. Chen, J. Lin, L. Li, B. Qiao, J. Liu, Y. Su, X. Wang, Identifying size effects of Pt as single atoms and nanoparticles supported on FeOnull for the water-gas shift reaction, ACS Catal. 8 (2) (2018) 859-868
[32] Y. Lou, Y.P. Zheng, X. Li, N. Ta, J. Xu, Y.F. Nie, K. Cho, J.Y. Liu, Pocketlike active site of Rh1/MoS₂ single-atom catalyst for selective crotonaldehyde hydrogenation, J Am. Chem. Soc. 141 (49) (2019) 19289-19295
[33] Y. Lou, Y. Cai, W. Hu, L. Wang, Q. Dai, W. Zhan, Y. Guo, P. Hu, X.-M. Cao, J. Liu, Y. Guo, Identification of active area as active center for CO oxidation over single Au atom catalyst, ACS Catal. 10 (11) (2020) 6094-6101
[34] C. Hammond, M.M. Forde, M.H. Ab Rahim, A. Thetford, Q. He, R.L. Jenkins, N. Dimitratos, J.A. Lopez-Sanchez, N.F. Dummer, D.M. Murphy, A.F. Carley, S.H. Taylor, D.J. Willock, E.E. Stangland, J. Kang, H. Hagen, C.J. Kiely, G.J. Hutchings, Direct catalytic conversion of methane to methanol in an aqueous medium by using copper-promoted Fe-ZSM-5, Angew. Chem. 124 (21) (2012) 5219-5223
[35] D.Y. Osadchii, A.I. Olivos-Suarez, Á. Szécsényi, G.N. Li, M.A. Nasalevich, I.A. Dugulan, P.S. Crespo, E.J.M. Hensen, S.L. Veber, M.V. Fedin, G. Sankar, E.A. Pidko, J. Gascon, Isolated Fe sites in metal organic frameworks catalyze the direct conversion of methane to methanol, ACS Catal. 8 (6) (2018) 5542-5548
[36] W.S. Zhao, Y.N. Shi, Y.H. Jiang, X.F. Zhang, C. Long, P.F. An, Y.F. Zhu, S.X. Shao, Z. Yan, G.D. Li, Z.Y. Tang, Fe-O clusters anchored on nodes of metal-organic frameworks for direct methane oxidation, Angew. Chem. Int. Ed. Engl. 60 (11) (2021) 5811-5815
[37] R.D. Armstrong, V. Peneau, N. Ritterskamp, C.J. Kiely, S.H. Taylor, G.J. Hutchings, The role of copper speciation in the low temperature oxidative upgrading of short chain alkanes over Cu/ZSM-5 catalysts, Chemphyschem 19 (4) (2018) 469-478
[38] C.C. Liu, C.Y. Mou, S.S.F. Yu, S.I. Chan, Heterogeneous formulation of the tricopper complex for efficient catalytic conversion of methane into methanol at ambient temperature and pressure, Energy Environ. Sci. 9 (4) (2016) 1361-1374
[39] M.H. Ab Rahim, M.M. Forde, R.L. Jenkins, C. Hammond, Q. He, N. Dimitratos, J.A. Lopez-Sanchez, A.F. Carley, S.H. Taylor, D.J. Willock, D.M. Murphy, C.J. Kiely, G.J. Hutchings, Oxidation of methane to methanol with hydrogen peroxide using supported gold-palladium alloy nanoparticles, Angew. Chem. Int. Ed. Engl. 52 (4) (2013) 1280-1284
[40] Z. Jin, L. Wang, E. Zuidema, K. Mondal, M. Zhang, J. Zhang, C.T. Wang, X.J. Meng, H.Q. Yang, C. Mesters, F.S. Xiao, Hydrophobic zeolite modification for in situ peroxide formation in methane oxidation to methanol, Science 367 (6474) (2020) 193-197
[41] N. Agarwal, S.J. Freakley, R.U. McVicker, S.M. Althahban, N. Dimitratos, Q. He, D.J. Morgan, R.L. Jenkins, D.J. Willock, S.H. Taylor, C.J. Kiely, G.J. Hutchings, Aqueous Au-Pd colloids catalyze selective CH₄ oxidation to CH₃OH with O₂ under mild conditions, Science 358 (6360) (2017) 223-227
[42] R. McVicker, N. Agarwal, S.J. Freakley, Q. He, S. Althahban, S.H. Taylor, C.J. Kiely, G.J. Hutchings, Low temperature selective oxidation of methane using gold-palladium colloids, Catal. Today 342 (2020) 32-38
[43] R. Serra-Maia, F.M. Michel, Y. Kang, E.A. Stach, Decomposition of hydrogen peroxide catalyzed by AuPd nanocatalysts during methane oxidation to methanol, ACS Catal. 10 (9) (2020) 5115-5123
[44] S.X. Bai, Q. Yao, Y. Xu, K.L. Cao, X.Q. Huang, Strong synergy in a lichen-like RuCu nanosheet boosts the direct methane oxidation to methanol, Nano Energy 71 (2020) 104566
[45] C. Samanta, V.R. Choudhary, Direct oxidation of H₂ to H₂O₂ over Pd/CeO₂ catalyst under ambient conditions: Influence of halide ions, Chem. Eng. J. 136 (2-3) (2008) 126-132
[46] S. Bai, Y. Xu, P. Wang, Q. Shao, X. Huan, Activating and converting CH₄ to CH₃OH via the CuPdO₂/CuO nanointerface, ACS Catal. 9 (8) (2019) 6938-6944
[47] L. Yang, J.X. Huang, R. Ma, R. You, H. Zeng, Z.B. Rui, Metal-organic framework-derived IrO₂/CuO catalyst for selective oxidation of methane to methanol, ACS Energy Lett. 4 (12) (2019) 2945-2951
[48] L. Yang, J.X. Huang, S. Dai, X. Tang, Z. Hu, M. Li, H. Zeng, R. Luque, P.G. Duan, Z.B. Rui, Uniphase ruthenium-iridium alloy-based electronic regulation for electronic structure-function study in methane oxidation to methanol, J. Mater. Chem. A 8 (45) (2020) 24024-24030
[49] X.J. Cui, H.B. Li, Y. Wang, Y.L. Hu, L. Hua, H.Y. Li, X.W. Han, Q.F. Liu, F. Yang, L.M. He, X.Q. Chen, Q.Y. Li, J.P. Xiao, D.H. Deng, X.H. Bao, Room-temperature methane conversion by graphene-confined single iron atoms, Chem 4 (8) (2018) 1902-1910
[50] K.X. Zhu, S.X. Liang, X.J. Cui, R. Huang, N.B. Wan, L. Hua, H.Y. Li, H.Y. Chen, Z.C. Zhao, G.J. Hou, M.R. Li, Q.K. Jiang, L. Yu, D.H. Deng, Highly efficient conversion of methane to formic acid under mild conditions at ZSM-5-confined Fe-sites, Nano Energy 82 (2021) 105718
[51] T. Yu, Z. Li, W. Jones, Y.S. Liu, Q. He, W.Y. Song, P.F. Du, B. Yang, H.Y. An, D.M. Farmer, C.W. Qiu, A.Q. Wang, B.M. Weckhuysen, A.M. Beale, W.H. Luo, Identifying key mononuclear Fe species for low-temperature methane oxidation, Chem. Sci. 12 (9) (2021) 3152-3160
[52] T. Zhang, D. Zhang, X. Han, T. Dong, X. Guo, C. Song, R. Si, W. Liu, Y. Liu, Z. Zhao, Preassembly strategy to fabricate porous hollow carbonitride spheres inlaid with single Cu-N₃ sites for selective oxidation of benzene to phenol, J. Am. Chem. Soc. 140 (49) (2018) 16936-16940
[53] X. Tang, L. Wang, B. Yang, C. Fei, T.Y. Yao, W. Liu, Y. Lou, Q.G. Dai, Y.F. Cai, X.M. Cao, W.C. Zhan, Y.L. Guo, X.Q. Gong, Y. Guo, Direct oxidation of methane to oxygenates on supported single Cu atom catalyst, Appl. Catal. B: Environ. 285 (2021) 119827
[54] W.X. Huang, S.R. Zhang, Y. Tang, Y.T. Li, L. Nguyen, Y.Y. Li, J.J. Shan, D.Q. Xiao, R. Gagne, A.I. Frenkel, F.F. Tao, Low-temperature transformation of methane to methanol on Pd₁O₄ single sites anchored on the internal surface of microporous silicate, Angew. Chem. Int. Ed. 55 (43) (2016) 13441-13445
[55] Y. Kwon, T.Y. Kim, G. Kwon, J. Yi, H. Lee, Selective activation of methane on single-atom catalyst of rhodium dispersed on zirconia for direct conversion, J. Am. Chem. Soc. 139 (48) (2017) 17694-17699
[56] S.X. Bai, F.F. Liu, B.L. Huang, F. Li, H.P. Lin, T. Wu, M.Z. Sun, J.B. Wu, Q. Shao, Y. Xu, X.Q. Huang, High-efficiency direct methane conversion to oxygenates on a cerium dioxide nanowires supported rhodium single-atom catalyst, Nat. Commun. 11 (1) (2020) 1-9
[57] J.J. Shan, M.W. Li, L.F. Allard, S. Lee, M. Flytzani-Stephanopoulos, Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts, Nature 551 (7682) (2017) 605-608
[58] Y. Tang, Y.T. Li, V. Fung, D.E. Jiang, W.X. Huang, S.R. Zhang, Y. Iwasawa, T. Sakata, L. Nguyen, X.Y. Zhang, A.I. Frenkel, F.F. Tao, Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions, Nat. Commun. 9 (1) (2018) 1231
[59] H. Zhou, T.Y. Liu, X.Y. Zhao, Y.F. Zhao, H. Lv, S. Fang, X.Q. Wang, F.Y. Zhou, Q. Xu, J. Xu, C. Xiong, Z.G. Xue, K. Wang, W.C. Cheong, W. Xi, L. Gu, T. Yao, S.Q. Wei, X. Hong, J. Luo, Y.F. Li, Y.E. Wu, Frontispiece: A supported nickel catalyst stabilized by a surface digging effect for efficient methane oxidation, Angew. Chem. Int. Ed
[60] Q.K. Shen, C.Y. Cao, R.K. Huang, L. Zhu, X. Zhou, Q.H. Zhang, L. Gu, W.G. Song, Single chromium atoms supported on titanium dioxide nanoparticles for synergic catalytic methane conversion under mild conditions, Angew. Chem. Int. Ed. 59 (3) (2020) 1216-1219
[61] K.A. Dubkov, N.S. Ovanesyan, A.A. Shteinman, E.V. Starokon, G.I. Panov, Evolution of iron states and formation of α-sites upon activation of FeZSM-5 zeolites, J. Catal. 207 (2) (2002) 341-352
[62] M.O. Ross, A.C. Rosenzweig, A tale of two methane monooxygenases, J. Biol. Inorg. Chem. 22 (2-3) (2017) 307-319
[63] J.C. da Silva, R.C. Pennifold, J.N. Harvey, W.R. Rocha, A radical rebound mechanism for the methane oxidation reaction promoted by the dicopper center of a pMMO enzyme: A computational perspective, Dalton Trans. 45 (6) (2016) 2492-2504
[64] C. Hammond, R.L. Jenkins, N. Dimitratos, J.A. Lopez-Sanchez, M.H. ab Rahim, M.M. Forde, A. Thetford, D.M. Murphy, H. Hagen, E.E. Stangland, J.M. Moulijn, S.H. Taylor, D.J. Willock, G.J. Hutchings, Catalytic and mechanistic insights of the low-temperature selective oxidation of methane over Cu-promoted Fe-ZSM-5, Chemistry 18 (49) (2012) 15735-15745
[65] K. Yoshizawa, Two-step concerted mechanism for methane hydroxylation on the diiron active site of soluble methane monooxygenase, J. Inorg. Biochem. 78 (1) (2000) 23-34
[66] C. Hammond, N. Dimitratos, R.L. Jenkins, J.A. Lopez-Sanchez, S.A. Kondrat, M. Hasbi ab Rahim, M.M. Forde, A. Thetford, S.H. Taylor, H. Hagen, E.E. Stangland, J.H. Kang, J.M. Moulijn, D.J. Willock, G.J. Hutchings, Elucidation and evolution of the active component within Cu/Fe/ZSM-5 for catalytic methane oxidation: From synthesis to catalysis, ACS Catal. 3 (4) (2013) 689-699
[67] C. Hammond, I. Hermans, N. Dimitratos, Biomimetic oxidation with Fe-ZSM-5 and H₂O₂? identification of an active, extra-framework binuclear core and an FeIIIOOH intermediate with resonance-enhanced Raman spectroscopy, ChemCatChem 7 (3) (2015) 434-440
[68] C. Hammond, N. Dimitratos, J.A. Lopez-Sanchez, R.L. Jenkins, G. Whiting, S.A. Kondrat, M.H. ab Rahim, M.M. Forde, A. Thetford, H. Hagen, E.E. Stangland, J.M. Moulijn, S.H. Taylor, D.J. Willock, G.J. Hutchings, Aqueous-phase methane oxidation over Fe-MFI zeolites; promotion through isomorphous framework substitution, ACS Catal. 3 (8) (2013) 1835-1844
[69] S. Al-Shihri, C.J. Richard, D. Chadwick, Selective oxidation of methane to methanol over ZSM-5 catalysts in aqueous hydrogen peroxide: Role of formaldehyde, ChemCatChem 9 (7) (2017) 1276-1283
[70] C. Kalamaras, D. Palomas, R. Bos, A. Horton, M. Crimmin, K. Hellgardt, Selective oxidation of methane to methanol over Cu- and Fe-exchanged zeolites: The effect of Si/Al molar ratio, Catal. Lett. 146 (2) (2016) 483-492
[71] Á. Szécsényi, G.N. Li, J. Gascon, E.A. Pidko, Mechanistic complexity of methane oxidation with H₂O₂ by single-site Fe/ZSM-5 catalyst, ACS Catal. 8 (9) (2018) 7961-7972
[72] Á. Szécsényi, G.N. Li, J. Gascon, E.A. Pidko, Unraveling reaction networks behind the catalytic oxidation of methane with H₂O₂ over a mixed-metal MIL-53(Al, Fe) MOF catalyst, Chem. Sci. 9 (33) (2018) 6765-6773
[73] V.L. Sushkevich, D. Palagin, J.A. Van Bokhoven, The effect of the active-site structure on the activity of copper mordenite in the aerobic and anaerobic conversion of methane into methanol, Angew. Chem. Int. Ed. 57 (29) (2018) 8906-8910
[74] M.A. Newton, A.J. Knorpp, A.B. Pinar, V.L. Sushkevich, D. Palagin, J.A. van Bokhoven, On the mechanism underlying the direct conversion of methane to methanol by copper hosted in zeolites; braiding Cu K-edge XANES and reactivity studies, J. Am. Chem. Soc. 140 (32) (2018) 10090-10093
[75] T. Ikuno, J. Zheng, A. Vjunov, M. Sanchez-Sanchez, M.A. Ortuño, D.R. Pahls, J.L. Fulton, D.M. Camaioni, Z.Y. Li, D. Ray, B.L. Mehdi, N.D. Browning, O.K. Farha, J.T. Hupp, C.J. Cramer, L. Gagliardi, J.A. Lercher, Methane oxidation to methanol catalyzed by Cu-oxo clusters stabilized in NU-1000 metal-organic framework, J. Am. Chem. Soc. 139 (30) (2017) 10294-10301
[76] J. Zheng, J.Y. Ye, M.A. Ortuño, J.L. Fulton, O.Y. Gutiérrez, D.M. Camaioni, R.K. Motkuri, Z.Y. Li, T.E. Webber, B.L. Mehdi, N.D. Browning, R.L. Penn, O.K. Farha, J.T. Hupp, D.G. Truhlar, C.J. Cramer, J.A. Lercher, Selective methane oxidation to methanol on Cu-oxo dimers stabilized by zirconia nodes of an NU-1000 metal-organic framework, J. Am. Chem. Soc. 141 (23) (2019) 9292-9304
[77] J. Baek, B. Rungtaweevoranit, X.K. Pei, M. Park, S.C. Fakra, Y.S. Liu, R. Matheu, S.A. Alshmimri, S. Alshehri, C.A. Trickett, G.A. Somorjai, O.M. Yaghi, Bioinspired metal-organic framework catalysts for selective methane oxidation to methanol, J. Am. Chem. Soc. 140 (51) (2018) 18208-18216
[78] Y. Zhou, F. Wei, J. Lin, L. Li, X. Li, H. Qi, X. Pan, X. Liu, C. Huang, S. Lin, X. Wang, Sulfate-modified NiAl mixed oxides as effective C-H bond-breaking agents for the sole production of ethylene from ethane, ACS Catal. 10 (2020) 7619-7629
[79] P. Zhou, F. Lv, N. Li, Y.L. Zhang, Z.J. Mu, Y.H. Tang, J.P. Lai, Y.G. Chao, M.C. Luo, F. Lin, J.H. Zhou, D. Su, S.J. Guo, Strengthening reactive metal-support interaction to stabilize high-density Pt single atoms on electron-deficient g-C₃N₄ for boosting photocatalytic H₂ production, Nano Energy 56 (2019) 127-137
[80] L. Zhao, Y. Zhang, L.B. Huang, X.Z. Liu, Q.H. Zhang, C. He, Z.Y. Wu, L.J. Zhang, J.P. Wu, W.L. Yang, L. Gu, J.S. Hu, L.J. Wan, Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts, Nat. Commun. 10 (1) (2019) 1278
[81] X. He, Q. He, Y. Deng, M. Peng, H. Chen, Y. Zhang, S. Yao, M. Zhang, D. Xiao, D. Ma, B. Ge, H. Ji, A versatile route to fabricate single atom catalysts with high chemoselectivity and regioselectivity in hydrogenation, Nat. Commun. 10 (1) (2019) 3663
[82] B. Wu, R.O. Yang, L. Shi, T.J. Lin, X. Yu, M. Huang, K. Gong, F.F. Sun, Z. Jiang, S.G. Li, L.S. Zhong, Y.H. Sun, Cu single-atoms embedded in porous carbon nitride for selective oxidation of methane to oxygenates, Chem. Commun. 56 (93) (2020) 14677-14680
[83] J.F. Weaver, C. Hakanoglu, A. Antony, A. Asthagiri, Alkane activation on crystalline metal oxide surfaces, Chem. Soc. Rev. 43 (22) (2014) 7536-7547
[84] K. Harrath, X. Yu, H. Xiao, J. Li, The Key role of support surface hydrogenation in the CH₄ to CH₃OH selective oxidation by a ZrO₂-supported single-atom catalyst, ACS Catal. 9 (10) (2019) 8903-8909
[85] D.H. Jiang, G.Q. Fang, Y.Q. Tong, X.Y. Wu, Y.F. Wang, D.S. Hong, W.H. Leng, Z. Liang, P.X. Tu, L. Liu, K.Y. Xu, J. Ni, X.N. Li, Multifunctional Pd@UiO-66 catalysts for continuous catalytic upgrading of ethanol to n-butanol, ACS Catal. 8 (12) (2018) 11973-11978
[86] J. Ni, W.H. Leng, J. Mao, J.G. Wang, J.Y. Lin, D.H. Jiang, X.N. Li, Tuning electron density of metal nickel by support defects in Ni/ZrO₂ for selective hydrogenation of fatty acids to alkanes and alcohols, Appl. Catal. B: Environ. 253 (2019) 170-178
[87] X.Y. Wu, G.Q. Fang, Y.Q. Tong, D.H. Jiang, Z. Liang, W.H. Leng, L. Liu, P.X. Tu, H.J. Wang, J. Ni, X.N. Li, Catalytic upgrading of ethanol to n-butanol: Progress in catalyst development, ChemSusChem 11 (1) (2018) 71-85
[88] S. Feng, X. Lin, X. Song, B. Mei, J. Mu, J. Li, Y. Liu, Z. Jiang, Y. Ding, Constructing efficient single Rh sites on activated carbon via surface carbonyl groups for methanol carbonylation, ACS Catal. 11 (2021) 682-690
[89] Z. Ren, Y. Liu, Y. Lyu, X.G. Song, C.Y. Zheng, S.Q. Feng, Z. Jiang, Y.J. Ding, Single-atom Rh based bipyridine framework porous organic polymer: A high active and superb stable catalyst for heterogeneous methanol carbonylation, J. Catal. 369 (2019) 249-256
[90] T. Moteki, N. Tominaga, M. Ogura, CO-assisted direct methane conversion into C1 and C2 oxygenates over ZSM-5 supported transition and platinum group metal catalysts using oxygen as an oxidant, ChemCatChem 12 (11) (2020) 2957-2961
[91] K. Narsimhan, V.K. Michaelis, G. Mathies, W.R. Gunther, R.G. Griffin, Y. Román-Leshkov, Methane to acetic acid over Cu-exchanged zeolites: Mechanistic insights from a site-specific carbonylation reaction, J. Am. Chem. Soc. 137 (5) (2015) 1825-1832
[92] J. Lin, X.D. Wang, Rh single atom catalyst for direct conversion of methane to oxygenates, Sci. China Mater. 61 (5) (2018) 758-760
[93] J. Kang, P. Puthiaraj, W.S. Ahn, E.D. Park, Direct synthesis of oxygenates via partial oxidation of methane in the presence of O₂ and H₂ over a combination of Fe-ZSM-5 and Pd supported on an acid-functionalized porous polymer, Appl. Catal. A: Gen. 602 (2020) 117711
[94] V.R. Choudhary, A.G. Gaikwad, S.D. Sansrae, Supported Pd metal catalysts for selective oxidation of hydrogen to hydrogen peroxide, Catal. Lett. 83 (2002) 235-239
[95] J.K. Edwards, B.E. Solsona, P. Landon, A.F. Carley, A. Herzing, C.J. Kiely, G.J. Hutchings, Direct synthesis of hydrogen peroxide from H₂ and O₂ using TiO₂-supported Au-Pd catalysts, J. Catal. 236 (1) (2005) 69-79
[96] Y.L. He, J.M. Liang, Y. Imai, K. Ueda, H.J. Li, X.Y. Guo, G.H. Yang, Y. Yoneyama, N. Tsubaki, Highly selective synthesis of methanol from methane over carbon materials supported Pd-Au nanoparticles under mild conditions, Catal. Today 352 (2020) 104-110
[97] M.H. Ab Rahim, R.D. Armstrong, C. Hammond, N. Dimitratos, S.J. Freakley, M.M. Forde, D.J. Morgan, G. Lalev, R.L. Jenkins, J.A. Lopez-Sanchez, S.H. Taylor, G.J. Hutchings, Low temperature selective oxidation of methane to methanol using titania supported gold palladium copper catalysts, Catal. Sci. Technol. 6 (10) (2016) 3410-3418
[98] C. Williams, J.H. Carter, N.F. Dummer, Y.K. Chow, D.J. Morgan, S. Yacob, P. Serna, D.J. Willock, R.J. Meyer, S.H. Taylor, G.J. Hutchings, Selective oxidation of methane to methanol using supported AuPd catalysts prepared by stabilizer-free Sol-immobilization, ACS Catal. 8 (3) (2018) 2567-2576
[99] Z. Liang, T. Li, M. Kim, A. Asthagiri, J.F. Weaver, Low-temperature activation of methane on the IrO₂(110) surface, Science 356 (6335) (2017) 299-303
[100] R. Jin, M. Peng, A. Li, Y. Deng, Z. Jia, F. Huang, Y. Ling, F. Yang, H. Fu, J. Xie, X. Han, D. Xiao, Z. Jiang, H. Liu, D. Ma, Low temperature oxidation of ethane to oxygenates by oxygen over iridium-cluster catalysts, J. Am. Chem. Soc. 141 (48) (2019) 18921-18925