AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

TiO2 nanofiber-supported copper nanoparticle catalysts for highly efficient methane conversion to C1 oxygenates under mild conditions

Wencui Li1,2,§, Yu Ren2,§, Zean Xie2,§, Yipeng Wang2, Hang Zhang2( ), Dianxiang Peng3, Hengfang Shen1, Hongfei Shi3( ), Jiaxin Cai1, Peng Wang2, Tongxin Zhang2, Zhen Zhao1,2( )
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China
Institute of Catalysis for Energy and Environment, College of Chemistry & Chemical Engineering, Shenyang Normal University, Shenyang 110034, China
Institute of Petrochemical Technology, Jilin Institute of Chemical Technology, Jilin 132022, China

§ Wencui Li, Yu Ren, and Zean Xie contributed equally to this work.

Show Author Information

Graphical Abstract

The intrinsic inertness of the C–H bond in methane poses a significant challenge for the direct conversion of methane into high-value-added chemicals. This study is focused on the design of a Cu/TiO2 nanofiber composite catalyst, which exhibits unparalleled performance in converting methane to oxygenates under mild conditions. Furthermore, this study emphasizes the pivotal role of valuable insights in advancing the development of non-noble metal/semiconductor materials with significantly enhanced catalytic performance.

Abstract

The selective oxidation of methane under mild conditions remains the “Holy Grail of Catalysis”. The key to activating methane and inhibiting over-oxidation of target oxygenates lies in designing active centers. Copper nanoparticles were loaded onto TiO2 nanofibers using the photo-deposition method. The resulting catalysts were found to effectively convert methane into C1 oxygenated products under mild conditions. Compared with previously reported catalysts, it delivers a superior performance of up to 2510.7 mmol·gCu−1·h−1 productivity with a selectivity of around 100% at 80 °C for 5 min. Microstructure characterizations and density functional theory (DFT) calculations indicate that TiO2 in the mixed phase of anatase and rutile significantly increases the Cu+/Cu0 ratio of the supported Cu species, and this ratio is linearly related to the formation rate of oxygen-containing species. The CuI site promotes the generation of active O species from H2O2 dissociation on Cu2O (111). These active O species reduce the energy barrier for breaking the C–H bond of CH4, thus boosting the catalytic activity. The methane conversion mechanism was proposed as a methyl radical pathway to form CH3OH and CH3OOH, and then the generated CH3OH is further oxidized to HOCH2OOH.

Keywords

TiO2 nanofibercopper nanoparticlesphoto-deposition methodmethane oxidationC1 oxygenates

Electronic Supplementary Material

Download File(s)
12274_2023_6356_MOESM1_ESM.pdf (2.4 MB)

References

[1]

Sun, X.; Chen, X. Y.; Fu, C.; Yu, Q. B.; Zheng, X. S.; Fang, F.; Liu, Y. X.; Zhu, J. F.; Zhang, W. H.; Huang, W. X. Molecular oxygen enhances H2O2 utilization for the photocatalytic conversion of methane to liquid-phase oxygenates. Nat. Commun. 2022, 13, 6677.
Crossref Google Scholar
[2]

Chen, F. Q.; Zheng, W.; Zhu, N.; Cheng, D. G.; Zhan, X. L. Oxidative coupling of methane over Na-W-Mn-Zr-S-P/SiO2 catalyst: Effect of S, P addition on the catalytic performance. Catal. Lett. 2008, 125, 348–351.
Crossref Google Scholar
[3]

Lunsford, J. H. The catalytic oxidative coupling of methane. Angew. Chem. Int. Ed. Engl. 1995, 34, 970–980.
Crossref Google Scholar
[4]

Kwapien, K.; Paier, J.; Sauer, J.; Geske, M.; Zavyalova, U.; Horn, R.; Schwach, P.; Trunschke, A.; Schlögl, R. Sites for methane activation on lithium-doped magnesium oxide surfaces. Angew. Chem., Int. Ed. 2014, 53, 8774–8778.
Crossref Google Scholar
[5]

Xu, Y. D.; Bao, X. H.; Lin, L. W. Direct conversion of methane under nonoxidative conditions. J. Catal. 2003, 216, 386–395.
Crossref Google Scholar
[6]

Hutchings, G. J.; Scurrell, M. S.; Woodhouse, J. R. Oxidative coupling of methane using oxide catalysts. Chem. Soc. Rev. 1989, 18, 251–283.
Crossref Google Scholar
[7]

Guo, X. G.; Fang, G. Z.; Li, G.; Ma, H.; Fan, H. J.; Yu, L.; Ma, C.; Wu, X.; Deng, D. H.; Wei, M. M. et al. Direct, nonoxidative conversion of methane to ethylene, aromatics, and hydrogen. Science 2014, 344, 616–619.
Crossref Google Scholar
[8]

Yu, X.; Zholobenko, V. L.; Moldovan, S.; Hu, D.; Wu, D.; Ordomsky, V. V.; Khodakov, A. Y. Stoichiometric methane conversion to ethane using photochemical looping at ambient temperature. Nat. Energy 2020, 5, 511–519.
Crossref Google Scholar
[9]

Schulz, H. Short history and present trends of Fischer-Tropsch synthesis. Appl. Catal. A: Gen. 1999, 186, 3–12.
Crossref Google Scholar
[10]

Sushkevich, V. L.; Palagin, D.; Ranocchiari, M.; van Bokhoven, J. A. Selective anaerobic oxidation of methane enables direct synthesis of methanol. Science 2017, 356, 523–527.
Crossref Google Scholar
[11]

Chen, X. W.; Peng, M.; Cai, X. B.; Chen, Y. L.; Jia, Z. M.; Deng, Y. C.; Mei, B. B.; Jiang, Z.; Xiao, D. Q.; Wen, X. D. et al. Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction. Nat. Commun. 2021, 12, 2664.
Crossref Google Scholar
[12]

Chen, X. W.; Qin, X. T.; Jiao, Y. Y.; Peng, M.; Diao, J. Y.; Ren, P. J.; Li, C. Y.; Xiao, D. Q.; Wen, X. D.; Jiang, Z. et al. Structure-dependence and metal-dependence on atomically dispersed Ir catalysts for efficient n-butane dehydrogenation. Nat. Commun. 2023, 14, 2588.
Crossref Google Scholar
[13]

Ab Rahim, M. H.; Forde, M. M.; Jenkins, R. L.; Hammond, C.; He, Q.; Dimitratos, N.; Lopez-Sanchez, J. A.; Carley, A. F.; Taylor, S. H.; Willock, D. J. et al. Oxidation of methane to methanol with hydrogen peroxide using supported gold-palladium alloy nanoparticles. Angew. Chem., Int. Ed. 2013, 52, 1280–1284.
Crossref Google Scholar
[14]

Hammond, C.; Forde, M. M.; Ab Rahim, M. H.; Thetford, A.; He, Q.; Jenkins, R. L.; Dimitratos, N.; Lopez-Sanchez, J. A.; Dummer, N. F.; Murphy, D. M. et al. Direct catalytic conversion of methane to methanol in an aqueous medium by using copper-promoted Fe-ZSM-5. Angew. Chem., Int. Ed. 2012, 51, 5129–5133.
Crossref Google Scholar
[15]

Armstrong, R. D.; Peneau, V.; Ritterskamp, N.; Kiely, C. J.; Taylor, S. H.; Hutchings, G. J. The role of copper speciation in the low temperature oxidative upgrading of short chain alkanes over Cu/ZSM-5 catalysts. ChemPhysChem 2018, 19, 469–478.
Crossref Google Scholar
[16]

Zhao, W. S.; Shi, Y. N.; Jiang, Y. H.; Zhang, X. F.; Long, C.; An, P. F.; Zhu, Y. F.; Shao, S. X.; Yan, Z.; Li, G. D. et al. Fe-O clusters anchored on nodes of metal-organic frameworks for direct methane oxidation. Angew. Chem., Int. Ed. 2021, 60, 5811–5815.
Crossref Google Scholar
[17]

Yang, L.; Huang, J. X.; Ma, R.; You, R.; Zeng, H.; Rui, Z. B. Metal-organic framework-derived IrO2/CuO catalyst for selective oxidation of methane to methanol. ACS Energy Lett. 2019, 4, 2945–2951.
Crossref Google Scholar
[18]

Shen, Q. K.; Cao, C. Y.; Huang, R. K.; Zhu, L.; Zhou, X.; Zhang, Q. H.; Gu, L.; Song, W. G. Single chromium atoms supported on titanium dioxide nanoparticles for synergic catalytic methane conversion under mild condition. Angew. Chem., Int. Ed. 2020, 59, 1216–1219.
Crossref Google Scholar
[19]

Agarwal, N.; Freakley, S. J.; McVicker, R. U.; Althahban, S. M.; Dimitratos, N.; He, Q.; Morgan, D. J.; Jenkins, R. L.; Willock, D. J.; Taylor, S. H. et al. Aqueous Au-Pd colloids catalyze selective CH4 oxidation to CH3OH with O2 under mild conditions. Science 2017, 358, 223–227.
Crossref Google Scholar
[20]

Mahlaba, S. V. L.; Hytoolakhan Lal Mahomed, N.; Govender, A.; Guo, J. F.; Leteba, G. M.; Cilliers, P. L.; van Steen, E. Platinum-catalysed selective aerobic oxidation of methane to formaldehyde in the presence of liquid water. Angew. Chem., Int. Ed. 2022, 61, e202206841.
Crossref Google Scholar
[21]

Zhang, P. Y.; Liu, H. Y.; Li, X. M. Photo-reduction synthesis of Cu nanoparticles as Plasmon-driven non-semiconductor photocatalyst for overall water splitting. Appl. Surf. Sci. 2021, 535, 147720.
Crossref Google Scholar
[22]

Wu, X. Y.; Zeng, Y.; Liu, H. C.; Zhao, J. Q.; Zhang, T. R.; Wang, S. L. Noble-metal-free dye-sensitized selective oxidation of methane to methanol with green light (550 nm). Nano Res. 2021, 14, 4584–4590.
Crossref Google Scholar
[23]

Guo, X. Y.; Hu, Z.; Lv, J. X.; Li, H.; Zhang, Q. H.; Gu, L.; Zhou, W.; Zhang, J. W.; Hu, S. Fine-tuning of Pd-Rh core–shell catalysts by interstitial hydrogen doping for enhanced methanol oxidation. Nano Res. 2022, 15, 1288–1294.
Crossref Google Scholar
[24]

Guo, H. M.; Wu, L.; Nie, S. Y.; Yang, D. R.; Wang, X. Ultrathin zirconium-porphyrin based nanobelts as photo-coupled electrocatalysis for CH4 oxidation to CO. Nano Res. 2023, 16, 12641–12646.
Crossref Google Scholar
[25]

Zeng, F.; Zhang, J.; Xu, R.; Zhang, R. J.; Ge, J. P. Highly dispersed Ni/MgO-mSiO2 catalysts with excellent activity and stability for dry reforming of methane. Nano Res. 2022, 15, 5004–5013.
Crossref Google Scholar
[26]

Nie, J.; Patrocinio, A. O. T.; Hamid, S.; Sieland, F.; Sann, J.; Xia, S.; Bahnemann, D. W.; Schneider, J. New insights into the plasmonic enhancement for photocatalytic H2 production by Cu-TiO2 upon visible light illumination. Phys. Chem. Chem. Phys. 2018, 20, 5264–5273.
Crossref Google Scholar
[27]

DeSario, P. A.; Pietron, J. J.; Brintlinger, T. H.; McEntee, M.; Parker, J. F.; Baturina, O.; Stroud, R. M.; Rolison, D. R. Oxidation-stable plasmonic copper nanoparticles in photocatalytic TiO2 nanoarchitectures. Nanoscale 2017, 9, 11720–11729.
Crossref Google Scholar
[28]

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
Crossref Google Scholar
[29]

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
Crossref Google Scholar
[30]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
Crossref Google Scholar
[31]

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
Crossref Google Scholar
[32]

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
Crossref Google Scholar
[33]

Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 2006, 27, 1787–1799.
Crossref Google Scholar
[34]

Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188–5192.
Crossref Google Scholar
[35]

Qiu, X. Q.; Miyauchi, M.; Sunada, K.; Minoshima, M.; Liu, M.; Lu, Y.; Li, D.; Shimodaira, Y.; Hosogi, Y.; Kuroda, Y. et al. Hybrid Cu x O/TiO2 nanocomposites as risk-reduction materials in indoor environments. ACS Nano 2012, 6, 1609–1618.
Crossref Google Scholar
[36]

Zhang, Q. Y.; Li, Y.; Ackerman, E. A.; Gajdardziska-Josifovska, M.; Li, H. L. Visible light responsive iodine-doped TiO2 for photocatalytic reduction of CO2 to fuels. Appl. Catal. A: Gen. 2011, 400, 195–202.
Crossref Google Scholar
[37]

Deiana, C.; Fois, E.; Coluccia, S.; Martra, G. Surface structure of TiO2 P25 nanoparticles: Infrared study of hydroxy groups on coordinative defect sites. J. Phys. Chem. C 2010, 114, 21531–21538.
Crossref Google Scholar
[38]

Zhang, J.; Li, M. J.; Feng, Z. C.; Chen, J.; Li, C. UV Raman spectroscopic study on TiO2. I. phase transformation at the surface and in the bulk. J. Phys. Chem. B 2006, 110, 927–935.
Crossref Google Scholar
[39]

Espinós, J. P.; Morales, J.; Barranco, A.; Caballero, A.; Holgado, J. P.; González-Elipe, A. R. Interface effects for Cu, CuO, and Cu2O Deposited on SiO2 and ZrO2. XPS determination of the valence state of copper in Cu/SiO2 and Cu/ZrO2 catalysts. J. Phys. Chem. B 2002, 106, 6921–6929.
Crossref Google Scholar
[40]

Dan, Z. H.; Yang, Y. L.; Qin, F. X.; Wang, H.; Chang, H. Facile fabrication of Cu2O nanobelts in ethanol on nanoporous Cu and their photodegradation of methyl orange. Materials 2018, 11, 446.
Crossref Google Scholar
[41]

Zhen, W. L.; Jiao, W. J.; Wu, Y. Q.; Jing, H. W.; Lu, G. X. The role of a metallic copper interlayer during visible photocatalytic hydrogen generation over a Cu/Cu2O/Cu/TiO2 catalyst. Catal. Sci. Technol. 2017, 7, 5028–5037.
Crossref Google Scholar
[42]

Wang, Y. T.; Zhou, W.; Jia, R. R.; Yu, Y. F.; Zhang, B. Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia. Angew. Chem., Int. Ed. 2020, 59, 5350–5354.
Crossref Google Scholar
[43]

Zhou, J. J.; Pan, F.; Yao, Q. F.; Zhu, Y. Q.; Ma, H. R.; Niu, J. F.; Xie, J. P. Achieving efficient and stable electrochemical nitrate removal by in-situ reconstruction of Cu2O/Cu electroactive nanocatalysts on Cu foam. Appl. Catal. B: Environ. 2022, 317, 121811.
Crossref Google Scholar
[44]

Jin, Z.; Wang, L.; Zuidema, E.; Mondal, K.; Zhang, M.; Zhang, J.; Wang, C. T.; Meng, X. J.; Yang, H. Q.; Mesters, C. et al. Hydrophobic zeolite modification for in situ peroxide formation in methane oxidation to methanol. Science 2020, 367, 193–197.
Crossref Google Scholar
[45]

Fang, G. Q.; Hu, J. N.; Tian, L. C.; Liang, J. X.; Lin, J.; Li, L.; Zhu, C.; Wang, X. D. Zirconium-oxo nodes of MOFs with tunable electronic properties provide effective ·OH species for enhanced methane hydroxylation. Angew. Chem., Int. Ed. 2022, 61, e202205077.
Crossref Google Scholar
[46]

Fan, J. C.; Liang, S. X.; Zhu, K. X.; Mao, J.; Cui, X. J.; Ma, C.; Yu, L.; Deng, D. H. Boosting room-temperature conversion of methane via confining Cu atoms in ultrathin Ru nanosheets. Chem Catal. 2022, 2, 2253–2261.
Crossref Google Scholar
[47]

Li, W. C.; Li, Z.; Zhang, H.; Liu, P. X.; Xie, Z. A.; Song, W. Y.; Liu, B. J.; Zhao, Z. Efficient catalysts of surface hydrophobic Cu-BTC with coordinatively unsaturated Cu(I) sites for the direct oxidation of methane. Proc. Natl. Acad. Sci. USA 2023, 120, e2206619120.
Crossref Google Scholar
[48]

Wu, L. N.; Tian, Z. Y.; Qin, W. DFT study on CO catalytic oxidation mechanism on the defective Cu2O (111) surface. J. Phys. Chem. C 2018, 122, 16733–16740.
Crossref Google Scholar
Nano Research
Volume 17 Issue 5,
May 2024
Pages 3844-3852
DOI: 10.1007/s12274-023-6356-9
Cite this article:
Li W, Ren Y, Xie Z, et al. TiO2 nanofiber-supported copper nanoparticle catalysts for highly efficient methane conversion to C1 oxygenates under mild conditions. Nano Research, 2024, 17(5): 3844-3852. https://doi.org/10.1007/s12274-023-6356-9
Topics:
Catalysts

824

Views

5

Crossref

3

Web of Science

4

Scopus

0

CSCD

Altmetrics
Received: 04 September 2023
Revised: 01 November 2023
Accepted: 21 November 2023
Published: 29 December 2023
© Tsinghua University Press 2023
Return