Optimizing the reaction pathway of methane photo-oxidation over single copper sites

被引：9

作者：

Feng, Chengyang ^{[1
,2
]}

Zuo, Shouwei ^{[1
,2
]}

Hu, Miao ^{[1
,2
]}

Ren, Yuanfu ^{[1
,2
]}

Xia, Liwei ^{[3
,4
]}

Luo, Jun ^{[5
,6
]}

Zou, Chen ^{[1
,2
]}

Wang, Sibo ^{[7
]}

Zhu, Yihan ^{[3
,4
]}

Rueping, Magnus ^{[2
]}

Han, Yu ^{[8
]}

Zhang, Huabin ^{[1
,2
]}

机构：

[1] King Abdullah Univ Sci & Technol, Ctr Renewable Energy & Storage Technol CREST, Phys Sci & Engn Div, Thuwal, Saudi Arabia

[2] King Abdullah Univ Sci & Technol KAUST, KAUST Catalysis Ctr KCC, Div Phys Sci & Engn, Thuwal, Saudi Arabia

[3] Zhejiang Univ Technol, Inst Frontier & Interdisciplinary Sci, Ctr Electron Microscopy, State Key Lab Breeding Base Green Chem Synth Techn, Hangzhou, Zhejiang, Peoples R China

[4] Zhejiang Univ Technol, Coll Chem Engn, Hangzhou, Zhejiang, Peoples R China

[5] Guangxi Univ, State Key Lab Featured Met Mat & Life Cycle Safety, MOE Key Lab New Proc Technol Nonferrous Met & Mat, Nanning, Peoples R China

[6] Guangxi Univ, Sch Resources Environm & Mat, Nanning, Peoples R China

[7] Fuzhou Univ, Coll Chem, State Key Lab Photocatalysis Energy & Environm, Fuzhou, Peoples R China

[8] South China Univ Technol, Electron Microscopy Ctr, Guangzhou, Peoples R China

来源：

NATURE COMMUNICATIONS | 2024年 / 15卷 / 01期

基金：

中国国家自然科学基金;

关键词：

METAL-ORGANIC FRAMEWORKS; OXIDATION; CO2; FORMALDEHYDE; CONVERSION;

D O I：

10.1038/s41467-024-53483-z

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Direct photocatalytic conversion of methane to value-added C1 oxygenate with O2 is of great interest but presents a significant challenge in achieving highly selective product formation. Herein, a general strategy for the construction of copper single-atom catalysts with a well-defined coordination microenvironment is developed on the basis of metal-organic framework for selective photo-oxidation of CH4 to HCHO. We propose the directional activation of O2 on the mono-copper site breaks the original equilibrium and tilts the balance of radical formation almost completely toward center dot OOH. The synchronously generated center dot OOH and center dot CH3 radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly selective HCHO production (nearly 100%) with a time yield of 2.75 mmol gcat-1 h-1. This work highlights the potential of rationally designing reaction sites to manipulate reaction pathways and achieve selective CH4 photo-oxidation, and could guide the further design of high-performance single-atom catalysts to meet future demand. Selective photo-oxidation of CH4 to value-added C1 oxygenates remains challenging. Here, the authors propose construct mono-copper sites within a framework platform to optimize O2 activation, enabling highly selective conversion of CH4 to HCHO.

引用

页数：11

共 56 条

[1] Ravi M., Ranocchiari M., van Bokhoven J.A., The direct catalytic oxidation of methane to methanol—a critical assessment, Angew. Chem. Int. Ed, 56, pp. 16464-16483, (2017)
[2] Schwach P., Pan X., Bao X., Direct conversion of methane to value-added chemicals over heterogeneous catalysts: challenges and prospects, Chem. Rev, 117, pp. 8497-8520, (2017)
[3] Gan Y., Et al., Highly selective photocatalytic methane oxidation to methanol using CO2 as a soft oxidant, ACS Sustain. Chem. Eng, 11, pp. 5537-5546, (2023)
[4] Saputera W.H., Yuniar G., Sasongko D., Light-driven methane conversion: unveiling methanol using a TiO2/TiOF2 photocatalyst, RSC Adv, 14, pp. 8740-8751, (2024)
[5] Luo L., Et al., Water enables mild oxidation of methane to methanol on gold single-atom catalysts, Nat. Commun, 12, (2021)
[6] Fan Y., Et al., Selective photocatalytic oxidation of methane by quantum-sized bismuth vanadate, Nat. Sustain, 4, pp. 509-515, (2021)
[7] Sushkevich V.L., Palagin D., Ranocchiari M., Van Bokhoven J.A., Selective anaerobic oxidation of methane enables direct synthesis of methanol, Science, 356, pp. 523-527, (2017)
[8] Ravi M., Et al., Misconceptions and challenges in methane-to-methanol over transition-metal-exchanged zeolites, Nat. Catal, 2, pp. 485-494, (2019)
[9] Kwon Y., Kim T.Y., Kwon G., Yi J., Lee H., Selective activation of methane on single-atom catalyst of rhodium dispersed on zirconia for direct conversion, J. Am. Chem. Soc, 139, pp. 17694-17699, (2017)
[10] Yuniar G., Et al., Recent advances in photocatalytic oxidation of methane to methanol, Molecules, 27, (2022)

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