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

FeOOH quantum dots decorated graphene sheet: An efficient electrocatalyst for ambient N2 reduction

Xiaojuan Zhu1,2,§, Jinxiu Zhao1,§, Lei Ji1, Tongwei Wu1, Ting Wang1, Shuyan Gao3, Abdulmohsen Ali Alshehri4, Khalid Ahmed Alzahrani4, Yonglan Luo2, Yimo Xiang5, Baozhan Zheng6( ), Xuping Sun1( )
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China
Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, China
School of Materials Science and Engineering, Henan Normal University, Xinxiang 453007, China
Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21589, Saudi Arabia
No. 12 Middle School, Chengdu 610041, China
College of Chemistry, Sichuan University, Chengdu 610064, China

§ Xiaojuan Zhu and Jinxiu Zhao contributed equally to this work.

Show Author Information

Graphical Abstract

Abstract

Electrochemical N2 reduction offers a promising alternative to the Haber-Bosch process for sustainable NH3 synthesis at ambient conditions, but it needs efficient catalysts for the N2 reduction reaction (NRR). Here, we report that FeOOH quantum dots decorated graphene sheet acts as a superior catalyst toward enhanced electrocatalytic N2 reduction to NH3 under ambient conditions. In 0.1 M LiClO4, this hybrid attains a large NH3 yield rate and a high Faradaic efficiency of 27.3 μg·h-1·mg-1cat. and 14.6% at -0.4 V vs. reversible hydrogen electrode, respectively, rivalling the current efficiency of all Fe-based NRR electrocatalysts in aqueous media. It also shows strong durability during the electrolytic process.

Keywords

FeOOH quantum dots decorated graphene sheetN2 reduction reactionNH3 electrosynthesisambient conditions

Electronic Supplementary Material

Download File(s)
12274_2019_2600_MOESM1_ESM.pdf (4.1 MB)

References

[1]
Gruber, N.; Galloway, J. N. An earth-system perspective of the global nitrogen cycle. Nature 2008, 451, 293-296.
Crossref Google Scholar
[2]
Schlögl, R. Catalytic synthesis of ammonia—A “never-ending story”. Angew. Chem., Int. Ed. 2003, 42, 2004-2008.
Crossref Google Scholar
[3]
Erisman, J. W.; Sutton, M. A.; Galloway, J.; Klimont, Z.; Winiwarter, W. How a century of ammonia synthesis changed the World. Nat. Geosci. 2008, 1, 636-639.
Crossref Google Scholar
[4]
Vegge, T.; Sørensen, R. Z.; Klerke, A.; Hummelshøj, J. S.; Johannessen, T.; Nørskov, J. K.; Christensen, C. H. Indirect hydrogen storage in metal ammines. In Solid-State Hydrogen Storage; Walker, G., Ed.; Woodhead Publishing: Cambridge, 2008; pp 533-564.
Crossref
[5]
Ertl, G. Elementary steps in ammonia synthesis. In Catalytic Ammonia Synthesis: Fundamentals and Practice; Jennings, J. R., Ed.; Plenum: New York, 1991.
Crossref
[6]
Dybkjaer, I. Ammonia production processes. In Ammonia: Catalysis and Manufacture; Nielsen, A., Ed.; Springer: Berlin Heidelberg, 1995; pp 199-308.
Crossref
[7]
Guo, C. X.; Ran, J. R.; Vasileff, A.; Qiao, S. Z. Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions. Energy Environ. Sci. 2018, 11, 45-56.
Crossref Google Scholar
[8]
Shipman, M. A.; Symes, M. D. Recent progress towards the electrosynthesis of ammonia from sustainable resources. Catal. Today 2017, 286, 57-68.
Crossref Google Scholar
[9]
Wang, Q. C.; Lei, Y. P.; Wang, D. S.; Li, Y. D. Defect engineering in earth-abundant electrocatalysts for CO2 and N2 reduction. Energy Environ. Sci. 2019, 12, 1730-1750.
Crossref Google Scholar
[10]
Zhao, R. B.; Xie, H. T.; Chang, L.; Zhang, X. X.; Zhu, X. J.; Tong, X.; Wang, T.; Luo, Y. L.; Wei, P. P.; Wang, Z. M. et al. Recent progress in the electrochemical ammonia synthesis under ambient conditions. EnergyChem 2019, 1, 100011.
Crossref Google Scholar
[11]
Liu, X.; Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S. Z. Building up a picture of the electrocatalytic nitrogen reduction activity of transition metal single-atom catalysts. J. Am. Chem. Soc. 2019, 141, 9664-9672.
Google Scholar
[12]
Wang, J.; Yu, L.; Hu, L.; Chen, G.; Xin, H. L.; Feng, X. F. Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential. Nat. Commun. 2018, 9, 1795.
Google Scholar
[13]
Xie, H. T.; Geng, X.; Zhu, X. J.; Luo, Y. L.; Chang, L.; Niu, X. B.; Shi, X. F.; Asiri, A. M.; Gao, S. Y.; Wang, Z. M. et al. PdP2 nanoparticles-reduced graphene oxide for electrocatalytic N2 conversion to NH3 under ambient conditions. J. Mater. Chem. A 2019, 7, 24760-24764.
Google Scholar
[14]
Deng, G. R.; Wang, T.; Alshehri, A. A.; Alzahrani, K. A.; Wang, Y.; Ye, H. J.; Luo, Y. L.; Sun, X. P. Improving the electrocatalytic N2 reduction activity of Pd nanoparticles through surface modification. J. Mater. Chem. A 2019, 7, 21674-21677.
Google Scholar
[15]
Bao, D.; Zhang, Q.; Meng, F. L.; Zhong, H. X.; Shi, M. M.; Zhang, Y.; Yan, J. M.; Jiang, Q.; Zhang, X. B. Electrochemical reduction of N2 under ambient conditions for artificial N2 fixation and renewable energy storage using N2/NH3 Cycle. Adv. Mater. 2017, 29, 1604799.
Google Scholar
[16]
Huang, L. S.; Wu, J. W.; Han, P.; Al-Enizi, A. M.; Almutairi, T. M.; Zhang, L. J.; Zheng, G. F. NbO2 electrocatalyst toward 32% Faradaic efficiency for N2 fixation. Small Methods 2019, 3, 1800386.
Google Scholar
[17]
Huang, H.; Gong, F.; Wang, Y.; Wang, H. B.; Wu, X. F.; Lu, W. B.; Zhao, R. B.; Chen, H. Y.; Shi, X. F.; Asiri, A. M. et al. Mn3O4 nanoparticles@reduced graphene oxide composite: An efficient electrocatalyst for artificial N2 fixation to NH3 at ambient conditions. Nano Res. 2019, 12, 1093-1098.
Google Scholar
[18]
Zhang, S. B.; Zhao, C. J.; Liu, Y. Y.; Li, W. Y.; Wang, J. L.; Wang, G. Z.; Zhang, Y. X.; Zhang, H. M.; Zhao, H. J. Cu doping in CeO2 to form multiple oxygen vacancies for dramatically enhanced ambient N2 reduction performance. Chem. Commun. 2019, 55, 2952-2955.
Google Scholar
[19]
Zhang, L.; Xie, X. Y.; Wang, H. B.; Ji, L.; Zhang, Y.; Chen, H. Y.; Li, T. S.; Luo, Y. L.; Cui, G. L.; Sun, X. P. Boosting electrocatalytic N2 reduction by MnO2 with oxygen vacancies. Chem. Commun. 2019, 55, 4627-4630.
Google Scholar
[20]
Wu, T. W.; Kong, W. H.; Zhang, Y.; Xing, Z.; Zhao, J. X.; Wang, T.; Shi, X. F.; Luo, Y. L.; Sun, X. P. Greatly enhanced electrocatalytic N2 reduction on TiO2 via V doping. Small Methods 2019, 3, 1900356.
Google Scholar
[21]
Lv, C. D.; Yan, C. S.; Chen, G.; Ding, Y.; Sun, J. X.; Zhou, Y. S.; Yu, G. H. An amorphous noble-metal-free electrocatalyst that enables nitrogen fixation under ambient conditions. Angew. Chem., Int. Ed. 2018, 57, 6073-6076.
Google Scholar
[22]
Wu, T. W.; Zhu, X. J.; Xing, Z.; Mou, S. Y.; Li, C. B.; Qiao, Y. X.; Liu, Q.; Luo, Y. L.; Shi, X. F.; Zhang, Y. N. et al. Greatly improving electrochemical N2 reduction over TiO2 nanoparticles by iron doping. Angew. Chem., Int. Ed. 2019, 58, 18449-18453.
Google Scholar
[23]
Jiang, P.; Liu, Q.; Liang, Y. H.; Tian, J. Q.; Asiri, A. M.; Sun, X. P. A cost-effective 3D hydrogen evolution cathode with high catalytic activity: FeP nanowire array as the active phase. Angew. Chem., Int. Ed. 2014, 53, 12855-12859.
Google Scholar
[24]
Buscagan, T. M.; Oyala, P. H.; Peters, J. C. N2-to-NH3 conversion by a triphos-iron catalyst and enhanced turnover under photolysis. Angew. Chem., Int. Ed. 2017, 56, 6921.
Google Scholar
[25]
Chen, S. M.; Perathoner, S.; Ampelli, C.; Mebrahtu, C.; Su, D. S.; Centi, G. Room-temperature electrocatalytic synthesis of NH3 from H2O and N2 in a gas-liquid-solid three-phase reactor. ACS Sustainable Chem. Eng. 2017, 5, 7393-7400.
Google Scholar
[26]
Kong, J. M.; Lim, A.; Yoon, C.; Jang, J. H.; Ham, H. C.; Han, J.; Nam, S.; Kim, D.; Sung, Y. E.; Choi, J. et al. Electrochemical synthesis of NH3 at low temperature and atmospheric pressure using a γ-Fe2O3 catalyst. ACS Sustainable Chem. Eng. 2017, 5, 10986-10995.
Google Scholar
[27]
Cui, X. Y.; Tang, C.; Liu, X. M.; Wang, C.; Ma, W. J.; Zhang, Q. Highly-selective electrochemical reduction of dinitrogen to ammonia at ambient temperature and pressure over iron oxide catalysts. Chem.—Eur. J. 2018, 24, 18494-18501.
Google Scholar
[28]
Liu, Q.; Zhang, X. X.; Zhang, B.; Luo, Y. L.; Cui, G. W.; Xie, F. Y.; Sun, X. P. Ambient N2 fixation to NH3 electrocatalyzed by a spinel Fe3O4 nanorod. Nanoscale 2018, 10, 14386-14389.
Google Scholar
[29]
Hu, L.; Khaniya, A.; Wang, J.; Chen, G.; Kaden, W. E.; Feng, X. F. Ambient electrochemical ammonia synthesis with high selectivity on Fe/Fe oxide catalyst. ACS Catal. 2018, 8, 9312-9319.
Google Scholar
[30]
Xiang, X. J.; Wang, Z.; Shi, X. F.; Fan, M. K.; Sun, X. P. Ammonia synthesis from electrocatalytic N2 reduction under ambient conditions by Fe2O3 nanorods. ChemCatChem 2018, 10, 4530-4535.
Google Scholar
[31]
Suryanto, B. H. R.; Kang, C. S. M.; Wang, D. B.; Xiao, C. L.; Zhou, F. L.; Azofra, L. M.; Cavallo, L.; Zhang, X. Y.; MacFarlane, D. R. Rational electrode-electrolyte design for efficient ammonia electrosynthesis under ambient conditions. ACS Energy Lett. 2018, 3, 1219-1224.
Google Scholar
[32]
Chen, S. M.; Perathoner, S.; Ampelli, C.; Mebrahtu, C.; Su, D. S.; Centi, G. Electrocatalytic synthesis of ammonia at room temperature and atmospheric pressure from water and nitrogen on a carbon-nanotube-based electrocatalyst. Angew. Chem., Int. Ed. 2017, 56, 2699-2703.
Google Scholar
[33]
Zhang, M. β-FeOOH nanorods enriched with bulk chloride as lithium-ion battery cathodes. J. Alloys Compd. 2015, 648, 134-138.
Google Scholar
[34]
Jung, J.; Song, K.; Bae, D. R.; Lee, S. W.; Lee, G.; Kang, Y. M. β-FeOOH nanorod bundles with highly enhanced round-trip efficiency and extremely low overpotential for lithium-air batteries. Nanoscale 2013, 5, 11845-11849.
Google Scholar
[35]
Xiao, F.; Li, W. T.; Fang, L. P.; Wang, D. S. Synthesis of akageneite (beta-FeOOH)/reduced graphene oxide nanocomposites for oxidative decomposition of 2-chlorophenol by Fenton-like reaction. J. Hazard. Mater. 2016, 308, 11-20.
Google Scholar
[36]
Xiong, Y. J.; Xie, Y.; Chen, S. W.; Li, Z. Q. Fabrication of self-supported patterns of aligned β-FeOOH nanowires by a low-temperature solution reaction. Chem.—Eur. J. 2003, 9, 4991-4996.
Google Scholar
[37]
Zhu, X. J.; Liu, Z. C.; Liu, Q.; Luo, Y. L.; Shi, X. F.; Asiri, A. M.; Wu, Y. P.; Sun, X. P. Efficient and durable N2 reduction electrocatalysis under ambient conditions: β-FeOOH nanorods as a non-noble-metal catalyst. Chem. Commun. 2018, 54, 11332-11335.
Google Scholar
[38]
Zhu, X. J.; Liu, Z. C.; Wang, H. B.; Zhao, R. B.; Chen, H. Y.; Wang, T.; Wang, F. X.; Luo, Y. L.; Wu, Y. P.; Sun, X. P. Boosting electrocatalytic N2 reduction to NH3 on β-FeOOH by fluorine doping. Chem. Commun. 2019, 55, 3987-3990.
Google Scholar
[39]
Liu, J. Q.; Zheng, M. B.; Shi, X. Q.; Zeng, H. B.; Xia, H. Amorphous FeOOH quantum dots assembled mesoporous film anchored on graphene nanosheets with superior electrochemical performance for supercapacitors. Adv. Funct. Mater. 2016, 26, 919-930.
Google Scholar
[40]
Chemelewski, W. D.; Lee, H. C.; Lin, J. F.; Bard, A. J.; Mullins, C. B. Amorphous FeOOH oxygen evolution reaction catalyst for photoelectrochemical water splitting. J. Am. Chem. Soc. 2014, 136, 2843-2850.
Google Scholar
[41]
Kuang, L. Y.; Liu, Y. Y.; Fu, D. D.; Zhao, Y. P. FeOOH-graphene oxide nanocomposites for fluoride removal from water: Acetate mediated nano FeOOH growth and adsorption mechanism. J. Colloid Interface Sci. 2017, 490, 259-269.
Google Scholar
[42]
Hummers Jr., W. S.; Offeman, R. E. Preparation of graphictic oxide. J. Am. Chem. Soc. 1958, 80, 1339.
Google Scholar
[43]
Zhu, D.; Zhang, L. H.; Ruthe, R. E.; Hamers, R. J. Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nat. Mater. 2013, 12, 836-841.
Google Scholar
[44]
Watt, G. W.; Chrisp, J. D. Spectrophotometric method for the determination of hydrazine. Anal. Chem. 1952, 24, 2006-2008.
Google Scholar
[45]
Carvalho, A. P.; Meireles, L. A.; Malcata, F. X. Rapid spectrophotometric determination of nitrates and nitrites in marine aqueous culture media. Analusis 1998, 26, 347-351.
Google Scholar
[46]
Abdel-Samad, H.; Watson, P. R. An XPS study of the adsorption of chromate on goethite (a-FeOOH). Appl. Surf. Sci. 1997, 108, 371-377.
Google Scholar
[47]
Mikosch, H.; Uzunova, E. L.; Nikolov, G. St. Interaction of molecular nitrogen and oxygen with extraframework cations in zeolites with double six-membered rings of oxygen-bridged silicon and aluminum atoms: A DFT study. J. Phys. Chem. B 2005, 109, 11119-11125.
Google Scholar
[48]
Papai, I.; Goursot, A.; Fajula, F.; Plee, D.; Weber, J. Modeling of N2 and O2 adsorption in zeolites. J. Phys. Chem. 1995, 99, 12925-12932.
Google Scholar
[49]
Qiu, W. B.; Xie, X. Y.; Qiu, J. D.; Fang, W. H.; Liang, R. P.; Ren, X.; Ji, X. Q.; Cui, G. W.; Asiri, A. M.; Cui, G. L. et al. High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalyst. Nat. Commun. 2018, 9, 3485.
Google Scholar
[50]
Ren, X.; Zhao, J. X. ; Wei, Q.; Ma, Y. J.; Guo, H. R.; Liu, Q.; Wang, Y.; Cui, G. W.; Asiri, A. M.; Li, B. H. et al. High-performance N2-to-NH3 conversion electrocatalyzed by Mo2C nanorod. ACS Cent. Sci. 2019, 5, 116-121.
Google Scholar
Nano Research
Volume 13 Issue 1,
January 2020
Pages 209-214
DOI: 10.1007/s12274-019-2600-8
Cite this article:
Zhu X, Zhao J, Ji L, et al. FeOOH quantum dots decorated graphene sheet: An efficient electrocatalyst for ambient N2 reduction. Nano Research, 2020, 13(1): 209-214. https://doi.org/10.1007/s12274-019-2600-8
Topics:
Chlorine compoundsElectrocatalystsGrapheneLithium compoundsNanocrystalsSemiconductor quantum dots

688

Views

52

Crossref

N/A

Web of Science

48

Scopus

9

CSCD

Altmetrics
Received: 07 November 2019
Revised: 02 December 2019
Accepted: 07 December 2019
Published: 20 December 2019
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019
Return