RESEARCH ARTICLE

Facile synthesis of hierarchical flower-like Ag/Cu2O and Au/Cu2O nanostructures and enhanced catalytic performance in electrochemical reduction of CO2

  • Mengyun Wang 1 ,
  • Shengbo Zhang 1 ,
  • Mei Li 1 ,
  • Aiguo Han 1 ,
  • Xinli Zhu 1 ,
  • Qingfeng Ge 1,2 ,
  • Jinyu Han 1 ,
  • Hua Wang , 1
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  • 1. Collaborative Innovation Center of Chemical Science and Engineering, Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
  • 2. Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, IL 62901, USA

Received date: 19 Mar 2019

Accepted date: 26 Apr 2019

Published date: 15 Oct 2020

Copyright

2019 Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature

Abstract

Novel, hierarchical, flower-like Ag/Cu2O and Au/Cu2O nanostructures were successfully fabricated and applied as efficient electrocatalysts for the electrochemical reduction of CO2. Cu2O nanospheres with a uniform size of ~180 nm were initially synthesized. Thereafter, Cu2O was used as a sacrificial template to prepare a series of Ag/Cu2O composites through galvanic replacement. By varying the Ag/Cu atomic ratio, Ag0.125/Cu2O, having a hierarchical, flower-like nanostructure with intersecting Ag nanoflakes encompassing an inner Cu2O sphere, was prepared. The as-prepared Agx/Cu2O samples presented higher Faradaic efficiencies (FE) for CO and relatively suppressed H2 evolution than the parent Cu2O nanospheres due to the combination of Ag with Cu2O in the former. Notably, the highest CO evolution rate was achieved with Ag0.125/Cu2O due to the larger electroactive surface area furnished by the hierarchical structure. The same hierarchical flower-like structure was also obtained for the Au0.6/Cu2O composite, where the FECO (10%) was even higher than that of Ag0.125/Cu2O. Importantly, the results reveal that Ag0.125/Cu2O and Au0.6/Cu2O both exhibit remarkably improved stability relative to Cu2O. This study presents a facile method of developing hierarchical metal-oxide composites as efficient and stable electrocatalysts for the electrochemical reduction of CO2.

Cite this article

Mengyun Wang , Shengbo Zhang , Mei Li , Aiguo Han , Xinli Zhu , Qingfeng Ge , Jinyu Han , Hua Wang . Facile synthesis of hierarchical flower-like Ag/Cu2O and Au/Cu2O nanostructures and enhanced catalytic performance in electrochemical reduction of CO2[J]. Frontiers of Chemical Science and Engineering, 2020 , 14(5) : 813 -823 . DOI: 10.1007/s11705-019-1854-8

Acknowledgements

We are grateful to the Analysis and Test Center of Tianjin University for providing XRD, SEM, and TEM characterization. We also acknowledge the National Natural Science Foundation of China (Grant Nos. 21576204 and 21206117) for financial support.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-019-1854-8 and is accessible for authorized users.
1
Jin Z, Li P, Liu G, Zheng B, Yuan H, Xiao D. Enhancing catalytic formaldehyde oxidation on CuO–Ag2O nanowires for gas sensing and hydrogen evolution. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(46): 14736–14743

DOI

2
Park J, Liu J, Peng H, Figueroa-Cosme L, Miao S, Choi S, Bao S, Yang X, Xia Y. Coating Pt–Ni octahedra with ultrathin Pt shells to enhance the durability without compromising the activity toward oxygen reduction. ChemSusChem, 2016, 9(16): 2209–2215

DOI

3
Liu H, Koenigsmann C, Adzic R R, Wong S S. Probing ultrathin one-dimensional Pd-Ni nanostructures as oxygen reduction reaction catalysts. ACS Catalysis, 2014, 4(8): 2544–2555

DOI

4
Wang Y, Zhang J. Structural engineering of transition metal-based nanostructured electrocatalysts for efficient water splitting. Frontiers of Chemical Science and Engineering, 2018, 12(4): 838–854

DOI

5
Qu X, Yang R, Tong F, Zhao Y, Wang M. Hierarchical ZnO microstructures decorated with Au nanoparticles for enhanced gas sensing and photocatalytic properties. Powder Technology, 2018, 330: 259–265

DOI

6
Su Y, Guo H, Wang Z, Long Y, Li W, Tu Y. Au@Cu2O core-shell structure for high sensitive non-enzymatic glucose sensor. Sensors and Actuators. B, Chemical, 2018, 255: 2510–2519

DOI

7
Pang M, Wang Q, Zeng H C. Self-Generated etchant for synthetic sculpturing of Cu2O-Au, Cu2O@Au, Au/Cu2O, and 3D-Au Nanostructures. Chemistry (Weinheim an der Bergstrasse, Germany), 2012, 18(46): 14605–14609

DOI

8
Rodrigues T S, Da Silva A G M, Alves R S, de Freitas I C, Oliveira D C, Camargo P H C. Controlling reduction kinetics in the galvanic replacement involving metal oxides templates: Elucidating the formation of bimetallic bowls, rattles, and dendrites from Cu2O Spheres. Particle & Particle Systems Characterization, 2018, 35(5): 1700175–1700184

DOI

9
Zhu H, Du M, Yu D, Wang Y, Zou M, Xu C, Fu Y. Selective growth of Au nanograins on specific positions (tips, edges and facets) of Cu2O octahedrons to form Cu2O–Au hierarchical heterostructures. Dalton Transactions (Cambridge, England), 2012, 41(45): 13795–13799

DOI

10
Polavarapu L, Zanaga D, Altantzis T, Rodal-Cedeira S, Pastoriza-Santos I, Pérez-Juste J, Bals S, Liz-Marzán L M. Galvanic replacement coupled to seeded growth as a route for shape-controlled synthesis of plasmonic nanorattles. Journal of the American Chemical Society, 2016, 138(36): 11453–11456

DOI

11
Zhu H, Du M L, Yu D L, Wang Y, Wang L N, Zou M L, Zhang M, Fu Y. A new strategy for the surface-free-energy-distribution induced selective growth and controlled formation of Cu2O–Au hierarchical heterostructures with a series of morphological evolutions. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(3): 919–929

DOI

12
Zhang Y, Zhou X, Zhao Y, Liu Z, Ma D, Chen S, Zhu G, Li X. One-step solvothermal synthesis of interlaced nanoflake-assembled flower-like hierarchical Ag/Cu2O composite microspheres with enhanced visible light photocatalytic properties. Royal Society of Chemistry Advances, 2017, 7(12): 6957–6965

DOI

13
Wang J, Wang H, Han Z, Han J. Electrodeposited porous Pb electrode with improved electrocatalytic performance for the electroreduction of CO2 to formic acid. Frontiers of Chemical Science and Engineering, 2015, 9(1): 57–63

DOI

14
Song G, Wu X, Xin F, Yin X. ZnFe2O4 deposited on BiOCl with exposed (001) and (010) facets for photocatalytic reduction of CO2 in cyclohexanol. Frontiers of Chemical Science and Engineering, 2017, 11(2): 197–204

DOI

15
Xie H, Wang J, Ithisuphalap K, Wu G, Li Q. Recent advances in Cu-based nanocomposite photocatalysts for CO2 conversion to solar fuels. Journal of Energy Chemistry, 2017, 26(6): 1039–1049

DOI

16
Qin T, Qian Y, Zhang F, Lin B. Cloride-derived copper electrode for efficient electrochemical reduction of CO2 to ethylene. Chinese Chemical Letters, 2019, 30(2): 314–318

DOI

17
He J, Johnson N J J, Huang A, Berlinguette C P. Electrocatalytic alloys for CO2 reduction. ChemSusChem, 2018, 11(1): 48–57

DOI

18
Singh S, Gautam R K, Malik K, Verma A. Ag-Co bimetallic catalyst for electrochemical reduction of CO2 to value added products. Journal of CO2 Utilization, 2017, 18: 139–146

19
Kim D, Resasco J, Yu Y, Asiri A M, Yang P. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles. Nature Communications, 2014, 5(1): 5948–5956

DOI

20
Yang J, Liu X, Cao H, Shi Y, Xie Y, Xiao J. Dendritic BiVO4 decorated with MnOx co-catalyst as an efficient hierarchical catalyst for photocatalytic ozonation. Frontiers of Chemical Science and Engineering, 2019, 13(1): 185–191

DOI

21
Zhang B, Zhang J. Rational design of Cu-based electrocatalysts for electrochemical reduction of carbon dioxide. Journal of Energy Chemistry, 2017, 26(6): 1050–1066

DOI

22
Kim J, Woo H, Yun S, Jung H, Back S, Jung Y, Kim Y. Highly active and selective Au thin layer on Cu polycrystalline surface prepared by galvanic displacement for the electrochemical reduction of CO2 to CO. Applied Catalysis B: Environmental, 2017, 213: 211–215

DOI

23
Kuo M, Hsiao C, Chiu Y, Lai T, Fang M, Wu J, Chen J, Wu C, Wei K, Lin H, Hsu Y. Au@Cu2O core@shell nanocrystals as dual-functional catalysts for sustainable environmental applications. Applied Catalysis B: Environmental, 2019, 242: 499–506

DOI

24
Lee S, Park G, Lee J. Importance of Ag-Cu biphasic boundaries for selective electrochemical reduction of CO2 to ethanol. ACS Catalysis, 2017, 7(12): 8594–8604

DOI

25
Jin W, Xu P, Xiong L, Jing Q, Zhang B, Sun K, Han X. SERS-active silver nanoparticle assemblies on branched Cu2O crystals through controlled galvanic replacement. Royal Society of Chemistry Advances, 2014, 4(96): 53543–53546

DOI

26
Chen S, Liu P, Su K, Li X, Qin Z, Xu W, Chen J, Li C, Qiu J. Electrochemical aptasensor for thrombin using co-catalysis of hemin/Gquadruplex DNAzyme and octahedral Cu2O-Au nanocomposites for signal amplification. Biosensors & Bioelectronics, 2018, 99: 338–345

DOI

27
Dai D, Liu H, Ma H, Huang Z, Gu C, Zhang M. In-situ synthesis of Cu2O-Au nanocomposites as nanozyme for colorimetric determination of hydrogen peroxide. Journal of Alloys and Compounds, 2018, 747: 676–683

DOI

28
Luo H, Zhou J, Zhong H, Zhou L, Jia Z, Tan X. Polyhedron Cu2O@Ag composite microstructures: Synthesis, mechanism analysis and structure dependent SERS properties. Royal Society of Chemistry Advances, 2016, 6(101): 99105–99113

DOI

29
Kandula S, Jeevanandam P. Synthesis of Cu2O@Ag polyhedral core–shell nanoparticles by a thermal decomposition approach for catalytic applications. European Journal of Inorganic Chemistry, 2016, 2016(10): 1548–1557

DOI

30
Wang Y, Gao T, Wang K, Wu X, Shi X, Liu Y, Lou S, Zhou S. Template-assisted synthesis of uniform nanosheet-assembled silver hollow microcubes. Nanoscale, 2012, 4(22): 7121–7126

DOI

31
Biesinger M C, Lau L W M, Gerson A R, Smart R S C. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn. Applied Surface Science, 2010, 257(3): 887–898

DOI

32
Li C W, Kanan M W. CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. Journal of the American Chemical Society, 2012, 134(17): 7231–7234

DOI

33
Raciti D, Livi K J, Wang C. Highly dense Cu nanowires for low-overpotential CO2 reduction. Nano Letters, 2015, 15(10): 6829–6835

DOI

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