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

doi:10.1007/s11705-019-1854-8

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (5) : 813-823 https://doi.org/10.1007/s11705-019-1854-8

RESEARCH ARTICLE

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

Mengyun Wang¹, Shengbo Zhang¹, Mei Li¹, Aiguo Han¹, Xinli Zhu¹, Qingfeng Ge^1,², Jinyu Han¹, Hua Wang¹(

)

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

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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, Ag_0.125/Cu₂O, having a hierarchical, flower-like nanostructure with intersecting Ag nanoflakes encompassing an inner Cu₂O sphere, was prepared. The as-prepared Ag_x/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 Ag_0.125/Cu₂O due to the larger electroactive surface area furnished by the hierarchical structure. The same hierarchical flower-like structure was also obtained for the Au_0.6/Cu₂O composite, where the FE_CO (10%) was even higher than that of Ag_0.125/Cu₂O. Importantly, the results reveal that Ag_0.125/Cu₂O and Au_0.6/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.

Keywords bimetallic nanostructure hierarchical metal/oxide nanomaterial galvanic replacement electrochemical reduction of CO₂

Corresponding Author(s): Hua Wang

Just Accepted Date: 24 October 2019 Online First Date: 02 January 2020 Issue Date: 25 May 2020

Cite this article:

Mengyun Wang,Shengbo Zhang,Mei Li, et al. Facile synthesis of hierarchical flower-like Ag/Cu₂O and Au/Cu₂O nanostructures and enhanced catalytic performance in electrochemical reduction of CO₂[J]. Front. Chem. Sci. Eng., 2020, 14(5): 813-823.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1854-8
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I5/813

Fig.1 Scheme 1 Schematic illustration of synthesis of Cu₂O and Ag/Cu₂O composites.

Fig.2 (a) SEM and (b) HRTEM images of Cu₂O nanospheres, (c) SEM image and (d) HRTEM image of Ag_0.125/Cu₂O, and (e) element mapping images of Cu, Ag, and O in Ag_0.125/Cu₂O.

Fig.3 SEM images of Ag/Cu₂O composites with different Ag/Cu atomic ratios: (a) Ag_0.25/Cu₂O, (b) Ag_0.5/Cu₂O, (c) Ag₁/Cu₂O, and (d) element mapping of Cu, Ag, and O in Ag_0.25/Cu₂O.

Fig.4 XRD patterns of Cu₂O nanospheres and Ag_x/Cu₂O composites.

Fig.5 (a) XPS spectrum of the flower-like hierarchical Ag_0.125/Cu₂O composite; enlarged spectra of (b) Ag 3d, (c) Cu 2p, (d) and O 1s.

Fig.6 LSV curves of (a) Cu₂O, (b) Ag_0.125/Cu₂O, (c) Ag_0.25/Cu₂O, (d) Ag_0.5/Cu₂O, (e) Ag₁/Cu₂O, and (f) partial current density for CO₂ reduction.

Fig.7 FEs of each product from CO₂ reduction catalyzed by (a) Cu₂O, (b) Ag_0.125/Cu₂O, (c) Ag_0.25/Cu₂O, (d) Ag_0.5/Cu₂O, (e) Ag₁/Cu₂O; (f) CO evolution rate over Ag_x/Cu₂O composites at ?1.0 V vs. RHE in CO₂-saturated 0.1 mol?L^?¹KHCO₃ over the course of 5 h.

Fig.8 Profiles of current density and Faradaic efficiency of H₂, CO, and HCOOH on Cu₂O and Ag_x/Cu₂O at -1.0 V in CO₂-saturated 0.1 mol?L^?¹ KHCO₃ solution over the course of 5 h.

Fig.9 (a) SEM images of hierarchical flower-like Au/Cu₂O composite, (b) XRD patterns of Au/Cu₂O composite, (c) LSV curves of Au/Cu₂O composite, and (d) profiles of current density and FC of H₂, CO, and HCOOH on Au/Cu₂O at 1.0 V in CO₂-saturated 0.1 mol?L^?¹KHCO₃solution over the course of 5 h.

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