SCIENCE CHINA Materials, Volume 63 , Issue 11 : 2314-2324(2020) https://doi.org/10.1007/s40843-020-1361-3

Heterophase engineering of SnO2/Sn3O4 drives enhanced carbon dioxide electrocatalytic reduction to formic acid

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  • ReceivedMar 17, 2020
  • AcceptedApr 17, 2020
  • PublishedJun 29, 2020


Funded by

We acknowledge the support from the National Natural Science Foundation of China(21573062,21631004,21901065)

the Natural Science Foundation of Heilongjiang Province(B2018008)

the Youth Science and Technology Innovation Team Project of Heilongjiang Province(2018-KYYWF-1593)

and the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(UNPYSCT-2018009)


We acknowledge the support from the National Natural Science Foundation of China (21573062, 21631004 and 21901065), the Natural Science Foundation of Heilongjiang Province (B2018008), the Youth Science and Technology Innovation Team Project of Heilongjiang Province (2018-KYYWF-1593), and the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province (UNPYSCT-2018009).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Wu J performed the experiments with help from Fu H, Ren Z and Wang G. Ren Z, Wu J and Fu H wrote this paper. All authors contributed to the general discussion.

Author information

Jun Wu received her BSc and MSc degrees from Heilongjiang University in 2013 and 2016, respectively. She is currently a PhD candidate in material science and engineering under the supervision of Prof. Guiling Wang and Prof. Honggang Fu at Harbin Engineering University. Her current research focuses on the design and synthesis of nanomaterials for energy conversion.

Zhiyu Ren received her BSc degree in 2001 and MSc degree in 2004 from Heilongjiang University. Then, she joined Heilongjiang University as an assistant professor. In 2008, she received her PhD degree from Jilin University. She became a full professor in 2014. Her interest focuses on the surface crystal engineering and defect regulation of advanced transition metal-based compounds and carbon-based nanocomposites for electrocatalysis (e.g., water splitting, carbon dioxide reduction, and organic smallmolecule oxidation).

Guiling Wang received his PhD in 2006 from the Institute of Chemical Engineering, Harbin Engineering University. He became a full professor at the College of Material Science and Chemical Engineering, Harbin Engineering University in 2007. His research interests focus on the design and controlled synthesis of electrode materials of NaBH4 fuel cells, H2O2 fuel cell, supercapacitors and lithium ion batteries.

Honggang Fu received his BSc degree in 1984 and MSc degree in 1987 from Jilin University. Then, he joined Heilongjiang University as an assistant professor. In 1999, he received his PhD degree from Harbin Institute of Technology. He became a full professor in 2000. Currently, he is a Cheung Kong Scholar. His interest focuses on the oxide-based semiconductor nanomaterials for solar energy conversion and photocatalysis, carbon-based nanomaterials for energy conversion and storage, and W(Mo,V)-based catalysts for HER and OER. Up to now, he has published over 300 peer-reviewed papers as corresponding author with more than 13,000 citations and H-index of 60.


Supplementary information

Experimental details and supporting data are available in the online version of the paper.


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  • Figure 1

    (a) Schematic illustration of the synthetic process for the heterophase SnO2/Sn3O4 nanosheets on CC. (b) XRD patterns of SnO2/Sn3O4, SnO2, and Sn3O4. (c–e) SEM, TEM and HRTEM images of SnO2/Sn3O4 on CC, respectively. The inset of (e) is the corresponding SAED pattern.

  • Figure 2

    (a, b) The high-resolution Sn 3d and O 1s XPS spectra of SnO2/Sn3O4, SnO2, and Sn3O4, respectively. (c) Sn L3-edge XANES spectra of SnO2/Sn3O4, SnO2, Sn3O4 and Sn foil. The inset is the pre-edge features of all samples. (d) Fourier transforms of k2-weighted EXAFS data for the Sn L3-edge of SnO2/Sn3O4, SnO2, Sn3O4 and Sn foil (without phase shift).

  • Figure 3

    (a) The LSV of SnO2/Sn3O4, SnO2 and Sn3O4 in Ar-saturated (dashed line) or CO2-saturated (solid line) 0.5 mol L−1 KHCO3 solution. (b) Potenital-dependent FEs of HCOOH, CO, and H2 for SnO2/Sn3O4, SnO2 and Sn3O4 under different applied potentials. (c) Partial current densities of HCOOH for three SnOx catalysts recorded under different applied potentials. (d) The chronoamperometry response and time-dependent FEHCOOH for SnO2/Sn3O4, SnO2 and Sn3O4 at −0.9 VRHE.

  • Figure 4

    (a) Surface-area-normalized current densities of SnO2/Sn3O4, SnO2 and Sn3O4 for HCOOH production, respectively. (b) Nyquist plots of SnO2/Sn3O4, SnO2 and Sn3O4 with the potential of −0.9 VRHE. The inset image is the equivalent circuit diagram. Rs and Rct represent the electrolyte and charge transfer resistance, respectively. (c) CO2-TPD profiles for SnO2/Sn3O4, SnO2 and Sn3O4. (d) Single oxidative LSV scans in Ar-saturated 0.5 mol L−1 KOH for SnO2/Sn3O4, SnO2 and Sn3O4.

  • Figure 5

    (a) DOS of the p- and sum-orbital of the SnOx catalysts. (b) Optimized adsorption configurations of CO2 on SnOx catalysts: (I) SnO2 (110) surface, (II) Sn3O4 (111) surface, and (III) SnO2 (110)/ Sn3O4 (111) surface; Sn: dark grey; O: red; C: light grey; H: white. (c) The calculated free energy diagrams of the electrocatalytic CO2RR into HCOOH without considering the effect of electrode potential (U=0 V).