Strong interactions of metal-support for efficient reduction of carbon dioxide into ethylene

doi:10.1016/j.nanoen.2021.106460

Nano Energy

Volume 89, Part B, November 2021, 106460

https://doi.org/10.1016/j.nanoen.2021.106460 Get rights and content

Highlights

•
The scaffolding process enables the formation of inseparable interface structure.
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Such unique structure facilitates the electrocatalytic conversion of carbon dioxide into ethylene.
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The enhanced performance endows a high solar-to-fuel conversion efficiency for overall CO₂ splitting.

Abstract

Electroreduction of carbon dioxide (CO₂) into high value-added fuels and chemicals with excellent efficiency is an attractive but challenging route to alleviate energy crisis and environmental pollution. Here, the hollow Cu/CeO₂ nanotubes synthesized via the self-templated method display a high faradaic efficiency (FE) of 78.3% for the electrochemical reduction of CO₂ into ethylene (C₂H₄) in flow cell at a low applied potential of −0.7 V vs. RHE. The high reduction efficiency of Cu/CeO₂ nanotubes catalyst can be attributed to the synergistic effects from the formation of inseparable interface structure between Cu and CeO₂, which enhance the effective adsorption of intermediates. More importantly, the Cu/CeO₂ nanotubes catalyst also exhibits excellent performance (FE(C₂H₄) of 65.5%) in the solar-driven overall CO₂ splitting reaction with a conversion efficiency of 4.2%. The results demonstrate the rational regulation of metal-support interactions for improving electrocatalytic CO₂ reduction into multicarbon (C₂₊) products.

Graphical Abstract

Cu/CeO₂ nanotubes with inseparable interface structure endow a high faradaic efficiency for electrocatalytic reduction CO₂ into C₂H₄ via the rational regulation of metal-support interaction, which also enable the sustainable applications in solar-driven overall CO₂ splitting.

Introduction

Excessive consumption of traditional fossil resources has caused the increasing CO₂ level in atmosphere [1], [2]. The controllable reduction of CO₂ is a highly promising strategy to mitigating the consumption of fossil fuels and the CO₂ emission [3], [4], [5]. Among these approaches, the electrocatalytic CO₂ reduction reaction (CO₂RR) is more attractive because it can be carried out under relatively mild conditions in simple reaction devices [6], [7]. More importantly, CO₂RR has good compatibility and complementarity with renewable energy sources (such as solar energy, wind and water energy) [8], [9], [10]. It can convert the excess electric energy into chemical energy and/or obtain economically valuable reduction products. However, CO₂ as an extremely inert molecule, requires a high energy input for the chemical conversion [11]. At the same time, the competitive hydrogen evolution reaction (HER) in an aqueous electrolyte also limits the reduction efficiency [12], [13]. The tremendous efforts have been devoted to enhance CO₂RR, and have promoted efficient reduction of CO₂ into C₁ products (e.g., carbon monoxide (CO), formic acid (HCOOH)) with high FEs [14], [15], [16], [17]. However, the electrocatalytic conversion of CO₂ into a high value-added C₂₊ product beyond CO and HCOOH is more attractive and still challenging due to the low efficiency and selectivity.

Cu is the metal catalyst that can realize the C-C coupling reaction to generate C₂₊ products in the CO₂RR due to its proper adsorption energies for intermediates (e.g., *CO and *H) [18], [19]. However, the low catalytic activity, poor selectivity and insufficient stability towards C₂₊ products are major challenges for Cu-based electrocatalysts. To date, several strategies for designing Cu-based electrocatalysts with high C₂₊ products activities have been proposed, such as micro- and nanostructures [20], [21], crystal facet or grain boundaries [22], [23], [24], structural defects/vacancy engineering [25], doping [26], and interface regulation [27], [28]. However, the interactions between metal and support are seldom exploited. Metal-support interactions play a crucial impact in regulating the catalytic activity of heterogeneous catalysts. Support can not only improve the dispersion of metal, but also optimize the electronic structure of metal and properties of metal-support interface [29], [30]. As a basic and reducible metal oxide support, the formation of Ce³⁺ sites and oxygen vacancies on CeO₂ surface would facilitate CO₂ adsorption and the subsequent reduction. With the unique properties of CeO₂, it is desirable to develop the in-situ loading strategy for enhancing the metal-support interactions, which would improve the dispersion of Cu and catalytic efficiency for CO₂RR.

Herein we demonstrated the in-situ formation of hollow Cu/CeO₂ nanotubes through self-templated method and electrochemical reduction method. The obtained Cu/CeO₂ nanotubes with well-dispersed Cu among CeO₂ demonstrate excellent catalytic efficiency for electrocatalytic CO₂ into C₂H₄, the FE(C₂H₄) can reach up to 69.8% at H cell in 0.1 M K₂SO₄ electrolyte and 78.3% at flow cell in 1.0 M KOH electrolyte, respectively. When paired with CuO/Co₃O₄ nanotubes catalyst to form a two-electrode electrocatalytic CO₂ reduction cell, the solar-to-fuel conversion efficiency for electrochemical reduction of CO₂ into C₂H₄ reaction is up to 4.2%. The remarkable catalytic efficiency can be attributed to the synergistic effects between Cu and CeO₂ via the interactions of metal-support for effectively adsorption of intermediates. Furthermore, the confinement effect of porous nanotubes would regulate the micro-environment inside the Cu/CeO₂ catalyst for further promoting C-C coupling reaction. In addition, the structural defects and oxygen vacancies are introduced during in-situ electroreduction conversion, which can expose more active sites to improve CO₂RR performances of Cu/CeO₂ nanotubes catalyst.

Section snippets

Chemicals

CO₂ (>99.999% purity) and N₂ (99.99%) provided Jinan Deyang Gas Co., Ltd. Cupric nitrate hydrate (Cu(NO₃)₂.3H₂O), Cerium nitrate hexahydrate (Ce(NO₃)₃.6H₂O), Cobaltous nitrate hexahydrate (Co(NO₃)₂.6H₂O) and polyacrylonitrile (PAN) (Mw = 150,000) were purchased from J&K Scientific Co., Ltd. N,N-Dimethylformamide (DMF), ethylene glycol, ethanol potassium sulphate (K₂SO₄) and potassium hydroxide (KOH) were provided by Sinopharm Chemical Reagent Beijing Co., Ltd. Nafion N117 membrane, Nafion D-521

Results and discussion

The fabrication process of hollow metal oxide nanotubes is shown in Fig. 1a. Typically, polyacrylonitrile (PAN) nanofibers (Fig. S1) prepared via the electrospinning technique were used as the hard template to synthesize the composite nanofibers (Fig. 1b). Then, the hollow nanotubes were obtained by calcination in air atmosphere at 500 °C for 2 h to remove the PAN template. Scanning electron microscopy (SEM) image shows the fibrous structure with the rough surface of as-prepared samples (Fig. 1

Conclusion

In summary, we have demonstrated the controllable regulation on the composition and structure of Cu/CeO₂ nanotubes for CO₂RR. The as-prepared Cu/CeO₂ nanotubes catalyst exhibits the excellent selectivity for CO₂ reduction into C₂H₄, the FE(C₂H₄) can reach up to 69.8% at a H-cell and 78.3% at a flow cell in 1.0 M KOH electrolyte, respectively. The excellent catalytic performances can be attributed to catalyst structure and the synergistic effects at the interface between Cu and CeO₂. The Cu/CeO₂

CRediT authorship contribution statement

Dongxing Tan, Bari Wulan, Jintao Zhang: Conceived the project, Carried out the syntheses and structural characterizations. Dongxing Tan, Bari Wulan: Conducted the CO₂RR experiments. Xueying Cao: Provided the analyses of the XANES and EXAFS. Dongxing Tan, Jintao Zhang: Helped to write this manuscript. Jintao Zhang: Was responsible for the overall direction of the project. All the other authors participated in preparing the manuscript and contributed to the discussion.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was financially supported by the Natural Scientific Foundation of Shandong Province (ZR2020JR09), Taishan Scholars Program of Shandong Province (No. tsqn20161004), Project for Scientific Research Innovation Team of Young Scholar in Colleges, Universities of Shandong Province (2019KJC025), and the Fundamental Research Funds of Shandong University (ZY202006).

Dongxing Tan received his Ph.D. in 2020 from University of Chinese Academy of Sciences. Currently, he is a postdoctoral fellow in Prof. Zhang’s group at Shandong University. His research focuses on the carbon dioxide resource utilization, including electrocatalytic and photocatalytic carbon dioxide reduction.

References (51)

X. Wang et al.
Universal domino reaction strategy for mass production of single-atom metal-nitrogen catalysts for boosting CO₂ electroreduction
Nano Energy
(2021)
K. Ye et al.
Synergy effects on Sn-Cu alloy catalyst for efficient CO₂ electroreduction to formate with high mass activity
Sci. Bull.
(2020)
Y.-R. Wang et al.
Chloroplast-like porous bismuth-based core-shell structure for high energy efficiency CO₂ electroreduction
Sci. Bull.
(2020)
Y. Xia et al.
Identification of dual-active sites in cobalt phthalocyanine for electrochemical carbon dioxide reduction
Nano Energy
(2020)
Z. Gu et al.
Efficient electrocatalytic CO₂ reduction to C₂₊ alcohols at defect-site-rich cu surface
Joule
(2021)
M.V. Grabchenko et al.
The role of metal-support interaction in Ag/CeO₂ catalysts for CO and soot oxidation
Appl. Catal. B: Environ.
(2020)
Z. Xiao et al.
Engineering oxygen vacancies and nickel dispersion on CeO₂ by Pr doping for highly stable ethanol steam reforming
Appl. Catal. B: Environ.
(2019)
N. Kato et al.
A large-sized cell for solar-driven CO₂ conversion with a solar-to-formate conversion efficiency of 7.2%
Joule
(2021)
S. Zhang et al.
CO₂ reduction: from homogeneous to heterogeneous electrocatalysis
Acc. Chem. Res.
(2020)
W. Wang et al.
Intrinsic carbon-defect-driven electrocatalytic reduction of carbon dioxide
Adv. Mater.
(2019)

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Bari Wulan received his bachelor’s degree in 2014 from Guilin university of electronic technology and master’s degree in 2018 from the Department of Materials Science and Engineering, Jilin university. Currently, he is pursuing his Ph. D. degree under the supervision of Prof. Jintao Zhang. His research focuses on the development of cost-effective nanomaterials for electrocatalytic carbon dioxide reduction.

Xueying Cao received her bachelor’s degree in 2016 and master’s degree in 2019 from the Department of Materials Science and Engineering, Qingdao University, China. Currently, she is a doctoral student in Prof. Jintao Zhang’s group. Her current research is focused on non-noble metal-based materials for electrochemical carbon dioxide reduction.

Jintao Zhang obtained his Ph.D. from the Department of Chemical and Biomolecular Engineering at the University of Singapore in 2012. He was a postdoctoral fellow at Nanyang Technological University (Singapore) and Case Western Reserve University (USA). In fall 2015, he joined the School of Chemistry and Chemical Engineering, Shandong University as a full professor. His research interests include the rational design and synthesis of advanced materials for electrocatalysis, electrochemical energy storage, and conversion (e.g., Zn-air battery, halogen-based batteries, fuel cells, and supercapacitors).

View full text

Strong interactions of metal-support for efficient reduction of carbon dioxide into ethylene

Highlights

Abstract

Graphical Abstract

Introduction

Section snippets

Chemicals

Results and discussion

Conclusion

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgments

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