Tuning the catalytic selectivity in electrochemical CO<sub>2</sub> reduction on copper oxide-derived nanomaterials

doi:10.1007/s11783-014-0742-1

Front. Environ. Sci. Eng.

2015, Vol. 9

Issue (5) : 861-866 https://doi.org/10.1007/s11783-014-0742-1

RESEARCH ARTICLE

Tuning the catalytic selectivity in electrochemical CO₂ reduction on copper oxide-derived nanomaterials

Jiafang XIE,Yuxi HUANG,Hanqing YU(

)

Department of Chemistry, University of Science and Technology of China, Hefei 230026, China

Download: PDF(853 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Electrochemical conversion of CO₂ to hydrocarbons can relieve both environmental and energy stresses. However, electrocatalysts for this reaction usually suffer from a poor product selectivity and a large overpotential. Here we report that tunable catalytic selectivity for hydrocarbon formation could be achieved on Cu nanomaterials with different morphologies. By tuning the electrochemical parameters, either Cu oxide nanowires or nanoneedles were fabricated and then electrochemically reduced to the corresponding Cu nanomaterials. The Cu nanowires preferred the formation of C₂H₄, while the Cu nanoneedles favored the production of more CH₄, rather than C₂H₄. Our work provides a facile synthetic strategy for preparing Cu-based nanomaterials to achieve selective CO₂ reduction.

Keywords electrochemical CO₂ reduction, Cu oxide, nanostructure, selectivity hydrocarbon formation

Corresponding Author(s): Hanqing YU

Issue Date: 08 October 2015

Cite this article:

Jiafang XIE,Yuxi HUANG,Hanqing YU. Tuning the catalytic selectivity in electrochemical CO₂ reduction on copper oxide-derived nanomaterials[J]. Front. Environ. Sci. Eng., 2015, 9(5): 861-866.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-014-0742-1
https://academic.hep.com.cn/fese/EN/Y2015/V9/I5/861

Fig.1 SEM images (a, d), XPS spectra (b, e), and AES spectra (c, f) of the Cu oxide nanomaterials. (a), (b), (c) belonged to Cu oxide NWs, and (d), (e), (f) belonged to Cu oxide NNs

Fig.2 Comparison of the CO₂ reduction activities on Cu NWs and NNs in the solution of 0.1 mol·L⁻¹ KHCO₃ at 10°C. (a) FEs for CH₄ and C₂H₄, (b) FEs for H₂ and HCOOH, (c) total current density, and (d) LSV of the two electrodes after catalysis from+ 0.5 V to −1.3 V with a scan rate of 2 mV·s⁻¹

Fig.3 The FE ratios of CH₄ and C₂H₄ in total hydrocarbons on Cu NWs (a) and Cu NNs (b)

1	Ballantyne A P, Alden C B, Miller J B, Tans P P, White J W. Increase in observed net carbon dioxide uptake by land and oceans during the past 50 years. Nature, 2012, 488(7409): 70–72 https://doi.org/10.1038/nature11299 pmid: 22859203
2	Parkinson B A, Weaver P F. Photoelectrochemical pumping of enzymatic CO2 reduction. Nature, 1984, 309(5964): 148–149 https://doi.org/10.1038/309148a0
3	Behrens M, Studt F, Kasatkin I, Kühl S, Hävecker M, Abild-Pedersen F, Zander S, Girgsdies F, Kurr P, Kniep B L, Tovar M, Fischer R W, Nørskov J K, Schlögl R. The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science, 2012, 336(6083): 893–897 https://doi.org/10.1126/science.1219831 pmid: 22517324
4	Chen Z, Deng S, Wei H, Wang B, Huang J, Yu G. Activated carbons and amine-modified materials for carbon dioxide capture — a review. Frontiers of Environmental Science & Engineering, 2013, 7(3): 326–340 https://doi.org/10.1007/s11783-013-0510-7
5	Oloman C, Li H. Electrochemical processing of carbon dioxide. ChemSusChem, 2008, 1(5): 385–391 https://doi.org/10.1002/cssc.200800015 pmid: 18702129
6	Kondratenko E V, Mul G, Baltrusaitis J, Larrazabal G O, Perez-Ramirez J. Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes. Energy & Environmental Science, 2013, 6(11): 3112–3135 https://doi.org/10.1039/c3ee41272e
7	Kumar B, Asadi M, Pisasale D, Sinha-Ray S, Rosen B A, Haasch R, Abiade J, Yarin A L, Salehi-Khojin A. Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction. Nature Communications, 2013, 4: 2819–2826 https://doi.org/10.1038/ncomms3819 pmid: 24292103
8	Studt F, Sharafutdinov I, Abild-Pedersen F, Elkjær C F, Hummelshøj J S, Dahl S, Chorkendorff I, Nørskov J K. Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol. Nature Chemistry, 2014, 6(4): 320–324 https://doi.org/10.1038/nchem.1873 pmid: 24651199
9	Lu Q, Rosen J, Zhou Y, Hutchings G S, Kimmel Y C, Chen J G, Jiao F. A selective and efficient electrocatalyst for carbon dioxide reduction. Nature Communications, 2014, 5: 3242–3247 https://doi.org/10.1038/ncomms4242 pmid: 24476921
10	Azuma M, Hashimoto K, Hiramoto M, Watanabe M, Sakata T. Electrochemical reduction of carbon dioxide on various metal electrodes in low-temperature aqueous KHCO3 media. Journal of the Electrochemical Society, 1990, 137(6): 1772–1778 https://doi.org/10.1149/1.2086796
11	Hori Y. Electrochemical CO2 reduction on metal electrodes. In: Vayenas C, White R, Gamboa-Aldeco M, eds. Modern Aspects of Electrochemistry. New York: Springer, 2008, 89–189
12	Wasmus S, Cattaneo E, Vielstich W. Reduction of carbon dioxide to methane and ethene — An on-line MS study with rotating electrodes. Electrochimica Acta, 1990, 35(4): 771–775 https://doi.org/10.1016/0013-4686(90)90014-Q
13	Jermann B, Augustynski J. Long-term activation of the copper cathode in the course of CO2 reduction. Electrochimica Acta, 1994, 39(11−12): 1891–1896 https://doi.org/10.1016/0013-4686(94)85181-6
14	Hori Y, Takahashi I, Koga O, Hoshi N. Selective formation of C2 compounds from electrochemical reduction of CO2 at a series of copper single crystal electrodes. Journal of Physical Chemistry B, 2002, 106(1): 15–17 https://doi.org/10.1021/jp013478d
15	Hori Y, Takahashi I, Koga O, Hoshi N. Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes. Journal of Molecular Catalysis A Chemical, 2003, 199(1−2): 39–47 https://doi.org/10.1016/S1381-1169(03)00016-5
16	Schouten K J P, Kwon Y, van der Ham C J M, Qin Z, Koper M T M. A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes. Chemical Science, 2011, 2(10): 1902–1909 https://doi.org/10.1039/c1sc00277e
17	Durand W J, Peterson A A, Studt F, Abild-Pedersen F, Nørskov J K. Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces. Surface Science, 2011, 605(15−16): 1354–1359 https://doi.org/10.1016/j.susc.2011.04.028
18	Schouten K J P, Pérez Gallent E, Koper M T M. Structure sensitivity of the electrochemical reduction of carbon monoxide on copper single crystals. ACS Catalysis, 2013, 3(6): 1292–1295 https://doi.org/10.1021/cs4002404
19	Reske R, Duca M, Oezaslan M, Schouten K J, Koper M T, Strasser P. Controlling catalytic selectivities during CO2 electroreduction on thin Cu metal overlayers. Journal of Physical Chemistry Letters, 2013, 4(15): 2410–2413 https://doi.org/10.1021/jz401087q
20	Tang W, Peterson A A, Varela A S, Jovanov Z P, Bech L, Durand W J, Dahl S, Nørskov J K, Chorkendorff I. The importance of surface morphology in controlling the selectivity of polycrystalline copper for CO2 electroreduction. Physical Chemistry Chemical Physics, 2012, 14(1): 76–81 https://doi.org/10.1039/c1cp22700a pmid: 22071504
21	Watanabe M, Shibata M, Kato A, Azuma M, Sakata T. Design of alloy electrocatalysts for CO2 reduction 3: the selectivity and reversible reduction of CO2 on Cu alloy electrodes. Journal of the Electrochemical Society, 1991, 128(11): 3382–3389 https://doi.org/10.1149/1.2085417
22	Kauffman D R, Ohodnicki P R, Kail B W, Matranga C. Selective electrocatalytic activity of ligand stabilized copper oxide nanoparticles. Journal of Physical Chemistry Letters, 2011, 2(16): 2038–2043 https://doi.org/10.1021/jz200850y
23	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 https://doi.org/10.1021/ja3010978 pmid: 22506621
24	Gonçalves M R, Gomes A, Condeço J, Fernandes T R C, Pardal T, Sequeira C A C, Branco J B. Electrochemical conversion of CO2 to C2 hydrocarbons using different ex situ copper electrodeposits. Electrochimica Acta, 2013, 102: 388–392 https://doi.org/10.1016/j.electacta.2013.04.015
25	Le M, Ren M, Zhang Z, Sprunger P T, Kurtz R L, Flake J C. Electrochemical reduction of CO2 to CH3OH at copper oxide surfaces. Journal of the Electrochemical Society, 2011, 158(5): E45–E49 https://doi.org/10.1149/1.3561636
26	Gattrell M, Gupta N, Co A. A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper. Journal of Electroanalytical Chemistry, 2006, 594(1): 1–19 https://doi.org/10.1016/j.jelechem.2006.05.013
27	Peterson A A, Abild-Pedersen F, Studt F, Rossmeisl J, Nørskov J K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy & Environmental Science, 2010, 3(9): 1311–1315 https://doi.org/10.1039/c0ee00071j
28	Yano J, Yamasaki S. Pulse-mode electrochemical reduction of carbon dioxide using copper and copper oxide electrodes for selective ethylene formation. Journal of Applied Electrochemistry, 2008, 38(12): 1721–1726 https://doi.org/10.1007/s10800-008-9622-3

Viewed

Full text

Abstract

Cited

Shared

Discussed