Selective Reduction of CO to Acetaldehyde with CuAg Electrocatalysts

Overview

Journal Proc Natl Acad Sci U S A

Specialty Science

Date 2020 Jan 26

PMID 31980521

Citations 14

Authors

Lei Wang

Drew C Higgins

Yongfei Ji

Carlos G Morales-Guio

Karen Chan

Christopher Hahn

Thomas F Jaramillo

Affiliations

Soon will be listed here.

Abstract

Electrochemical CO reduction can serve as a sequential step in the transformation of CO into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of -0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.

Citing Articles

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References

Cole E, Lakkaraju P, Rampulla D, Morris A, Abelev E, Bocarsly A . Using a one-electron shuttle for the multielectron reduction of CO2 to methanol: kinetic, mechanistic, and structural insights. J Am Chem Soc. 2010; 132(33):11539-51. DOI: 10.1021/ja1023496. View

Clark E, Hahn C, Jaramillo T, Bell A . Electrochemical CO Reduction over Compressively Strained CuAg Surface Alloys with Enhanced Multi-Carbon Oxygenate Selectivity. J Am Chem Soc. 2017; 139(44):15848-15857. DOI: 10.1021/jacs.7b08607. View

Gao D, Zhou H, Wang J, Miao S, Yang F, Wang G . Size-dependent electrocatalytic reduction of CO2 over Pd nanoparticles. J Am Chem Soc. 2015; 137(13):4288-91. DOI: 10.1021/jacs.5b00046. View

Resasco J, Chen L, Clark E, Tsai C, Hahn C, Jaramillo T . Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide. J Am Chem Soc. 2017; 139(32):11277-11287. DOI: 10.1021/jacs.7b06765. View

Liu M, Pang Y, Zhang B, De Luna P, Voznyy O, Xu J . Enhanced electrocatalytic CO reduction via field-induced reagent concentration. Nature. 2016; 537(7620):382-386. DOI: 10.1038/nature19060. View

Lee C, Yang K, Nam D, Jang J, Cho N, Im S . Defining a Materials Database for the Design of Copper Binary Alloy Catalysts for Electrochemical CO Conversion. Adv Mater. 2018; 30(42):e1704717. DOI: 10.1002/adma.201704717. View

Yoon Y, Hall A, Surendranath Y . Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels. Angew Chem Int Ed Engl. 2016; 55(49):15282-15286. DOI: 10.1002/anie.201607942. View

Schouten K, Qin Z, Perez Gallent E, Koper M . Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes. J Am Chem Soc. 2012; 134(24):9864-7. DOI: 10.1021/ja302668n. View

Liu X, Xiao J, Peng H, Hong X, Chan K, Norskov J . Understanding trends in electrochemical carbon dioxide reduction rates. Nat Commun. 2017; 8:15438. PMC: 5458145. DOI: 10.1038/ncomms15438. View

10.

Li C, Ciston J, Kanan M . Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature. 2014; 508(7497):504-7. DOI: 10.1038/nature13249. View

11.

Kortlever R, Shen J, Schouten K, Calle-Vallejo F, Koper M . Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide. J Phys Chem Lett. 2016; 6(20):4073-82. DOI: 10.1021/acs.jpclett.5b01559. View

12.

Ren D, Fong J, Yeo B . The effects of currents and potentials on the selectivities of copper toward carbon dioxide electroreduction. Nat Commun. 2018; 9(1):925. PMC: 5834446. DOI: 10.1038/s41467-018-03286-w. View

13.

Reske R, Mistry H, Behafarid F, Cuenya B, Strasser P . Particle size effects in the catalytic electroreduction of CO₂ on Cu nanoparticles. J Am Chem Soc. 2014; 136(19):6978-86. DOI: 10.1021/ja500328k. View

14.

Rasul S, Anjum D, Jedidi A, Minenkov Y, Cavallo L, Takanabe K . A highly selective copper-indium bimetallic electrocatalyst for the electrochemical reduction of aqueous CO2 to CO. Angew Chem Int Ed Engl. 2014; 54(7):2146-50. DOI: 10.1002/anie.201410233. View

15.

Huan T, Simon P, Rousse G, Genois I, Artero V, Fontecave M . Porous dendritic copper: an electrocatalyst for highly selective CO reduction to formate in water/ionic liquid electrolyte. Chem Sci. 2017; 8(1):742-747. PMC: 5299793. DOI: 10.1039/c6sc03194c. View

16.

He J, Dettelbach K, Huang A, Berlinguette C . Brass and Bronze as Effective CO Reduction Electrocatalysts. Angew Chem Int Ed Engl. 2017; 56(52):16579-16582. DOI: 10.1002/anie.201709932. View

17.

Perez-Gallent E, Figueiredo M, Calle-Vallejo F, Koper M . Spectroscopic Observation of a Hydrogenated CO Dimer Intermediate During CO Reduction on Cu(100) Electrodes. Angew Chem Int Ed Engl. 2017; 56(13):3621-3624. DOI: 10.1002/anie.201700580. View

18.

Kuhl K, Hatsukade T, Cave E, Abram D, Kibsgaard J, Jaramillo T . Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. J Am Chem Soc. 2014; 136(40):14107-13. DOI: 10.1021/ja505791r. View

19.

Rosen B, Salehi-Khojin A, Thorson M, Zhu W, Whipple D, Kenis P . Ionic liquid-mediated selective conversion of CO₂ to CO at low overpotentials. Science. 2011; 334(6056):643-4. DOI: 10.1126/science.1209786. View

20.

Weng Z, Zhang X, Wu Y, Huo S, Jiang J, Liu W . Self-Cleaning Catalyst Electrodes for Stabilized CO Reduction to Hydrocarbons. Angew Chem Int Ed Engl. 2017; 56(42):13135-13139. DOI: 10.1002/anie.201707478. View