Selective CO Electroreduction to Ethylene and Multicarbon Alcohols Via Electrolyte-Driven Nanostructuring

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2019 Sep 3

PMID 31476272

Citations 27

Authors

Dunfeng Gao

Ilya Sinev

Fabian Scholten

Rosa M Aran-Ais

Nuria J Divins

Kristina Kvashnina

Janis Timoshenko

Beatriz Roldan Cuenya

Affiliations

Soon will be listed here.

Abstract

Production of multicarbon products (C ) from CO electroreduction reaction (CO RR) is highly desirable for storing renewable energy and reducing carbon emission. The electrochemical synthesis of CO RR catalysts that are highly selective for C products via electrolyte-driven nanostructuring is presented. Nanostructured Cu catalysts synthesized in the presence of specific anions selectively convert CO into ethylene and multicarbon alcohols in aqueous 0.1 m KHCO solution, with the iodine-modified catalyst displaying the highest Faradaic efficiency of 80 % and a partial geometric current density of ca. 31.2 mA cm for C products at -0.9 V vs. RHE. Operando X-ray absorption spectroscopy and quasi in situ X-ray photoelectron spectroscopy measurements revealed that the high C selectivity of these nanostructured Cu catalysts can be attributed to the highly roughened surface morphology induced by the synthesis, presence of subsurface oxygen and Cu species, and the adsorbed halides.

Citing Articles

Electrolyte Anions Suppress Hydrogen Generation in Electrochemical CO Reduction on Cu.

Fuller L, Zhang G, Noh S, Van Lehn R, Schreier M Angew Chem Int Ed Engl. 2024; 64(10):e202421196.

PMID: 39724507 PMC: 11878348. DOI: 10.1002/anie.202421196.

Direct low concentration CO electroreduction to multicarbon products via rate-determining step tuning.

Xie L, Cai Y, Jiang Y, Shen M, Chun-Ho Lam J, Zhu J Nat Commun. 2024; 15(1):10386.

PMID: 39613736 PMC: 11607466. DOI: 10.1038/s41467-024-54590-7.

Recent advances in microenvironment regulation for electrocatalysis.

Xu Z, Tan X, Chen C, Wang X, Sui R, Zhuang Z Natl Sci Rev. 2024; 11(12):nwae315.

PMID: 39554232 PMC: 11562841. DOI: 10.1093/nsr/nwae315.

Selectively electrolyzing CO to ethylene by a Cu-CuO/rGO catalyst derived from copper hydroxide nanostrands/graphene oxide nanosheets.

Peng C, Yao B, Wang L, Wan X RSC Adv. 2024; 14(49):36602-36609.

PMID: 39553279 PMC: 11566724. DOI: 10.1039/d4ra07259f.

Restructuring of Cu-based Catalysts during CO Electroreduction: Evidence for the Dominant Role of Surface Defects on the C Product Selectivity.

Rollier F, Muravev V, Parastaev A, van de Poll R, Heinrichs J, Ligt B ACS Catal. 2024; 14(17):13246-13259.

PMID: 39263539 PMC: 11385435. DOI: 10.1021/acscatal.4c02718.

References

Montoya J, Shi C, Chan K, Norskov J . Theoretical Insights into a CO Dimerization Mechanism in CO2 Electroreduction. J Phys Chem Lett. 2015; 6(11):2032-7. DOI: 10.1021/acs.jpclett.5b00722. View

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

Xiao H, Goddard 3rd W, Cheng T, Liu Y . Cu metal embedded in oxidized matrix catalyst to promote CO activation and CO dimerization for electrochemical reduction of CO. Proc Natl Acad Sci U S A. 2017; 114(26):6685-6688. PMC: 5495255. DOI: 10.1073/pnas.1702405114. View

Hirsch O, Kvashnina K, Luo L, Suess M, Glatzel P, Koziej D . High-energy resolution X-ray absorption and emission spectroscopy reveals insight into unique selectivity of La-based nanoparticles for CO₂. Proc Natl Acad Sci U S A. 2015; 112(52):15803-8. PMC: 4702991. DOI: 10.1073/pnas.1516192113. View

Weng Z, Wu Y, Wang M, Jiang J, Yang K, Huo S . Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat Commun. 2018; 9(1):415. PMC: 5788987. DOI: 10.1038/s41467-018-02819-7. View

Verdaguer-Casadevall A, Li C, Johansson T, Scott S, McKeown J, Kumar M . Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts. J Am Chem Soc. 2015; 137(31):9808-11. DOI: 10.1021/jacs.5b06227. View

Mistry H, Varela A, Bonifacio C, Zegkinoglou I, Sinev I, Choi Y . Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene. Nat Commun. 2016; 7:12123. PMC: 4931497. DOI: 10.1038/ncomms12123. View

Eilert A, Cavalca F, Roberts F, Osterwalder J, Liu C, Favaro M . Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction. J Phys Chem Lett. 2016; 8(1):285-290. DOI: 10.1021/acs.jpclett.6b02273. View

Ma S, Sadakiyo M, Heima M, Luo R, Haasch R, Gold J . Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu-Pd Catalysts with Different Mixing Patterns. J Am Chem Soc. 2016; 139(1):47-50. DOI: 10.1021/jacs.6b10740. View

10.

Zhou Y, Che F, Liu M, Zou C, Liang Z, De Luna P . Dopant-induced electron localization drives CO reduction to C hydrocarbons. Nat Chem. 2018; 10(9):974-980. DOI: 10.1038/s41557-018-0092-x. View

11.

Kim D, Kley C, Li Y, Yang P . Copper nanoparticle ensembles for selective electroreduction of CO to C-C products. Proc Natl Acad Sci U S A. 2017; 114(40):10560-10565. PMC: 5635920. DOI: 10.1073/pnas.1711493114. View

12.

Rahn B, Wen R, Deuchler L, Stremme J, Franke A, Pehlke E . Coadsorbate-Induced Reversal of Solid-Liquid Interface Dynamics. Angew Chem Int Ed Engl. 2018; 57(21):6065-6068. DOI: 10.1002/anie.201712728. View

13.

Huang Y, Ong C, Yeo B . Effects of Electrolyte Anions on the Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper (100) and (111) Surfaces. ChemSusChem. 2018; 11(18):3299-3306. DOI: 10.1002/cssc.201801078. View

14.

Aran-Ais R, Gao D, Cuenya B . Structure- and Electrolyte-Sensitivity in CO Electroreduction. Acc Chem Res. 2018; 51(11):2906-2917. DOI: 10.1021/acs.accounts.8b00360. View

15.

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

16.

Roberts F, Kuhl K, Nilsson A . High selectivity for ethylene from carbon dioxide reduction over copper nanocube electrocatalysts. Angew Chem Int Ed Engl. 2015; 54(17):5179-82. DOI: 10.1002/anie.201412214. View

17.

Seh Z, Kibsgaard J, Dickens C, Chorkendorff I, Norskov J, Jaramillo T . Combining theory and experiment in electrocatalysis: Insights into materials design. Science. 2017; 355(6321). DOI: 10.1126/science.aad4998. View

18.

Grosse P, Gao D, Scholten F, Sinev I, Mistry H, Cuenya B . Dynamic Changes in the Structure, Chemical State and Catalytic Selectivity of Cu Nanocubes during CO Electroreduction: Size and Support Effects. Angew Chem Int Ed Engl. 2018; 57(21):6192-6197. DOI: 10.1002/anie.201802083. View

19.

Gao D, Sinev I, Scholten F, Aran-Ais R, Divins N, Kvashnina K . Selective CO Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte-Driven Nanostructuring. Angew Chem Int Ed Engl. 2019; 58(47):17047-17053. PMC: 6899694. DOI: 10.1002/anie.201910155. View

20.

Gunter T, Carvalho H, Doronkin D, Sheppard T, Glatzel P, Atkins A . Structural snapshots of the SCR reaction mechanism on Cu-SSZ-13. Chem Commun (Camb). 2015; 51(44):9227-30. DOI: 10.1039/c5cc01758k. View