CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives

Han, Zhiji; Kortlever, Ruud; Chen, Hsiang-Yun; Peters, Jonas C.; Agapie, Theodor

doi:10.1021/acscentsci.7b00180

Title: CO₂ Reduction Selective for C_≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives

Journal Article · Fri Jul 21 00:00:00 EDT 2017 · ACS Central Science

DOI:https://doi.org/10.1021/acscentsci.7b00180· OSTI ID:1372119

Han, Zhiji ^[1]; Kortlever, Ruud ^[1]; Chen, Hsiang-Yun ^[1]; Peters, Jonas C. ^[1];

^[1]

Division of Chemistry and Chemical Engineering and Joint Center for Artificial Photosynthesis, California Institute of Technology, Pasadena, California 91125, United States

Electrocatalytic CO₂ reduction to generate multicarbon products is of interest for applications in artificial photosynthetic schemes. This is a particularly attractive goal for CO₂ reduction by copper electrodes, where a broad range of hydrocarbon products can be generated but where selectivity for C–C coupled products relative to CH₄ and H₂ remains an impediment. Herein we report a simple yet highly selective catalytic system for CO₂ reduction to C_≥2 hydrocarbons on a polycrystalline Cu electrode in bicarbonate aqueous solution that uses N-substituted pyridinium additives. Selectivities of 70–80% for C₂ and C₃ products with a hydrocarbon ratio of C_≥2/CH₄ significantly greater than 100 have been observed with several additives. ¹³C-labeling studies verify CO₂ to be the sole carbon source in the C_≥2 hydrocarbons produced. Upon electroreduction, the N-substituted pyridinium additives lead to film deposition on the Cu electrode, identified in one case as the reductive coupling product of N-arylpyridinium. As a result, product selectivity can also be tuned from C_≥2 species to H₂ (~90%) while suppressing methane with certain N-heterocyclic additives.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0004993

OSTI ID:: 1372119

Alternate ID(s):: OSTI ID: 1417626

Journal Information:: ACS Central Science, Journal Name: ACS Central Science; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 162 works

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Title: CO₂ Reduction Selective for C_≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives