Title: Understanding three-dimensionally interconnected porous oxide-derived copper electrocatalyst for selective carbon dioxide reduction

Abstract

In this study, we have investigated a hierarchical CuO-derived inverse opal (CuO-IO) catalyst with high CO selectivity up to 80–90% and minimal H₂ evolution at moderate potentials for CO₂ electroreduction. The three-dimensionally (3D) structured, porous catalyst was composed of small CuO nanoparticles and exhibited a peak CO faradaic efficiency (FE) of 72.5% (±1.8), complete suppression of H₂ formation, and good stability over 24 hours operation at –0.6 V versus the reversible hydrogen electrode (RHE). In situ Raman, X-ray absorption spectroscopy and X-ray diffraction measurements indicated reduction of the catalyst into metallic Cu0 oxidation state with dominant Cu(111) orientation under electrocatalytic conditions. We suggest that rapid depletion of CO₂ and protons at the highly roughened catalyst surface likely increased the local pH during the electrolysis. The combination of C₁ favoring Cu(111) surfaces and reduced local proton/CO₂ availability facilitated selective conversion of CO₂ into CO and reduced H₂ and C₂ products. Our work provides additional understanding of the structure–property relationships of 3D porous electrocatalysts for CO₂ reduction applications by evaluating the crystallographic orientation, oxidation state, and crystallite size of a CO-selective CuO-IO catalyst under realistic working conditions.

Authors:

Nguyen-Phan, Thuy-Duong  ^[1];

• Search DOE PAGES for author "Nguyen-Phan, Thuy-Duong"
• Search DOE PAGES for ORCID "0000-0002-6932-8851"

Wang, Congjun ^[1]; Marin, Chris M. ^[1]; Zhou, Yunyun ^[2]; Stavitski, Eli ^[3]; Popczun, Eric J. ^[2]; Yu, Yang ^[2]; Xu, Wenqian ^[4]; Howard, Bret H. ^[2]; Stuckman, Mengling Y. ^[1]; Waluyo, Iradwikanari  ^[3];

• Search DOE PAGES for author "Waluyo, Iradwikanari"
• Search DOE PAGES for ORCID "0000-0002-4046-9722"

Ohodnicki, Jr., Paul R. ^[2]; Kauffman, Douglas R.  ^[2]

• Search DOE PAGES for author "Kauffman, Douglas R."
• Search DOE PAGES for ORCID "0000-0002-7855-3428"

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+ Show Author Affiliations

1. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States); Leidos Research Support Team, Pittsburgh, PA (United States)
2. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
3. Brookhaven National Lab. (BNL), Upton, NY (United States)
4. Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:

Fri Dec 20 00:00:00 EST 2019

Research Org.:

Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Carnegie Mellon University; USDOE Office of Fossil Energy (FE)

OSTI Identifier:

1583111

Alternate Identifier(s):

OSTI ID: 1576679; OSTI ID: 1605136; OSTI ID: 1607748

Report Number(s):

BNL-213530-2020-JAAM
Journal ID: ISSN 2050-7488; JMCAET

Grant/Contract Number:  

SC0012704; AC02-06CH11357; 89243318CFE000003; MCF-677785

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Materials Chemistry. A

Additional Journal Information:

Journal Volume: 7; Journal Issue: 48; Journal ID: ISSN 2050-7488

Publisher:

Royal Society of Chemistry

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE