Title: Electrocatalytic CO ₂ Reduction over Cu ₃ P Nanoparticles Generated via a Molecular Precursor Route

Abstract

The design of nanoparticles (NPs) with tailored morphologies and finely tuned electronic and physical properties has become a key strategy for controlling selectivity and improving conversion efficiency in a variety of important electrocatalytic transformations. Transition metal phosphide NPs, in particular, have emerged as a versatile class of catalytic materials due to their multifunctional active sites and composition- and phase-dependent properties. Access to targeted transition metal phosphide NPs with controlled features is necessary to tune the catalytic activity. To this end, we have established a solution-synthesis route utilizing a molecular precursor containing M–P bonds to generate solid metal phosphide NPs with controlled stoichiometry and morphology. Additionally, we expand here the application of molecular precursors in metal phosphide NP synthesis to include the preparation of phase-pure Cu₃P NPs from the thermal decomposition of [Cu(H)(PPh₃)]6. The mechanism of [Cu(H)(PPh₃)]₆ decomposition and subsequent formation of Cu3P was investigated through modification of the reaction parameters. Identification and optimization of the critical reaction parameters (i.e., time, temperature, and oleylamine concentration) enabled the synthesis of phase-pure 9–11 nm Cu₃P NPs. To probe the multifunctionality of this materials system, Cu₃P NPs were investigated as an electrocatalyst for CO₂ reduction. At low overpotential (-0.30 V versus RHE) in 0.1more » M KHCO₃ electrolyte, Cu₃P-modified carbon paper electrodes produced formate (HCOO-) at a maximum Faradaic efficiency of 8%.« less

Authors:

Downes, Courtney A.  ^[1];

• Search DOE PAGES for author "Downes, Courtney A."
• Search DOE PAGES for ORCID "0000-0001-8631-1579"

Libretto, Nicole J. ^[2]; Harman-Ware, Anne E. ^[3]; Happs, Renee M. ^[3]; Ruddy, Daniel A.  ^[1];

• Search DOE PAGES for author "Ruddy, Daniel A."
• Search DOE PAGES for ORCID "0000-0003-2654-3778"

Baddour, Frederick G.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-5837-5804"

Ferrell III, Jack R.  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-3041-8742"

Habas, Susan E.  ^[1];

• Search DOE PAGES for author "Habas, Susan E."
• Search DOE PAGES for ORCID "0000-0002-3893-8454"

Schaidle, Joshua A.  ^[1]

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• Search DOE PAGES for ORCID "0000-0003-2189-5678"

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+ Show Author Affiliations

1. Catalytic Carbon Transformation and Scale-Up Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
2. Davidson School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
3. Renewable Resources and Enabling Sciences Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States

Publication Date:

Tue Oct 27 00:00:00 EDT 2020

Research Org.:

National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF)

OSTI Identifier:

2316095

Alternate Identifier(s):

OSTI ID: 1713286

Report Number(s):

NREL/JA-5100-77006
Journal ID: ISSN 2574-0962

Grant/Contract Number:  

AC36-08GO28308; EEC1647722; AC02-06CH11357

Resource Type:

Published Article

Journal Name:

ACS Applied Energy Materials

Additional Journal Information:

Journal Name: ACS Applied Energy Materials Journal Volume: 3 Journal Issue: 11; Journal ID: ISSN 2574-0962

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon utilization; CO2 reduction; copper phosphide; electrocatalysis; metal phosphide nanoparticles