Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters

Qing Tang, Yongjin Lee, Dai Ying Li, Woojun Choi, C. W. Liu, Dongil Lee, De En Jiang

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

Copper electrocatalysts can reduce CO2 to hydrocarbons at high overpotentials. However, a mechanistic understanding of CO2 reduction on nanostructured Cu catalysts has been lacking. Herein we show that the structurally precise ligand-protected Cu-hydride nanoclusters, such as Cu32H20L12 (L is a dithiophosphate ligand), offer unique selectivity for electrocatalytic CO2 reduction at low overpotentials. Our density functional theory (DFT) calculations predict that the presence of the negatively charged hydrides in the copper cluster plays a critical role in determining the selectivity of the reduction product, yielding HCOOH over CO with a lower overpotential. The HCOOH formation proceeds via the lattice-hydride mechanism: first, surface hydrides reduce CO2 to HCOOH product, and then the hydride vacancies are readily regenerated by the electrochemical proton reduction. DFT calculations further predict that hydrogen evolution is less competitive than HCOOH formation at the low overpotential. Confirming the predictions, electrochemical tests of CO2 reduction on the Cu32H20L12 cluster demonstrate that HCOOH is indeed the main product at low overpotential, while H2 production dominates at higher overpotential. The unique selectivity afforded by the lattice-hydride mechanism opens the door for further fundamental and applied studies of electrocatalytic CO2 reduction by copper-hydride nanoclusters and other metal nanoclusters that contain hydrides.

Original languageEnglish
Pages (from-to)9728-9736
Number of pages9
JournalJournal of the American Chemical Society
Volume139
Issue number28
DOIs
Publication statusPublished - 2017 Jul 19

Fingerprint

Nanoclusters
Hydrides
Copper
Ligands
Carbon Monoxide
Hydrocarbons
Protons
Hydrogen
Metals
Density functional theory
Electrocatalysts
Vacancies
Catalysts

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Tang, Qing ; Lee, Yongjin ; Li, Dai Ying ; Choi, Woojun ; Liu, C. W. ; Lee, Dongil ; Jiang, De En. / Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 28. pp. 9728-9736.
@article{f4c4facf2c4749bf9967038139d8f859,
title = "Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters",
abstract = "Copper electrocatalysts can reduce CO2 to hydrocarbons at high overpotentials. However, a mechanistic understanding of CO2 reduction on nanostructured Cu catalysts has been lacking. Herein we show that the structurally precise ligand-protected Cu-hydride nanoclusters, such as Cu32H20L12 (L is a dithiophosphate ligand), offer unique selectivity for electrocatalytic CO2 reduction at low overpotentials. Our density functional theory (DFT) calculations predict that the presence of the negatively charged hydrides in the copper cluster plays a critical role in determining the selectivity of the reduction product, yielding HCOOH over CO with a lower overpotential. The HCOOH formation proceeds via the lattice-hydride mechanism: first, surface hydrides reduce CO2 to HCOOH product, and then the hydride vacancies are readily regenerated by the electrochemical proton reduction. DFT calculations further predict that hydrogen evolution is less competitive than HCOOH formation at the low overpotential. Confirming the predictions, electrochemical tests of CO2 reduction on the Cu32H20L12 cluster demonstrate that HCOOH is indeed the main product at low overpotential, while H2 production dominates at higher overpotential. The unique selectivity afforded by the lattice-hydride mechanism opens the door for further fundamental and applied studies of electrocatalytic CO2 reduction by copper-hydride nanoclusters and other metal nanoclusters that contain hydrides.",
author = "Qing Tang and Yongjin Lee and Li, {Dai Ying} and Woojun Choi and Liu, {C. W.} and Dongil Lee and Jiang, {De En}",
year = "2017",
month = "7",
day = "19",
doi = "10.1021/jacs.7b05591",
language = "English",
volume = "139",
pages = "9728--9736",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "28",

}

Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters. / Tang, Qing; Lee, Yongjin; Li, Dai Ying; Choi, Woojun; Liu, C. W.; Lee, Dongil; Jiang, De En.

In: Journal of the American Chemical Society, Vol. 139, No. 28, 19.07.2017, p. 9728-9736.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters

AU - Tang, Qing

AU - Lee, Yongjin

AU - Li, Dai Ying

AU - Choi, Woojun

AU - Liu, C. W.

AU - Lee, Dongil

AU - Jiang, De En

PY - 2017/7/19

Y1 - 2017/7/19

N2 - Copper electrocatalysts can reduce CO2 to hydrocarbons at high overpotentials. However, a mechanistic understanding of CO2 reduction on nanostructured Cu catalysts has been lacking. Herein we show that the structurally precise ligand-protected Cu-hydride nanoclusters, such as Cu32H20L12 (L is a dithiophosphate ligand), offer unique selectivity for electrocatalytic CO2 reduction at low overpotentials. Our density functional theory (DFT) calculations predict that the presence of the negatively charged hydrides in the copper cluster plays a critical role in determining the selectivity of the reduction product, yielding HCOOH over CO with a lower overpotential. The HCOOH formation proceeds via the lattice-hydride mechanism: first, surface hydrides reduce CO2 to HCOOH product, and then the hydride vacancies are readily regenerated by the electrochemical proton reduction. DFT calculations further predict that hydrogen evolution is less competitive than HCOOH formation at the low overpotential. Confirming the predictions, electrochemical tests of CO2 reduction on the Cu32H20L12 cluster demonstrate that HCOOH is indeed the main product at low overpotential, while H2 production dominates at higher overpotential. The unique selectivity afforded by the lattice-hydride mechanism opens the door for further fundamental and applied studies of electrocatalytic CO2 reduction by copper-hydride nanoclusters and other metal nanoclusters that contain hydrides.

AB - Copper electrocatalysts can reduce CO2 to hydrocarbons at high overpotentials. However, a mechanistic understanding of CO2 reduction on nanostructured Cu catalysts has been lacking. Herein we show that the structurally precise ligand-protected Cu-hydride nanoclusters, such as Cu32H20L12 (L is a dithiophosphate ligand), offer unique selectivity for electrocatalytic CO2 reduction at low overpotentials. Our density functional theory (DFT) calculations predict that the presence of the negatively charged hydrides in the copper cluster plays a critical role in determining the selectivity of the reduction product, yielding HCOOH over CO with a lower overpotential. The HCOOH formation proceeds via the lattice-hydride mechanism: first, surface hydrides reduce CO2 to HCOOH product, and then the hydride vacancies are readily regenerated by the electrochemical proton reduction. DFT calculations further predict that hydrogen evolution is less competitive than HCOOH formation at the low overpotential. Confirming the predictions, electrochemical tests of CO2 reduction on the Cu32H20L12 cluster demonstrate that HCOOH is indeed the main product at low overpotential, while H2 production dominates at higher overpotential. The unique selectivity afforded by the lattice-hydride mechanism opens the door for further fundamental and applied studies of electrocatalytic CO2 reduction by copper-hydride nanoclusters and other metal nanoclusters that contain hydrides.

UR - http://www.scopus.com/inward/record.url?scp=85025088005&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85025088005&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b05591

DO - 10.1021/jacs.7b05591

M3 - Article

AN - SCOPUS:85025088005

VL - 139

SP - 9728

EP - 9736

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 28

ER -