Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts

Meyan Cui, Xingyu Ding, Xiaochun Huang, Zechao Shen, Tien-Lin Lee, Freddy Oropeza Palacio (Corresponding author), Jan Philipp Hofmann, Emiel Hensen, Kelvin H.L. Zhang (Corresponding author)

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Uittreksel

This work reports a systematical study on the relationship of electronic structure to oxygen evolution reaction (OER) activity of NixCo3-xO4 (x = 0-1) mixed oxides. The specific OER activity is substantially increased by 16 times from 0.02 mA cm-2 BET for pure Co3O4 to 0.32 mA cm-2 BET for x = 1 at an overpotential of 0.4 V and exhibits a strong correlation with the amount of Ni ions in the +3 oxidation state. X-ray spectroscopic study reveals that inclusion of Ni3+ ions upshifts the occupied valence band maximum (VBM) by 0.27 eV toward the Fermi level (EF), and creates a new hole (unoccupied) state located ∼1 eV above the EF. Such electronic features favor the adsorption of OH surface intermediates on NixCo3-xO4, resulting in enhanced OER. Furthermore, the emerging hole state effectively reduces the energy barrier for electron transfer from 1.19 to 0.39 eV, and thereby improves the kinetics for OER. The electronic structure features that lead to a higher OER in NixCo3-xO4 can be extended to other transition metal oxides for rational design of highly active catalysts.

TaalEngels
Pagina's7618-7625
TijdschriftChemistry of Materials
Volume31
Nummer van het tijdschrift18
Vroegere onlinedatum2019
DOI's
StatusGepubliceerd - 22 aug 2019

Vingerafdruk

Electrocatalysts
Oxygen
Oxides
Electronic structure
Ions
Energy barriers
Valence bands
Fermi level
Transition metals
Adsorption
X rays
Oxidation
Catalysts
Kinetics
Electrons

Citeer dit

Cui, M., Ding, X., Huang, X., Shen, Z., Lee, T-L., Oropeza Palacio, F., ... Zhang, K. H. L. (2019). Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts. Chemistry of Materials, 31(18), 7618-7625. DOI: 10.1021/acs.chemmater.9b02453
Cui, Meyan ; Ding, Xingyu ; Huang, Xiaochun ; Shen, Zechao ; Lee, Tien-Lin ; Oropeza Palacio, Freddy ; Hofmann, Jan Philipp ; Hensen, Emiel ; Zhang, Kelvin H.L./ Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts. In: Chemistry of Materials. 2019 ; Vol. 31, Nr. 18. blz. 7618-7625
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title = "Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts",
abstract = "This work reports a systematical study on the relationship of electronic structure to oxygen evolution reaction (OER) activity of NixCo3-xO4 (x = 0-1) mixed oxides. The specific OER activity is substantially increased by 16 times from 0.02 mA cm-2 BET for pure Co3O4 to 0.32 mA cm-2 BET for x = 1 at an overpotential of 0.4 V and exhibits a strong correlation with the amount of Ni ions in the +3 oxidation state. X-ray spectroscopic study reveals that inclusion of Ni3+ ions upshifts the occupied valence band maximum (VBM) by 0.27 eV toward the Fermi level (EF), and creates a new hole (unoccupied) state located ∼1 eV above the EF. Such electronic features favor the adsorption of OH surface intermediates on NixCo3-xO4, resulting in enhanced OER. Furthermore, the emerging hole state effectively reduces the energy barrier for electron transfer from 1.19 to 0.39 eV, and thereby improves the kinetics for OER. The electronic structure features that lead to a higher OER in NixCo3-xO4 can be extended to other transition metal oxides for rational design of highly active catalysts.",
author = "Meyan Cui and Xingyu Ding and Xiaochun Huang and Zechao Shen and Tien-Lin Lee and {Oropeza Palacio}, Freddy and Hofmann, {Jan Philipp} and Emiel Hensen and Zhang, {Kelvin H.L.}",
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Cui, M, Ding, X, Huang, X, Shen, Z, Lee, T-L, Oropeza Palacio, F, Hofmann, JP, Hensen, E & Zhang, KHL 2019, 'Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts' Chemistry of Materials, vol. 31, nr. 18, blz. 7618-7625. DOI: 10.1021/acs.chemmater.9b02453

Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts. / Cui, Meyan; Ding, Xingyu; Huang, Xiaochun; Shen, Zechao; Lee, Tien-Lin; Oropeza Palacio, Freddy (Corresponding author); Hofmann, Jan Philipp; Hensen, Emiel; Zhang, Kelvin H.L. (Corresponding author).

In: Chemistry of Materials, Vol. 31, Nr. 18, 22.08.2019, blz. 7618-7625.

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

TY - JOUR

T1 - Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts

AU - Cui,Meyan

AU - Ding,Xingyu

AU - Huang,Xiaochun

AU - Shen,Zechao

AU - Lee,Tien-Lin

AU - Oropeza Palacio,Freddy

AU - Hofmann,Jan Philipp

AU - Hensen,Emiel

AU - Zhang,Kelvin H.L.

PY - 2019/8/22

Y1 - 2019/8/22

N2 - This work reports a systematical study on the relationship of electronic structure to oxygen evolution reaction (OER) activity of NixCo3-xO4 (x = 0-1) mixed oxides. The specific OER activity is substantially increased by 16 times from 0.02 mA cm-2 BET for pure Co3O4 to 0.32 mA cm-2 BET for x = 1 at an overpotential of 0.4 V and exhibits a strong correlation with the amount of Ni ions in the +3 oxidation state. X-ray spectroscopic study reveals that inclusion of Ni3+ ions upshifts the occupied valence band maximum (VBM) by 0.27 eV toward the Fermi level (EF), and creates a new hole (unoccupied) state located ∼1 eV above the EF. Such electronic features favor the adsorption of OH surface intermediates on NixCo3-xO4, resulting in enhanced OER. Furthermore, the emerging hole state effectively reduces the energy barrier for electron transfer from 1.19 to 0.39 eV, and thereby improves the kinetics for OER. The electronic structure features that lead to a higher OER in NixCo3-xO4 can be extended to other transition metal oxides for rational design of highly active catalysts.

AB - This work reports a systematical study on the relationship of electronic structure to oxygen evolution reaction (OER) activity of NixCo3-xO4 (x = 0-1) mixed oxides. The specific OER activity is substantially increased by 16 times from 0.02 mA cm-2 BET for pure Co3O4 to 0.32 mA cm-2 BET for x = 1 at an overpotential of 0.4 V and exhibits a strong correlation with the amount of Ni ions in the +3 oxidation state. X-ray spectroscopic study reveals that inclusion of Ni3+ ions upshifts the occupied valence band maximum (VBM) by 0.27 eV toward the Fermi level (EF), and creates a new hole (unoccupied) state located ∼1 eV above the EF. Such electronic features favor the adsorption of OH surface intermediates on NixCo3-xO4, resulting in enhanced OER. Furthermore, the emerging hole state effectively reduces the energy barrier for electron transfer from 1.19 to 0.39 eV, and thereby improves the kinetics for OER. The electronic structure features that lead to a higher OER in NixCo3-xO4 can be extended to other transition metal oxides for rational design of highly active catalysts.

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U2 - 10.1021/acs.chemmater.9b02453

DO - 10.1021/acs.chemmater.9b02453

M3 - Article

VL - 31

SP - 7618

EP - 7625

JO - Chemistry of Materials

T2 - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 18

ER -

Cui M, Ding X, Huang X, Shen Z, Lee T-L, Oropeza Palacio F et al. Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3- xO4 Electrocatalysts. Chemistry of Materials. 2019 aug 22;31(18):7618-7625. Beschikbaar vanaf, DOI: 10.1021/acs.chemmater.9b02453