Operando Identification of Active Species and Intermediates on Sulfide Interfaced by Fe3O4for Ultrastable Alkaline Oxygen Evolution at Large Current Density

Qianqian Ji; Yuan Kong; Hao Tan; Hengli Duan; Na Li; Bing Tang; Yao Wang; Sihua Feng; Liyang Lv; Chao Wang; Fengchun Hu; Wenhua Zhang; Liang Cai; Wensheng Yan

doi:10.1021/acscatal.2c01090

Operando Identification of Active Species and Intermediates on Sulfide Interfaced by Fe₃O₄for Ultrastable Alkaline Oxygen Evolution at Large Current Density

Qianqian Ji, Yuan Kong, Hao Tan, Hengli Duan, Na Li, Bing Tang, Yao Wang, Sihua Feng, Liyang Lv, Chao Wang, Fengchun Hu, Wenhua Zhang, Liang Cai, Wensheng Yan

Research output: Contribution to journal › Article › peer-review

108 Scopus citations

Abstract

Transition-metal sulfides are investigated as promising electrocatalysts for oxygen evolution reaction (OER) in alkaline media; however, the real active species remain elusive and the development of oxyhydroxides reconstructed from sulfides delivering stable large current density at low applied potentials is a great challenge. Here, we report a synergistic hybrid catalyst, composed of nanoscale heterostructures of Co₉S₈and Fe₃O₄, that exhibits only a low potential of 350 mV and record stability of 120 h at the 500 mA cm^-2in 1.0 M KOH. Voltage-dependent soft X-ray absorption spectroscopy (XAS) and Operando Raman spectroscopy demonstrate that the initial Co₉S₈@Fe₃O₄is reconstructed into CoOOH/CoO_x@Fe₃O₄and further to complete CoOOH@Fe₃O₄. Operando XAS and electron microscopy imaging analyses reveal that the completely reconstructed CoOOH acts as active species and Fe₃O₄components prevent the aggregation of CoOOH. Operando infrared spectroscopy indicates cobalt superoxide species (*OOH) as the active intermediates during the OER process. Density functional theory calculations demonstrate the formation of *OOH as the rate-determining step of OER and CoOOH@Fe₃O₄exhibits a lower energy barrier for OER. Our results provide an in-depth understanding of the dynamic surface structure evolutions of sulfide electrocatalysts for alkaline OER and insights into the design of excellent nanocatalysts for stable large current density.

Original language	English (US)
Pages (from-to)	4318-4326
Number of pages	9
Journal	ACS Catalysis
Volume	12
Issue number	8
DOIs	https://doi.org/10.1021/acscatal.2c01090
State	Published - Apr 15 2022

Bibliographical note

Funding Information:
This work was financially supported by the Excellence Program of Hefei Science Center CAS (Nos. 2019HSC-UE002, 2020HSC-UE002, and 2021HSC-UE002), the National Natural Science Foundation of China (Grants No. 11975234, 11775225, 12075243, 12005227, and U1932211), and the Fundamental Research Funds for the Central Universities (WK2310000103). Financial supports by the Postdoctoral Science Foundation of China (Grants No. 2020M682041 and 2020TQ0316) and the Ministry of Science and Technology of China (Grant No. 2017YFA0204904) are also acknowledged. This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. The authors would like to thank the Beijing Synchrotron Radiation Facility (BSRF), the Shanghai Synchrotron Radiation Facility (SSRF), and Beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at NSRL for the synchrotron beamtime.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

Keywords

large current density
nanoscale heterostructures
OER electrocatalysis
operando spectroscopy
surface reconstruction process
transition-metal sulfides

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1021/acscatal.2c01090

Cite this

Ji, Q., Kong, Y., Tan, H., Duan, H., Li, N., Tang, B., Wang, Y., Feng, S., Lv, L., Wang, C., Hu, F., Zhang, W., Cai, L., & Yan, W. (2022). Operando Identification of Active Species and Intermediates on Sulfide Interfaced by Fe₃O₄for Ultrastable Alkaline Oxygen Evolution at Large Current Density. ACS Catalysis, 12(8), 4318-4326. https://doi.org/10.1021/acscatal.2c01090

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title = "Operando Identification of Active Species and Intermediates on Sulfide Interfaced by Fe3O4for Ultrastable Alkaline Oxygen Evolution at Large Current Density",

abstract = "Transition-metal sulfides are investigated as promising electrocatalysts for oxygen evolution reaction (OER) in alkaline media; however, the real active species remain elusive and the development of oxyhydroxides reconstructed from sulfides delivering stable large current density at low applied potentials is a great challenge. Here, we report a synergistic hybrid catalyst, composed of nanoscale heterostructures of Co9S8and Fe3O4, that exhibits only a low potential of 350 mV and record stability of 120 h at the 500 mA cm-2in 1.0 M KOH. Voltage-dependent soft X-ray absorption spectroscopy (XAS) and Operando Raman spectroscopy demonstrate that the initial Co9S8@Fe3O4is reconstructed into CoOOH/CoOx@Fe3O4and further to complete CoOOH@Fe3O4. Operando XAS and electron microscopy imaging analyses reveal that the completely reconstructed CoOOH acts as active species and Fe3O4components prevent the aggregation of CoOOH. Operando infrared spectroscopy indicates cobalt superoxide species (*OOH) as the active intermediates during the OER process. Density functional theory calculations demonstrate the formation of *OOH as the rate-determining step of OER and CoOOH@Fe3O4exhibits a lower energy barrier for OER. Our results provide an in-depth understanding of the dynamic surface structure evolutions of sulfide electrocatalysts for alkaline OER and insights into the design of excellent nanocatalysts for stable large current density.",

keywords = "large current density, nanoscale heterostructures, OER electrocatalysis, operando spectroscopy, surface reconstruction process, transition-metal sulfides",

author = "Qianqian Ji and Yuan Kong and Hao Tan and Hengli Duan and Na Li and Bing Tang and Yao Wang and Sihua Feng and Liyang Lv and Chao Wang and Fengchun Hu and Wenhua Zhang and Liang Cai and Wensheng Yan",

note = "Funding Information: This work was financially supported by the Excellence Program of Hefei Science Center CAS (Nos. 2019HSC-UE002, 2020HSC-UE002, and 2021HSC-UE002), the National Natural Science Foundation of China (Grants No. 11975234, 11775225, 12075243, 12005227, and U1932211), and the Fundamental Research Funds for the Central Universities (WK2310000103). Financial supports by the Postdoctoral Science Foundation of China (Grants No. 2020M682041 and 2020TQ0316) and the Ministry of Science and Technology of China (Grant No. 2017YFA0204904) are also acknowledged. This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. The authors would like to thank the Beijing Synchrotron Radiation Facility (BSRF), the Shanghai Synchrotron Radiation Facility (SSRF), and Beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at NSRL for the synchrotron beamtime. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

month = apr,

day = "15",

doi = "10.1021/acscatal.2c01090",

language = "English (US)",

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T1 - Operando Identification of Active Species and Intermediates on Sulfide Interfaced by Fe3O4for Ultrastable Alkaline Oxygen Evolution at Large Current Density

AU - Ji, Qianqian

AU - Kong, Yuan

AU - Tan, Hao

AU - Duan, Hengli

AU - Li, Na

AU - Tang, Bing

AU - Wang, Yao

AU - Feng, Sihua

AU - Lv, Liyang

AU - Wang, Chao

AU - Hu, Fengchun

AU - Zhang, Wenhua

AU - Cai, Liang

AU - Yan, Wensheng

N1 - Funding Information: This work was financially supported by the Excellence Program of Hefei Science Center CAS (Nos. 2019HSC-UE002, 2020HSC-UE002, and 2021HSC-UE002), the National Natural Science Foundation of China (Grants No. 11975234, 11775225, 12075243, 12005227, and U1932211), and the Fundamental Research Funds for the Central Universities (WK2310000103). Financial supports by the Postdoctoral Science Foundation of China (Grants No. 2020M682041 and 2020TQ0316) and the Ministry of Science and Technology of China (Grant No. 2017YFA0204904) are also acknowledged. This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. The authors would like to thank the Beijing Synchrotron Radiation Facility (BSRF), the Shanghai Synchrotron Radiation Facility (SSRF), and Beamlines MCD-A and MCD-B (Soochow Beamline for Energy Materials) at NSRL for the synchrotron beamtime. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/4/15

Y1 - 2022/4/15

N2 - Transition-metal sulfides are investigated as promising electrocatalysts for oxygen evolution reaction (OER) in alkaline media; however, the real active species remain elusive and the development of oxyhydroxides reconstructed from sulfides delivering stable large current density at low applied potentials is a great challenge. Here, we report a synergistic hybrid catalyst, composed of nanoscale heterostructures of Co9S8and Fe3O4, that exhibits only a low potential of 350 mV and record stability of 120 h at the 500 mA cm-2in 1.0 M KOH. Voltage-dependent soft X-ray absorption spectroscopy (XAS) and Operando Raman spectroscopy demonstrate that the initial Co9S8@Fe3O4is reconstructed into CoOOH/CoOx@Fe3O4and further to complete CoOOH@Fe3O4. Operando XAS and electron microscopy imaging analyses reveal that the completely reconstructed CoOOH acts as active species and Fe3O4components prevent the aggregation of CoOOH. Operando infrared spectroscopy indicates cobalt superoxide species (*OOH) as the active intermediates during the OER process. Density functional theory calculations demonstrate the formation of *OOH as the rate-determining step of OER and CoOOH@Fe3O4exhibits a lower energy barrier for OER. Our results provide an in-depth understanding of the dynamic surface structure evolutions of sulfide electrocatalysts for alkaline OER and insights into the design of excellent nanocatalysts for stable large current density.

AB - Transition-metal sulfides are investigated as promising electrocatalysts for oxygen evolution reaction (OER) in alkaline media; however, the real active species remain elusive and the development of oxyhydroxides reconstructed from sulfides delivering stable large current density at low applied potentials is a great challenge. Here, we report a synergistic hybrid catalyst, composed of nanoscale heterostructures of Co9S8and Fe3O4, that exhibits only a low potential of 350 mV and record stability of 120 h at the 500 mA cm-2in 1.0 M KOH. Voltage-dependent soft X-ray absorption spectroscopy (XAS) and Operando Raman spectroscopy demonstrate that the initial Co9S8@Fe3O4is reconstructed into CoOOH/CoOx@Fe3O4and further to complete CoOOH@Fe3O4. Operando XAS and electron microscopy imaging analyses reveal that the completely reconstructed CoOOH acts as active species and Fe3O4components prevent the aggregation of CoOOH. Operando infrared spectroscopy indicates cobalt superoxide species (*OOH) as the active intermediates during the OER process. Density functional theory calculations demonstrate the formation of *OOH as the rate-determining step of OER and CoOOH@Fe3O4exhibits a lower energy barrier for OER. Our results provide an in-depth understanding of the dynamic surface structure evolutions of sulfide electrocatalysts for alkaline OER and insights into the design of excellent nanocatalysts for stable large current density.

KW - large current density

KW - nanoscale heterostructures

KW - OER electrocatalysis

KW - operando spectroscopy

KW - surface reconstruction process

KW - transition-metal sulfides

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U2 - 10.1021/acscatal.2c01090

DO - 10.1021/acscatal.2c01090

M3 - Article

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