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Title: Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

Abstract

Spinel NiCo2O4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo2O4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists the formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo2O4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo2O4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo2O4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achievedmore » with an onset potential of 1.48 V and a current density of 15 mA/cm2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [1]; ORCiD logo [2];  [4]; ORCiD logo [1]
  1. Univ. at Buffalo, NY (United States). Dept. of Chemical and Biological Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
  4. Giner Inc., Newston, MA (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Univ. at Buffalo (SUNY), Buffalo, NY (United States); National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1425005
Report Number(s):
BNL-114859-2017-JAAM
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
SC0012704; CBET-1604392; EE000696
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 51; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
29 ENERGY PLANNING, POLICY AND ECONOMY

Citation Formats

Devaguptapu, Surya V., Hwang, Sooyeon, Karakalos, Stavros, Zhao, Shuai, Gupta, Shiva, Su, Dong, Xu, Hui, and Wu, Gang. Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media. United States: N. p., 2017. Web. doi:10.1021/acsami.7b16389.
Devaguptapu, Surya V., Hwang, Sooyeon, Karakalos, Stavros, Zhao, Shuai, Gupta, Shiva, Su, Dong, Xu, Hui, & Wu, Gang. Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media. United States. doi:10.1021/acsami.7b16389.
Devaguptapu, Surya V., Hwang, Sooyeon, Karakalos, Stavros, Zhao, Shuai, Gupta, Shiva, Su, Dong, Xu, Hui, and Wu, Gang. Wed . "Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media". United States. doi:10.1021/acsami.7b16389. https://www.osti.gov/servlets/purl/1425005.
@article{osti_1425005,
title = {Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media},
author = {Devaguptapu, Surya V. and Hwang, Sooyeon and Karakalos, Stavros and Zhao, Shuai and Gupta, Shiva and Su, Dong and Xu, Hui and Wu, Gang},
abstractNote = {Spinel NiCo2O4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo2O4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists the formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo2O4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo2O4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo2O4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.},
doi = {10.1021/acsami.7b16389},
journal = {ACS Applied Materials and Interfaces},
number = 51,
volume = 9,
place = {United States},
year = {2017},
month = {12}
}

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Works referencing / citing this record:

Synthesis and electromagnetic wave absorption performance of NiCo 2 O 4 nanomaterials with different nanostructures
journal, January 2019

  • Zhu, Qinghai; Zhang, Zilong; Lv, Yangyang
  • CrystEngComm, Vol. 21, Issue 31
  • DOI: 10.1039/c9ce00858f

Design strategies for developing non-precious metal based bi-functional catalysts for alkaline electrolyte based zinc–air batteries
journal, January 2019

  • Han, Chao; Li, Weijie; Liu, Hua-Kun
  • Materials Horizons, Vol. 6, Issue 9
  • DOI: 10.1039/c9mh00502a

Synthesis and electromagnetic wave absorption performance of NiCo 2 O 4 nanomaterials with different nanostructures
journal, January 2019

  • Zhu, Qinghai; Zhang, Zilong; Lv, Yangyang
  • CrystEngComm, Vol. 21, Issue 31
  • DOI: 10.1039/c9ce00858f

Design strategies for developing non-precious metal based bi-functional catalysts for alkaline electrolyte based zinc–air batteries
journal, January 2019

  • Han, Chao; Li, Weijie; Liu, Hua-Kun
  • Materials Horizons, Vol. 6, Issue 9
  • DOI: 10.1039/c9mh00502a