Cobalt-based hydroxide nanoparticles @ N-doping carbonic frameworks core–shell structures as highly efficient bifunctional electrocatalysts for oxygen evolution and oxygen reduction reactions
),
Dongsheng Xu(
)
Download citation
594
Views
15
Downloads
36
Crossref
N/A
WoS
36
Scopus
4
CSCD
The development of highly efficient and earth-abundant oxygen evolution/reduction reaction (OER/ORR) catalysts is essential for rechargeable metal–air batteries. Herein, cobalt-based hydroxide nanoparticles @ N-doping carbonic framework (CoOHCat@NCF) core–shell structures have been designed as highly stable and efficient OER/ORR bifunctional catalysts. The obtained composite shows enhanced catalytic activities and excellent stability in alkaline media. In the OER, a high turnover frequency (2.03 s–1 at an overpotential of 0.36 V), low overpotential at high current density (100 mA·cm–2 requiring an overpotential of 0.38 V), and excellent stability (100 mA·cm–2 for one week with no activity loss) have been achieved. Furthermore, although cobalt species-based catalysts are known as good ORR catalysts, their hybridization with NCF obtained from metal organic frameworks successfully enhanced their ORR activities. The efficient activity of CoOHCat@NCF as a bifunctional oxygen electrocatalyst can be ascribed to the core–shell structures stabilizing the active catalytic sites and the porous shell structure favoring electrocatalysis-related mass transport.
menu
Cobalt-based hydroxide nanoparticles @ N-doping carbonic frameworks core–shell structures as highly efficient bifunctional electrocatalysts for oxygen evolution and oxygen reduction reactions
), Dongsheng Xu(
)
Abstract
The development of highly efficient and earth-abundant oxygen evolution/reduction reaction (OER/ORR) catalysts is essential for rechargeable metal–air batteries. Herein, cobalt-based hydroxide nanoparticles @ N-doping carbonic framework (CoOHCat@NCF) core–shell structures have been designed as highly stable and efficient OER/ORR bifunctional catalysts. The obtained composite shows enhanced catalytic activities and excellent stability in alkaline media. In the OER, a high turnover frequency (2.03 s–1 at an overpotential of 0.36 V), low overpotential at high current density (100 mA·cm–2 requiring an overpotential of 0.38 V), and excellent stability (100 mA·cm–2 for one week with no activity loss) have been achieved. Furthermore, although cobalt species-based catalysts are known as good ORR catalysts, their hybridization with NCF obtained from metal organic frameworks successfully enhanced their ORR activities. The efficient activity of CoOHCat@NCF as a bifunctional oxygen electrocatalyst can be ascribed to the core–shell structures stabilizing the active catalytic sites and the porous shell structure favoring electrocatalysis-related mass transport.
References(46)
Bidault, F.; Brett, D. J. L.; Middleton, P. H.; Brandon, N. P. Review of gas diffusion cathodes for alkaline fuel cells. J. Power Sources 2009, 187, 39–48.
Cheng, F. Y.; Chen, J. Metal–air batteries: From oxygen reduction electrochemistry to cathode catalysts. Chem. Soc. Rev. 2012, 41, 2172–2192.
Lee, J. S.; Kim, S. T.; Cao, R. G.; Choi, N. S.; Liu, M. L.; Lee, K. T.; Cho, J. Metal–air batteries with high energy density: Li–air versus Zn–air. Adv. Energy Mater. 2011, 1, 34–50.
Lu, Y. C.; Kwabi, D. G.; Yao, K. P. C.; Harding, J. R.; Zhou, J. G.; Zuin, L.; Shao-Horn, Y. The discharge rate capability of rechargeable Li–O2 batteries. Energy Environ. Sci. 2011, 4, 2999–3007.
Lee, J. S.; Park, G. S.; Lee, H. I.; Kim, S. T.; Cao, R. G.; Liu, M. L.; Cho, J. Ketjenblack carbon supported amorphous manganese oxides nanowires as highly efficient electrocatalyst for oxygen reduction reaction in alkaline solutions. Nano Lett. 2011, 11, 5362–5366.
Chen, Z. W.; Higgins, D.; Yu, A. P.; Zhang, L.; Zhang, J. J. A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Environ. Sci. 2011, 4, 3167–3192.
Zhao, S. L.; Yin, H. J.; Du, L.; He, L. C.; Zhao, K.; Chang, L.; Yin, G. P.; Zhao, H. J.; Liu, S. Q.; Tang, Z. Y. Carbonized nanoscale metal–organic frameworks as high performance electrocatalyst for oxygen reduction reaction. ACS Nano 2014, 8, 12660–12668.
Sun, J. Q.; Yin, H. J.; Liu, P. R.; Wang, Y.; Yao, X. D.; Tang, Z. Y.; Zhao, H. J. Molecular engineering of Ni-/Coporphyrin multilayers on reduced graphene oxide sheets as bifunctional catalysts for oxygen evolution and oxygen reduction reactions. Chem. Sci. 2016, 7, 5640–5646.
Zhao, S. L.; Wang, Y.; Dong, J. C.; He, C. T.; Yin, H. J.; An, P. F.; Zhao, K.; Zhang, X. F.; Gao, C.; Tang, Z. Y. et al. Ultrathin metal-organic framework nanosheets for electrocatalytic oxygen evolution. Nat. Energy 2016, 1, 16184.
Lee, Y.; Suntivich, J.; May, K. J.; Perry, E. E.; Yang, S. H. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett. 2012, 3, 399–404.
Spendelow, J. S.; Wieckowski, A. Electrocatalysis of oxygen reduction and small alcohol oxidation in alkaline media. Phys. Chem. Chem. Phys. 2007, 9, 2654–2675.
Cui, X. J.; Ren, P. J.; Deng, D. H.; Deng, J.; Bao, X. H. Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation. Energy Environ. Sci. 2016, 9, 123–129.
Suntivich, J.; May, K. J.; Gasteiger, H. A.; Goodenough, J. B.; Yang, S. H. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 2011, 334, 1383–1385.
Wang, Z. L.; Xiao, S.; Zhu, Z.; Long, X. L.; Zheng, X. L.; Lu, X. H.; Yang, S. H. Cobalt-embedded nitrogen doped carbon nanotubes: A bifunctional catalyst for oxygen electrode reactions in a wide pH range. ACS Appl. Mater. Interfaces 2015, 7, 4048–4055.
Liang, Y. Y.; Li, Y. G.; Wang, H. L.; Zhou, J. G.; Wang, J.; Regier, T.; Dai, H. J. Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat. Mater. 2011, 10, 780–786.
Masa, J.; Xia, W.; Sinev, I.; Zhao, A. Q.; Sun, Z. Y.; Grützke, S.; Weide, P.; Muhler, M.; Schuhmann, W. MnxOy/NC and CoxOy/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes. Angew. Chem., Int. Ed. 2014, 53, 8508–8512.
Liu, X. E.; Park, M.; Kim, M. G.; Gupta, S.; Wu, G.; Cho, J. Integrating NiCo alloys with their oxides as efficient bifunctional cathode catalysts for rechargeable zinc–air batteries. Angew. Chem., Int. Ed. 2015, 54, 9654–9658.
Zhang, T. T.; He, C. S.; Sun, F. Z.; Ding, Y. Q.; Wang, M. C.; Peng, L.; Wang, J. H.; Lin, Y. Q. Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide as a multifunctional catalyst for H2O2 reduction, oxygen reduction and evolution reaction. Sci. Rep. 2017, 7, 43638.
Kim, J. E.; Lim, J.; Lee, G. Y.; Choi, S. H.; Maiti, U. N.; Lee, W. J.; Lee, H. J.; Kim, S. O. Subnanometer cobalthydroxide- anchored N-doped carbon nanotube forest for bifunctional oxygen catalyst. ACS Appl. Mater. Interfaces 2016, 8, 1571–1577.
Ishikawa, T.; Matijević, E. Preparation and properties of uniform colloidal metal phosphates Ⅲ. Cobalt(Ⅱ) Phosphate. J. Colloid Interface Sci. 1988, 123, 122–128.
Springsteen, L. L.; Matijevic, E. Preparation and properties of uniform colloidal metal phosphates Ⅳ. Cadmium-, nickel-, and manganese(Ⅱ)-phosphate. Colloid Polym. Sci. 1989, 267, 1007–1015.
Zhao, M. T.; Deng, K.; He, L. C.; Liu, Y.; Li, G. D.; Zhao, H. J.; Tang, Z. Y. Core–shell palladium nanoparticle@metal–organic frameworks as multifunctional catalysts for cascade reactions. J. Am. Chem. Soc. 2014, 136, 1738–1741.
He, L. C.; Liu, Y.; Liu, J. Z.; Xiong, Y. S.; Zheng, J. Z.; Liu, Y. L.; Tang, Z. Y. Core–shell noble-metal@metal-organicframework nanoparticles with highly selective sensing property. Angew. Chem., Int. Ed. 2013, 52, 3741–3745.
Zhao, M. T.; Yuan, K.; Wang, Y.; Li, G. D.; Guo, J.; Gu, L.; Hu, W. P.; Zhao, H. J.; Tang, Z. Y. Metal–organic frameworks as selectivity regulators for hydrogenation reactions. Nature 2016, 539, 76–80.
Liu, X. E.; Liu, W.; Ko, M.; Park, M.; Kim, M. G.; Oh, P.; Chae, S.; Park, S.; Casimir, A.; Wu, G. et al. Metal (Ni, Co)–metal oxides/graphene nanocomposites as multifunctional electrocatalysts. Adv. Funct. Mater. 2015, 25, 5799–5808.
Ke, F.; Qiu, L. G.; Yuan, Y. P.; Jiang, X.; Zhu, J. F. Fe3O4@MOF core–shell magnetic microspheres with a designable metal–organic framework shell. J. Mater. Chem. 2012, 22, 9497–9500.
Bennett, T. D.; Cheetham, A. K. Amorphous metal–organic frameworks. Acc. Chem. Res. 2014, 47, 1555–1562.
Lee, H. J.; We, J.; Kim, J. O.; Kim, D.; Cha, W.; Lee, E.; Sohn, J.; Oh, M. Morphological and structural evolutions of metal–organic framework particles from amorphous spheres to crystalline hexagonal rods. Angew. Chem., Int. Ed. 2015, 54, 10564–10568.
Jin, H.; Wang, J.; Su, D. F.; Wei, Z. Z.; Pang, Z. F.; Wang, Y. In situ cobalt–cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution. J. Am. Chem. Soc. 2015, 137, 2688–2694.
Li, L. L.; Tian, T.; Jiang, J.; Ai, L. H. Hierarchically porous Co3O4 architectures with honeycomb-like structures for efficient oxygen generation from electrochemical water splitting. J. Power Sources 2015, 294, 103–111.
Wu, J.; Ren, Z. Y.; Du, S. C.; Kong, L. J.; Liu, B. W.; Xi, W.; Zhu, J. Q.; Fu, H. G. A highly active oxygen evolution electrocatalyst: Ultrathin CoNi double hydroxide/CoO nanosheets synthesized via interface-directed assembly. Nano Res. 2016, 9, 713–725.
Zhang, T. T.; Cui, S. W.; Yu, B.; Liu, Z. L.; Wang, D. A. Surface engineering for an enhanced photoelectrochemical response of TiO2 nanotube arrays by simple surface air plasma treatment. Chem. Commun. 2015, 51, 16940–16943.
McCrory, C. C. L.; Jung, S.; Peters, J. C.; Jaramillo, T. F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 2013, 135, 16977–16987.
Wang, J.; Li, K.; Zhong, H. X.; Xu, D.; Wang, Z. L.; Jiang, Z.; Wu, Z. J.; Zhang, X. B. Synergistic effect between metal–nitrogen–carbon sheets and NiO nanoparticles for enhanced electrochemical water-oxidation performance. Angew. Chem., Int. Ed. 2015, 54, 10530–10534.
Pintado, S.; Goberna-Ferrón, S.; Escudero-Adán, E. C.; Galán-Mascarós, J. R. Fast and persistent electrocatalytic water oxidation by Co–Fe prussian blue coordination polymers. J. Am. Chem. Soc. 2013, 135, 13270–13273.
Sayeed, M. A.; Herd, T.; O'Mullane, A. P. Direct electrochemical formation of nanostructured amorphous Co(OH)2 on gold electrodes with enhanced activity for the oxygen evolution reaction. J. Mater. Chem. A 2016, 4, 991–999.
Will, F. G. Electrochemical oxidation of hydrogen on partially immersed platinum electrodes I. Experiments and interpretation. J. Electrochem. Soc. 1963, 110, 145–151.
Kanan, M. W.; Nocera, D. G. In situ formation of an oxygenevolving catalyst in neutral water containing phosphate and Co2+. Science 2008, 321, 1072–1075.
Surendranath, Y.; Kanan, M. W.; Nocera, D. G. Mechanistic studies of the oxygen evolution reaction by a cobalt–phosphate catalyst at neutral pH. J. Am. Chem. Soc. 2010, 132, 16501–16509.
González-Flores, D.; Sánchez, I.; Zaharieva, I.; Klingan, K.; Heidkamp, J.; Chernev, P.; Menezes, P. W.; Driess, M.; Dau, H.; Montero, M. L. Heterogeneous water oxidation: Surface activity versus amorphization activation in cobalt phosphate catalysts. Angew. Chem., Int. Ed. 2015, 54, 2472–2476.
Kanan, M. W.; Yano, J.; Surendranath, Y.; Dincă, M.; Yachandra, V. K.; Nocera, D. G. Structure and valency of a cobalt–phosphate water oxidation catalyst determined by in situ X-ray spectroscopy. J. Am. Chem. Soc. 2010, 132, 13692–13701.
Irebo, T.; Reece, S. Y.; Sjödin, M.; Nocera, D. G.; Hammarström, L. Proton-coupled electron transfer of tyrosine oxidation: Buffer dependence and parallel mechanisms. J. Am. Chem. Soc. 2007, 129, 15462–15464.
Mattioli, G.; Giannozzi, P.; Amore Bonapasta, A.; Guidoni, L. Reaction pathways for oxygen evolution promoted by cobalt catalyst. J. Am. Chem. Soc. 2013, 135, 15353–15363.
Dai, L. M.; Xue, Y. H.; Qu, L. T.; Choi, H. J.; Baek, J. B. Metal-free catalysts for oxygen reduction reaction. Chem. Rev. 2015, 115, 4823–4892.
Lai, Q. X.; Zheng, L. R.; Liang, Y. Y.; He, J. P.; Zhao, J. X.; Chen, J. H. Metal–organic-framework-derived Fe-N/C electrocatalyst with five-coordinated Fe-Nx sites for advanced oxygen reduction in acid media. ACS Catal. 2017, 7, 1655–1663.
Publication history
Copyright
Acknowledgements
The authors acknowledge financial support from the National Basic Research Program of China (Nos. 2013CB932601 and 2014CB239303) and the National Natural Science Foundation of China (No. 21133001).
FEEDBACK 
TOP