Journal Home > Volume 12 , Issue 6

Neutral water splitting is attractive for its use of non-corrosive and environmentally friendly electrolytes. However, catalyst development for hydrogen and oxygen evolution remains a challenge under neutral conditions. Here we report a simple electrodeposition and reductive annealing procedure to produce a highly active Ni-Co-Cr metal/metal oxide heterostructured catalyst directly on Ni foam. The resulting electrocatalyst for hydrogen evolution reaction (HER) requires only 198 mV of overpotential to reach 100 mA/cm2 in 1 M potassium phosphate (pH = 7.4) and can operate for at least two days without significant performance decay. Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) imaging reveals a Ni-Co alloy core decorated with blended oxides layers of NiO, CoO and Cr2O3. The metal/metal oxide interfaces are suggested to be responsible for the high HER activity.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

An electrodeposition approach to metal/metal oxide heterostructures for active hydrogen evolution catalysts in near-neutral electrolytes

Show Author's information Michael J. Kenney1,§Jianan Erick Huang1,§Yong Zhu2,§Yongtao Meng1,3,§Mingquan Xu2Guanzhou Zhu1Wei-Hsuan Hung1,4Yun Kuang1,5Mengchang Lin3Xiaoming Sun5Wu Zhou2Hongjie Dai1( )
Department of Chemistry,Stanford University,Stanford, CA,94305,USA;
School of Physical Sciences and CAS Center for Excellence in Topological Quantum Computation,University of Chinese Academy of Sciences,Beijing,100049,China;
College of Electrical Engineering and Automation,Shandong University of Science and Technology,Qingdao,266590,China;
Department of Materials Science and Engineering,Feng Chia University,Taichung,40724,Taiwan, China;
State Key laboratory of Chemical Resource Engineering and Beijing Advanced Innovation Center for Soft Matter Science and Engineering,Beijing University of Chemical Technology,Beijing,100029,China;

§ Michael J. Kenney, Jianan Erick Huang, Yong Zhu, and Yongtao Meng contributed equally to this work.

Abstract

Neutral water splitting is attractive for its use of non-corrosive and environmentally friendly electrolytes. However, catalyst development for hydrogen and oxygen evolution remains a challenge under neutral conditions. Here we report a simple electrodeposition and reductive annealing procedure to produce a highly active Ni-Co-Cr metal/metal oxide heterostructured catalyst directly on Ni foam. The resulting electrocatalyst for hydrogen evolution reaction (HER) requires only 198 mV of overpotential to reach 100 mA/cm2 in 1 M potassium phosphate (pH = 7.4) and can operate for at least two days without significant performance decay. Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) imaging reveals a Ni-Co alloy core decorated with blended oxides layers of NiO, CoO and Cr2O3. The metal/metal oxide interfaces are suggested to be responsible for the high HER activity.

Keywords: catalysis, water splitting, hydrogen evolution, nanostructured materials, chemical mapping

References(20)

1

Lewis, N. S.; Nocera, D. G. Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl. Acad. Sci. USA 2006, 103, 15729-15735.

2

Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q. X.; Santori, E. A.; Lewis, N. S. Solar water splitting cells. Chem. Rev. 2010, 110, 6446-6473.

3

Carmo, M.; Fritz, D. L.; Mergel, J.; Stolten, D. A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 2013, 38, 4901-4934.

4

Esswein, A. J.; Surendranath, Y.; Reece, S. Y.; Nocera, D. G. Highly active cobalt phosphate and borate based oxygen evolving catalysts operating in neutral and natural waters. Energy Environ. Sci. 2011, 4, 499-504.

5

Kanan, M. W.; Nocera, D. G. In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science 2008, 321, 1072-1075.

6

Liu, C.; Colón, B. C.; Ziesack, M.; Silver, P. A.; Nocera, D. G. Water splitting-biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis. Science 2016, 352, 1210-1213.

7

Torella, J. P.; Gagliardi, C. J.; Chen, J. S.; Bediako, D. K.; Colón, B.; Way, J. C.; Silver, P. A.; Nocera, D. G. Efficient solar-to-fuels production from a hybrid microbial-water-splitting catalyst system. Proc. Natl. Acad. Sci. USA 2015, 112, 2337-2342.

8

Feng, L. L.; Yu, G.; Wu, Y. T.; Li, G. D.; Li, H.; Sun, Y. H.; Asefa, T.; Chen, W.; Zou, X. X. High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting. J. Am. Chem. Soc. 2015, 137, 14023-14026.

9

Sun, Y. J.; Liu, C.; Grauer, D. C.; Yano, J.; Long, J. R.; Yang, P. D.; Chang, C. J. Electrodeposited cobalt-sulfide catalyst for electrochemical and photoelectrochemical hydrogen generation from water. J. Am. Chem. Soc. 2013, 135, 17699-17702.

10

Callejas, J. F.; McEnaney, J. M.; Read, C. G.; Crompton, J. C.; Biacchi, A. J.; Popczun, E. J.; Gordon, T. R.; Lewis, N. S.; Schaak, R. E. Electrocatalytic and photocatalytic hydrogen production from acidic and neutral-pH aqueous solutions using iron phosphide nanoparticles. ACS Nano 2014, 8, 11101-11107.

11

Jin, H. Y.; 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.

12

Tian, J. Q.; Liu, Q.; Asiri, A. M.; Sun, X. P. Self-supported nanoporous cobalt phosphide nanowire arrays: An efficient 3D hydrogen-evolving cathode over the wide range of pH 0-14. J. Am. Chem. Soc. 2014, 136, 7587-7590.

13

Zhang, R.; Wang, X. X.; Yu, S. J.; Wen, T.; Zhu, X. W.; Yang, F. Y.; Sun, X. N.; Wang, X. K.; Hu, W. P. Ternary NiCo2Px nanowires as pH-universal electrocatalysts for highly efficient hydrogen evolution reaction. Adv. Mater. 2017, 29, 1605502.

14

Zhang, L. H.; Han, L. L.; Liu, H. X.; Liu, X. J.; Luo, J. Potential-cycling synthesis of single platinum atoms for efficient hydrogen evolution in neutral media. Angew. Chem. , Int. Ed. 2017, 56, 13694-13698.

15

Gong, M.; Zhou, W.; Kenney, M. J.; Kapusta, R.; Cowley, S.; Wu, Y. P.; Lu, B. A.; Lin, M. C.; Wang, D. Y.; Yang, J. et al. Blending Cr2O3 into a NiO-Ni electrocatalyst for sustained water splitting. Angew. Chem. , Int. Ed. 2015, 54, 11989-11993.

16

Gong, M.; Zhou, W.; Tsai, M. C.; Zhou, J. G.; Guan, M. Y.; Lin, M. C.; Zhang, B.; Hu, Y. F.; Wang, D. Y.; Yang, J. et al. Nanoscale nickel oxide/ nickel heterostructures for active hydrogen evolution electrocatalysis. Nat. Commun. 2014, 5, 4695.

17

Subbaraman, R.; Tripkovic, D.; Strmcnik, D.; Chang, K. C.; Uchimura, M.; Paulikas, A. P.; Stamenkovic, V.; Markovic, N. M. Enhancing hydrogen evolution activity in water splitting by tailoring Li+-Ni(OH)2-Pt interfaces. Science 2011, 334, 1256-1260.

18

Surendranath, Y.; Dinca, M.; Nocera, D. G. Electrolyte-dependent electrosynthesis and activity of cobalt-based water oxidation catalysts. J. Am. Chem. Soc. 2009, 131, 2615-2620.

19

Danilovic, N.; Subbaraman, R.; Strmcnik, D.; Chang, K. C.; Paulikas, A. P.; Stamenkovic, V. R.; Markovic, N. M. Enhancing the alkaline hydrogen evolution reaction activity through the bifunctionality of Ni(OH)2/metal catalysts. Angew. Chem. , Int. Ed. 2012, 51, 12495-12498.

20

Dinh, C. T.; Jain, A.; de Arquer, F. P. G.; De Luna, P.; Li, J.; Wang, N.; Zheng, X. L.; Cai, J.; Gregory, B. Z.; Voznyy, O. et al. Multi-site electrocatalysts for hydrogen evolution in neutral media by destabilization of water molecules. Nat. Energy 2019, 4, 107-114.

File
12274_2019_2379_MOESM1_ESM.pdf (2 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 07 February 2019
Revised: 07 March 2019
Accepted: 12 March 2019
Published: 29 May 2019
Issue date: June 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

This work was partially supported by US Department of Energy DOE DE-SC0016165. Y. K. and X. M. S. acknowledge the financial support from the National Natural Science Foundation of China, the National Key Research and Development Project of China (No. 2016YFF0204402). Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. The electron-microscopy work was performed in the CAS Key Laboratory of Vacuum Sciences with financial support from the Key Research Program of Frontier Sciences of Chinese Academy of Sciences (CAS) and the National Natural Science Foundation of China (No. 51622211).

Return