Atomistic Structure of Cobalt-Phosphate Nanoparticles for Catalytic Water Oxidation

View Author Information
CNR-IOM Istituto Officina dei Materiali, Centro DEMOCRITOS, Scuola Internazionale Superiore di Studi Avanzati (SISSA), and Italian Institute of Technology (IIT-SISSA Unit), Via Bonomea 265, I-34136, Trieste, Italy
*Address correspondence to [email protected]; [email protected]
Cite this: ACS Nano 2012, 6, 12, 10497–10504
Publication Date (Web):November 12, 2012
Copyright © 2012 American Chemical Society
Article Views
Read OnlinePDF (3 MB)
Supporting Info (1)»


Solar-driven water splitting is a key photochemical reaction that underpins the feasible and sustainable production of solar fuels. An amorphous cobalt-phosphate catalyst (Co-Pi) based on earth-abundant elements has been recently reported to efficiently promote water oxidation to protons and dioxygen, a main bottleneck for the overall process. The structure of this material remains largely unknown. We here exploit ab initio and classical atomistic simulations combined with metadynamics to build a realistic and statistically meaningful model of Co-Pi nanoparticles. We demonstrate the emergence and stability of molecular-size ordered crystallites in nanoparticles initially formed by a disordered Co–O network and phosphate groups. The stable crystallites consist of bis-oxo-bridged Co centers that assemble into layered structures (edge-sharing CoO6 octahedra) as well as in corner- and face-sharing cubane units. These layered and cubane motifs coexist in the crystallites, which always incorporate disordered phosphate groups at the edges. Our computational nanoparticles, although limited in size to ∼1 nm, can contain more than one crystallite and incorporate up to 18 Co centers in the cubane/layered structures. The crystallites are structurally stable up to high temperatures. We simulate the extended X-ray absorption fine structure (EXAFS) of our nanoparticles. Those containing several complete and incomplete cubane motifs—which are believed to be essential for the catalytic activity—display a very good agreement with the experimental EXAFS spectra of Co-Pi grains. We propose that the crystallites in our nanoparticles are reliable structural models of the Co-Pi catalyst surface. They will be useful to reveal the origin of the catalytic efficiency of these novel water-oxidation catalysts.

Supporting Information

Jump To

Fitting and testing of the shell model parameters for Co-Pi; atomistic structures of crystallites in grains 4, 5, and 6; metadynamics trajectories using CV3; calculated radial distribution functions restricted to crystallites; total and projected density of electronic states for grain 6; and coordinates of the grains in Figures 1 and 2. This material is available free of charge via the Internet at

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 53 publications.

  1. Jiachen Li, Qingwen Zhou, Chenglin Zhong, Shengwen Li, Zihan Shen, Jun Pu, Jinyun Liu, Yongning Zhou, Huigang Zhang, Haixia Ma. (Co/Fe)4O4 Cubane-Containing Nanorings Fabricated by Phosphorylating Cobalt Ferrite for Highly Efficient Oxygen Evolution Reaction. ACS Catalysis 2019, 9 (5) , 3878-3887.
  2. Shaoqi Zhan, Mårten S. G. Ahlquist. Dynamics and Reactions of Molecular Ru Catalysts at Carbon Nanotube–Water Interfaces. Journal of the American Chemical Society 2018, 140 (24) , 7498-7503.
  3. Ruixiang Ge, Hongbin Du, Kai Tao, Qiuju Zhang, and Liang Chen . Cobalt-Borate Nanoarray: An Efficient and Durable Electrocatalyst for Water Oxidation under Benign Conditions. ACS Applied Materials & Interfaces 2017, 9 (18) , 15383-15387.
  4. Yingxue Chang, Nai-En Shi, Shulin Zhao, Dongdong Xu, Chunyan Liu, Yu-Jia Tang, Zhihui Dai, Ya-Qian Lan, Min Han, and Jianchun Bao . Coralloid Co2P2O7 Nanocrystals Encapsulated by Thin Carbon Shells for Enhanced Electrochemical Water Oxidation. ACS Applied Materials & Interfaces 2016, 8 (34) , 22534-22544.
  5. Giuseppe Mattioli, Ivelina Zaharieva, Holger Dau, and Leonardo Guidoni . Atomistic Texture of Amorphous Manganese Oxides for Electrochemical Water Splitting Revealed by Ab Initio Calculations Combined with X-ray Spectroscopy. Journal of the American Chemical Society 2015, 137 (32) , 10254-10267.
  6. Jaeyune Ryu, Namgee Jung, Jong Hyun Jang, Hyoung-Juhn Kim, and Sung Jong Yoo . In Situ Transformation of Hydrogen-Evolving CoP Nanoparticles: Toward Efficient Oxygen Evolution Catalysts Bearing Dispersed Morphologies with Co-oxo/hydroxo Molecular Units. ACS Catalysis 2015, 5 (7) , 4066-4074.
  7. Amendra Fernando, K. L. Dimuthu M. Weerawardene, Natalia V. Karimova, and Christine M. Aikens . Quantum Mechanical Studies of Large Metal, Metal Oxide, and Metal Chalcogenide Nanoparticles and Clusters. Chemical Reviews 2015, 115 (12) , 6112-6216.
  8. Markus D. Kärkäs, Oscar Verho, Eric V. Johnston, and Björn Åkermark . Artificial Photosynthesis: Molecular Systems for Catalytic Water Oxidation. Chemical Reviews 2014, 114 (24) , 11863-12001.
  9. Huijie Shi and Guohua Zhao . Water Oxidation on Spinel NiCo2O4 Nanoneedles Anode: Microstructures, Specific Surface Character, and the Enhanced Electrocatalytic Performance. The Journal of Physical Chemistry C 2014, 118 (45) , 25939-25946.
  10. Kyoungsuk Jin, Jimin Park, Joohee Lee, Ki Dong Yang, Gajendra Kumar Pradhan, Uk Sim, Donghyuk Jeong, Hae Lin Jang, Sangbaek Park, Donghun Kim, Nark-Eon Sung, Sun Hee Kim, Seungwu Han, and Ki Tae Nam . Hydrated Manganese(II) Phosphate (Mn3(PO4)2·3H2O) as a Water Oxidation Catalyst. Journal of the American Chemical Society 2014, 136 (20) , 7435-7443.
  11. Delina Barats-Damatov, Linda J. W. Shimon, Lev Weiner, Roy E. Schreiber, Pablo Jiménez-Lozano, Josep M. Poblet, Coen de Graaf, and Ronny Neumann . Dicobalt-μ-oxo Polyoxometalate Compound, [(α2-P2W17O61Co)2O]14–: A Potent Species for Water Oxidation, C–H Bond Activation, and Oxygen Transfer. Inorganic Chemistry 2014, 53 (3) , 1779-1787.
  12. Karolina Kwapien, Simone Piccinin, and Stefano Fabris . Energetics of Water Oxidation Catalyzed by Cobalt Oxide Nanoparticles: Assessing the Accuracy of DFT and DFT+U Approaches against Coupled Cluster Methods. The Journal of Physical Chemistry Letters 2013, 4 (24) , 4223-4230.
  13. Giuseppe Mattioli, Paolo Giannozzi, Aldo Amore Bonapasta, and Leonardo Guidoni . Reaction Pathways for Oxygen Evolution Promoted by Cobalt Catalyst. Journal of the American Chemical Society 2013, 135 (41) , 15353-15363.
  14. Nan Jiang, Zhiwei Zhu, Wenjie Xue, Bao Yu Xia, Bo You. Emerging Electrocatalysts for Water Oxidation under Near‐Neutral CO 2 Reduction Conditions. Advanced Materials 2021, , 2105852.
  15. Pawan Rekha, Sarika Yadav, Lovjeet Singh. A review on cobalt phosphate-based materials as emerging catalysts for water splitting. Ceramics International 2021, 47 (12) , 16385-16401.
  16. Xunbiao Zhou, Xiaobin Liao, Xuelei Pan, Mengyu Yan, Liang He, Peijie Wu, Yan Zhao, Wen Luo, Liqiang Mai. Unveiling the role of surface P–O group in P-doped Co3O4 for electrocatalytic oxygen evolution by On-chip micro-device. Nano Energy 2021, 83 , 105748.
  17. Hui Zhao, Zhong‐Yong Yuan. Design Strategies of Transition‐Metal Phosphate and Phosphonate Electrocatalysts for Energy‐Related Reactions. ChemSusChem 2021, 14 (1) , 130-149.
  18. Qu Yue, Taotao Gao, Yi Wu, Hongyan Yuan, Dan Xiao. S-doped Co-Fe-Pi nanosheets as highly efficient oxygen evolution electrocatalysts in alkaline media. Electrochimica Acta 2020, 362 , 137123.
  19. Quande Che, Xiaobin Xie, Qian Ma, Junpeng Wang, Yuanna Zhu, Ruixia Shi, Ping Yang. In-situ transformation of Co(OH)2 into NH4CoPO4•H2O on Co foil: 3D self-supported electrocatalyst with asymmetric local atomic and electronic structure for enhanced oxygen evolution reaction. Journal of Energy Chemistry 2020, 51 , 167-174.
  20. Hui Zhao, Zhong‐Yong Yuan. Insights into Transition Metal Phosphate Materials for Efficient Electrocatalysis. ChemCatChem 2020, 12 (15) , 3797-3810.
  21. Ran Zhang, Jing Xian Dong, Guo Liang Gao, Xue Lu Wang, Ye-Feng Yao. Facile Synthesis of Amorphous C3N4ZnxOy (x, y = 0.32–1.10) with High Photocatalytic Efficiency for Antibiotic Degradation. Catalysts 2020, 10 (5) , 514.
  22. Quande Che, Xiaobin Xie, Qian Ma, Junpeng Wang, Yuanna Zhu, Ruixia Shi, Ping Yang. Coordination environment evolution of Co( ii ) during dehydration and re-crystallization processes of KCoPO 4 ·H 2 O towards enhanced electrocatalytic oxygen evolution reaction. RSC Advances 2020, 10 (25) , 14972-14978.
  23. Giovanni Bussi, Alessandro Laio, Pratyush Tiwary. Metadynamics: A Unified Framework for Accelerating Rare Events and Sampling Thermodynamics and Kinetics. 2020,,, 565-595.
  24. Chwen-Haw Liao, Kun Fan, Song-Song Bao, Hao Fan, Xi-Zhang Wang, Zheng Hu, Mohamedally Kurmoo, Li-Min Zheng. From a layered iridium( iii )–cobalt( ii ) organophosphonate to an efficient oxygen-evolution-reaction electrocatalyst. Chemical Communications 2019, 55 (92) , 13920-13923.
  25. Wenbin Wang, Ruidong Xu, Bohao Yu, Xuanbin Wang, Suyang Feng. Electrochemical fabrication of FeS x films with high catalytic activity for oxygen evolution. RSC Advances 2019, 9 (55) , 31979-31987.
  26. J. Timoshenko, Z. Duan, G. Henkelman, R.M. Crooks, A.I. Frenkel. Solving the Structure and Dynamics of Metal Nanoparticles by Combining X-Ray Absorption Fine Structure Spectroscopy and Atomistic Structure Simulations. Annual Review of Analytical Chemistry 2019, 12 (1) , 501-522.
  27. Peipei Li, Runbo Zhao, Hongyu Chen, Huanbo Wang, Peipei Wei, Hong Huang, Qian Liu, Tingshuai Li, Xifeng Shi, Youyu Zhang, Meiling Liu, Xuping Sun. Recent Advances in the Development of Water Oxidation Electrocatalysts at Mild pH. Small 2019, 15 (13) , 1805103.
  28. Ronghui Guo, Xiaoxu Lai, Jianwen Huang, Xinchuan Du, Yichao Yan, Yinghui Sun, Guifu Zou, Jie Xiong. Phosphate‐Based Electrocatalysts for Water Splitting: Recent Progress. ChemElectroChem 2018, 5 (24) , 3822-3834.
  29. Jingqi Guan, Zhiyao Duan, Fuxiang Zhang, Shelly D. Kelly, Rui Si, Michel Dupuis, Qinge Huang, John Qianjun Chen, Chunhua Tang, Can Li. Water oxidation on a mononuclear manganese heterogeneous catalyst. Nature Catalysis 2018, 1 (11) , 870-877.
  30. Peng Zhang, Tuo Wang, Jinlong Gong. Current Mechanistic Understanding of Surface Reactions over Water-Splitting Photocatalysts. Chem 2018, 4 (2) , 223-245.
  31. Giovanni Bussi, Alessandro Laio, Pratyush Tiwary. Metadynamics: A Unified Framework for Accelerating Rare Events and Sampling Thermodynamics and Kinetics. 2018,,, 1-31.
  32. Zheng Chen, Zhiyao Duan, Zhiliang Wang, Xiaoyan Liu, Lin Gu, Fuxiang Zhang, Michel Dupuis, Can Li. Amorphous Cobalt Oxide Nanoparticles as Active Water-Oxidation Catalysts. ChemCatChem 2017, 9 (19) , 3641-3645.
  33. Lanlan Chen, Xiang Ren, Wanqing Teng, Pengfei Shi. Amorphous Nickel-Cobalt-Borate Nanosheet Arrays for Efficient and Durable Water Oxidation Electrocatalysis under Near-Neutral Conditions. Chemistry - A European Journal 2017, 23 (41) , 9741-9745.
  34. Jiayuan Li, Zeqiong Zhao, Yuanyuan Ma, Yongquan Qu. Graphene and Their Hybrid Electrocatalysts for Water Splitting. ChemCatChem 2017, 9 (9) , 1554-1568.
  35. Yipu Liu, Qiuju Li, Rui Si, Guo-Dong Li, Wang Li, Da-Peng Liu, Dejun Wang, Lei Sun, Yu Zhang, Xiaoxin Zou. Coupling Sub-Nanometric Copper Clusters with Quasi-Amorphous Cobalt Sulfide Yields Efficient and Robust Electrocatalysts for Water Splitting Reaction. Advanced Materials 2017, 29 (13) , 1606200.
  36. Hannah J. King, Shannon A. Bonke, Shery L. Y. Chang, Leone Spiccia, Bernt Johannessen, Rosalie K. Hocking. Engineering Disorder into Heterogenite-Like Cobalt Oxides by Phosphate Doping: Implications for the Design of Water-Oxidation Catalysts. ChemCatChem 2017, 9 (3) , 511-521.
  37. Lisi Xie, Rong Zhang, Liang Cui, Danni Liu, Shuai Hao, Yongjun Ma, Gu Du, Abdullah M. Asiri, Xuping Sun. High-Performance Electrolytic Oxygen Evolution in Neutral Media Catalyzed by a Cobalt Phosphate Nanoarray. Angewandte Chemie 2017, 129 (4) , 1084-1088.
  38. Lisi Xie, Rong Zhang, Liang Cui, Danni Liu, Shuai Hao, Yongjun Ma, Gu Du, Abdullah M. Asiri, Xuping Sun. High-Performance Electrolytic Oxygen Evolution in Neutral Media Catalyzed by a Cobalt Phosphate Nanoarray. Angewandte Chemie International Edition 2017, 56 (4) , 1064-1068.
  39. Dong Wang, Didier Astruc. The recent development of efficient Earth-abundant transition-metal nanocatalysts. Chemical Society Reviews 2017, 46 (3) , 816-854.
  40. Hui Zhao, Zhong-Yong Yuan. Transition metal–phosphorus-based materials for electrocatalytic energy conversion reactions. Catalysis Science & Technology 2017, 7 (2) , 330-347.
  41. Ruixiang Ge, Min Ma, Xiang Ren, Fengli Qu, Zhiang Liu, Gu Du, Abdullah M. Asiri, Liang Chen, Baozhan Zheng, Xuping Sun. A NiCo 2 O 4 @Ni–Co–Ci core–shell nanowire array as an efficient electrocatalyst for water oxidation at near-neutral pH. Chemical Communications 2017, 53 (55) , 7812-7815.
  42. Xiang Ren, Ruixiang Ge, Yong Zhang, Danni Liu, Dan Wu, Xu Sun, Bin Du, Qin Wei. Cobalt–borate nanowire array as a high-performance catalyst for oxygen evolution reaction in near-neutral media. Journal of Materials Chemistry A 2017, 5 (16) , 7291-7294.
  43. Bishnu Prasad Bastakoti, Yunqi Li, Sudhina Guragain, Malay Pramanik, Saad M. Alshehri, Tansir Ahamad, Zongwen Liu, Yusuke Yamauchi. Synthesis of Mesoporous Transition‐Metal Phosphates by Polymeric Micelle Assembly. Chemistry – A European Journal 2016, 22 (22) , 7463-7467.
  44. Markus D. Kärkäs, Björn Åkermark. Water oxidation using earth-abundant transition metal catalysts: opportunities and challenges. Dalton Transactions 2016, 45 (37) , 14421-14461.
  45. Shaohui Zheng, Jim Pfaendtner. Enhanced sampling of chemical and biochemical reactions with metadynamics. Molecular Simulation 2015, 41 (1-3) , 55-72.
  46. Ya-Rong Zheng, Min-Rui Gao, Qiang Gao, Hui-Hui Li, Jie Xu, Zhen-Yu Wu, Shu-Hong Yu. An Efficient CeO 2 /CoSe 2 Nanobelt Composite for Electrochemical Water Oxidation. Small 2015, 11 (2) , 182-188.
  47. Tianhua Zhou, Danping Wang, Simon Chun-Kiat Goh, Jindui Hong, Jianyu Han, Jianggao Mao, Rong Xu. Bio-inspired organic cobalt( ii ) phosphonates toward water oxidation. Energy & Environmental Science 2015, 8 (2) , 526-534.
  48. Debora Ressnig, Menny Shalom, Jörg Patscheider, René Moré, Fabio Evangelisti, Markus Antonietti, Greta R. Patzke. Photochemical and electrocatalytic water oxidation activity of cobalt carbodiimide. Journal of Materials Chemistry A 2015, 3 (9) , 5072-5082.
  49. Marcel Risch, Katharina Klingan, Ivelina Zaharieva, Holger Dau. Water Oxidation by Co-Based Oxides with Molecular Properties. 2014,,, 163-185.
  50. Timothy C. Davenport, Hyun S. Ahn, Micah S. Ziegler, T. Don Tilley. A molecular structural analog of proposed dinuclear active sites in cobalt-based water oxidation catalysts. Chemical Communications 2014, 50 (48) , 6326.
  51. Daniele Bovi, Daniele Narzi, Leonardo Guidoni. Magnetic interactions in the catalyst used by nature to split water: a DFT + U multiscale study on the Mn 4 CaO 5 core in photosystem II. New Journal of Physics 2014, 16 (1) , 015020.
  52. Ye Zhang, Chunsong Zhao, Xuezeng Dai, Hong Lin, Bai Cui, Jianbao Li. Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst. Journal of Power Sources 2013, 243 , 908-912.
  53. Eric J. Bylaska, Jonathan Q. Weare, John H. Weare. Extending molecular simulation time scales: Parallel in time integrations for high-level quantum chemistry and complex force representations. The Journal of Chemical Physics 2013, 139 (7) , 074114.