Homogeneous Photochemical Water Oxidation with Cobalt Chloride in Acidic Media

View Author Information
Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland
Laboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 2, CH-8093 Zurich, Switzerland
Cite this: ACS Catal. 2015, 5, 9, 4994–4999
Publication Date (Web):July 24, 2015
Copyright © 2015 American Chemical Society
Article Views
Read OnlinePDF (1 MB)
Supporting Info (1)»


The precise mechanisms of four-electron-transfer water oxidation processes remain to be further understood. Oxide-based precipitation from molecular catalysts as a frequent observation during water oxidation has raised extensive debates on the differentiation between homogeneous and heterogeneous catalysis. Although soluble cobalt salts are known to be active in water oxidation, CoOx species formed in situ were generally considered to be the true catalyst. Here we report on the possibility homogeneous water oxidation with cobalt chloride in acidic conditions, which prevent CoOx precipitation. Interestingly, both the buffer media and counteranions were found to significantly influence the oxygen evolution activity, and their roles in the water oxidation process were analyzed with various techniques. This study sheds new light on Co2+ ions in key transformation processes of homogeneous water oxidation catalysts.

Supporting Information

Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.5b01101.

  • Experimental details and further data (additional photochemical and electrochemical water oxidation results, 1H NMR, DLS, SEM-EDX, and UV/vis data, 18O labeling experiments, and quantum chemical calculations) (PDF)

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: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 17 publications.

  1. Koteswara Rao Gorantla, Bhabani S. Mallik. Mechanism and Dynamics of Formation of Bisoxo Intermediates and O–O Bond in the Catalytic Water Oxidation Process. The Journal of Physical Chemistry A 2021, 125 (1) , 279-290. https://doi.org/10.1021/acs.jpca.0c09943
  2. Florian H. Hodel and Sandra Luber . Dehydrogenation Free Energy of Co2+(aq) from Density Functional Theory-Based Molecular Dynamics. Journal of Chemical Theory and Computation 2017, 13 (3) , 974-981. https://doi.org/10.1021/acs.jctc.6b01077
  3. Merve Aksoy, Satya Vijaya Kumar Nune, and Ferdi Karadas . A Novel Synthetic Route for the Preparation of an Amorphous Co/Fe Prussian Blue Coordination Compound with High Electrocatalytic Water Oxidation Activity. Inorganic Chemistry 2016, 55 (9) , 4301-4307. https://doi.org/10.1021/acs.inorgchem.6b00032
  4. Mauro Schilling, Greta R. Patzke, Jürg Hutter, and Sandra Luber . Computational Investigation and Design of Cobalt Aqua Complexes for Homogeneous Water Oxidation. The Journal of Physical Chemistry C 2016, 120 (15) , 7966-7975. https://doi.org/10.1021/acs.jpcc.6b00712
  5. Paul F. Smith, Liam Hunt, Anders B. Laursen, Viral Sagar, Shivam Kaushik, Karin U. D. Calvinho, Gabriele Marotta, Edoardo Mosconi, Filippo De Angelis, and G. Charles Dismukes . Water Oxidation by the [Co4O4(OAc)4(py)4]+ Cubium is Initiated by OH– Addition. Journal of the American Chemical Society 2015, 137 (49) , 15460-15468. https://doi.org/10.1021/jacs.5b09152
  6. Koteswara Rao Gorantla, Bhabani S. Mallik. Understanding the role of fluorination in the mechanistic nature of the water splitting process catalyzed by cobalt tris-(2-pyridylmethyl)amine complexes. Sustainable Energy & Fuels 2021, 5 (8) , 2313-2324. https://doi.org/10.1039/D0SE01487G
  7. Yinjuan Dong, Qing Han, Kangwei Ma, Fangyuan Song, Shoutian Zheng, Yong Ding. Study two kind different catalytic behaviors for K4H1.2[Co0.6(H2O)0.6SiW11.4O39.4]-cocatalyzed visible light driven water oxidation in pH 1–7 media. Journal of Catalysis 2020, 392 , 29-38. https://doi.org/10.1016/j.jcat.2020.09.031
  8. Lingjing Chen, Gui Chen, Chi-Fai Leung, Claudio Cometto, Marc Robert, Tai-Chu Lau. Molecular quaterpyridine-based metal complexes for small molecule activation: water splitting and CO 2 reduction. Chemical Society Reviews 2020, 49 (20) , 7271-7283. https://doi.org/10.1039/D0CS00927J
  9. Hossain M. Shahadat, Hussein A. Younus, Nazir Ahmad, Shiguo Zhang, Serge Zhuiykov, Francis Verpoort. Macrocyclic cyanocobalamin (vitamin B 12 ) as a homogeneous electrocatalyst for water oxidation under neutral conditions. Chemical Communications 2020, 56 (13) , 1968-1971. https://doi.org/10.1039/C9CC08838E
  10. Totan Ghosh, Galia Maayan. Efficient Homogeneous Electrocatalytic Water Oxidation by a Manganese Cluster with an Overpotential of Only 74 mV. Angewandte Chemie 2019, 131 (9) , 2811-2816. https://doi.org/10.1002/ange.201813895
  11. Totan Ghosh, Galia Maayan. Efficient Homogeneous Electrocatalytic Water Oxidation by a Manganese Cluster with an Overpotential of Only 74 mV. Angewandte Chemie International Edition 2019, 58 (9) , 2785-2790. https://doi.org/10.1002/anie.201813895
  12. Junqi Lin, Baochun Ma, Mindong Chen, Yong Ding. Water oxidation catalytic ability of polypyridine complex containing a μ-OH, μ-O2 dicobalt(iii) core. Chinese Journal of Catalysis 2018, 39 (3) , 463-471. https://doi.org/10.1016/S1872-2067(17)62923-1
  13. Yong-Jun Yuan, Zhen-Tao Yu, Da-Qin Chen, Zhi-Gang Zou. Metal-complex chromophores for solar hydrogen generation. Chemical Society Reviews 2017, 46 (3) , 603-631. https://doi.org/10.1039/C6CS00436A
  14. Yan Zhang, Jingwei Huang, Yong Ding. Porous Co 3 O 4 /CuO hollow polyhedral nanocages derived from metal-organic frameworks with heterojunctions as efficient photocatalytic water oxidation catalysts. Applied Catalysis B: Environmental 2016, 198 , 447-456. https://doi.org/10.1016/j.apcatb.2016.05.078
  15. Ryota Terao, Takashi Nakazono, Alexander Rene Parent, Ken Sakai. Photochemical Water Oxidation Catalyzed by a Water-Soluble Copper Phthalocyanine Complex. ChemPlusChem 2016, 81 (10) , 1064-1067. https://doi.org/10.1002/cplu.201600263
  16. Shunichi Fukuzumi, Jieun Jung, Yusuke Yamada, Takahiko Kojima, Wonwoo Nam. Homogeneous and Heterogeneous Photocatalytic Water Oxidation by Persulfate. Chemistry – An Asian Journal 2016, 11 (8) , 1138-1150. https://doi.org/10.1002/asia.201501329
  17. Gang-Yi Luo, Hai-Hua Huang, Jia-Wei Wang, Tong-Bu Lu. Further Investigation of a Nickel-Based Homogeneous Water Oxidation Catalyst with Two cis Labile Sites. ChemSusChem 2016, 9 (5) , 485-491. https://doi.org/10.1002/cssc.201501474