Skip to main content Accessibility help

Perspectives on the photoelectrochemical storage of solar energy

  • Roel van de Krol (a1) and Bruce A. Parkinson (a2)


Direct photoelectrochemical water splitting offers several advantages over PV-powered electrolysis and may become the technology of choice in the future. However, significant R&D efforts and breakthroughs are needed to accomplish this goal.

The sustainable production of hydrogen would be an important first step for both powering fuel cells and for enabling large-scale and technologically mature gas phase processes to reduce CO2 and nitrogen to get desired products. Specifically, the central challenge is to produce hydrogen from water using sunlight. Photovoltaics and wind-powered electrolysis are likely to be the technology of choice to produce renewable hydrogen for the next few decades. However, the integration of light absorption and catalysis in ‘direct’ photoelectrolysis routes offers several advantages, such as lower current densities and better heat management, and may become technologically relevant in the second half of this century. This article discusses the research and development efforts and needed breakthroughs to achieve this goal. New chemically stable semiconductors with a band gap between 1.5 and 2.0 eV and long carrier lifetimes are urgently needed to make efficient tandem devices. Scale-up of these research level devices beyond a few cm2 introduces mass transport limitations that require creative electrochemical engineering solutions. Last but not least, standardized methods for measuring efficiencies and stabilities need to be implemented and should lead to official benchmarking and certification laboratories to guide commercial scale up efforts.

  • View HTML
    • Send article to Kindle

      To send this article to your Kindle, first ensure is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about sending to your Kindle. Find out more about sending to your Kindle.

      Note you can select to send to either the or variations. ‘’ emails are free but can only be sent to your device when it is connected to wi-fi. ‘’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

      Find out more about the Kindle Personal Document Service.

      Perspectives on the photoelectrochemical storage of solar energy
      Available formats

      Send article to Dropbox

      To send this article to your Dropbox account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Dropbox.

      Perspectives on the photoelectrochemical storage of solar energy
      Available formats

      Send article to Google Drive

      To send this article to your Google Drive account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Google Drive.

      Perspectives on the photoelectrochemical storage of solar energy
      Available formats


Corresponding author

a) Address all correspondence to Roel van de Krol at


Hide All
1. Our (conservative) estimate of the total expenditure is based on data in the following presentation, to which we added the budgets of several other European initiatives that we are aware of: S. Dasgupta: Global Centers for Solar Fuels & Artificial Photosynthesis [Online]. Available at: (accessed October 15, 2017).
2. Turan, B., Becker, J.P., Urbain, F., Finger, F., Rau, U., and Haas, S.: Upscaling of integrated photoelectrochemical water-splitting devices to large areas. Nat. Commun. 7, 12681 (2016).
3. May, M.M., Lewerenz, H.J., Lackner, D., Dimroth, F., and Hannappel, T.: Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure. Nat. Commun. 6, 8286 (2015).
4. Bornoz, P., Abdi, F.F., Tilley, S.D., Dam, B., van de Krol, R., Grätzel, M., and Sivula, K.: A bismuth vanadate-cuprous oxide tandem cell for overall solar water splitting. J. Phys. Chem. C 118, 16959 (2014).
5. Jia, J.Y., Seitz, L.C., Benck, J.D., Huo, Y.J., Chen, Y.S., Ng, J.W.D., Bilir, T., Harris, J.S., and Jaramillo, T.F.: Solar water splitting by photovoltaic-electrolysis with a solar-to-hydrogen efficiency over 30%. Nat. Commun. 7, 12237 (2016).
6. Chung, D., Davidson, C., Fu, R., Ardani, K., and Margolis, R.: U.S. Photovoltaic Prices and Cost Breakdowns: Q1 2015 Benchmarks for Residential, Commercial, and Utility-Scale Systems [Report] (National Renewable Energy Laboratory (NREL), Golden, CO, 2015).
7. Miller, E., Ainscough, C., and Talapatra, A.: Hydrogen Production Status 2006–2013 [Report] (United States Department of Energy, Washington, DC, 2014).
8. Bundesnetzagentur announces successful bids in photovoltaic auction with Denmark [Online]. Available at: (accessed October 15, 2017).
9. Newman, J., Hoertz, P.G., Bonino, C.A., and Trainham, J.A.: Review: An economic perspective on liquid solar fuels. J. Electrochem. Soc. 159, A1722 (2012).
10. Dumortier, M., Tembhurne, S., and Haussener, S.: Holistic design guidelines for solar hydrogen production by photo-electrochemical routes. Energy Environ. Sci. 8, 3614 (2015).
11. Pinaud, B.A., Benck, J.D., Seitz, L.C., Forman, A.J., Chen, Z.B., Deutsch, T.G., James, B.D., Baum, K.N., Baum, G.N., Ardo, S., Wang, H.L., Miller, E., and Jaramillo, T.F.: Technical and economic feasibility of centralized facilities for solar hydrogen production via photocatalysis and photoelectrochemistry. Energy Environ. Sci. 6, 1983 (2013).
12. Haussener, S., Hu, S., Xiang, C.X., Weber, A.Z., and Lewis, N.S.: Simulations of the irradiation and temperature dependence of the efficiency of tandem photoelectrochemical water-splitting systems. Energy Environ. Sci. 6, 3605 (2013).
13. Würfel, P.: Physics of Solar Cells (Wiley-VCH, Weinheim, 2005).
14. Tembhurne, S. and Haussener, S.: Integrated photo-electrochemical solar fuel generators under concentrated irradiation II. Thermal management a crucial design consideration. J. Electrochem. Soc. 163, H999 (2016).
15. Ye, X., Melas-Kyriazi, J., Feng, Z.A., Melosh, N.A., and Chueh, W.C.: A semiconductor/mixed ion and electron conductor heterojunction for elevated-temperature water splitting. Phys. Chem. Chem. Phys. 15, 15459 (2013).
16. Parkinson, B.: Advantages of solar hydrogen compared to direct carbon dioxide reduction for solar fuel production. ACS Energy Lett. 1, 1057 (2016).
17. Reller, C., Krause, R., Volkova, E., Schmid, B., Neubauer, S., Rucki, A., Schuster, M., and Schmid, G.: Selective electroreduction of CO2 toward ethylene on nano dendritic copper catalysts at high current density. Adv. Energy Mater. 7, 1602114 (2017).
18. LeCompte, C.: Fertilizer Plants Spring up to Take Advantage of U.S.’s Cheap Natural Gas, Scientific American [Online]. Available at: (accessed August 7, 2017).
19. Fertilizer and crop production [Online]. Available at: (accessed August 11, 2017).
20. Yu, M.Z., McCulloch, W.D., Huang, Z.J., Trang, B.B., Lu, J., Amine, K., and Wu, Y.Y.: Solar-powered electrochemical energy storage: An alternative to solar fuels. J. Mater. Chem. A 4, 2766 (2016).
21. Wedege, K., Azevedo, J., Khataee, A., Bentien, A., and Mendes, A.: Direct solar charging of an organic-inorganic, stable, and aqueous alkaline redox flow battery with a hematite photoanode. Angew. Chem., Int. Ed. 55, 7142 (2016).
22. Manassen, J., Hodes, G., and Cahen, D.: Photoelectrochemical energy—conversion and storage—polycrystalline CdSe cell with different storage modes. J. Electrochem. Soc. 124, 532 (1977).
23. Porter, W.A., Lathrop, J.W., and Kilby, J.S.: Solar energy conversion. U.S. Patent No. 0402132, 1975.
24. Porter, W.A., Lathrop, J.W., and Kilby, J.S.: Light energy conversion. U.S. Patent No. 4100051, 1976.
25. Fornarini, L., Nozik, A.J., and Parkinson, B.A.: The energetics of P/N photoelectrolysis cells. J. Phys. Chem. 88, 3238 (1984).
26. Hu, S., Lewis, N.S., Ager, J.W., Yang, J.H., McKone, J.R., and Strandwitz, N.C.: Thin-film materials for the protection of semiconducting photoelectrodes in solar-fuel generators. J. Phys. Chem. C 119, 24201 (2015).
27. Verlage, E., Hu, S., Liu, R., Jones, R.J.R., Sun, K., Xiang, C.X., Lewis, N.S., and Atwater, H.A.: A monolithically integrated, intrinsically safe, 10% efficient, solar-driven water-splitting system based on active, stable earth-abundant electrocatalysts in conjunction with tandem III–V light absorbers protected by amorphous TiO2 films. Energy Environ. Sci. 8, 3166 (2015).
28. McCrory, C.C.L., Jung, S., Ferrer, I.M., Chatman, S.M., Peters, J.C., and Jaramillo, T.F.: Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J. Am. Chem. Soc. 137, 4347 (2015).
29. Kanan, M.W. and Nocera, D.G.: In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+ . Science 321, 1072 (2008).
30. Seh, Z.W., Kibsgaard, J., Dickens, C.F., Chorkendorff, I.B., Norskov, J.K., and Jaramillo, T.F.: Combining theory and experiment in electrocatalysis: Insights into materials design. Science 355, 146 (2017).
31. Seitz, L.C., Chen, Z.B., Forman, A.J., Pinaud, B.A., Benck, J.D., and Jaramillo, T.F.: Modeling practical performance limits of photoelectrochemical water splitting based on the current state of materials research. ChemSusChem 7, 1372 (2014).
32. Weber, M.F. and Dignam, M.J.: Efficiency of splitting water with semiconducting photoelectrodes. J. Electrochem. Soc. 131, 1258 (1984).
33. Hu, S., Xiang, C.X., Haussener, S., Berger, A.D., and Lewis, N.S.: An analysis of the optimal band gaps of light absorbers in integrated tandem photoelectrochemical water-splitting systems. Energy Environ. Sci. 6, 2984 (2013).
34. Sivula, K. and van de Krol, R.: Semiconducting materials for photoelectrochemical energy conversion. Nat. Rev. Mater. 1, 15010 (2016).
35. Pihosh, Y., Turkevych, I., Mawatari, K., Uemura, J., Kazoe, Y., Kosar, S., Makita, K., Sugaya, T., Matsui, T., Fujita, D., Tosa, M., Kondo, M., and Kitamori, T.: Photocatalytic generation of hydrogen by core–shell WO3/BiVO4 nanorods with ultimate water splitting efficiency. Sci. Rep. 5, 11141 (2015).
36. Woodhouse, M. and Parkinson, B.A.: Combinatorial approaches for the identification and optimization of oxide semiconductors for efficient solar photoelectrolysis. Chem. Soc. Rev. 38, 197 (2009).
37. Rowley, J.G., Do, T.D., Cleary, D.A., and Parkinson, B.A.: Combinatorial discovery through a distributed outreach Program: Investigation of the photoelectrolysis activity of p-type Fe, Cr, Al oxides. ACS Appl. Mater. Interfaces 6, 9046 (2014).
38. Baeck, S.H., Jaramillo, T.F., Brandli, C., and McFarland, E.W.: Combinatorial electrochemical synthesis and characterization of tungsten-based mixed-metal oxides. J. Comb. Chem. 4, 563 (2002).
39. Keller, D.A., Ginsburg, A., Barad, H.N., Shirnanovich, K., Bouhadana, Y., Rosh-Hodesh, E., Takeuchi, I., Aviv, H., Tischler, Y.R., Anderson, A.Y., and Zaban, A.: Utilizing pulsed laser deposition lateral inhomogeneity as a tool in combinatorial material science. ACS Comb. Sci. 17, 209 (2015).
40. Koinuma, H. and Takeuchi, I.: Combinatorial solid-state chemistry of inorganic materials. Nat. Mater. 3, 429 (2004).
41. Yan, Q.M., Yu, J., Suram, S.K., Zhou, L., Shinde, A., Newhouse, P.F., Chen, W., Li, G., Persson, K.A., Gregoire, J.M., and Neaton, J.B.: Solar fuels photoanode materials discovery by integrating high-throughput theory and experiment. Proc. Natl. Acad. Sci. U. S. A. 114, 3040 (2017).
42. Abdi, F.F., Chemseddine, A., Berglund, S.P., and van de Krol, R.: Assessing the suitability of iron tungstate (Fe2WO6) as a photoelectrode material for water oxidation. J. Phys. Chem. C 121, 153 (2017).
43. Ager, J.W., Shaner, M.R., Walczak, K.A., Sharp, I.D., and Ardo, S.: Experimental demonstrations of spontaneous, solar-driven photoelectrochemical water splitting. Energy Environ. Sci. 8, 2811 (2015).
44. Modestino, M.A., Hashemi, S.M.H., and Haussener, S.: Mass transport aspects of electrochemical solar-hydrogen generation. Energy Environ. Sci. 9, 1533 (2016).
45. Sasaki, Y., Iwase, A., Kato, H., and Kudo, A.: The effect of co-catalyst for Z-scheme photocatalysis systems with an Fe3+/Fe2+ electron mediator on overall water splitting under visible light irradiation. J. Catal. 259, 133 (2008).
46. Maeda, K., Teramura, K., Lu, D., Saito, N., Inoue, Y., and Domen, K.: Noble-metal/Cr2O3 core/shell nanoparticles as a cocatalyst for photocatalytic overall water splitting. Angew. Chem., Int. Ed. 45, 7806 (2006).
47. Dionigi, F., Vesborg, P.C.K., Pedersen, T., Hansen, O., Dahl, S., Xiong, A.K., Maeda, K., Domen, K., and Chorkendorff, I.: Suppression of the water splitting back reaction on GaN:ZnO photocatalysts loaded with core/shell cocatalysts, investigated using a mu-reactor. J. Catal. 292, 26 (2012).
48. Sayama, K., Mukasa, K., Abe, R., Abe, Y., and Arakawa, H.: Stoichiometric water splitting into H2 and O2 using a mixture of two different photocatalysts and an IO3 /I shuttle redox mediator under visible light irradiation. Chem. Commun., 0(23), 2416 (2001).
49. Miseki, Y., Fujiyoshi, S., Gunji, T., and Sayama, K.: Photocatalytic Z-scheme water splitting for independent H2/O2 production via a stepwise operation employing a vanadate redox mediator under visible light. J. Phys. Chem. C 121, 9691 (2017).
50. Liu, C., Colon, B.C., Ziesack, M., Silver, P.A., and Nocera, D.G.: Water splitting-biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis. Science 352, 1210 (2016).
51. May, M.M., Lackner, D., Ohlmann, J., Dimroth, F., van de Krol, R., Hannappel, T., and Schwarzburg, K.: On the benchmarking of multi-junction photoelectrochemical fuel generating devices. Sustainable Energy Fuels 1, 492 (2017).
52. Döscher, H., Young, J.L., Geisz, J.F., Turner, J.A., and Deutsch, T.G.: Solar-to-hydrogen efficiency: Shining light on photoelectrochemical device performance. Energy Environ. Sci. 9, 74 (2016).
53. Döscher, H., Geisz, J.F., Deutsch, T.G., and Turner, J.A.: Sunlight absorption in water—efficiency and design implications for photoelectrochemical devices. Energy Environ. Sci. 7, 2951 (2014).
54. McCrory, C.C.L., Jung, S.H., Peters, J.C., and Jaramillo, T.F.: Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 135, 16977 (2013).
55. Chen, Z.B., Jaramillo, T.F., Deutsch, T.G., Kleiman-Shwarsctein, A., Forman, A.J., Gaillard, N., Garland, R., Takanabe, K., Heske, C., Sunkara, M., McFarland, E.W., Domen, K., Miller, E.L., Turner, J.A., and Dinh, H.N.: Accelerating materials development for photoelectrochemical hydrogen production: Standards for methods, definitions, and reporting protocols. J. Mater. Res. 25, 3 (2010).
56. Parkinson, B.: On the efficiency and stability of photoelectrochemical devices. Acc. Chem. Res. 17, 431 (1984).


Related content

Powered by UNSILO

Perspectives on the photoelectrochemical storage of solar energy

  • Roel van de Krol (a1) and Bruce A. Parkinson (a2)


Altmetric attention score

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed.