The efficient catalysis of the four-electron oxidation of water to molecular oxygen is a central challenge for the development of devices for the production of solar fuels. This is equally true for artificial leaf-type structures and electrolyzer systems. Inspired by the oxygen evolving complex of Photosystem II, the biological catalyst for this reaction, scientists around the globe have investigated the possibility to use manganese oxides (“MnOx”) for this task. This perspective article will look at selected examples from the last about 10 years of research in this field. At first, three aspects are addressed in detail which have emerged as crucial for the development of efficient electrocatalysts for the anodic oxygen evolution reaction (OER): (1) the structure and composition of the “MnOx” is of central importance for catalytic performance and it seems that amorphous, MnIII/IV oxides with layered or tunnelled structures are especially good choices; (2) the type of support material (e.g. conducting oxides or nanostructured carbon) as well as the methods used to immobilize the MnOx catalysts on them greatly influence OER overpotentials, current densities and long-term stabilities of the electrodes and (3) when operating MnOx-based water-oxidizing anodes in electrolyzers, it has often been observed that the electrocatalytic performance is also largely dependent on the electrolyte’s composition and pH and that a number of equilibria accompany the catalytic process, resulting in “adaptive changes” of the MnOx material over time. Overall, it thus has become clear over the last years that efficient and stable water-oxidation electrolysis by manganese oxides can only be achieved if at least four parameters are optimized in combination: the oxide catalyst itself, the immobilization method, the catalyst support and last but not least the composition of the electrolyte. Furthermore, these parameters are not only important for the electrode optimization process alone but must also be considered if different electrode types are to be compared with each other or with literature values from literature. Because, as without their consideration it is almost impossible to draw the right scientific conclusions. On the other hand, it currently seems unlikely that even carefully optimized MnOx anodes will ever reach the superb OER rates observed for iridium, ruthenium or nickel-iron oxide anodes in acidic or alkaline solutions, respectively. So at the end of the article, two fundamental questions will be addressed: (1) are there technical applications where MnOx materials could actually be the first choice as OER electrocatalysts? and (2) do the results from the last decade of intensive research in this field help to solve a puzzle already formulated in 2008: “Why did nature choose manganese to make oxygen?”.
On the path to an energy transition away from fossil fuels to sustainable sources, the European Union is for the moment keeping pace with the objectives of the Strategic Energy Technology-Plan. For this trend to continue after 2020, scientific breakthroughs must be achieved. One main objective is to produce solar fuels from solar energy and water in direct processes to accomplish the efficient storage of solar energy in a chemical form. This is a grand scientific challenge. One important approach to achieve this goal is Artificial Photosynthesis. The European Energy Research Alliance has launched the Joint Programme “Advanced Materials & Processes for Energy Applications” (AMPEA) to foster the role of basic science in Future Emerging Technologies. European researchers in artificial photosynthesis recently met at an AMPEA organized workshop to define common research strategies and milestones for the future. Through this work artificial photosynthesis became the first energy research sub-field to be organised into what is designated “an Application” within AMPEA. The ambition is to drive and accelerate solar fuels research into a powerful European field – in a shorter time and with a broader scope than possible for individual or national initiatives. Within AMPEA the Application Artificial Photosynthesis is inclusive and intended to bring together all European scientists in relevant fields. The goal is to set up a thorough and systematic programme of directed research, which by 2020 will have advanced to a point where commercially viable artificial photosynthetic devices will be under development in partnership with industry.