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The high world energy consumption, the depletion of global oil reserves and pollution of the environment, mainly caused by the combustion of fossil fuels, are spurring the research community to develop environmentally friendly fuel alternatives. Hydrogen is regarded as one of the most important substitutes of fossil fuels, since it fulfills the environmental restrictions, generates energy and produces only water after combustion. However, most of the hydrogen commercially available is mainly produced by reforming of natural gas, involving the final production of CO2. The electrolysis of water to produce hydrogen and oxygen is well known; however, the process is expensive and is energy intensive. In order for this reaction to become economically affordable, the development of new electrocatalysts is very important. Among the catalysts used for this reaction, metal phosphides are very active and interesting materials. In this review, the synthesis, characterisation and application of metal phosphides, mainly as catalysts in the electrolysis of water, will be discussed. Furthermore, the advantages and drawbacks of these electrocatalysts are highlighted. A brief description of the electrolysis of water and basic concepts are also included. Finally, the challenges for the use of metal phosphides as catalysts in the electrolysis of water are outlined.

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