Abstract
Hydrogenation is a pivotal process in organic synthesis and various catalytic strategies have been developed in achieving effective hydrogenation of diverse substrates. Despite the competence of these methods, the predominant reliance on molecular hydrogen (H(2)) gas under high temperature and elevated pressure presents operational challenges. Other alternative hydrogen sources such as inorganic hydrides and organic acids are often prohibitively expensive, limiting their practical utility on a large scale. In contrast, employing water as a hydrogen source for organic hydrogenation presents an attractive and sustainable alternative, promising to overcome the drawbacks associated with traditional hydrogen sources. Integrated with electricity as the sole driving force under ambient conditions, hydrogenation using water as the sole hydrogen source aligns well with the environmental sustainability goals but also offers a safer and potentially more cost-effective solution. This article starts with the discussion on the inherent advantages and limitations of conventional hydrogen sources compared to water in hydrogenation reactions, followed by the introduction of representative electrocatalytic systems that successfully utilize water as the hydrogen source in realizing a large number of organic hydrogenation transformations, with a focus on heterogeneous electrocatalysts. In summary, transitioning to water as a hydrogen source in organic hydrogenation represents a promising direction for sustainable chemistry. In particular, by exploring and optimizing electrocatalytic hydrogenation systems, the chemical industry can reduce its reliance on hazardous and expensive hydrogen sources, paving the way for safer, greener, and less energy-intensive hydrogenation processes.