Catalytic Innovations for High-Yield Biohydrogen Production in Integrated Dark Fermentation and Microbial Electrolysis Systems

Biohydrogen, a low-carbon footprint technology, can play a significant role in decarbonizing the energy system. It uses existing infrastructure, is easily transportable, and produces no greenhouse gas emissions. Four technologies can be used to produce biohydrogen: photosynthetic biohydrogen, dark fermentation (DF), photo-fermentation, and microbial electrolysis cells (MECs). DF produces more biohydrogen and is flexible with organic substrates, making it a sustainable method of waste repurposing. However, low achievable biohydrogen yields are a common issue. To overcome this, catalytic mechanisms, including enzymatic systems such as [Fe-Fe]- and [Ni-Fe]-hydrogenases in DF and electroactive microbial consortia in MECs, alongside advanced electrode catalysts which collectively surmount thermodynamic and kinetic constraints, and the two stage system, such as DF connection to photo-fermentation and anaerobic digestion (AD) to microbial electrolysis cells (MECs), have been investigated. MECs can generate biohydrogen at better yields by using sugars or organic acids, and combining DF and MEC technologies could improve biohydrogen production. As such, this review highlights the challenges and possible solutions for coupling DF–MEC while also offering knowledge regarding the technical and microbiological aspects.