Molecular electro- and photocatalytic approach to artificial nitrogen fixation for the synthesis of green ammonia

Ammonia (NH3) stands as a cornerstone compound across industries, pivotal in agriculture, chemicals, and energy sectors. However, the conventional Haber-Bosch process demands high pressures, temperatures, and fossil fuels, calling for sustainable alternatives. Electrocatalytic Nitrogen Reduction Reactions (E-NRRs) and Photocatalytic Nitrogen Reduction Reactions (Photo-NRRs) present innovative routes, leveraging electricity and direct sunlight to convert nitrogen (N2) to NH3 under mild conditions, reducing emissions and softening energy requirements. Catalysts play a strategic role in these approaches, overcoming activation barriers and enhancing efficiency. However, some challenges still need to be addressed. Indeed, noble metals exhibit limits and their scarcity, geopolitical involvement, and often fluctuating costs inhibit large-scale use. Non-noble metals offer promise but require optimization and face durability concerns. Finally, carbon-based catalysts present challenges in optimization and doping. In this scenario, a molecular-based approach, comprising both specific single coordination-based molecules with transition metal centres and either metal centre coordination-based or fully organic multi-dimensional networks originating from direct molecular organic precursors, overcomes these issues while keeping the benefits of the previously mentioned classes of compounds. This mini-review explores the molecular approach to E-NRRs and Photo-NRRs from coordination compounds carrying porphyrins and phthalocyanines as organic ligands to polymeric networks based on coordination compounds between metallic centres and organic ligands (Metal-Organic Frameworks), and to networks of molecular organic units into multi-dimensional structures (Covalent Organic Frameworks). Mechanistic insights into E-NRRs and Photo-NRRs pathways elucidate N2 conversion to NH3. A critical comparative evaluation of reported catalysts has been carried out to highlight the limits and the possibilities of each class of compounds. Although challenges persist in terms of stability, cost and complexity of the synthesis, the use of a molecular approach in NRRs represents one of the most promising routes towards the sustainable preparation of ammonia.