Metal-modified covalent organic frameworks for photocatalytic CO2 reduction toward a circular economy: Novel structural designs to high-value renewable fuels
Coordination Chemistry Reviews, cilt.568, 2026 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Derleme
- Cilt numarası: 568
- Basım Tarihi: 2026
- Doi Numarası: 10.1016/j.ccr.2026.218381
- Dergi Adı: Coordination Chemistry Reviews
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core, Chimica, Academic Search Ultimate (EBSCO)
- Anahtar Kelimeler: Data-driven catalyst design, Metal-modified covalent organic frameworks, Photocatalytic CO2 reduction, Structure-activity relationships, Sustainable carbon conversion
- Sivas Cumhuriyet Üniversitesi Adresli: Evet
Özet
Photocatalytic reduction of carbon dioxide (CO2) to value-added fuels and chemicals is a promising route to achieving carbon neutrality and sustainable energy conversion. Covalent-organic frameworks (COFs) are considered a promising material for photocatalysis due to their crystalline regularity, tunable porosity, π-conjugated skeletons and reticulate chemistry-fabricated modular engineering. However, pristine COFs suffer from several shortcomings, including inadequate activity and inefficient charge separation, which compromise catalytic selectivity. To overcome these intrinsic shortcomings, COF structures with heterometallic species have emerged as a promising approach to form electronically and catalytically active systems. In this review article, we focus on recent advancements in metal-modified COFs (MCOFs) for photocatalytic CO2 reduction and critically analyse the mechanistic roles of metal centres in controlling electronic structure, charge transfer ability, and reaction selectivity. The underlying principles of selective CO2 activation, emphasizing the role of single-site metal atoms, metal clusters, and bimetal sites enabling CO2 adsorption, stabilize key intermediates (∗COOH and ∗CO), and escape from competitive hydrogen evolution reactions. In addition, synthesis methods involving pre-synthetic, in-situ, and post-synthetic metal introduction are systematically summarized in terms of their effects on the resulting metal coordination environments as well as framework crystallinity. Finally, current challenges and future perspectives are discussed to provide direction for the rational design of an M-COF-based next-generation photocatalyst for highly efficient and selective CO2 reduction.