Activating Nonenzymatic Hemoglobin for Highly Selective CO ₂ -to-Formate Photoreduction in Water through Supramolecular Phenolic Mesocrystal Encapsulation

Photocatalytic CO 2 reduction offers a promising solar-to-chemical route, but most systems struggle to meet economic and scalability benchmarks. Current approaches fall short of the U.S. Department of Energy’s Carbon Negative Shot target of < $100/t CO 2 removed. Here, we develop an all-biomolecular nanophotosystem ( Hb -EA) without the involvement of synthetic metal catalysts, pairing a nonenzymatic protein with a plant-derived photosensitizer. Hemoglobin ( Hb ), a ubiquitous oxygen-carrier protein with reversible CO 2 -binding and redox-active heme sites that serve as biologically embedded metal centers, is supramolecularly encapsulated by crystalline ellagic acid (EA), forming an Hb -EA nanohybrid where π–π stacking and hydrogen bonding create an organic-semiconductor-like shell with a 2.44 eV bandgap and broad visible absorption. Upon illumination, the EA shell efficiently harvests light and funnels electrons into Hb heme centers, selectively capturing and reducing CO 2 to formic acid. Hb -EA achieves a benchmark-leading CO 2 -to-formate production rate of 397.61 μmol h –1 USD –1 with ∼93% selectivity, significantly surpassing prior systems in cost-normalized performance. This biobased photocatalyst uses no noble metals or external cocatalysts and is assembled from inexpensive biobuilding blocks. Scalability is demonstrated by a 100 × 60 cm Hb -EA membrane photoreactor under outdoor sunlight, where it maintained high activity and stability, establishing a paradigm for artificial photosynthesis linking structural biochemistry with sustainable photonic materials for green, economically viable CO 2 reduction.