Trevor Smith

Sensitive detection of surface- and size-dependent direct and indirect band gap transitions in ferritin

Ferritin is a protein nano-cage that encapsulates minerals inside an 8 nm cavity. Previous band gap measurements on the native mineral, ferrihydrite, have reported gaps as low as 1.0 eV and as high as 2.5-3.5 eV. To resolve this discrepancy we have used optical absorption spectroscopy, a well-established technique for measuring both direct and indirect band gaps. Our studies included controls on the protein nano-cage, ferritin with the native ferrihydrite mineral, and ferritin with reconstituted ferrihydrite cores of different sizes. We report measurements of an indirect band gap for native ferritin of 2.140 ± 0.015 eV (579.7 nm), with a direct transition appearing at 3.053 ± 0.005 eV (406.1 nm). We also see evidence of a defect-related state having a binding energy of 0.220 ± 0.010 eV . Reconstituted ferrihydrite minerals of different sizes were also studied and showed band gap energies which increased with decreasing size due to quantum confinement effects. Molecules that interact with the surface of the mineral core also demonstrated a small influence following trends in ligand field theory, altering the native minerals band gap up to 0.035 eV.

Ferritin as a model for developing 3rd generation nano architecture organic/inorganic hybrid photo catalysts for energy conversion

Solar power is the best option to replace fossil fuels to meet global energy demands. Current photovoltaic and artificial photosynthetic systems require improvements and include the development of: 1) inexpensive, abundant, non-toxic charge separation catalysts that absorb visible light; 2) stable catalysts with high turnover numbers that possess self-healing mechanisms to prevent photo corrosion; 3) catalysts capable of oxidizing a broad range of electron donors; and 4) hybrid organic/inorganic nano architectures that bridge charge flow from electron donors to electron acceptors. The ferritin nanocage is a model system of such an organic/inorganic hybrid catalyst capable of overcoming these photochemical limitations.

Permanganate-based synthesis of manganese oxide nanoparticles in ferritin

This paper investigates the comproportionation reaction of MnII with [Formula: see text] as a route for manganese oxide nanoparticle synthesis in the protein ferritin. We report that [Formula: see text] serves as the electron acceptor and reacts with MnII in the presence of apoferritin to form manganese oxide cores inside the protein shell. Manganese loading into ferritin was studied under acidic, neutral, and basic conditions and the ratios of MnII and permanganate were varied at each pH. The manganese-containing ferritin samples were characterized by transmission electron microscopy, UV/Vis absorption, and by measuring the band gap energies for each sample. Manganese cores were deposited inside ferritin under both the acidic and basic conditions. All resulting manganese ferritin samples were found to be indirect band gap materials with band gap energies ranging from 1.01 to 1.34 eV. An increased UV/Vis absorption around 370 nm was observed for samples formed under acidic conditions, suggestive of MnO2 formation inside ferritin.

Non-native Co-, Mn-, and Ti-oxyhydroxide nanocrystals in ferritin for high efficiency solar energy conversion

Quantum dot solar cells seek to surpass the solar energy conversion efficiencies achieved by bulk semiconductors. This new field requires a broad selection of materials to achieve its full potential. The 12 nm spherical protein ferritin can be used as a template for uniform and controlled nanocrystal growth, and to then house the nanocrystals for use in solar energy conversion. In this study, precise band gaps of titanium, cobalt, and manganese oxyhydroxide nanocrystals within ferritin were measured, and a change in band gap due to quantum confinement effects was observed. The range of band gaps obtainable from these three types of nanocrystals is 2.19-2.29 eV, 1.93-2.15 eV, and 1.60-1.65 eV respectively. From these measured band gaps, theoretical efficiency limits for a multi-junction solar cell using these ferritin-enclosed nanocrystals are calculated and found to be 38.0% for unconcentrated sunlight and 44.9% for maximally concentrated sunlight. If a ferritin-based nanocrystal with a band gap similar to silicon can be found (i.e. 1.12 eV), the theoretical efficiency limits are raised to 51.3% and 63.1%, respectively. For a current matched cell, these latter efficiencies become 41.6% (with an operating voltage of 5.49 V), and 50.0% (with an operating voltage of 6.59 V), for unconcentrated and maximally concentrated sunlight respectively.

Tuning the band gap of ferritin nanoparticles by co-depositing iron with halides or oxo-anions

Iron-containing ferritin has been used for light harvesting and as a photocatalyst. In this study, we test the hypothesis that changing the iron mineral core composition can alter the light harvesting and photocatalytic properties of ferritin, by co-depositing iron in the presence of halides or oxo-anions. This caused the anions to be incorporated into the iron mineral. We report that some of these new iron minerals possess different band gaps than the original ferrihydrite within ferritin. We found an increase in band gap of up to 0.288 eV or a decrease by as much as 0.104 eV, depending on the type of anion and amount of anions incorporated into the ferrihydrite mineral.