Search

Spinel iron oxide nanocrystals (NCs) have been reported to have atomic-level core and surface structural features that differ from those of the bulk material. Recent advances in a continuous growth synthesis of metal oxide NCs make it possible to prepare a series of NCs with subnanometer control of size with diameters below 10 nm that are well-suited for investigating size-dependent structure and reactivity. Here, we study the evolution of size-dependent structure in spinel iron oxide and determine how nanoscale structure influences the growth of NCs. We synthesized spinel iron oxide NCs via a continuous growth method that permits layer-by-layer control of size in order to monitor nanoscale structure over 16 core sizes between 3 and 10 nm. X-ray total scattering data were collected and analyzed with pair distribution function (PDF) analysis in order to refine quantitative structural features including cation occupancies that could be used to detect changes both in the oxidation state and the presence of tetrahedrally coordinated cation vacancies in the NCs. We find that the average iron oxidation state increases as core diameters decrease from 8 down to 3 nm. The trend in iron oxidation state can be explained by the oxidation of surface layers in the NCs. For samples exposed to air for several weeks, oxidation appears to cease when a volume equivalent to that of an ∼1.3 nm shell is converted to the more oxidized maghemite. The number of tetrahedrally coordinated cation vacancies also increases as the NC core size decreases. The correlation between the number of these vacancies and the faster growth for smaller NCs suggests that these reactive vacancies may be responsible for the rapid growth observed for nanocrystals with diameters smaller than 8 nm.

Most studies on iron oxide nanocrystals (NCs) suggest that the magnetic properties depend strongly on size for diameters below 10 nm, but there is less agreement about how the structure of the NC surface influences magnetic properties. Because the magnetic properties of iron oxide NCs hold promise for applications from cancer detection and therapeutics to environmental remediation, it is imperative to understand how size influences those properties. In most cases, the effective magnetic size is significantly lower than the measured physical size, a finding attributed to spin canting or disorder at the NC surface. A complicating factor is that the reaction conditions used to produce samples influence their magnetic properties. Thus, we employed a continuous growth method involving layer-by-layer addition of precursor to produce single-crystalline, spherical cores with subnanometer precision over a range of sizes under the same reaction conditions. Analysis of the NCs by small-angle X-ray scattering, transm...

Materials such as trans-Fe(DMeOPrPE)2(X)(H2O)+ (DMeOPrPE = 1,2-[bis(dimethoxypropyl)phosphino]ethane; X = Cl or H) show considerable promise as sorbents for the removal of N2 from natural gas in a pressure swing process. One problem, however, is that in long-term tests these sorbents slowly degrade over a period of many weeks. This study probed the degradation mechanism for the purpose of finding ways to stabilize the sorbents. To investigate the likelihood of degradation initiated by Fe–P bond dissociation, the fluxional behavior of the related cis-Fe(DMeOPrPE)2(H)2 complex was investigated by variable temperature 1P{1H} NMR spectroscopy. Analysis of the spectra gave the following activation parameters for the fluxional process: ΔH‡ = 11.6 kcal/mol and ΔS‡ = −9.2 cal/mol K. These results suggest that Fe–P bond dissociation (20–45 kcal/mol) is not occurring in the fluxional process and by implication that Fe–P bond dissociation is not initiating the decomposition of the trans-Fe(DMeOPrPE)2(X)(H2O)+ sorbents. Consequently, macrocycle ligands may not be the best approach for stabilizing the sorbents, as we have previously proposed. A “tetrahedral jump” mechanism is proposed for the fluxional process in cis-Fe(DMeOPrPE)2(H)2.