Crystal dissolution by particle detachment.

Crystal dissolution, which is a fundamental process in both natural and technological settings, has been predominately viewed as a process of ion-by-ion detachment into a surrounding solvent. Here we report a mechanism of dissolution by particle detachment (DPD) that dominates in mesocrystals formed via crystallization by particle attachment (CPA). Using liquid phase electron microscopy to directly observe dissolution of hematite crystals - both compact rhombohedra and mesocrystals of coaligned nanoparticles - we find that the mesocrystals evolve into branched structures, which disintegrate as individual sub-particles detach. The resulting dissolution rates far exceed those for equivalent masses of compact single crystals. Applying a numerical generalization of the Gibbs-Thomson effect, we show that the physical drivers of DPD are curvature and strain inherently tied to the original CPA process. Based on the generality of the model, we anticipate that DPD is widespread for both natural minerals and synthetic crystals formed via CPA.

Particle-based hematite crystallization is invariant to initial particle morphology.

SignificanceMany crystallization processes occurring in nature produce highly ordered hierarchical architectures. Their formation cannot be explained using classical models of monomer-by-monomer growth. One of the possible pathways involves crystallization through the attachment of oriented nanocrystals. Thus, it requires detailed understanding of the mechanism of particle dynamics that leads to their precise crystallographic alignment along specific faces. In this study, we discover a particle-morphology-independent oriented attachment mechanism for hematite nanocrystals. Independent of crystal morphology, particles always align along the [001] direction driven by aligning interactions between (001) faces and repulsive interactions between other pairs of hematite faces. These results highlight that strong face specificity along one crystallographic direction can render oriented attachment to be independent of initial particle morphology.

Facet-Dependent Photodegradation of Methylene Blue by Hematite Nanoplates in Visible Light.

The expression of specific crystal facets in different nanostructures is known to play a vital role in determining the sensitivity toward the photodegradation of organics, which can generally be ascribed to differences in surface structure and energy. Herein, we report the synthesis of hematite nanoplates with controlled relative exposure of basal (001) and edge (012) facets, enabling us to establish direct correlation between the surface structure and the photocatalytic degradation efficiency of methylene blue (MB) in the presence of hydrogen peroxide. MB adsorption experiments showed that the capacity on (001) is about three times larger than on (012). Density functional theory calculations suggest the adsorption energy on the (001) surface is 6.28 kcal/mol lower than that on the (012) surface. However, the MB photodegradation rate on the (001) surface is around 14.5 times faster than on the (012) surface. We attribute this to a higher availability of the photoelectron accepting surface Fe3+ sites on the (001) facet. This facilitates more efficient iron valence cycling and the heterogeneous photo-Fenton reaction yielding MB-oxidizing hydroxyl radicals at the surface. Our findings help establish a rational basis for the design and optimization of hematite nanostructures as photocatalysts for environmental remediation.

Synthesis of 2D Hexagonal Hematite Nanosheets and the Crystal Growth Mechanism.

Nanostructure engineering of hematite is a promising strategy to overcome its performance limitations as a photodegradation catalyst for organic dyes or toxic organic chemicals. Precise control of exposed facets plays a vital role as an optimization strategy. Although great progress has been made in the synthesis of different crystal morphologies, design principles remain ad hoc, awaiting systematic control of facet expression within a clean synthesis protocol yielding versatile results. Herein, we report a simple method that enables precise morphology control to synthesize 2D hexagonal hematite nanosheets from two-line ferrihydrite. Nanosheet sizes and facet proportions were successfully tuned by changing the pH, the ratio of solvent ethanol to water, and the concentration of FeIII ions. The growth mechanism appears to involve a combination of ferrihydrite solid-state transformation and assembly into hematite, followed by an ion-by-ion growth that perfects the surface terminations. The finding helps to establish a rational basis for the design and optimization of hematite nanostructures.

Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles.

Hematite nanoparticles are abundant in the photic zone of aquatic environments, where they play a prominent role in photocatalytic transformations of bound organics. Here, we examine the photocatalytic degradation of rhodamine B by visible light using two different structurally well-defined hematite nanoparticle morphologies. In addition to detailed solid characterization and aqueous kinetics measurements, we also exploit species-selective scavengers in electron paramagnetic resonance spectroscopy to sequester specific reaction channels and thereby assess their impact. The photodegradation rates for nanoplates dominated by {001} facets and nanocubes dominated by {012} facets were 0.13 and 0.7 h-1, respectively, and the turnover frequencies for the active sites on {001} and {012} were 7.89 × 10-3 and 3.07× 10-3 s-1, yielding apparent activation energies of 17.13 and 24.94 kcal/mol within the energetic span model, respectively. Facet-specific differences appear to be directly not linked with the simple aerial cation site density but instead with their extent of undercoordination. By establishing this linkage, the findings lay a foundation for predicting the photocatalytic degradation efficiency for the myriad of possible hematite nanoparticle morphologies and more broadly help unveil key reactions at the interface that may govern photocatalytic organic transformations in natural and engineered aquatic environments.

Cr(III) Adsorption by Cluster Formation on Boehmite Nanoplates in Highly Alkaline Solution.

The development of advanced functional nanomaterials for selective adsorption in complex chemical environments requires partner studies of binding mechanisms. Motivated by observations of selective Cr(III) adsorption on boehmite nanoplates (γ-AlOOH) in highly caustic multicomponent solutions of nuclear tank waste, here we unravel the adsorption mechanism in molecular detail. We examined Cr(III) adsorption to synthetic boehmite nanoplates in sodium hydroxide solutions up to 3 M, using a combination of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), scanning/transmission electron microscopy (S/TEM), electron energy loss spectroscopy (EELS), high-resolution atomic force microscopy (HR-AFM), time-of-fight secondary ion mass spectrometry (ToF-SIMS), Cr K-edge X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS), and electron paramagnetic resonance (EPR). Adsorption isotherms and kinetics were successfully fit to Langmuir and pseudo-second-order kinetic models, respectively, consistent with monotonic uptake of Cr(OH)4- monomers until saturation coverage of approximately half the aluminum surface site density. High resolution AFM revealed monolayer cluster self-assembly on the (010) basal surfaces with increasing Cr(III) loading, possessing a structural motif similar to guyanaite (ß-CrOOH), stabilized by corner-sharing Cr-O-Cr bonds and attached to the surface with edge-sharing Cr-O-Al bonds. The selective uptake appears related to short-range surface templating effects, with bridging metal connections likely enabled by hydroxyl anion ligand exchange reactions at the surface. Such a cluster formation mechanism, which stops short of more laterally extensive heteroepitaxy, could be a metal uptake discrimination mechanism more prevalent than currently recognized.