Linked Reactivity at Mineral-Water Interfaces Through Bulk Crystal Conduction

  title={Linked Reactivity at Mineral-Water Interfaces Through Bulk Crystal Conduction},
  author={Svetlana V. Yanina and Kevin M. Rosso},
  pages={218 - 222}
The semiconducting properties of a wide range of minerals are often ignored in the study of their interfacial geochemical behavior. We show that surface-specific charge density accumulation reactions combined with bulk charge carrier diffusivity create conditions under which interfacial electron transfer reactions at one surface couple with those at another via current flow through the crystal bulk. Specifically, we observed that a chemically induced surface potential gradient across hematite… 

Electrochemical Signatures of Crystallographic Orientation and Counterion Binding at the Hematite/Water Interface

The interfacial electrochemistry of hematite (α-Fe2O3) is a key aspect for understanding the behavior of this important mineral phase in photocatalytic water-splitting devices as well as in

Potential‐Specific Structure at the Hematite–Electrolyte Interface

The atomic‐scale structure of the interface between a transition metal oxide and aqueous electrolyte regulates the interfacial chemical reactions fundamental to (photo)electrochemical energy

Electrostatic potential of specific mineral faces.

Insight gained from this method will aid in predicting the fate of migrating contaminants, mineral growth/dissolution processes, and mineral-microbiological interactions and in testing surface complexation theories.

Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics

Large-scale hybrid density functional theory-based molecular dynamics simulations for the hematite(001)-liquid water interface find that charged oxyanions and doubly protonated oxygens can be formed on the iron terminated layer via autoionization of neutral -OH groups, but no charged species are found for the oxygen terminated surface.

Dynamic Stabilization of Metal Oxide-Water Interfaces.

Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locations and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies, and pKa prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface.

Fast Interconversion of Hydrogen Bonding at the Hematite (001)-Liquid Water Interface.

It is found that the protons terminating the surface form binary patterns by either pointing in-plane or out-of-plane, which forms the basis for a better fundamental understanding of electron transfer coupled to proton transfer reactions at this important interface.

Reductive Dissolution Mechanisms at the Hematite-Electrolyte Interface Probed by in Situ X-ray Scattering

The electron-catalyzed dissolution and reprecipitation of iron (oxyhydr)oxides constitute critical steps in natural geochemical iron cycling. However, the atomic-scale mechanisms of reductive

Electrochemical properties and relaxation times of the hematite/water interface.

  • K. ShimizuJ. Boily
  • Materials Science
    Langmuir : the ACS journal of surfaces and colloids
  • 2014
Findings are underpinning important relationships between classical views on mineral surface complexation reactions and electrochemical views of semiconductor/water interfaces.

Proton Dynamics on Goethite Nanoparticles and Coupling to Electron Transport.

Implementation of replica-exchange constant-pH molecular dynamics simulations that use classical molecular dynamics for exploring configurational space and Metropolis Monte Carlo walking through protonation space with a simulated annealing escape route from metastable configurations are reported.



Effect of different crystal faces on experimental interaction force and aggregation of hematite

Charging is a basic property of the solid/solution interface of minerals. The charging at different crystal faces depends on the surface chemical composition, that is, the type and number of

Charge Transport in Metal Oxides: A Theoretical Study of Hematite α-Fe2O3

Transport of conduction electrons and holes through the lattice of α-Fe2O3 (hematite) is modeled as a valence alternation of iron cations using ab initio electronic structure calculations and

Surface and bulk electrical properties of the hematite phase Fe2O3

Electrical properties of Fe2O3 were studied by using several electrical methods such as electrical conductivity, thermopower (Seebeck effect) and work function. The studies were performed at elevated

Dynamics of interfacial charge transfer in iron(III) oxide colloids

The kinetics of electron and proton transfer to colloidal Fe(III) oxides have been examined as a function of pH, colloid size, crystal structure, and reductant concentration. Electron injection into