Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets
Not Available
54 ENVIRONMENTAL SCIENCES↗
Engineering topics
Huang, Xiaopeng
Publications and source records attributed to Huang, Xiaopeng.
Solar thermal aerogel receiver and materials therefor
A silica aerogel having a mean pore size less than 5 nm with a standard deviation of 3 nm. The silica aerogel may have greater than 95% solar-weighted transmittance at a thickness of 8 mm for wavelengths in the range of 250 nm to 2500 nm, and a 400° C. black-body weighted specific extinction coefficient of greater than 8 m2/kg for wavelengths of 1.5 μm to 15 μm. Silica aerogel synthesis methods are described. A solar thermal aerogel receiver (STAR) may include an opaque frame defining an opening, an aerogel layer disposed in the opaque frame, with at least a portion of the aerogel layer being proximate the opening, and a heat transfer fluid pipe in thermal contact with and proximate the aerogel layer. A concentrating solar energy system may include a STAR and at least one reflector to direct sunlight to an opening in the STAR.
Chen, Gang↗
Interplay between Facets and Defects during the Dissociative and Molecular Adsorption of Water on Metal Oxide Surfaces
Both surface terminations and defects play a central role in determining how water interacts with metal oxides, thereby setting important properties of the interface that govern reactivity such as the type and distribution of hydroxyl groups. However, the interconnections between facets and defects remain poorly understood, limiting the usefulness of conventional notions such as that hydroxylation is controlled by metal cation exposure at the surface. Here, using hematite (α-Fe 2 O 3 ) as a model system, we show how oxygen vacancies overwhelm surface cation-dependent hydroxylation behavior. Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy was used to monitor the adsorption of molecular water and its dissociation to form hydroxyl groups in situ on (001), (012), or (104) facet-engineered hematite nanoparticles. Supported by density functional theory calculations of the respective surface energies and oxygen vacancy formation energies, the findings show how oxygen vacancies are more prone to form on higher energy facets and induce surface hydroxylation at extremely low relative humidity values of 5 x10 - 5 %. Further, when these vacancies are eliminated, the extent of surface hydroxylation across the facets is as expected from the areal density of exposed iron cations at the surface. These findings help answer fundamental questions about the nature of reducible metal oxide-water interfaces in natural and technological settings and lay the groundwork for rational design of improved oxide-based catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Photocatalyzed electron exchange between organic chromophores and hematite nanoparticles and the role of solid-state charge transport
Understanding photocatalyzed redox interactions between Fe(III)–(oxyhydr)oxide mineral nanoparticles and adsorbed chromophoric organic matter is critical for accurately predicting bioavailable iron fluxes in the euphotic zone of natural aquatic systems, and for improving the effectiveness of nano-iron-based water purification systems. However, the electron transfer processes that underpin photoreductive dissolution at particle/organic/solution interfaces occur on ultrafast timescales and thus remain difficult to probe. In this work, we report an ultrafast transient absorption spectroscopy (TAS) study of suspensions of hematite nanoplatelets (HNPs) sensitized by adsorbed rhodamine B (RhB) dye as a function of solution media and pH. The TAS results indicate a substantially longer fluorescence lifetime of RhB adsorbed on HNPs across a wide range of pH conditions, consistent with transient photoinduced electron transfer to the oxide with recombination kinetics controlled by electron migration back to the interface via small polaron hopping. Normalization of the observed kinetics to the measured surface loading of RhB at different pH values shows that the recombination rates are insensitive to environmental variables, likely controlled instead by particle properties that determine small polaron diffusion behavior.
54 ENVIRONMENTAL SCIENCES↗
Self-similar mesocrystals form via interface-driven nucleation and assembly
Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.
36 MATERIALS SCIENCE↗
Solar thermal aerogel receiver and materials therefor
A silica aerogel having a mean pore size less than 5 nm with a standard deviation of 3 nm. The silica aerogel may have greater than 95% solar-weighted transmittance at a thickness of 8 mm for wavelengths in the range of 250 nm to 2500 nm, and a 400° C. black-body weighted specific extinction coefficient of greater than 8 m 2 /kg for wavelengths of 1.5 μm to 15 μm. Silica aerogel synthesis methods are described. A solar thermal aerogel receiver (STAR) may include an opaque frame defining an opening, an aerogel layer disposed in the opaque frame, with at least a portion of the aerogel layer being proximate the opening, and a heat transfer fluid pipe in thermal contact with and proximate the aerogel layer. A concentrating solar energy system may include a STAR and at least one reflector to direct sunlight to an opening in the STAR.
Chen, Gang↗
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 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 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), and this is supported by density functional theory calculations suggesting adsorption energies about 1.5 times higher. However, this alone cannot explain the observed MB photodegradation rate, which is around 14.5 times faster on (001) than (012). The enhancement we attribute to a higher availability of 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 design and optimization of hematite nanostructures as photocatalysts for environmental remediation.
Zong, Meirong↗
Photo-production of reactive oxygen species and degradation of dissolved organic matter by hematite nanoplates functionalized by adsorbed oxalate
The geochemical cycling of iron and carbon can couple in unique ways in the euphotic zone of aquatic systems.
Huang, Xiaopeng↗