Thermal Transport in Disordered Materials

ABSTRACT

We review the status of research on thermal/phonon transport in disordered materials. The term disordered materials is used here to encompass both structural and compositional disorder. It includes structural deviations ranging from an ideal crystal with disordered arrangements of defects all the way to fully amorphous materials, as well as crystals with impurities up through multi-component random alloys. Both types of disorder affect phonons by breaking the symmetry of an idealized crystal and changing their character/mode shapes. These effects have important implications with regard to phonon–phonon interactions, phonon transport and phonon interactions with other quantum particles, which are being actively investigated. Herein, we synthesize the current theoretical understanding, identify the aspects of the problem that require more work, and pose open questions. Abbreviations: BTE: Boltzmann transport equation; DFT: Density functional theory; EPP: Eigenvector periodicity parameter; FAFDTR: Fiber-aligned frequency domain thermoreflectance; GK: Green–Kubo; GKMA: Green–Kubo modal analysis; HCACF: Heat current autocorrelation function; IXS: Inelastic X-ray scattering; LD: Lattice dynamics; LJ: Lennard–Jones; MD: Molecular dynamics; MFP: Mean free path; NEMD: Non-equilibrium molecular dynamics; NMD: Normal-mode dynamics; PDL: Propagon, diffuson, locon; PGM: Phonon gas model; PR: Participation ratio; SCLD: Supercell lattice dynamics; SED: Spectral energy density; TDTR: Time-domain thermoreflectance; VCA: Virtual crystal approximation;     

Conjugated Porous Polymers Based on BODIPY and BOPHY Dyes in Hybrid Heterojunctions for Artificial Photosynthesis

Developing highly efficient photocatalysts for artificial photosynthesis is one of the grand challenges in solar energy conversion. Among advanced photoactive materials, conjugated porous polymers (CPPs) possess a powerful combination of high surface areas, intrinsic porosity, cross-linked nature, and fully π-conjugated electronic systems. Here, based on these fascinating properties, organic–inorganic hybrid heterostructures composed of CPPs and TiO₂ for the photocatalytic CO₂ reduction and H₂ evolution from water are developed. The study is focused on CPPs based on the boron dipyrromethene (BODIPY) and boron pyrrol hydrazine (BOPHY) families of compounds. It is shown that hybrid photocatalysts are active for the conversion of CO₂ mainly into CH₄ and CO, with CH₄ production 4 times over the benchmark TiO₂. Hydrogen evolution from water surpassed by 37.9-times that of TiO₂, reaching 200 mmol g_cat⁻¹ and photonic efficiency of 20.4% in the presence of Pt co-catalyst (1 wt% Pt). Advanced photophysical studies, based on time-resolved photoluminescence and transient absorption spectroscopy, reveal the creation of a type II heterojunction in the hybrids. The unique interfacial interaction between CPPs and TiO₂ results in longer carriers’ lifetimes and a higher driving force for electron transfer, opening the door to a new generation of photocatalysts for artificial photosynthesis.     

New results on the polymerisation of the itaconic acid in aqueous medium

Summary Itaconic acid has been polymerised in aqueous medium using potassium persulphate as initiator. An important dependence on the polymer yield with the initial pH of the reaction medium is observed. Polymers obtained on this work showed to be mainly atactic, with around 1.14 of polydispersity and molecular weight around 5 × 10⁵ ,g/mol. All the Polymers synthesized were characterized by FTIR, ¹H-NMR, ¹³C-NMR, gpc, thermogravimetry and acid number. Analysis of these materials seem to indicate a decrease of acidity related to the lost of one carboxylic group from the itaconic acid residue, probably due to intramolecular interactions when the monomer is incorporated into the polyiner growing chain. Received: 22 April 2002/Revised Version: 15 August 2002/ Accepted: 16 August 2002 RID="1*" ID="1*"Universidad del País Vasco, Facultad de Ciencias, Departamento de Química Bilbao, Espa?ia. Correspondence to Cristóbal Lárez V     

A field survey of metal binding to metallothionein and other cytosolic ligands in liver of eels using an on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS)

The effect of metal exposure on the accumulation and cytosolic speciation of metals in livers of wild populations of European eel with special emphasis on metallothioneins (MT) was studied. Four sampling sites in Flanders showing different degrees of heavy metal contamination were selected for this purpose. An on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS) was used to study the cytosolic speciation of the metals. The distribution of the metals Cd, Cu, Ni, Pb and Zn among cytosolic fractions displayed strong differences. The cytosolic concentration of Cd, Ni and Pb increased proportionally with the total liver levels. However, the cytosolic concentrations of Cu and Zn only increased above a certain liver tissue threshold level. Cd, Cu and Zn, but not Pb and Ni, were largely associated with the MT pool in correspondence with the environmental exposure and liver tissue concentrations. Most of the Pb and Ni and a considerable fraction of Cu and Zn, but not Cd, were associated to High Molecular Weight (HMW) fractions. The relative importance of the Cu and Zn in the HMW fraction decreased with increasing contamination levels while the MT pool became progressively more important. The close relationship between the cytosolic metal load and the total MT levels or the metals bound on the MT pool indicates that the metals, rather than other stress factors, are the major factor determining MT induction.     

Pathogenesis of Helicobacter pullorum infections in broilers

Four groups of 23 one-day-old broiler chickens were each inoculated by gavage with a different Helicobacter pullorum strain isolated from humans or poultry. As a control, a fifth group of eight animals was inoculated with phosphate-buffered saline. Faecal samples were collected weekly and tested for the presence of H. pullorum DNA using PCR. At 1, 8, 15, 22 and 42 days postinoculation, birds were euthanized and samples from the liver and intestinal tract were histologically, immunohistochemically and bacteriologically examined. The samples were also tested for the presence of H. pullorum DNA by PCR. All animals remained clinically healthy throughout the experiment although mild lesions in the caeca were present in animals inoculated with H. pullorum. In all H. pullorum-inoculated groups, DNA of this bacterium was detected in faecal samples until 42 days postinoculation. The main site of colonization was the caecum. Immunohistochemical examination revealed that the bacterium was closely associated with the caecal epithelial cells. It was concluded that H. pullorum may colonize the caecum of broilers and is excreted in their faeces until slaughter age. This implies that chicken meat might constitute a source of infection for human beings.     

Surface-induced synthesis and self-assembly of metal suprastructures

A systematic study on the synthesis of a series of self-assembled suprastructures, such as cubes, stars, belts, and microspheres, of Ag nanoparticles (AgNPs) in borosilicate glassware heavily cleaned with aqua regia is presented. These self-assembled structures are mostly formed from the crystallographically iso-oriented AgNPs, and exhibit well-defined shapes. In regular washed glassware, only Ag nanowires are synthesized. The formation mechanisms of these self-assembled Ag structures, based on monitoring of their structural evolution in glassware decorated with different molecules, are proposed. This work not only demonstrates that the surface energy of glassware can affect chemical synthesis, but also provides an interesting approach to the shape-controlled synthesis of novel self-assembled suprastructures of AgNPs, which could be potentially used as synthesis templates, drug vessels, and microreactors.     

Separation of polyolefins based on comonomer content using high‐temperature gradient adsorption liquid chromatography with a graphitic carbon column

This report describes the application of a recently developed polyolefin characterization tool based upon gradient adsorption high‐temperature liquid chromatography (HT‐LC) using a graphitic carbon stationary phase to polyolefin homopolymer and previously unreported copolymer systems. Polyolefin‐based materials find utility in a broad range of applications and are differentiated by parameters such as molecular weight and comonomer content. Polymer comonomer distribution is commonly determined by crystallinity‐based separations (ATREF, CRYSTAF). These techniques, however, are time consuming. In addition, some semicrystalline polymers undergo cocrystallization, impacting the techniques' universal utility. Adsorption‐based HT‐LC can ideally overcome the limitations of crystallinity‐based separations, shedding new light on the composition of randomly‐polymerized polyolefins. In this report the basic separation capability of the adsorption HT‐LC technique, using a graphitic carbon column, is demonstrated for poly (ethylene‐co‐octene) and poly(ethylene‐co‐propylene) systems and compared with select precipitation/redissolution HT‐LC and ATREF results. Select results in this paper are also compared and contrasted to other recent publications on similar separations of polyolefins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Yolk–Shell Hybrid Materials with a Periodic Mesoporous Organosilica Shell: Ideal Nanoreactors for Selective Alcohol Oxidation

This contribution describes the preparation of multifunctional yolk–shell nanoparticles (YSNs) consisting of a core of silica spheres and an outer shell based on periodic mesoporous organosilica (PMO) with perpendicularly aligned mesoporous channels. The new yolk–shell hybrid materials were synthesised through a dual mesophase and vesicle soft templating method. The mesostructure of the shell, the dimension of the hollow space (4～52 nm), and the shell thickness (16～34 nm) could be adjusted by precise tuning of the synthesis parameters, as evidenced by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen sorption investigations. Various metal nanoparticles (e.g., Au, Pt, and Pd) were encapsulated and confined in the void space between the core and the shell using impregnation and reduction of adequate metal precursors. The selective oxidation of various alcohol substrates was then carried out to illustrate the benefits of such an architecture in catalysis. High conversion (～100%) and excellent selectivity (～99%) were obtained over Pd nanoparticles encapsulated in the hybrid PMO yolk–shell structures.     

One-pot encapsulation of luminescent quantum dots synthesized in aqueous solution by amphiphilic polymers

A simple one-pot polymer encapsulation method is developed for group II-VI semiconductor quantum dots (QDs) synthesized in aqueous solution. The micelles of amphiphilic polymers, such as octadecylamine-modified poly(acrylic acid), capture and encapsulate the QDs when the original hydrophilic ligands, namely 3-mercaptopropionic acid (MPA), capped on the CdTe/CdS core/shell QDs are partially or fully exchanged by the hydrophobic ligands, 1-dodecanethiol. The molar ratio of the amphiphilic polymer to QDs plays a crucial role in determining the final morphology of the encapsulated structures, including the number of QDs encapsulated in one polymeric micelle. Importantly, the polymer coating significantly improves the optical properties of the QDs, which enhances the photoluminescence quantum yield by about 50%. Furthermore, the photostability of the amphiphilic polymer-coated QDs is much better than that of the synthesized QDs capped with MPA.