Black Silver: Three-Dimensional Ag Hybrid Plasmonic Nanostructures with Strong Photon Coupling for Scalable Photothermoelectric Power Generation.

The conversion of solar energy into electric power has been extensively studied, for example, by photovoltaics. However, photo-thermoelectric (P-TE) conversion as an effective solar-to-electricity conversion process is less studied. Here, we present an efficient full-solar-spectrum plasmonic absorber for scalable P-TE conversion based on a simple integration of light absorber and commercial thermoelectric modules. Our developed light absorber of silica-silver hybrid structures achieves an average absorption of 99.4% in the wavelength range from 200 to 2500 nm, which covers over 98% solar energy in this range. It thus appears fully matte black and is named black silver. The light absorber includes a hierarchical structure with Ag nanoparticles attached on three-dimensional SiO2 nanostructures, resulting in ultrahigh absorption. Strong localized surface plasmon resonance hybridization together with multiple scattering causes the perfect light absorption. Using the black silver as a light absorber for P-TE power generation, it can achieve a peak voltage density as high as 82.5 V m-2 under a solar intensity of 100 mW cm-2, which is large enough to power numerous electronic devices. By assembling 20 thermoelectric modules in series, we test their possibility of practical application, and they can also achieve an average voltage density of 70.66 V m-2. Our work opens up a promising technology that facilitates high-efficiency and scalable solar energy conversion via the P-TE effect.

Structural and chemical heterogeneity of Proterozoic organic microfossils of the ca. 1 Ga old Angmaat Formation, Baffin Island, Canada.

Organic microfossils in Meso- and Neoproterozoic rocks are of key importance to track the emergence and evolution of eukaryotic life. An increasing number of studies combine Raman spectroscopy with synchrotron-based methods to characterize these microfossils. A recurring observation is that Raman spectra of organic microfossils show negligible variation on a sample scale and that variation between different samples can be explained by differences in thermal maturation or in the biologic origin of organic precursor material. There is a paucity of work, however, that explores the extent to which the petrographic framework and diagenetic processes might influence the chemical structure of organic materials. We present a detailed Raman spectroscopy-based study of a complex organic microfossil assemblage in the ca. 1 Ga old Angmaat Formation, Baffin Island, Canada. This formation contains abundant early diagenetic chert that preserves silicified microbial mats with numerous, readily identifiable organic microfossils. Individual chert beds show petrographic differences with discrete episodes of cementation and recrystallization. Raman spectroscopy reveals measurable variation of organic maturity between samples and between neighboring organic microfossils of the same taxonomy and taphonomic state. Scanning transmission X-ray microscopy performed on taphonomically similar coccoidal microfossils from the same thin section shows distinct chemical compositions, with varying ratios of aromatic compounds to ketones and phenols. Such observations imply that geochemical variation of organic matter is not necessarily coupled to thermal alteration or organic precursor material. Variation of the Raman signal across single samples is most likely linked to the diagenetic state of analyzed materials and implies an association between organic preservation and access to diagenetic fluids. Variation in the maturity of individual microfossils may be a natural outcome of local diagenetic processes and potentially exceeds differences derived from precursor organic material. These observations stress the importance of detailed in situ characterization by Raman spectroscopy to identify target specimens for further chemical analysis.

Metastable Atomic Layer Deposition: 3D Self-Assembly toward Ultradark Materials.

Black body materials are promising candidates to meet future energy demands, as they are able to harvest energy from the total bandwidth of solar radiation. Here, we report on high-absorption near-blackbody-like structures (>98% for a wide solar spectrum range from 220 to 2500 nm) consisting of a silica scaffold and Ag nanoparticles with a layer thickness below 10 µm, fabricated using metastable atomic layer deposition (MS-ALD). Several effects contribute collectively and in a synergistic manner to the ultrahigh absorption, including the pronounced heterogeneity of the nanoparticles in size and shape, particle plasmon hybridization, and the trapping of omnidirectionally scattered light in the 3D hierarchical hybrid structures. We propose that, in the future, MS-ALD needs to be considered as a simple and promising method to fabricate blackbody materials with excellent broadband absorption.

Giant Faraday Rotation through Ultrasmall Fe0n Clusters in Superparamagnetic FeO-SiO2 Vitreous Films.

Magnetooptical (MO) glasses and, in particular, Faraday rotators are becoming key components in lasers and optical information processing, light switching, coding, filtering, and sensing. The common design of such Faraday rotator materials follows a simple path: high Faraday rotation is achieved by maximizing the concentration of paramagnetic ion species in a given matrix material. However, this approach has reached its limits in terms of MO performance; hence, glass-based materials can presently not be used efficiently in thin film MO applications. Here, a novel strategy which overcomes this limitation is demonstrated. Using vitreous films of xFeO·(100 - x)SiO2, unusually large Faraday rotation has been obtained, beating the performance of any other glassy material by up to two orders of magnitude. It is shown that this is due to the incorporation of small, ferromagnetic clusters of atomic iron which are generated in line during laser deposition and rapid condensation of the thin film, generating superparamagnetism. The size of these clusters underbids the present record of metallic Fe incorporation and experimental verification in glass matrices.

New insights into the toxicity of mineral fibres: A combined in situ synchrotron µ-XRD and HR-TEM study of chrysotile, crocidolite, and erionite fibres found in the tissues of Sprague-Dawley rats.

Along the line of the recent research topic aimed at understanding the in vivo activity of mineral fibres and their mechanisms of toxicity, this work describes the morpho-chemical characteristics of the mineral fibres found in the tissues of Sprague-Dawley rats subjected to intraperitoneal/intrapleural injection of UICC chrysotile, UICC crocidolite and erionite-Na from Nevada (USA). The fibres are studied with in situ synchrotron powder diffraction and high resolution transmission electron microscopy to improve our understanding of the mechanisms of toxicity of these mineral fibres. In contact with the tissues of the rats, chrysotile fibres are prone to dissolve, with leaching of Mg and production of a silica rich relict. On the other hand, crocidolite and erionite-Na fibres are stable even for very long contact times within the tissues of the rats, showing just a thin dissolution amorphous halo. These findings support the model of a lower biopersistence of chrysotile with respect to crocidolite and erionite-Na but the formation of a silica-rich fibrous residue after the pseudo-amorphization of chrysotile may justify a higher cytotoxic potential and intense inflammatory activity of chrysotile in the short term in contact with the lung tissues.

Where is iron in erionite? A multidisciplinary study on fibrous erionite-Na from Jersey (Nevada, USA).

Fibrous erionite is a mineral fibre of great concern but to date mechanisms by which it induces cyto- and geno-toxic damage, and especially the role of iron associated to this zeolite species, remain poorly understood. One of the reasons is that we still don't know exactly where iron is in natural erionite. This work is focused on fibrous erionite-Na from Jersey (Nevada, USA) and attempts to draw a general model of occurrence of iron in erionite and relationship with toxicity mechanisms. It was found that iron is present as 6-fold coordinated Fe3+ not part of the zeolite structure. The heterogeneous nature of the sample was revealed as receptacle of different iron-bearing impurities (amorphous iron-rich nanoparticles, micro-particles of iron oxides/hydroxides, and flakes of nontronite). If iron is not part of the structure, its role should be considered irrelevant for erionite toxicity, and other factors like biopersistence should be invoked. An alternative perspective to the proposed model is that iron rich nano-particles and nontronite dissolve in the intracellular acidic environment, leaving a residue of iron atoms at specific surface sites anchored to the windows of the zeolite channels. These sites may be active later as low nuclearity groups.

Redox stability of As(III) on schwertmannite surfaces.

As(III)-enriched mine discharge often drains through Fe(III)-mineral abundant land covers which makes the understanding of its fate and redox behaviour extremely important. We therefore conducted batch kinetic and equilibrium studies at pH 3.0±0.05 in anoxic media coupled with spectroscopic and microscopic examinations at variable conditions to understand possible As(III) binding mechanisms and the redox stability of As(III) on schwertmannite, a prominent ferric mineral in acid mine drainage environments. Schwertmannite acted as an efficient scavenger for As(III) compared to goethite at identical sorbent:solute ratios. As K-edge X-ray absorption near-edge structure (XANES) demonstrated partial oxidation of sorbed As(III) to As(V) on both the minerals depending on the Fe(III)/As(III) ratios (goethite acted as a better oxidant than schwertmannite). Sorbed As(III) and As(V) coordinated in a bidentate binuclear binding mechanism with As(III)/As(V)-O and As(III)/As(V)-Fe interatomic distances as 1.78/1.69 and 3.37/3.31Å, respectively. Scanning (SEM-EDX) and transmission (TEM) electron microscopic, and IR spectroscopic measurements revealed the formation of As-containing surface coatings by sorbed As on schwertmannite.