Tuning Electron Delocalization of Redox-Active Porous Aromatic Framework for Low-Temperature Aqueous Zn-K Hybrid Batteries with Air Self-Chargeability.

Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Pore-Scale Mechanisms for Spectral Induced Polarization of Calcite Precipitation Inferred from Geo-Electrical Millifluidics.

Spectral induced polarization (SIP) has the potential for monitoring reactive processes in the subsurface. While strong SIP responses have been measured in response to calcite precipitation, their origin and mechanism remain debated. Here we present a novel geo-electrical millifluidic setup designed to observe microscale reactive transport processes while performing SIP measurements. We induced calcite precipitation by injecting two reactive solutions into a porous medium, which led to highly localized precipitates at the mixing interface. Strikingly, the amplitude of the SIP response increased by 340% during the last 7% increase in precipitate volume. Furthermore, while the peak frequency in SIP response varied spatially over 1 order of magnitude, the crystal size range was similar along the front, contradicting assumptions in the classical grain polarization model. We argue that the SIP response of calcite precipitation in such mixing fronts is governed by Maxwell-Wagner polarization due to the establishment of a precipitate wall. Numerical simulations of the electric field suggested that spatial variation in peak frequency was related to the macroscopic shape of the front. These findings provide new insights into the SIP response of calcite precipitation and highlight the potential of geoelectrical millifluidics for understanding and modeling electrical signatures of reactive transport processes.

Enhancement of Ultrahigh Rate Chargeability by Interfacial Nanodot BaTiO3 Treatment on LiCoO2 Cathode Thin Film Batteries.

Nanodot BaTiO3 supported LiCoO2 cathode thin films can dramatically improve high-rate chargeability and cyclability. The prepared BaTiO3 nanodot is <3 nm in height and 35 nm in diameter, and its coverage is <5%. Supported by high dielectric constant materials on the surface of cathode materials, Li ion (Li+) can intercalate through robust Li paths around the triple-phase interface consisting of the dielectric, cathode, and electrolyte. The current concentration around the triple-phase interface is observed by the finite element method and is in good agreement with the experimental data. The interfacial resistance between the cathode and electrolyte with nanodot BaTiO3 is smaller than that without nanodot BaTiO3. The decomposition of the organic solvent electrolyte can prevent the fabrication of a solid electrolyte interface around the triple-phase interface. Li+ paths may be created at non solid electrolyte interface covered regions by the strong current concentration originating from high dielectric constant materials on the cathode. Robust Li+ paths lead to excellent chargeability and cyclability.

Application and limitations of time domain-induced polarization tomography for the detection of hydrocarbon pollutants in soils with electro-metallic components: a case study.

Nowadays, the growing concern about the environmental problems affecting the subsoil has focussed efforts on the detection and characterization of contaminated sites through geophysical prospecting methods. In the present study, a case of a contaminated site by hydrocarbons and their study by means of time domain-induced polarization tomography is presented. The response in chargeability of porous media due to this kind of pollutant allows its delimitation using this method. However, one of the limitations for the application of this technique is the presence of lithologies that contain electro-metallic salts. These salts can produce anomalies of chargeability and mask those due to nonaqueous phase liquids. The studies were conducted in an area contaminated by fuel leaks from supply tanks within a train maintenance facility. Those leaks occurred while the tanks were in use, but since their dismantling, the leak stopped. The geology of the area presented strong heterogeneities and the access was limited by train tracks. In order to locate and characterize the contaminant plume, measurements of resistivity and chargeability were carried out. A grid of monitoring wells in this area was also available from which information about free-phase pollutants was obtained, and a new drilling was carried out to verify an unexpected anomaly. The results obtained show that the location of the plume by the geophysical techniques employed can lead to ambiguity, as an anomaly that does not correspond to contaminated areas appeared but to the presence of clays rich in electro-metallic components such as Mg, Fe, Mn and Al.

Development of novel resistivity-chargeability statistical relationships for subsurface characterization at Langkawi, Kedah.

The significance of resistivity-chargeability relationships has been acknowledged and applied in various geologic terrains and different environmental conditions. However, there remains an underexplored opportunity to fully utilize these methods in complex geological terrains with a mixture of granitic and sedimentary rocks where empirical relationships have not been established. Such discoveries are crucial for accurately delineating petrophysical and geomechanical properties, which are essential in addressing urgent environmental concerns like landslides, foundation collapse, groundwater shortages, and pollution. To address this research gap, a novel approach was employed: resistivity-chargeability data with simple linear regression modeling. The study focused on developing resistivity-chargeability relationships specifically tailored for tropical granitic environments, using a typical example from Kedah Langkawi, Malaysia. The regions are characterized by complex geological features, ruggedness, and irregular progressive weathering and fracturing of subsurface strata, making the task challenging. Despite these complexities, the study successfully derived an efficient resistivity-chargeability empirical relation that correlates resistivity and chargeability. The derived empirical relationship exhibited high accuracy, surpassing 87%, in predicting chargeability from resistivity datasets or vice versa. This achievement holds great promise in promptly and accurately addressing environmental issues specific to the target region under study. By utilizing this novel resistivity-chargeability relationship, geoscientists, engineers, and environmental practitioners can make informed decisions and effectively manage environmental challenges in these regions, especially during the pre-development stage.

Photocurable liquid crystal hydrogels with different chargeability and tunable viscoelasticity based on chitin whiskers.

We develop a kind of photocurable liquid crystal hydrogels with bone extracellular matrix (ECM)-like liquid crystal state and viscoelasticity, as well as different chargeability. First, positively charged chitin whiskers (CHWs) and negatively charged maleic anhydride chitin whiskers (mCHWs) were prepared, which further self-assemble to form chiral nematic liquid crystals under ultrasonic treatment, respectively. Subsequently, poly (ethylene glycol) diacrylate (PEGDA) and photo initiator were added, and then two kinds of liquid crystal hydrogels with bone ECM-like viscoelasticity and different chargeability were prepared under ultraviolet (UV) irradiation. Benefiting from the bone ECM-like liquid crystal state and viscoelasticity, the prepared liquid crystal hydrogels exhibit remarkable cell affinity and osteogenic ability. Moreover, the liquid crystal hydrogel with negatively charged mCHWs is more favorable for cell adhesion, spreading and osteogenic differentiation than that with positively charged CHWs. This work provides a promising strategy to prepare the hydrogels with bone ECM-like liquid crystal properties and viscoelasticity for bone repair.

Time-domain induced polarization as a tool to image clogging in treatment wetlands.

During the last decade, treatment (artificial) wetlands have flourished all over Europe for the treatment of sewages from small communities thanks to their low cost of operation. The clogging of the filter of these wetlands is an issue affecting their efficiency and considered as their main operational problem. The present work shows the results of the application of a geophysical method called time-domain induced polarization. It is used to non-intrusively image, in 3D, the clogging of the gravel filters in a quick and efficient way. Induced polarization characterizes the ability of a porous material to reversibly store electrical charges when submitted to an electrical field. The material property characterizing this ability is called normalized chargeability. A set of laboratory experiments allows to determine an empirical relationship between the normalized chargeability and the weight amount of clogging. Induced polarization measurements have been performed in the field over a treatment wetland to get a 3D reconstructed image (tomography) of the normalized chargeability. From this tomography and the previously defined relationship, we are able to image in 3D the distribution of clogging and where it is concentrated in the filter. We can therefore identify the areas requiring preventive measures to minimize this clogging issue.

Liquid crystalline and rheological properties of chitin whiskers with different chemical structures and chargeability.

The liquid crystalline and rheological properties of chitin whiskers (CHWs) are significant for their application in fabrication of highly ordered composite materials and optical components. The aim of this work was to elucidate the influence of chemical structure and chargeability (zeta potential, electropositivity, electronegativity or zwitterionic character) on the liquid crystalline and rheological properties of CHWs. Firstly, CHWs with different chemical structure, including positively charged whiskers (CHWs and CHWs-D/60 min) and negatively charged whiskers (mCHWs), were designed via acid hydrolysis, deacetylation, and maleation, respectively. Subsequently, the chargeability of the above whiskers was further regulated by protonation or deprotonation. The whisker aqueous suspensions with high zeta potential behaved as nematic liquid crystals or chiral nematic liquid crystals, whereas those with low zeta potential had no liquid crystal characteristics. The viscosity, G', and G" values of the CHWs and CHWs-D/60 min aqueous suspensions treated with protonation were lower than those of the corresponding whiskers treated with deprotonation. However, the mCHWs exhibited different changes in their rheological properties under protonation or deprotonation due to the electronegativity and zwitterionic characteristics. In addition, the effects of ionic strength and pH on the liquid crystalline and rheological properties of CHWs, CHWs-D/60 min, and mCHWs aqueous suspensions varied since the chemical structure and chargeability of whiskers differ.

Combined use of geophysical and geochemical methods to assess areas of active, degrading and restored blanket bog.

Here we combine the use of geo-electrical techniques with geochemical analysis of the solid and liquid phase to determine subsurface properties and general peatland health. Active, degrading and restored peat locations were analysed from the same blanket bog site (ensuring they were under the same environmental conditions, such as rainfall and temperature) at the Garron Plateau, Northern Ireland. A normalized chargeability (ratio of resistivity (inverse of conductivity) and chargeability) profile was compared with organic composition analysis of the solid and liquid phases from active, degrading and restored locations. Results show that the degrading location is undergoing high rates of decomposition and loss of organic matter into the interstitial water, whereas the opposite is true for the active location. The restored peat is showing low rates of decomposition however has a high concentration of organic material in the porewater, primarily composing long chain aliphatic compounds, sourced from vascular plants. The ingression of vascular plants permits the diffusion of oxygen via roots into the subsurface and supports the oxidation of phenols by phenol oxidase, which produces phenoxy radicals and quinones (CO double bonds). This production of conjugated quinones, which are characterized by a CO double bond, in the aerated degrading and restored locations, increase the polarity, cation exchange capacity, and the normalized chargeability of the peat. This higher chargeability is not evident in the active peat due to decreased aerobic decomposition and a domination of sphagnum mosses.

Relações entre condutividade hidráulica, transmissividade, condutância longitudinal e sólidos totais dissolvidos para o aquífero livre de Caçapava do Sul (RS), Brasil / Relationship among hydraulic conductivity, transmissivity, longitudinal conductance and total dissolved solids for the free aquifer of Caçapava do Sul (RS), Brazil

A água subterrânea é um importante recurso ao abastecimento público, principalmente para comunidades periféricas em grandes cidades ou pequenos municípios, onde a instalação ou prolongamento de sistemas de distribuição são economicamente inviáveis. Estudos voltados à análise da vulnerabilidade de aquíferos são relevantes para subsídio a políticas públicas em saneamento básico e preservação ambiental. Este estudo contou com o cadastro de 23 poços rasos localizados no município de Caçapava do Sul (RS), onde foram realizadas medidas de resistividade elétrica e cargabilidade por meio de geofísica, e medidas diretas de condutividade hidráulica e sólidos totais dissolvidos. A análise estatística dos dados demonstrou diversos graus de correlação entre parâmetros, basicamente condicionados a fatores geológicos como porosidade, permeabilidade e sólidos totais dissolvidos.

Groundwater is an important resource for the public supply, mainly for the attendance of peripheral communities in large cities or small cities, where the installation or prolongation of distribution systems is economically unfeasible. Studies related to the vulnerability analysis in aquifers are important for subsiding public policies in basic sanitation and environmental preservation. This study was supported by the cadaster of 23 shallow wells localized in Caçapava do Sul (RS). Measurements of electric resistivity and chargeability were performed by geophysical methods, direct measures of hydraulic conductivity and total dissolved solids. The data statistics analysis demonstrated several degrees among parameters, conditioned to geological factors as porosity, permeability and total dissolved solids.

Aplicação de métodos geofísicos no monitoramento de área contaminada sob atenuação natural / Applications of geophysical methods in monitoring contaminated area under natural attenuation

Estudos geofísicos em áreas impactadas por derivados de petróleo descrevem anomalias tanto de baixa quanto de elevada resistividade, confirmada como fase contaminante por meio de análises químicas. Esta aparente contradição pode refletir processos de degradação, associada ao tempo de residência de contaminantes no meio, por meio da geração de subprodutos que alteram as propriedades físicas do meio, principalmente pela dissolução mineral por ação de ácidos orgânicos e pela neoformação de minerais de óxidos e hidróxidos de ferro. Este trabalho apresenta resultados da aplicação do método de eletrorresistividade e polarização induzida em uma área industrial contaminada por benzeno, tolueno, xileno, 1,2 dicloroetano e sais inorgânicos, em processo de atenuação natural. Os resultados indicam a neoformação mineral no centro e nas adjacências da área contaminada, conforme sugerem as alterações apontadas nos parâmetros físicos medidos.

Geophysical studies in impacted areas by petroleum products may be described by anomalies of both low and high resistivity, confirmed as contaminant by chemical analyses. This apparent contradiction can reflect processes of contaminants degradation, directly associated with its residence time in the soil, through the generation of by-products that change the physical properties of the soil and groundwater, principally for the mineral dissolution by action of organic acids and by neoformation minerals of oxides and hydroxides minerals. This paper presents the application of electrical resistivity and induced polarization methods in a contaminated industrial area for benzene, toluene, xylene, 1,2 dichloroethene and inorganic salts, in natural attenuation process. The results indicated the mineral neoformation in the center and adjacencies of contaminated area, as it suggested the alterations in physical parameters measured.