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Our society largely relies on inorganic semiconductor devices which are, so far, fabricated using expensive and complex processes requiring ultra‐high vacuum equipment. Here we report on the possibility of growing a p–n junction taking advantage of electrochemical processes based on the use of aqueous solutions. The growth of the junction has been carried out using the Electrochemical Atomic Layer Deposition (E‐ALD) technique, which allowed to sequentially deposit two different semiconductors, CdS and Cu2S, on an Ag(111) substrate, in a single procedure. The growth process was monitored in situ by Surface X‐Ray Diffraction (SXRD) and resulted in the fabrication of a thin double‐layer structure with a high degree of crystallographic order and a well‐defined interface. The high‐performance electrical characteristics of the device were analysed ex‐situ and show the characteristic feature of a diode. [ABSTRACT FROM AUTHOR]

In this article, we present an in-situ and operando time-resolved X-ray Absorption Spectroscopy (XAS) technique which exploits a combination of Grazing Incidence XAS (GIXAS) and Fixed Energy X-ray Absorption Voltammetry (FEXRAV), the Grazing Incidence FEXRAV (GI-FEXRAV). A case-study is also outlined. Palladium ultra-low loadings were deposited above Au polycrystalline iso-oriented substrates adopting three different deposition methods: surface-controlled electrochemical methods, direct electrodeposition, and physical vapour deposition (PVD). These catalytical surfaces were prepared for the investigation by GI-FEXRAV of the Pd oxidation/dissolution phenomenon that could occur when the metal is used in the anodic compartment of Direct Alcohol Fuel Cells (DAFCs) or in electrochemical reformers. Moreover, we report a robust, low cost and versatile procedure to obtain wide and flat iso-oriented gold substrates that can mimic monocrystalline gold (1 1 1) in the electrochemical response. The use of GI-FEXRAV for the operando characterization of the catalysts, in conjunction with the designed experimental cell and our flexible Au-based electrochemical substrates show an invaluable potential in the operando study of fundamental phenomena in heterogeneous electrocatalysis model systems and, due to its versatility, paves the way to further studies on a wide selection of electrochemical systems. [ABSTRACT FROM AUTHOR]

Potential CO2 leakage from deep geologic reservoirs requires evaluation on a site-specific basis to assess risk and arrange mitigation strategies. In this study, a heterogeneous and realistic numerical model was developed to investigate CO2 migration pathways and uprising time in a shaly overburden, located in the Malaysian off-shore. Fluid flow and reactive transport simulations were performed by TOUGHREACT to evaluate the: (1) seepage through the caprock; (2) CO2-rich brine leakage through a fault connecting the reservoir with seabed. The effect of several factors, which may contribute to CO2 migration, including different rock types and permeability, Fickian and Knudsen diffusion and CO2 adsorption in the shales were investigated. Obtained results show that permeability mainly ruled CO2 uprising velocity and pathways. CO2 migrates upward by buoyancy without any important lateral leakages due to poor-connection of permeable layers and comparable values of vertical and horizontal permeability. Diffusive flux and the Knudsen flow are negligible with respect to the Darcy regime, despite the presence of shales. Main geochemical reactions deal with carbonate and pyrite weathering which easily reach saturation due to low permeability and allowing for re-precipitation as secondary phases. CO2 adsorption on shales together with dissolved CO2 constituted the main trapping mechanisms, although the former represents likely an overestimation due to estimated thermodynamic parameters. Developed models for both scenarios are validated by the good agreement with the pressure profiles recorded in the exploration wells and the seismic data along a fault (the F05 fault), suggesting that they can accurately reproduce the main processes occurring in the system. [ABSTRACT FROM AUTHOR]

The evaluation of caprock integrity and reservoir efficiency is critical for safe CO2 geological storage management. It is therefore important to investigate geochemical reactions between CO2-rich fluids and host rocks and their contribution in retaining CO2 at depth. This study deals with diffusive reaction experiments on shales and carbonate samples cored from an offshore structure in the Malaysian basin, a potential target for CO2-enhanced gas recovery. The aim is to evaluate the CO2 reaction front velocity in a typical shaly caprock and the mineral response of the reservoir. Rock samples were characterized in terms of texture, chemistry, and mineralogy by X-ray diffraction, electron microscopy (SEM), microanalysis (EDS), infrared spectroscopy (FT-IR), rock geochemistry (XRF), and mercury injection capillary permeability (MICP). Performed analyses show mineralogical alteration induced by CO2 as it penetrated into the samples. Carbonate dissolution and weathering of pyrite to form secondary carbonates belonging to siderite-ankerite series were observed along two reaction fronts. Estimated diffusion coefficients of CO2 are two orders of magnitude lower than CO2(aq) molecular diffusion in pure water and from half to an order of magnitude lower than diffusivity computed on unaltered sample, highlighting the important effect of gas–water–rock reactions on the CO2(aq) diffusivities in shales and carbonates. Results obtained in this study provide an insight regarding the effect of geochemical reactions on CO2 transport and represent a further discussion point on the diffusion coefficients. [ABSTRACT FROM AUTHOR]

Our society largely relies on inorganic semiconductor devices which are, so far, fabricated using expensive and complex processes requiring ultra-high vacuum equipment. Here we report on the possibility of growing a p-n junction taking advantage of electrochemical processes based on the use of aqueous solutions. The growth of the junction has been carried out using the Electrochemical Atomic Layer Deposition (E-ALD) technique, which allowed to sequentially deposit two different semiconductors, CdS and Cu 2 S, on an Ag(111) substrate, in a single procedure. The growth process was monitored in situ by Surface X-Ray Diffraction (SXRD) and resulted in the fabrication of a thin double-layer structure with a high degree of crystallographic order and a well-defined interface. The high-performance electrical characteristics of the device were analysed ex-situ and show the characteristic feature of a diode., (© 2024 Wiley-VCH GmbH.)