Atomic Manipulation to Create High-Valent Fe4+ for Efficient and Ultrastable Oxygen Evolution at Industrial-Level Current Density.

Manipulating the electronic structure of a catalyst at the atomic level is an effective but challenging way to improve the catalytic performance. Here, by stretching the Fe-O bond in FeOOH with an inserted Mo atom, a Fe-O-Mo unit can be created, which will induce the formation of high-valent Fe4+ during the alkaline oxygen evolution reaction (OER). The highly active Fe4+ state has been clearly revealed by in situ X-ray absorption spectroscopy, which can both enhance the oxidation capability and lead to an efficient and stable adsorbate evolution mechanism (AEM) pathway for the OER. As a result, the obtained Fe-Mo-Ni3S2 catalyst exhibits both superior OER activity and outstanding stability, which can achieve an industrial-level current density of 1 A cm-2 at a low overpotential of 259 mV (at 60 °C) and can stably work at the large current for more than 2000 h. Moreover, by coupling with commercial Pt/C, the Fe-Mo-Ni3S2∥Pt/C system can be used in the anion exchange membrane cell to acquire 1 A cm-2 for overall water splitting at 1.68 V (2.03 V for 4 A cm-2), outperforming the benchmark RuO2∥Pt/C system. The efficient, low-cost, and ultrastable OER catalyst enabled by manipulating the atomic structure may provide potential opportunities for future practical water splitting.

Toxicology assessment of deep-sea mining impacts on Gigantidas platifrons: A comparative in situ and laboratory metal exposure study.

Deep-sea toxicology is essential for deep-sea environmental impact assessment. Yet most toxicology experiments are conducted solely in laboratory settings, overlooking the complexities of the deep-sea environment. Here we carried out metal exposure experiments in both the laboratory and in situ, to compare and evaluate the response patterns of Gigantidas platifrons to metal exposure (copper [Cu] or cadmium [Cd] at 100 µg/L for 48 h). Metal concentrations, traditional biochemical parameters, and fatty acid composition were assessed in deep-sea mussel gills. The results revealed significant metal accumulation in deep-sea mussel gills in both laboratory and in situ experiments. Metal exposure could induce oxidative stress, neurotoxicity, an immune response, altered energy metabolism, and changes to fatty acid composition in mussel gills. Interestingly, the metal accumulating capability, biochemical response patterns, and fatty acid composition each varied under differing experimental systems. In the laboratory setting, Cd-exposed mussels exhibited a higher value for integrated biomarker response (IBR) while in situ the Cu-exposed mussels instead displayed a higher IBR value. This study emphasizes the importance of performing deep-sea toxicology experiments in situ and contributes valuable data to a standardized workflow for deep-sea toxicology assessment.

Twenty-five years of Open-Top Chambers in tropical environments: where, how, and what are we looking at regarding flora response to climate change?

MAIN CONCLUSION: Open-Top Chambers should be more used in tropical ecosystems to study climate change effects in plants as they are still insufficient to extract plant response patterns in these ecosystems. Understanding flora response to climate change (CC) is critical for predicting future ecosystem dynamics. Open-Top Chambers (OTCs) have been widely used to study the effects of CC on plants and are very popular in temperate ecosystems but are still underused in tropical regions. In this systematic review, we aimed to discuss the use of OTCs in the study of the effects of different agents of climate change on tropical flora by presenting scientometric data, discussing the technical aspects of its use and enumerating some observations on plant response patterns to climatic alterations in the tropics. Our analysis indicated that the bottleneck in choosing an OTC shape is not strictly related to its purpose or the type of parameter modulated; instead, passive or active approaches seem to be a more sensitive point. The common critical point in using this technique in warmer regions is overheating and decoupling, but it can be overcome with simple adaptations and extra features. The most frequently parameter modulated was CO2, followed by O3 and temperature. The plant families with more representatives in the studies analyzed were Fabaceae, Myrtaceae, and Poaceae, and the most represented biome was tropical and subtropical moist broadleaf forests. In conclusion, OTCs are a valuable and feasible tool to study CC effects on various tropical ecosystems, regardless of structure, active/passive approach, or other technical features. One of the primary advantages of this methodology is its applicability for in situ use, eliminating the need for plant transplantation. We encourage studies using OTC experimental design for plant conservation in the tropics.

Heitt Mjölnir: a heated miniature triaxial apparatus for 4D synchrotron microtomography.

Third- and fourth-generation synchrotron light sources with high fluxes and beam energies enable the use of innovative X-ray translucent experimental apparatus. These experimental devices access geologically relevant conditions whilst enabling in situ characterization using the spatial and temporal resolutions accessible at imaging beamlines. Here, Heitt Mjölnir is introduced, a heated miniature triaxial rig based on the design of Mjölnir, but covering a wider temperature range and larger sample volume at similar pressure capacities. This device is designed to investigate coupled thermal, chemical, hydraulic and mechanical processes from grain to centimetre scales using cylindrical samples of 10 mm × 20 mm (diameter × length). Heitt Mjölnir can simultaneously reach confining (hydraulic) pressures of 30 MPa and 500 MPa of axial stress with independently controlled sample pore fluid pressure < 30 MPa. This internally heated apparatus operates to temperatures up to 573 K with a minimal vertical thermal gradient in the sample of <0.3 K mm-1. This new apparatus has been deployed in operando studies at the TOMCAT (Swiss Light Source), I12 JEEP (Diamond Light Source) and PSICHÉ (Synchrotron SOLEIL) beamlines for 4D X-ray microtomography with scan intervals of a few minutes. Heitt Mjölnir is portable and modular, allowing a wide range of 4D characterizations of low-grade metamorphism and deformational processes. It enables spatially and temporally resolved fluid-rock interaction studies at conditions of crustal reservoirs and is suitable for characterization of material properties in geothermal, carbonation or subsurface gas storage applications. Technical drawings and an operation guide are included in this publication.

Field site soil aquifer treatment shows enhanced wastewater quality: Evidence from vadose zone hydro-geophysical observations.

Soil aquifer treatment (SAT) is an emerging, nature-based, economically viable wastewater treatment solution. Currently, most SAT experiments are done at the laboratory scale, which cannot generate the same conditions as natural field sites and limits the understanding of treatment efficiency. The current study carried out in situ SAT experiments in the Musi River basin in India, where wastewater irrigation is a common practice. SAT efficiency was determined using an integrated approach, including electrical resistivity tomography (ERT) surveys, soil investigations (grain size, permeability, and moisture measurements), and biochemical characterization of raw and SAT treated wastewater. The ERT scans of SAT column show lower order electrical resistivity 10-30 Ω-m with enhanced chargeability >5-6 mV/V attributed to the vadose zone, characterized by clay-rich soil and sandy soil up to 5-6 m depth. The increase in sand percentage (>70%) below 140-160 cm depth corroborates with the high moisture content (23.5%). The vadose zone permeability (K) 1.58 m/day and discharge (Q) 38.19 m3/day is used to determine the pollutants reduction efficiency of SAT column. Hydrogeological and biogeochemical observations reveal that the improved dissolved oxygen from <1.0 to 5-6 mg/L in the vadose zone catalyzes the oxidation of organic matter resulting in the reduction of BOD and COD up to 92% and 97%, respectively, and denitrification reducing NO3-- (0.55 kg/day). In addition, the precipitation and adsorption by kaolinite clay prompted the reduction of PO42- (0.26 kg/day). Furthermore, the oxic-vadose zone could not support the growth of coliforms and faecal coliforms, and the reduction observed was up to 99.99% in the SAT production well. Overall, the results indicated a positive outcome with SAT efficiency and framed the SAT sitting criteria for different geological environments.

Biodiversity mitigates trade-offs among species functional traits underpinning multiple ecosystem services.

Biodiversity loss and its effects on humanity is of major global concern. While a growing body of literature confirms positive relationships between biodiversity and multiple ecological functions, the links between biodiversity, ecological functions and multiple ecosystem services is yet unclear. Studies of biodiversity-functionality relationships are mainly based on computer simulations or controlled field experiments using only few species. Here, we use a trait-based approach to integrate plant functions into an ecosystem service assessment to address impacts of restoration on species-rich grasslands over time. We found trade-offs among functions and services when analysing contributions from individual species. At the community level, these trade-offs disappeared for almost all services with time since restoration as an effect of increased species diversity and more evenly distributed species. Restoration to enhance biodiversity also in species-rich communities is therefore essential to secure higher functional redundancy towards disturbances and sustainable provision of multiple ecosystem services over time.

Evaluation of Sub-Antarctic and Antarctic sea urchins' thermal reaction norm through righting behavior and comparison with in situ measurements.

Sea urchin's survival may depend on their capacity to recover proper orientation rapidly and effectively after inversion, enabling escape from predator and preventing desiccation. This righting behavior has been used as a repeatable and reliable indicator to assess echinoderms performance across environmental conditions, including thermal sensitivity and thermal stress. The current study aims at evaluating and comparing the thermal reaction norm for righting behavior (time for righting (TFR) and capacity to self-right) of three common sea urchins from high latitude, the Patagonian sea urchins Loxechinus albus and Pseudechinus magellanicus, and the Antarctic sea urchin Sterechinus neumayeri. In addition, to infer the ecological implications of our experiments, we compared laboratory-based and in situ TFR of these three species. We observed that populations of the Patagonian sea urchins L. albus and P. magellanicus presented similar trend of righting behavior, overly accelerating with increasing temperature (from 0 to 22°C). Little variations and high inter-individual variability were observed below 6°C in the Antarctic sea urchin TFR, and righting success strongly decreased between 7 and 11°C. For the three species, TFR was lower in in situ experiments compared to the laboratory. Overall, our results suggest that the populations of Patagonian sea urchin exhibit a wide thermal tolerance and, based on S. neumayeri's TFR, aligning with the narrow thermal tolerance of Antarctic benthos. Finally, the differences between laboratory and in situ experiments highlights the importance of considering the complexity of marine environments for future predictions.

Analysis, Design and Realization of a Furnace for In Situ Wettability Experiments at High Temperatures under X-ray Microtomography.

In this study, we analyzed the problem of a compact furnace, to be used for in situ experiments in a cone-beam X-ray microtomography commercial system. The design process was accomplished and outlined through its main steps, until the realization of a prototype. The furnace was conceived to carry out wettability experiments at temperatures up to 700 °C and under inert atmosphere on sessile droplets of a molten metal alloy, with a few millimeters diameter, posed on a thin ceramic substrate. X-ray imaging of the molten droplet is expected to permit an accurate three-dimensional reconstruction of the droplet profile and a robust estimation of the related quantities (such as the contact angle and the surface tension) utilized for the assessment of metal-ceramic joints by brazing. The challenges faced during this project, mostly related to the constraints of the setup, and the novel solutions implemented were discussed also with the support of analytical and numerical tools, in terms of interaction of X-rays with matter, geometry and working principle, heat transfer and insulation, material selection.

Bamboo's tissue structure facilitates large bending deflections.

Bamboo is becoming increasingly popular as an engineering material and source of bio-inspiration for instance in architecture and for the manufacture of a variety of woven products. Besides the properties of bamboo products for construction purposes, the bending deformability of thin bamboo slivers is of interest, as it appears that extraordinary large deflection can be achieved. To unravel the underlying mechanisms that may contribute to the high deformability at the tissue and cell level, bending deflection tests and additionalin situexperiments were performed to record the deflection of bamboo slivers in dependence of the tissue composition and the deformations of individual cells. For the latter, a simple bending deflection setup was used employing micro-CT measurements to analyze the deformation of individual parenchyma cells (PCs), fiber bundles and vessel elements at different stages of bending deformation of the bamboo slivers. The results showed that the degree of displacement and the characteristic fracture behavior strongly depend on the volume fractions of PCs and fibres determined by the position in the bamboo culm. For slivers with a sufficiently high fibre volume content, the very high bending deformability could be facilitated by the deformation of PCs, which are squeezed between the fibre bundles during increasing bending deflection.

Bragg Coherent Diffraction Imaging for In Situ Studies in Electrocatalysis.

Electrocatalysis is at the heart of a broad range of physicochemical applications that play an important role in the present and future of a sustainable economy. Among the myriad of different electrocatalysts used in this field, nanomaterials are of ubiquitous importance. An increased surface area/volume ratio compared to bulk makes nanoscale catalysts the preferred choice to perform electrocatalytic reactions. Bragg coherent diffraction imaging (BCDI) was introduced in 2006 and since has been applied to obtain 3D images of crystalline nanomaterials. BCDI provides information about the displacement field, which is directly related to strain. Lattice strain in the catalysts impacts their electronic configuration and, consequently, their binding energy with reaction intermediates. Even though there have been significant improvements since its birth, the fact that the experiments can only be performed at synchrotron facilities and its relatively low resolution to date (∼10 nm spatial resolution) have prevented the popularization of this technique. Herein, we will briefly describe the fundamentals of the technique, including the electrocatalysis relevant information that we can extract from it. Subsequently, we review some of the computational experiments that complement the BCDI data for enhanced information extraction and improved understanding of the underlying nanoscale electrocatalytic processes. We next highlight success stories of BCDI applied to different electrochemical systems and in heterogeneous catalysis to show how the technique can contribute to future studies in electrocatalysis. Finally, we outline current challenges in spatiotemporal resolution limits of BCDI and provide our perspectives on recent developments in synchrotron facilities as well as the role of machine learning and artificial intelligence in addressing them.

Memory Effect on a LDH/zeolite A Composite: An XRD In Situ Study.

In this memory effect study, hydrotalcite-type compounds in the lamellar double hydroxide-like (LDH)/zeolite A composite material were analyzed using X-Ray Diffration XRD) in situ experiments. Three samples were analyzed: Al,Mg-LDH, Al,Mg-LDH/ZA composite, and a physical mixture (50/50 wt%) of zeolite A and Al,Mg-LDH. The Al,Mg-LDH sample was treated at 500 °C in an O2 atmosphere and subsequently rehydrated. The Al,Mg-LDH/ZA composites had three treatments: one was performed at 300 °C in a He atmosphere, and two treatments were performed with an O2 atmosphere at 300 and 500 °C. In the physical mixture, two treatments were carried out under O2 flow at 500 °C and under He flow at 300 °C. Both went through the rehydration process. All samples were also analyzed by energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM). The results show that the LDH phase in the Al,Mg-LDH/ZA compounds has memory effects, and thus, the compound can be calcined and rehydrated. For the LDH in the composite, the best heat treatment system is a temperature of 300 °C in an inert atmosphere.

Effectiveness of reducing the influence of CTAB at the surface of metal nanoparticles during in situ heating studies by TEM.

In situ TEM is a valuable technique to offer novel insights in the behavior of nanomaterials under various conditions. However, interpretation of in situ experiments is not straightforward since the electron beam can impact the outcome of such measurements. For example, ligands surrounding metal nanoparticles transform into a protective carbon layer upon electron beam irradiation and may impact the apparent thermal stability during in situ heating experiments. In this work, we explore the effect of different treatments typically proposed to remove such ligands. We found that plasma treatment prior to heating experiments for Au nanorods and nanostars increased the apparent thermal stability of the nanoparticles, while an activated carbon treatment resulted in a decrease of the observed thermal stability. Treatment with HCl barely changed the experimental outcome. These results demonstrate the importance of carefully selecting pre-treatments procedures during in situ heating experiments.

A matter of size? Material, structural and mechanical strategies for size adaptation in the elytra of Cetoniinae beetles.

Nature's masterfully synthesized biological materials take on greater relevance when viewed through the perspective of evolutionary abundance. The fact that beetles (order Coleoptera) account for a quarter of all extant lifeforms on Earth, makes them prime exponents of evolutionary success. In fact, their forewings are acknowledged as key traits to their radiative-adaptive success, which makes the beetle elytra a model structure for next-generation bioinspired synthetic materials. In this work, the multiscale morphological and mechanical characteristics of a variety of beetle species from the Cetoniinae subfamily are investigated with the aim of unraveling the underlying principles behind Nature's adaptation of the elytral bauplan to differences in body weight spanning three orders of magnitude. Commensurate with the integral implications of size variation in organisms, a combined material, morphological, and mechanical characterization framework, across spatial scales, was pursued. The investigation revealed the simultaneous presence of size-invariant strategies (chemical compositions, layered-fibrous architectures, graded motifs) as well as size-dependent features (scaling of elytral layers and characteristic dimensions of building blocks), synergistically combined to achieve similar levels of biomechanical functionality (stiffness, energy absorption, strength, deformation and toughening mechanisms) in response to developmental and selection constraints. The integral approach here presented seeks to shed light on Nature's solution to the problem of size variation, which underpins the diversity of beetles and the living world.

In Situ Measurement of Breathing Strain and Mechanical Degradation in Organic Electrochromic Polymers.

Organic mixed ionic-electronic conductors (OMIECs) are an emerging family of materials crucial in the development of flexible, bio-, and optoelectronics. In electrochromic polymers, the cyclic redox reaction is associated with a mechanical breathing strain, which deforms the OMIECs and degrades the device reliability. We set forth an in situ nanoindentation approach to measure the breathing strain of a poly(3,4-propylenedioxythiophene) (PProDOT) thin film in a customized liquid cell during electrochromic cycles. A breathing volumetric strain of 12-25% is persistent in different sets of electrolytes of various solvents, salts, and salt molarities. The electrochemical conditioning, intermittence time, and cyclic protocol have minor effects on the mechanical response of PProDOT. The mechanical behavior and anion diffusivity measurement further infer the redox kinetics. Heavily cycled PProDOT films show reduced volumetric strain and accumulated mechanical damage of channel cracks and dysfunctional regions of slow and inhomogeneous electrochromic switching. This work is a systematic characterization of mechanical deformation and damage in a model OMIEC and informs the mechanical reliability of organic electrochromic devices.

Pushing the temporal resolution in absorption and Zernike phase contrast nanotomography: enabling fast in situ experiments.

Hard X-ray nanotomography enables 3D investigations of a wide range of samples with high resolution (<100 nm) with both synchrotron-based and laboratory-based setups. However, the advantage of synchrotron-based setups is the high flux, enabling time resolution, which cannot be achieved at laboratory sources. Here, the nanotomography setup at the imaging beamline P05 at PETRA III is presented, which offers high time resolution not only in absorption but for the first time also in Zernike phase contrast. Two test samples are used to evaluate the image quality in both contrast modalities based on the quantitative analysis of contrast-to-noise ratio (CNR) and spatial resolution. High-quality scans can be recorded in 15 min and fast scans down to 3 min are also possible without significant loss of image quality. At scan times well below 3 min, the CNR values decrease significantly and classical image-filtering techniques reach their limitation. A machine-learning approach shows promising results, enabling acquisition of a full tomography in only 6 s. Overall, the transmission X-ray microscopy instrument offers high temporal resolution in absorption and Zernike phase contrast, enabling in situ experiments at the beamline.

Multiple Mechanical Gradients are Responsible for the Strong Adhesion of Spider Attachment Hair.

Wandering spiders climb vertically and walk upside-down on rough and smooth surfaces using a nanostructured attachment system on their feet. The spiders are assumed to adhere by intermolecular van der Waals forces between the adhesive structures and the substrate. The adhesive elements are arranged highly ordered on the hierarchically structured attachment hair (setae). While walking, it has been suggested that the spiders apply a shear force on their legs to increase friction. However, the detailed mechanical behavior of the hair's structures during attachment and detachment remains unknown. Here, gradients of the mechanical properties of the attachment hair on different length scales that have evolved to support attachment, stabilize adhesion in contact, and withstand high stress at detachment, examined by in situ experiments, are shown. Shearing helps to self-align the adhesive elements with the substrate. The study is anticipated to contribute to the development of optimized artificial dry adhesives.

Anomalous Spin Behavior in Fe3GeTe2 Driven by Current Pulses.

Recently, 2D ferromagnetic materials have aroused wide interest for their magnetic properties and potential applications in spintronic and topological devices. However, their actual applications have been severely hindered by intricate challenges such as the unclear spin arrangement. In particular, the evolution of spin texture driven by high-density electron current, which is an essential condition for fabricating devices, remains unclear. Herein, the current-pulse-driven spin textures in 2D ferromagnetic material Fe3GeTe2 have been thoroughly investigated by in situ Lorentz transmission electron microscopy. The dynamic experiments reveal that the stripe domain structure in the AB and AC planes can be broken and rearranged by the high-density current. In particular, the density of domain walls can be modulated, which offers an avenue to achieve a high-density domain structure. This phenomenon is attributed to the weak interlayer exchange interaction in 2D metallic ferromagnetic materials and the strong disturbance from the high-density current. Therefore, a bubble domain structure and random magnetization in Fe3GeTe2 can be acquired by synchronous current pulses and magnetic fields. These achievements reveal domain structure transitions driven by the current in 2D metallic magnetic materials and provide references for the practical applications.

Potential effects of deep seawater discharge by an Ocean Thermal Energy Conversion plant on the marine microorganisms in oligotrophic waters.

Installation of an Ocean Thermal Energy Conversion pilot plant (OTEC) off the Caribbean coast of Martinique is expected to use approximately 100,000 m3 h-1 of deep seawater for its functioning. This study examined the potential effects of the cold nutrient-rich deep seawater discharge on the phytoplankton community living in the surface warm oligotrophic waters before the installation of the pilot plant. Numerical simulations of deep seawater upwelled by the OTEC, showed that a 3.0 °C temperature change, considered as a critical threshold for temperature impact, was never reached during an annual cycle on the top 150 m of the water column on two considered sections centered on the OTEC. The thermal effect should be limited, <1 km2 on the area exhibited a temperature difference of 0.3 °C (absolute value), producing a negligible thermic impact on the phytoplankton assemblage. The impact on phytoplankton of the resulting mixed deep and surface seawater was evaluated by in situ microcosm experiments. Two scenarios of water mix ratio (2% and 10% of deep water) were tested at two incubation depths (deep chlorophyll-a maximum: DCM and bottom of the euphotic layer: BEL). The larger impact was obtained at DCM for the highest deep seawater addition (10%), with a development of diatoms and haptophytes, whereas 2% addition induced only a limited change of the phytoplankton community (relatively higher Prochlorococcus sp. abundance, but without significant shift of the assemblage). This study suggested that the OTEC plant would significantly modify the phytoplankton assemblage with a shift from pico-phytoplankton toward micro-phytoplankton only in the case of a discharge affecting the DCM and would be restricted to a local scale. Since the lower impact on the phytoplankton assemblage was obtained at BEL, this depth can be recommended for the discharge of the deep seawater to exploit the OTEC plant.

In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts.

Nanoscale electrocatalysts have exhibited promising activity and stability, improving the kinetics of numerous electrochemical reactions in renewable energy systems such as electrolyzers, fuel cells, and metal-air batteries. Due to the size effect, nano particles with extreme small size have high surface areas, complicated morphology, and various surface terminations, which make them different from their bulk phases and often undergo restructuring during the reactions. These restructured materials are hard to probe by conventional ex-situ characterizations, thus leaving the true reaction centers and/or active sites difficult to determine. Nowadays, in situ techniques, particularly X-ray absorption spectroscopy (XAS), have become an important tool to obtain oxidation states, electronic structure, and local bonding environments, which are critical to investigate the electrocatalysts under real reaction conditions. In this review, we go over the basic principles of XAS and highlight recent applications of in situ XAS in studies of nanoscale electrocatalysts.

Mechanistic Origin of the High Performance of Yolk@Shell Bi2S3@N-Doped Carbon Nanowire Electrodes.

High-performance lithium-ion batteries are commonly built with heterogeneous composite electrodes that combine multiple active components for serving various electrochemical and structural functions. Engineering these heterogeneous composite electrodes toward drastically improved battery performance is hinged on a fundamental understanding of the mechanisms of multiple active components and their synergy or trade-off effects. Herein, we report a rational design, fabrication, and understanding of yolk@shell Bi2S3@N-doped mesoporous carbon (C) composite anode, consisting of a Bi2S3 nanowire (NW) core within a hollow space surrounded by a thin shell of N-doped mesoporous C. This composite anode exhibits desirable rate performance and long cycle stability (700 cycles, 501 mAhg-1 at 1.0 Ag-1, 85% capacity retention). By in situ transmission electron microscopy (TEM), X-ray diffraction, and NMR experiments and computational modeling, we elucidate the dominant mechanisms of the phase transformation, structural evolution, and lithiation kinetics of the Bi2S3 NWs anode. Our combined in situ TEM experiments and finite element simulations reveal that the hollow space between the Bi2S3 NWs core and carbon shell can effectively accommodate the lithiation-induced expansion of Bi2S3 NWs without cracking C shells. This work demonstrates an effective strategy of engineering the yolk@shell-architectured anodes and also sheds light onto harnessing the complex multistep reactions in metal sulfides to enable high-performance lithium-ion batteries.