Covalent organic frameworks (COFs) are ideal platforms to spatially control the integration of multiple molecular motifs throughout a single nanoporous framework. Despite this design flexibility, COFs are typically synthesized using only two monomers. One bears the functional motif for the envisioned application, while the other is used as an inert connecting building block. Integrating more than one functional motif extends the functionality of COFs immensely, which is particularly useful for multistep reactions such as electrochemical reduction of CO2. In this systematic study, we synthesized five Ni(II)- and Zn(II)-porphyrin-based COFs, including two pure component COFs (Ni100 and Zn100) and three mixed Ni/Zn-COFs (Ni75/Zn25, Ni50/Zn50, and Ni25/Zn75). Among these, the Ni50/Zn50-COF exhibited the highest catalytic performance for the electroreduction of CO2 to CO and formate at −0.6 V vs RHE, as was observed in an H-cell. The catalytic performance of the COF catalysts was further extended to a zero-gap membrane electrode assembly (MEA) operation where, utilizing Ni50/Zn50, CH4 was detected along with CO and formate at a high current density of 150 mA cm–2. In contrast, under these conditions predominantly H2 and CO were detected at Ni100 and Zn100 respectively, indicating a clear synergistic effect between the Ni- and Zn-porphyrin units.@en

Superelastic metallic materials possessing large recoverable strains are widely used in automotive, aerospace and energy conversion industries. Superelastic materials working at high temperatures and with a wide temperature range are increasingly required for demanding applications. Until recently, high-temperature superelasticity has only been achievable with multicomponent alloys fabricated by complex processes. In this study, a novel framework of multi-scale models enabling texture and microstructure design is proposed for high-performance NiTi fabrication via laser powder bed fusion. Based on the developed framework, a Ni-lean Ni(49.4 at.%)-Ti alloy is, for the first time, endowed with a 4% high-temperature compressive superelasticity. A 001 texture, unfavorable for plastic slip, is created to realize enhanced functionality. The unprecedented superelasticity can be maintained up to 453 K, which is comparable with but has a wider superelastic temperature range (∼110 K) than rare earth alloyed NiTi alloys, previously only realizable with grain refinement, and other complicated post-processing operations. At the same time, its shape memory stability is also improved due to existing textured 100 martensite and intergranular precipitation of Ti₂NiOx. This discovery reframes the way that we design superior performance NiTi based alloys through directly tailoring crystallographic orientations during additive manufacturing.

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Additive manufacturing of NiTi shape memory alloys has attracted attention in recent years, due to design flexibility and feasibility to achieve four-dimensional (4D) function response. To obtain customized 4D functional responses in NiTi structures, tailorable phase transformation temperatures and stress windows as well as one-way or two-way shape memory properties are required. To achieve this goal, various heat treatments, including direct aging, annealing and annealing followed by aging, were optimized for the Ti-rich NiTi (Ni49.6Ti (at. %)) fabricated by laser powder bed fusion (L-PBF). Microstructural evolution, phase transformation, precipitation and shape memory behaviour were systematically investigated by multiscale correlative microstructural, differential scanning calorimetry analysis and thermomechanical analysis. Based on optimized heat treatments, ∼25 K phase transformation temperature windows and ∼90 MPa stress windows were achieved for the one-way shape memory effect. Solutionized annealing was found to be the most effective way to improve one-way shape memory degradation resistance, due to the reduction of defects and solid solution strengthening. One of the main findings of this study is that the heterogonous microstructures between hard intergranular Ti₂NiO_x and soft NiTi matrix, induced by solutionized annealing with subsequent aging, result in strain partitioning and enclosing the internal stress state, which was found to promote a pronounced two-way shape memory effect response. The results of this work provide in-depth knowledge on tailoring and designing functional shape memory characteristics via heat treatments, which contributes to expanding L-PBF NiTi application fields, such as biomedical implants, aerospace components, and other advanced engineering applications.

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Despite the promising performance of Ru nanoparticles or nanoclusters on nanostructured TiO₂ in photocatalytic and photothermal reactions, a mechanistic understanding of the photophysics is limited. The aim of this study is to uncover the nature of light-induced processes in Ru/TiO₂ and the role of UV versus visible excitation by time-resolved photoluminescence (PL) spectroscopy. The PL at a 267 nm excitation is predominantly due to TiO₂, with a minor contribution of the Ru nanoclusters. Relative to TiO₂, the PL of Ru/TiO₂ following a 267 nm excitation is significantly blue-shifted, and the bathochromic shift with time is smaller. We show by global analysis of the spectrotemporal PL behavior that for both TiO₂ and Ru/TiO₂ the bathochromic shift with time is likely caused by the diffusion of electrons from the TiO₂ bulk toward the surface. During this directional motion, electrons may recombine (non)radiatively with relatively immobile hole polarons, causing the PL spectrum to red-shift with time following excitation. The blue-shifted PL spectra and smaller bathochromic shift with time for Ru/TiO₂ relative to TiO₂ indicate surface PL quenching, likely due to charge transfer from the TiO₂ surface into the Ru nanoclusters. When deposited on SiO₂ and excited at 532 nm, Ru shows a strong emission. The PL of Ru when deposited on TiO₂ is completely quenched, demonstrating interfacial charge separation following photoexcitation of the Ru nanoclusters with a close to unity quantum yield. The nature of the charge-transfer phenomena is discussed, and the obtained insights indicate that Ru nanoclusters should be deposited on semiconducting supports to enable highly effective photo(thermal)catalysis.

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Silicon-aluminum-oxigen (SiAlO) coatings doped with Sm²⁺ and prepared by reactive magnetron co-sputtering of Si, Al, and Sm targets, are attractive for luminescence solar concentrator applications but suffer from the low absorption between 300 and 600 nm. This article reports that the main cause of low absorption is a high concentration of undesired Sm³⁺. This finding is supported by optical transmittance, photoluminescence emission and excitation characterization, and X-ray photoelectron spectroscopy data of the Sm's 3d^5/2 edge. We present an alternative deposition process for obtaining Sm doped SiAlO layers with enhanced Sm²⁺ absorption by incorporating Sm through the use of multilayer thin-film precursors composed of metallic Sm and SiAlO layers. After thermal post-deposition treatments, diffusion and reaction of the metallic Sm layers with the SiAlO host results in coatings showing the characteristic 5d → 4f transitions of Sm²⁺ in the region between 250 and 600 nm which were not detectable in Sm-doped single layers. This same deposition strategy produces Tm doped SiAlO coatings with Tm²⁺‘s characteristic luminescence at 1132 nm when the SiAlO host is in the mullite composition region. The photoluminescence excitation spectrum of Tm²⁺ is compared to phosphor with similar composition and covers the range between 300 and 700 nm.

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Thin films of transition metal oxides such as molybdenum oxide (MoO_x) are attractive for application in silicon heterojunction solar cells for their potential to yield large short-circuit current density. However, full control of electrical properties of thin MoO_x layers must be mastered to obtain an efficient hole collector. Here, we show that the key to control the MoO_x layer quality is the interface between the MoO_x and the hydrogenated intrinsic amorphous silicon passivation layer underneath. By means of ab initio modelling, we demonstrate a dipole at such interface and study its minimization in terms of work function variation to enable high performance hole transport. We apply this knowledge to experimentally tailor the oxygen content in MoO_x by plasma treatments (PTs). PTs act as a barrier to oxygen diffusion/reaction and result in optimal electrical properties of the MoO_x hole collector. With this approach, we can thin down the MoO_x thickness to 1.7 nm and demonstrate short-circuit current density well above 40 mA/cm² and a champion device exhibiting 23.83% conversion efficiency.

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Preparing supported nanoparticles with a well-defined structure, uniform particle size, and composition using conventional catalyst synthesis methods, such as impregnation, precipitation, and deposition-precipitation is challenging. Furthermore, these liquid phase methods require significant solvent consumption, which has sustainable issues and requires complex purification processes, usually leaving impurities on the catalyst, affecting its selectivity and activity. In this work, we employed atomic layer deposition (ALD, a vapor phase synthesis method) to synthesize electrocatalysts with well-controlled core-shell and alloy structures for CO₂ reduction to formic acid. With this approach, the structural control of the catalysts is down to the atomic scale, and the effect of core-shell and alloy structure on Pt−Pd bimetallic catalysts has been investigated. It is shown that the Pt−Pd alloy catalyst displays a 46 % faradaic efficiency toward formic acid, outperforming Pt@Pd and Pd@Pt core-shell structures that show faradaic efficiencies of 22 % and 11 %, respectively. Moreover, both core-shell bimetallic catalysts (Pd@Pt and Pt@Pd) are not stable under electroreduction conditions. These catalysts restructure to more thermodynamically stable structures, such as segregated clusters or alloy particles, during the electrochemical reduction reaction, altering the catalytic selectivity.

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Constant stress creep experiments at 550 °C were performed on a high-purity Fe-3Au-4W (wt.%) ternary alloy with about 1 at.% supersaturation for Au and W in order to study self healing of grain-boundary cavities by both Au-rich and W-rich precipitates. Using synchrotron X-ray nano-tomography, the development of the creep cavities and the healing precipitates at different stages of creep was visualised using two spatial resolutions (30 and 100 nm voxel size) for separate samples taken after different loading times. The healing kinetics was found to strongly depend on the nucleation time of the cavities. Cavities nucleated at an early stage of creep could be fully healed, while the healing of the late-nucleated cavities is much slower due to a decrease in the diffusional flux of the healing supersaturated solutes over time, as a result of (i) a decrease in inter-cavity spacing caused by cavity nucleation and (ii) a gradual depletion of the supersaturated solutes near the grain boundaries. The interaction between the competing healing mechanisms for creep cavities by Au-rich and W-rich precipitates is discussed. It was found that Au-rich precipitates are formed much faster than the W-rich precipitates, and thereby effectively provide creep damage healing on different time scales.

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Low parasitic absorption and high conductivity enable (n)-type hydrogenated nanocrystalline silicon [(n)nc-Si:H], eventually alloyed with oxygen [(n)nc-SiO_x:H], to be deployed as window layer in high-efficiency silicon heterojunction (SHJ) solar cells. Besides the appropriate opto-electrical properties of these nanocrystalline films, reduction of their thickness is sought for minimizing parasitic absorption losses. Many strategies proposed so far reveal practical limits of the minimum (n)-layer thickness that we address and overcome in this manuscript. We demonstrated the successful application of an ultra-thin layer of only 3-nm-thick based on (n)nc-Si:H PECVD plasma growth conditions without the use of additional contact or buffer layers. For simplicity, we still name (n)nc-Si:H this ultra-thin layer and the solar cell endowed with it delivers a certified efficiency η of 22.20%. This cell shows a 0.61 mA/cm² overall J_SC gain over the (n)a-Si:H counterpart mainly owing to the higher transparency of (n)nc-Si:H, while maintaining comparable V_OC > 714 mV and FF > 80%. Our optimized (n)nc-Si:H layer yields low absorption losses that are commonly measured for (n)nc-SiO_x:H films. In this way, we are able to avoid the detrimental effect that oxygen incorporation has on the electrical parameters of these functional layers. Further, by applying a MgF₂/ITO double-layer anti-reflection coating, a cell with 3-nm-thick (n)nc-Si:H exhibits a J_SC,EQE up to 40.0 mA/cm². By means of EDX elemental mapping, we additionally identified the (n)nc-Si:H/ITO interface as critical for electron transport due to unexpected oxidation. To avoid this interfacial oxidation, insertion of a 2-nm-thick (n)a-Si:H on the 3-nm-thick (n)nc-Si:H contributes to FF gains of 1.4%_abs. (FF increased from 78.6% to 80.0%), and showing further room for improvements.

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Catalyst passivation refers to the formation of a protective oxide layer on the active metal particles that prevents their oxidation when exposed to air. Common passivation procedures, when applied to Ni/ Al2O3 catalysts, typically result in a significant decrease of the overall Ni surface area and, accordingly, the catalytic activity. Nevertheless, passivation and reactivation is an attractive pre-treatment option for this system. Ni/ Al2O3 typically requires reduction temperatures much higher than the desired reaction temperature, whereas reactivation of passivated samples is a low-temperature reduction. This can be used to avoid temperature limitations of existing systems. Thus, more insight into the passivation process of this system is desirable. In this work we analyzed the impact of passivation on the catalytic performance of a series of Ni/ Al2O3 catalysts in dry reforming of methane. This approach allows for the elimination of scale effects during passivation. We show that changes in conversion and especially of the coke content can be used to track sintering of Ni particles. These metrics allows to identify an adverse effects of catalyst passivation in excess O2, which gives rise to rapid local overheating and, accordingly, Ni sintering even when operating at tens of mg catalyst scale. Our study demonstrates that such problems are not limited to scaling issues and sufficient care must be taken even on a lab-scale when passivating Ni/ Al2O3 catalysts.@en

Liquid-phase transmission electron microscopy (LP-TEM) has provided corrosion scientists with a unique opportunity to directly correlate nanoscopic morphological and compositional evolutions to the corresponding electrochemical response of corroding thin TEM specimens. Electrochemical liquid cell designs are key components of a LP-TEM study towards an implementation which is representative for realistic exposure conditions of bulk samples. However, the application of commercially available liquid cells in corrosion studies brings along an important shortcoming of galvanic coupling effects due to the inevitable connection of the TEM specimens with Pt patterned electrodes. Here, we introduce an approach of fabricating electrochemical liquid cells to alleviate the current cell design challenge for corrosion studies. Besides, we present a protocol for preparing thin specimens to be electrochemically investigated with our home-made electrochemical liquid cell. We finally confirm the effectiveness of this methodology by electrochemically evaluating thin specimens of AA2024-T3 in an open-cell configuration through open circuit potential and potentiodynamic polarisation measurements.

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In this work, we studied the mechanical and thermal stability of ~100 nm Pd thin films magnetron sputter deposited on a bare oxidized Si(100) wafer, a sputtered Titanium (Ti) intermediate layer, and a spin-coated Polyimide (PI) intermediate layer. The dependence of the film stability on the film morphology and the film-substrate interaction was investigated. It was shown that a columnar morphology with elongated voids at part of the grain boundaries is resistant to embrittlement induced by the hydride formation (α↔β phase transitions). For compact film morphology, depending on the rigidity of the intermediate layer and the adherence to the substrate, complete transformation (Pd-PI-SiO₂/Si) or partly suppression (Pd-Ti-SiO₂/Si) of the α to β-phase was observed. In the case of Pd without intermediate layer (Pd-SiO₂/Si), buckling delamination occurred. The damage and deformation mechanisms could be understood by the analysis of the stresses and dislocation (defects) behavior near grain boundaries and the film-substrate interface. From diffraction line-broadening combined with microscopy analysis, we showed that in Pd thin films, stresses relax at critical stress values via different relaxation pathways depending on film-microstructure and film-substrate interaction. On the basis of the in-situ hydriding experiments, it was concluded that a Pd film on a flexible PI intermediate layer exhibits free-standing film-like behavior besides being strongly clamped on a stiff SiO₂/Si substrate.

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Lithium leaching coatings have recently been developed as eco-friendly active corrosion protection technology for aerospace aluminium alloys (AAs) by the formation of a conversion layer at coating defects. While general conversion layer formation characteristics were studied and reported before, here we study the local layer formation process with sub-micron resolution at and around intermetallic particles (IMPs) in AA2024-T3. Top- and cross-sectional-view morphological electron micrograph observations along with open circuit potential (OCP) measurements are performed, mimicking coating defect conditions upon lithium carbonate leaching from the coating matrix. The results revealed five stages of the conversion process in which the alloy matrix and different IMPs evolve morphologically, compositionally, and electrochemically. Besides, we found a correlation between the OCP response of the AA2024-T3 system and the morphological and compositional evolutions of the alloy matrix and IMPs at different stages of exposure. Passive layer and alloy matrix dissolution leading to surface Cu-enrichment and S-phase dealloying occur at early stages of exposure. They precede the formation of a columnar layer on the alloy, followed by the establishment of a dense-like layer at the final stage. Dealloying of Al₂CuMg can assist the conversion process by providing local supersaturation. Through complementary experiments in a sodium carbonate solution and besides X-ray diffraction analysis, we found out that lithium plays a critical role in stabilising the corrosion product throughout the conversion process.

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Lithium salts have been proposed as promising environmentally friendly alternatives to carcinogenic hexavalent chromium-based inhibitors for the corrosion protection of aerospace aluminium alloys (AAs). Incorporated into organic coatings, lithium salts are released at damaged locations to establish a conversion layer in which distinct sublayers have different barrier characteristics. Thus, detailed knowledge on the sequence of formation events from the early stages of nucleation towards the final multi-layered arrangement is essential for developing and optimising lithium-leaching technology for protective coatings. Here, liquid-phase-transmission electron microscopy (LP-TEM) is employed to observe nanoscopic morphological evolutions in situ during the lithium-based conversion process of AA2024-T3. Thanks to dedicated preparation of delicate sandwiched TEM specimens allowing us to explore the events cross-sectionally, we provide real-time direct mechanistic information on the conversion process from the initiation to an advanced growth stage. In parallel, we perform supplementary ex situ SEM and TEM investigations to support and validate the LP-TEM findings. The unprecedented experimental approach developed and executed in this study provides an inspiring base for studying also other complicated surface conversion processes in situ and at the nanoscopic scale.

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Cerium-based compounds have been studied for decades as non-toxic candidates for the protection of aerospace aluminium alloys (AAs) like AA2024-T3. However, the complex heterogeneous microstructure of these alloys has hindered a thorough understanding of the subsequent stages of corrosion protection provided by this class of inhibitors. Thus, this work is devoted to unravelling the interaction mechanisms of different intermetallic particles (IMPs) in AA2024-T3 with cerium nitrate at the nanoscopic scale. This has been fulfilled through detailed top-view and cross-sectional analytical TEM investigations along with electrochemical evaluations. In line with our recent findings, we here report dealloying of IMPs as the main factor governing the rate of local cerium precipitation in contrast to micro-galvanic corrosion between IMPs and the surrounding matrix. Furthermore, we discuss a connection between the electrochemical response of the AA2024-T3 system and the morphological and compositional evolutions of individual IMPs including Al2CuMg, Al2Cu, Al7Cu2Fe(Mn) and Al76Cu6Fe7Mn5Si6 at different stages of a 96-h exposure.

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Autonomous healing of creep-induced grain boundary cavities by Au-rich and W-rich precipitates was studied in a Fe-3Au-4W (wt pct) alloy at a fixed temperature of 823 K (550 °C) with different applied stresses. The ternary alloy, with two supersaturated healing solutes, serves as a model system to study the interplay between two separate healing agents. The creep properties are evaluated and compared with those of the previously studied Fe-Au and Fe-W binary systems. The microstructures of the creep-failed samples are studied by electron microscopy to investigate the cavity filling behavior and the mass transfer of supersaturated solute to the defect sites. Compared to the Fe-Au and Fe-W alloys, the new Fe-Au-W alloy has the lowest steady-state strain rate and the longest lifetime. The site-selective filling of the creep-induced cavities is attributed to two different categories of precipitates: micron-sized Au-rich precipitates and nano-sized W-rich precipitates. The Au-rich precipitates are found capable to fully heal the cavities, while the W-rich precipitates show only a limited degree of healing. The two types of precipitates show a reluctance to coexistence, and the formation of W-rich precipitates is suppressed strongly. A model is proposed to describe the competitive healing behavior of the Au-rich and W-rich precipitates.

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Nanoscopic characterization of heterogeneous intermetallic particles (IMPs) which microstructurally and compositionally evolve during local corrosion is crucial in unravelling the mechanisms and sequence of initial and local corrosion events. Herein, we study site-specific initiation events focused on microscopic constituent intermetallic compounds and nanoscopic dispersoids in AA2024-T3 at the nanoscale using a combined quasi in-situ and ex-situ analytical TEM approach. Our findings show a dealloying-driven local corrosion initiation at the studied IMPs that have been considered as cathodic phases traditionally. Besides, local degradation which is a result of galvanic interactions between dealloyed regions of IMPs and their adjacent alloy matrix is largely governed by the intrinsic electrochemical instability of intermetallic compounds.

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Identifying corrosion initiation events in metals and alloys demands techniques that can provide temporal and spatial resolution simultaneously. Transmission electron microscopy (TEM) enables one to obtain microstructural and chemical descriptors of materials at atomic/nanoscopic level and has been used in corrosion studies of many metal-electrolyte combinations. Conventionally, ex situ and quasi in situ TEM studies of pre- and post-corroded samples were performed, but possible experimental artifacts such as dehydrated surfaces might not fully represent the real interfacial conditions as compared to those when actually immersed in the electrolyte. Recent advances in liquid cell transmission electron microscopy (LC-TEM) allows for in situ monitoring morphological and even compositional evolutions in materials resulting from interaction with gas or liquid environments. Corrosion science, as a challenging field of research, can benefit from this unparalleled opportunity to investigate many complicated corroding systems in aqueous environments at high resolution. However, “real life” corrosion with LC-TEM is still not straightforward in implementation and there are limitations and challenging experimental considerations for conducting reliable examinations. Thus, this study has been devoted to discussing the challenges of in situ LC-TEM wherein state-of-the-art achievements in the field of relevance are reviewed.@en

This work focuses on the cross-sectional characterization of the protective conversion layer formed on AA2024-T3 by lithium-leaching from a polyurethane coating in a corrosive environment. The layer shows a multi-layered arrangement comprising nanoscopic local phases. Transmission electron microscopy (TEM) and complementary high-resolution secondary ion mass spectroscopy (SIMS) were employed to observe the cross-sections of the entire layer formed at different locations of a 1-mm-wide scribe, in terms of morphology, structure and chemical composition. The conversion layer was comprised of two ubiquitous sublayers; a thin dense layer (i.e. 150 nm) adjacent the alloy substrate and a porous layer. The former represents an amorphous lithium-containing pseudoboehmite phase, Li-pseudoboehmite, whereas the latter is composed of amorphous and crystalline products; an outer columnar layer merely seen on the peripheral region is also crystalline. Through a sandwich structure and the d₍₀₀₃₎ basal spacing, the crystalline phases were identified as Li-Al layered double hydroxide. Although lithium was found uniformly spread within different regions, the local phases with no/low concentration of lithium were revealed with energy filtered TEM and confirmed with SIMS analysis.

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In microstructural corrosion studies, knowledge on the initiation of corrosion on an nm-scale is lacking. In situ transmission electron microscope (TEM) studies can elucidate where/how the corrosion starts, provided that the proper corrosive conditions are present during the investigation. In wet corrosion studies with liquid cell nanoreactors (NRs), the liquid along the electron beam direction leads to strong scattering and therefore image blurring. Thus, a quick liquid removal or thickness control of the liquid layer is preferred. This can be done by the use of a Peltier element embedded in an NR. As a prelude to such in situ work, we demonstrate the local wetting of a TEM sample, by creating a temperature decrease of 10 ± 2°C on the membrane of an NR with planar Sb/BiSb thermoelectric materials for the Peltier element. TEM samples were prepared and loaded in an NR using a dual-beam focused ion beam scanning electron microscope. A mixture of water vapor and carrier gas was passed through a chamber, which holds the micro-electromechanical system Peltier device and resulted in quick formation of a water layer/droplets on the sample. The TEM analysis after repeated corrosion of the same sample (ex situ studies) shows the onset and progression of O2 and H2S corrosion of the AA2024-T3 alloy and cold-rolled HCT980X steel lamellae.

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