Time-of-flight Secondary Ion Mass Spectrometry Analysis Research Articles

Enhanced marmatite activation by copper with ammonium sulfate: An experimental and DFT investigation

The presence of iron atoms on the marmatite surface hinders effective interaction between the activator and the mineral, leading to unsatisfactory flotation performance through direct copper (Cu) activation. Hence, this study introduced ammonium sulfate to enhance the marmatite-activation capability by Cu ions. Additionally, the reinforcement mechanism was investigated through microflotation tests, atomic force microscopy (AFM), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and density-functional theory (DFT) calculations. Microflotation results demonstrated that the addition of ammonium sulfate as a complexing reagent increased the flotation recovery of marmatite by 17.36%. AFM analysis revealed that marmatite subjected to enhanced activation (i.e., in the presence of ammonium sulfate) exhibited a considerably higher surface roughness than that subjected to direct Cu activation. Moreover, the average height of hill-shaped materials on the marmatite surface notably increased to 9.6 nm after enhanced Cu activation. SEM-EDS analysis revealed that the concentration of Cu atoms (2.2%) on the marmatite surface after enhanced Cu activation was nearly three times that (0.8%) after direct Cu activation. Additionally, XPS results indicated a considerably higher presence of the Cu–S component on the marmatite surface after enhanced Cu activation than after direct Cu activation. ToF-SIMS analysis indicated an increase in the fragment peaks of Cu+, CuOCS2+, OCS2−, and OC2H2S2− on the surface of enhanced-activated marmatite. Additionally, DFT calculations indicated that the presence of NH3 molecules enhanced electron transfer between Cu and S on the hydrated marmatite surface. The marmatite (1 1 0) surface exhibited more negative adsorption energy of Cu ions after the action of NH3 molecules, and NH3–Cu showed a more stable adsorption configuration than Cu. Therefore, the addition of ammonium sulfate enhanced the Cu activation for marmatite, thereby improving flotation performance.

Studying microbially induced corrosion on glass using ToF-SIMS.

Microbially induced corrosion (MIC) is an emerging topic that has huge environmental impacts, such as long-term evaluation of microbial interactions with radioactive waste glass, environmental cleanup and disposal of radioactive material, and weathering effects of microbes. Time-of-flight secondary ion mass spectrometry (ToF-SIMS), a powerful mass spectral imaging technique with high surface sensitivity, mass resolution, and mass accuracy, can be used to study biofilm effects on different substrates. Understanding how to prepare biofilms on MIC susceptible substrates is critical for proper analysis via ToF-SIMS. We present here a step-by-step protocol for preparing bacterial biofilms for ToF-SIMS analysis, comparing three biofilm preparation techniques: no desalination, centrifugal spinning (CS), and water submersion (WS). Comparisons of two desalinating methods, CS and WS, show a decrease in the media peaks up to 99% using CS and 55% using WS, respectively. Proper desalination methods also can increase biological signals by over four times for fatty acids using WS, for example. ToF-SIMS spectral results show chemical compositional changes of the glass exposed in a Paenibacillus polymyxa SCE2 biofilm, indicating its capability to probe microbiologically induced corrosion of solid surfaces. This represents the proper desalination technique to use without significantly altering biofilm structure and substrate for ToF-SIMS analysis. ToF-SIMS spectral results showed chemical compositional changes of the glass exposed by a Paenibacillus bacterial biofilm over 3-month inoculation. Possible MIC products include various phosphate phase molecules not observed in any control samples with the highest percent increases when experimental samples were compared with biofilm control samples.

Comprehensive Characterization of Porous Transport Electrodes with SEM, XPS, and Tof-SIMS

Advancements towards more efficient design and manufacturability of polymer electrolyte membrane electrolyzers include recent efforts to better integrate the porous transport layer (PTL) and adjacent anodic catalyst layer (CL), forming the porous transport electrode (PTE). It is well known that characterizations of the PTL alone, especially when combined with a protective coating, present numerous challenges. The PTE structure is even more complex, and it is difficult to comprehensively characterize all components and interfaces. In prior work, we established Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) as a characterization technique for the PTLs coated with protective coatings. This work demonstrates ToF-SIMS as a powerful technique for the characterization of PTLs integrated with CLs. A series of sintered Ti PTLs were first coated with protective Pt coatings and then coated with various IrOx and IrRuOx catalysts via electrodeposition. Prepared PTE samples ranged in catalyst loadings and catalyst composition. Selected samples were also subjected to annealing post-treatments to further modify catalyst composition. X-ray photoelectron spectroscopy (XPS) was conducted to identify surface chemical speciation and states of the catalysts. ToF-SIMS analysis was conducted using Cs in both positive and negative modes to identify chemical species, including Ir, Ru, and their oxides as a function of catalyst layer depth. These two methods were complemented by Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy (SEM- EDS) analysis to evaluate morphology and distribution of catalysts. This comprehensive physical and chemical characterization of the PTEs provides insights that are useful for the characterization of as produced, modified, and degraded PTE samples.

A study on the surface responses and degradation mechanisms of epoxy-amine coating subjected to UV accelerated weathering and hygrothermal ageing using ToF-SIMS and FTIR analysis

Epoxy amine coatings were subjected to hygrothermal ageing and accelerated weathering conditions that is comprised of neutral salt spray test and UV accelerated degradation condition. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and Fourier Transform Infrared Spectroscopy (FTIR) were employed to study the surface responses and spectral variation of epoxy amine coatings subjected to different ageing conditions. As a result, principal component analysis (PCA) of ToF-SIMS positive ion spectra illustrated that principal component 1 (PC1) has collected information on a variation of surface responses caused by accelerated weathering and hygrothermal ageing conditions as compared to fresh epoxy amine coatings. On the other hand, principal component 2 (PC2) has distinguished the different surface responses generated on epoxy amine coatings that were subjected to UV accelerated degradation conditions and those that were not. FTIR analysis has demonstrated the hydrolysis and photooxidation of epoxy amine coatings from the growth of two absorption bands at 1709 cm−1 and 1650 cm−1, indicating the formation of carbonyl-containing groups such as ketones, aldehydes, phenyl formates, imine or tertiary amides. This comprehensive analysis provides significant insights into the degradation mechanisms of epoxy amine coatings subjected to corrosion under insulation (CUI) and/or artificial weathering (AW) environment. Understanding these mechanisms is pivotal for industries reliant on epoxy coatings, such as oil and gas, ensuring enhanced performance and extended lifespan of their products under varying environmental conditions. The findings also contribute to the broader field of materials science by offering methodologies and analytical approaches that can be applied to other polymeric coatings and materials.

Study on the effects of a novel imidazoline siliconophilic collector in the desilication process of magnesite: Separation experiments, adsorption mechanisms, and separation model

This study innovatively introduced heptadecenyl amine ethyl imidazoline quaternary ammonium salt (ODD) as a siliconophilic flotation collector, effectively facilitating the achievement of high-efficiency separation of magnesite from quartz. ODD exhibits unique properties such as high selectivity and environmental friendliness. Through a comprehensive series of experiments, including flotation tests, zeta potential characterization, atomic force microscopy (AFM) imaging, Fourier-transform infrared (FTIR) spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS), the flotation performance and selective adsorption mechanisms of ODD were thoroughly investigated. The experiments demonstrated that at a pH of 7.00 and an ODD concentration of 40 mg/L, quartz achieved a flotation recovery rate of 95.16 %, while magnesite was only 2.99 %, underscoring the high selectivity of ODD in mineral separation. Zeta potential measurements indicated that ODD exhibits strong adsorption interactions with quartz over magnesite. AFM observations confirmed that ODD forms significant adsorption structures on quartz surfaces, in contrast to weaker interactions with magnesite. FTIR analysis further revealed the robust interactions between ODD and quartz through hydrogen bonds and electrostatic forces, which were significantly diminished on magnesite surfaces. ToF-SIMS analysis provided direct evidence of ODD’s selective adsorption on quartz, contributing to a better understanding of the flotation mechanisms involved. This research not only offers a novel approach for the purification of magnesite and effective removal of quartz but also demonstrates the potential of ODD as an eco-friendly collector in mineral processing, potentially advancing a green transformation in the industry. The findings provide a solid theoretical and experimental basis for future industrial applications and innovative development of flotation collectors.

Enhancing ToF-SIMS OLED Data Analysis with Neural Networks and Mathematical Spectral Mixing.

This study presents a method employing artificial neural networks (ANN) for automated interpretation and depth profiling of organic multilayers using a limited set of time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra. To overcome the challenges of acquiring massive data sets for OLEDs, training data was generated by combining existing ToF-SIMS data sets with mathematically generated spectra. The classification model achieved an impressive 99.9% accuracy in identifying the mixed layers of the OLED dyes. The study demonstrates the synergy of ToF-SIMS and ANN analysis for effective classification and depth profiling of the OLED layers, providing valuable insights for the development and optimization of organic electronic devices.

Selective depression mechanism of polyaspartic acid and calcium oxide on arsenopyrite after copper ions activation and its effect on flotation separation performance

The arsenopyrite activated by copper ions have similar flotation properties to chalcopyrite. Polyaspartic acid (PASP) and calcium oxide (CaO) using as combination depressants for the selective separation of copper-activated arsenopyrite and chalcopyrite were carried out by micro-flotation experiments, contact angle measurements, surface adsorption capacity tests, zeta potential measurements, X-ray photoelectron spectroscopy (XPS) analyses, inductively coupled plasma-optical emission spectrometer (ICP-OES) tests and time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses, and its depression mechanism was investigated. The results of flotation experiments showed that the recovery of arsenopyrite after addition of the depressants reached only 7.80 %, while the recovery of chalcopyrite reached 94.02 %. The results of contact angles, adsorption capacity tests and zeta potential measurements showed that the PASP-CaO can selectively enhance the hydrophilicity of arsenopyrite surface, but has little effect on the chalcopyrite. XPS analyses and ICP-OES tests further verified that the depressants first eliminated the activation of copper ions and then selectively adsorbed on the surface of arsenopyrite. ToF-SIMS analyses showed that the PASP-CaO would achieve selective depression of arsenopyrite in the form of PASP, PASP-Ca complexes and Ca(OH)+, respectively. Finally, the mechanism diagram of PASP-CaO selectively depressing arsenopyrite was derived. These results will provide an excellent theoretical reference for the flotation separation of copper arsenic sulfide ore.

Utilizing phosphonyl carboxylic acid copolymer as an efficient depressant for flotation separation of chalcopyrite from galena: Experimental and DFT study

The research proposes an innovative galena depressant, known as Phosphonyl carboxylic acid copolymer (POCA), to enhance the efficiency of flotation separation between chalcopyrite and galena. Mineral flotation tests were conducted to investigate the flotation performance of chalcopyrite and galena. The inhibition mechanism of POCA on galena was studied using multiple characterization techniques including Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES) testing, Zeta potential testing, X-ray photoelectron spectroscopy (XPS) analysis, atomic force microscopy (AFM) testing, contact angle testing, time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis, and density functional theory (DFT) calculations. In the flotation test, at a concentration of 10 mg/L sodium butyl xanthate (SBX) and pH 9, adding 50 mg/L POCA can reduce the flotation recovery of galena from 83.50 % to below 5 %, whereas the recovery of chalcopyrite was almost influenced. The testing conducted via ICP-OES revealed that POCA promotes the dissolution of Pb2+ from the galena surface. The adsorption of POCA on the galena surface was confirmed through zeta potential testing, XPS testing, contact angle, AFM testing, and ToF-SIMS analysis, it was noted that POCA exhibited high levels of adsorption on the galena surface. Density Functional Theory (DFT) calculations suggest that the chemical interaction between the sulfonic acid present in POCA and the Pb2+ active site of galena is regarded as the primary inhibition mechanism.

Characteristics of the Discoloration Switching Phenomenon of 4H-SiC Single Crystals Grown by PVT Method Using ToF-SIMS and Micro-Raman Analysis.

The discoloration switching appearing in the initial and final growth stages of 4H-silicon carbide (4H-SiC) single crystals grown using the physical vapor transport (PVT) technique was investigated. This phenomenon was studied, investigating the correlation with linear-type micro-pipe defects on the surface of 4H-SiC single crystals. Based on the experimental results obtained using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and micro-Raman analysis, it was deduced that the orientation of the 4H-SiC c-axis causes an axial change that correlates with low levels of carbon. In addition, it was confirmed that the incorporation of additional elements and the concentrations of these doped impurity elements were the main causes of discoloration and changes in growth orientation. Overall, this work provides guidelines for evaluating the discoloration switching in 4H-SiC single crystals and contributes to a greater understanding of this phenomenon.

High-Throughput Quantitative Analysis of Amino Acids in Freeze-Dried Drops Using Time-of-Flight Secondary Ion Mass Spectrometry.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has become a promising analytical tool for molecular profiling in biological applications. However, its ultrahigh vacuum environment and matrix effects hamper the absolute quantitation of solution samples. Herein, we present a rapid high-throughput platform for quantitative ToF-SIMS analysis of amino acids in matrix deposits formed from freeze-dried solution drops through ice sublimation on a parylene film microarray substrate. Droplets of the amino acid solutions, which were mixed with stable isotope-labeled phenylalanine (F*) of high concentration (10 mM), were loaded on wells of the microarray, then frozen and evaporated slowly below the freezing point, forming continuous solid-phase F* matrix deposits. The amino acids (≤500 μM), adequately well dispersed throughout the F* matrix deposits on each well, were quantitatively analyzed by ToF-SIMS in a rapid and high-throughput fashion. The lower limit of quantitation reached below 10 μM.

Effect of polyaspartic acid as an environmental-friendly depressant on flotation separation of chalcopyrite from arsenopyrite

The selection of environmental-friendly and high-efficiency depressants is a major research priority for removing arsenic from copper concentrates. The polyaspartic acid (PASP, (C4H6O3N) n) was used for the selective separation of chalcopyrite from arsenopyrite to explore the depression mechanism of PASP using micro-flotation experiments, contact angle measurements, zeta potential measurements, fourier transform infrared spectroscopy (FT-IR), local electrochemical impedance (LEIS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The flotation results showed that recovery of chalcopyrite reached up 90.18 %, while the recovery of arsenopyrite was only 23.48 %, when the PASP was added. The contact angle measurements and zeta potential measurements showed that PASP selectively adsorbed on the surface of arsenopyrite, but was not adsorbed on the surface of chalcopyrite. The FT-IR tests further confirmed that the adsorption was chemical adsorption. The LEIS tests revealed that the conductivity of arsenopyrite surface increased with the addition of PASP, while chalcopyrite was almost unaffected. The ToF-SIMS analyses illustrated that the arsenopyrite with Fe and As sites was reacted with —NH– in the structure of PASP to form stable complexes. Finally, the mechanism diagram was designed to provide insight into the adsorption mechanism of PASP on the surface of arsenopyrite and its selective inhibition of arsenopyrite.

A study on the mechanism of flotation separation between chalcopyrite and sphalerite using a novel environmental depressant derived from grape peel extract GPE

In this study, we explored the application of GPE, a novel environmental depressant derived from grape peel extract, for the flotation separation of sphalerite and chalcopyrite. We employed a range of techniques to investigate the depressant’s efficacy and mechanism, including micro-flotation tests, contact angle measurements, zeta potential measurements, adsorption measurements, X-ray photoelectron spectroscopic (XPS) analysis, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Our findings revealed that the use of 9.375 mg/L GPE effectively separated chalcopyrite from sphalerite. Zeta potential and adsorption studies demonstrated that GPE adsorbed onto both mineral surfaces, albeit with a lower affinity for chalcopyrite. XPS analysis suggested that GPE’s adsorption on the sphalerite surface was likely due to physical adsorption. Furthermore, ToF-SIMS analysis revealed that the structural components of GPE, C6H4O2- and C6H5O2-, can interact with the sphalerite surface, hindering the adsorption of the collector BX.

Adsorption of uranium (VI) complexes with polymer-based spherical activated carbon

Adsorption processes with carbon-based adsorbents have received substantial attention as a solution to remove uranium from drinking water. This study investigated uranium adsorption by a polymer-based spherical activated carbon (PBSAC) characterised by a uniformly smooth exterior and an extended surface of internal cavities accessible via mesopores. The static adsorption of uranium was investigated applying varying PBSAC properties and relevant solution chemistry. Spatial time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to visualise the distribution of the different uranium species in the PBSAC. The isotherms and thermodynamics calculations revealed monolayer adsorption capacities of 28–667 mg/g and physical adsorption energies of 13–21 kJ/mol. Increasing the surface oxygen content of the PBSAC to 10 % enhanced the adsorption and reduced the equilibrium time to 2 h, while the WHO drinking water guideline of 30 µgU/L could be achieved for an initial concentration of 250 µgU/L. Uranium adsorption with PBSAC was favourable at the pH 6–8. At this pH range, uranyl carbonate complexes (UO2CO3(aq), UO2(CO3)22–, (UO2)2CO3(OH)3–) predominated in the solution, and the ToF-SIMS analysis revealed that the adsorption of these complexes occurred on the surface and inside the PBSAC due to intra-particle diffusion. For the uranyl cations (UO22+, UO2OH+) at pH 2–4, only shallow adsorption in the outermost PBSAC layers was observed. The work demonstrated the effective removal of uranium from contaminated natural water (67 µgU/L) and meeting both German (10 µgU/L) and WHO guideline concentrations. These findings also open opportunities to consider PBSAC in hybrid treatment technologies for uranium removal, for instance, from high-level radioactive waste.

Bruch's Membrane Calcification in Pseudoxanthoma Elasticum: Comparing Histopathology and Clinical Imaging

To investigate the histology of Bruch's membrane (BM) calcification in pseudoxanthoma elasticum (PXE) and correlate this to clinical retinal imaging. Experimental study with clinicopathological correlation. Six postmortem eyes from 4 PXE patients and 1 comparison eye from an anonymous donor without PXE. One of the eyes had a multimodal clinical image set for comparison. Calcification was labeled with OsteSense 680RD, a fluorescent dye specific for hydroxyapatite, and visualized with confocal microscopy. Scanning electron microscopy coupled with energy-dispersive x-ray spectroscopy (SEM-EDX) and time-of-flight secondary ion mass spectrometry (TOF-SIMs) were used to analyze the elemental and ionic composition of different anatomical locations. Findings on cadaver tissues were compared with clinical imaging of 1 PXE patient. The characteristics and topographical distribution of hydroxyapatite in BM in eyes with PXE were compared with the clinical manifestations of the disease. Analyses of whole-mount and sectioned PXE eyes revealed an extensive, confluent OsteoSense labeling in the central and midperipheral BM, transitioning to a speckled labeling in the midperiphery. These areas corresponded to hyperreflective and isoreflective zones on clinical imaging. Scanning electron microscopy coupled with energy-dispersive x-ray spectroscopy and TOF-SIMs analyses identified these calcifications as hydroxyapatite in BM of PXE eyes. The confluent fluorescent appearance originates from heavily calcified fibrous structures of both the collagen and the elastic layers of BM. Calcification was also detected in an aged comparison eye, but this was markedly different from PXE eyes and presented as small snowflake-like deposits in the posterior pole. Pseudoxanthoma elasticum eyes show extensive hydroxyapatite deposition in the inner and outer collagenous and elastic BM layers in the macula with a gradual change toward the midperiphery, which seems to correlate with the clinical phenotype. The snowflake-like calcification in BM of an aged comparison eye differed markedly from the extensive calcification in PXE. Proprietary or commercial disclosure may be found in the Footnotes and Disclosures at the end of this article.

Lithium Self-Diffusion in a Polymer Electrolyte for Solid-State Batteries: ToF-SIMS/ssNMR Correlative Characterization and Modeling Based on Lithium Isotopic Labeling.

Manufacturers aim to commercialize efficient and safe batteries by finding new strategies. Solid-state electrolytes can be seen as an opportunity to develop batteries with a high energy density. They allow the use of lithium foil as the anode, increasing the energy density. Also, they are composed of nonflammable materials making them safer than liquid electrolytes. However, to enhance the electrochemical performances of forthcoming solid-state lithium metal batteries, phenomena governing ionic conductivity have yet to be mastered in such devices. Lithium isotopic tracing was successfully used in previous works to further understand lithium ion transport mechanisms in batteries. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 6/7Li high-resolution solid-state nuclear magnetic resonance (ssNMR) spectroscopy are two complementary techniques probing local and global scale, respectively. Both techniques can distinguish lithium isotopes. Here, four polymer membranes were elaborated with the same lithium concentration, but with various isotopic enrichments from 7.6 to 95.4% of 6Li. The selected material was a poly(ethylene oxide) (PEO) membrane containing lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) as lithium salt. They are widely studied in the lithium battery field. First, reliable ToF-SIMS and ssNMR methodologies were validated in light of the converging results. They led to accurate determination of lithium isotopic abundance of polymer membranes with a 1 or a 2% uncertainty, respectively. Then, the developed methodologies were applied to characterize lithium self-diffusion in a polymer membrane. Furthermore, numerical simulations based on a two-dimensional diffusion model compared with ToF-SIMS analyses allowed us to extract a lithium self-diffusion coefficient of 1.6 × 10-12 m2·s-1 at 60 °C, which complements other published values. The robust methodologies described in this work can be extended to various applications and materials. They stand as powerful strategies to better understand lithium ionic transport, especially in multiphase materials, for example, in hybrid solid-state electrolytes.

Characterization of Sr2Fe1,5Mo0,5O6-δ Based Solid Oxide Electrolysis Cells

Hydrogen electrodes of solid oxide electrolysis cells (SOEC) are typically made of Ni-YSZ cermet. Despite having excellent catalytic activity Ni-based electrodes suffer from poor redox stability and Ni volatility [1]. Sr2Fe1,5Mo0,5O6-δ (SFM) mixed ionic- and electric conducting (MIEC) double perovskite has been proposed as promising hydrogen electrode material for solid oxide electrolysis cells (SOEC) because of its excellent catalytic properties and good conductivity. In this study SOEC single cells were prepared using SFM hydrogen electrode and (La0,6Sr0,4)0,99Co0,96Ti0,04O3-δ (LSCT) as well as (La0.6Sr0.4)0.95Co0.2Fe0.8O3-δ (LSCF) air electrodes [2, 3].Studied cells were prepared using 19 mm 10Sc1CeSZ electrolyte substrates. Screen printed 6 μm thick Ce0.9Gd0.1O1.95 (GDC) layer was applied to both sides of the cell to prevent formation of insulating SrZrO3 layer. GDC layer was sintered to the electrolyte at 1300°C for 5h. SFM or 50%SFM/50%GDC electrode layer with 0,52cm2 surface area was screen printed to the GDC layer and was sintered at 1200°C and at 1150°C to optimize electrode composition and thermal treatment program of electrode. Afterwards LSCT or LSCF oxygen electrodes were screen printed to the other side of the cell and sintered at 1100°C for 2 h. Finally, cells were characterized using electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and time-of flight secondary ion mass spectrometry (TOF-SIMS).Impedance spectroscopy analysis showed that cells with 50%SFM/50%GDC hydrogen electrode sintered at 1150°C and LSCT oxygen electrode had highest current densities, reaching 1,59 A/cm2 at 1,5V and 850°C with 67,5% water in hydrogen electrode compartment. However, stability of the cells needs to be further investigated. With TOF-SIMS analysis it became apparent that Sr is moving through GDC intermediate layer and poorly conducting phases are formed in the GDC/10Sc1CeSZ boundary.[1] C. Singhal, K. Kendall (Eds.), High-Temperature Solid Oxide Fuel Cells: Fundamentals, Design and Applications, Elsevier, Oxford, 2003.[2]Bernadet, C. Moncasi, M. Torell, A. Tarancon, High-performing electrolyte-supported symmetrical solid oxide electrolysis cells operating under steamelectrolysis and co-electrolysis modes, Int. J. Hydrogen Energy 45 (2020)14208–14217[3]Sanna, W. Zhang, P. Costamagna, P. HoltappelsSynthesis and electrochemical characterization of electrospun nanofiber cathodes for intermediate- temperature solid oxide fuel cells Int. J. Hydrog. Energy (2020), pp. 1-14

Degradation and chemical stability of graphitic carbon nitride during ultraviolet light irradiation

Graphitic carbon nitride (g-C3N4) was synthesized by pyrolysis of urea at 450 °C for 2 h. X-ray diffraction and transmission electron microscopy confirmed the formation of the stacked hexagonal layers and platelet-like structure of g-C3N4. The sample was irradiated by ultraviolet (UV, 370 nm) light for about 62 h and X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), Nitrogen adsorption–desorption isotherm, and photoluminescence spectroscopy (PL) were used to investigate the degradation. XPS spectra of C 1s electrons revealed four components associated with adventitious carbon, the –C≡N group, heptazine/triazine and carboxyl/carbonate species. Quantitative XPS analysis indicated an increase in the peak areas associated with the –C≡N group and carboxyl/carbonate species, accompanied by a decrease in the areas of the components associated with the heptazine/triazine and adventitious carbon. XPS spectra of N 1s were fitted using four components which were assigned to pyridinic nitrogen (C–N=C), nitrile group (N≡C), amine groups (NHx) and tertiary nitrogen (N-(C)3). The relative areas of peaks associated with the amine and nitrile groups have slightly increased after UV irradiation whereas the peak associated with pyridinic nitrogen decreased. FTIR spectra suggested a reduction in the C–N and C=N heterocycle bonds and slight variation in the C≡N bonds after UV irradiation. BET analysis revealed that the surface area and pore volume have decreased after irradiation. ToF-SIMS analysis indicate the formation of NOx, CNO, NHx, and C4H3NO2 species after irradiation. PL spectra of the g-C3N4 showed a broad blue-green emission which was fitted using three bands and ascribed to the δ*-LP, π-LP, and π-π* transitions within the bandgap. During UV irradiation, the g-C3N4 powder lost about 22% of its blue-green emission intensity after nearly 45 h and then remained stable for further irradiation time. This study confirmed the degradation of g-C3N4 under UV irradiation, which should be further studied for better integration of this material in photoexcited applications.

Imaging of Ancient Microbial Biomarkers within Miocene Dolomite (Kuwait) Using Time-of-Flight Secondary Ion Mass Spectrometry

Time-of-Flight–Secondary Ion Mass Spectrometry (ToF-SIMS) using a bismuth liquid metal ion source was utilized to characterize and image microbial biomarkers within dolomite from early-middle Miocene coastal mud volcano outcrops in Kuwait. ToF-SIMS analysis revealed biomarkers of ancient microbial consortia of sulfate reducers and methane oxidizers participating in the anaerobic oxidation of methane. The identified lipid biomarkers comprised 17α(H),21β(H)-Norhopane, Hop-17(21)-ene or Hop-22(29)-ene (diploptene), non-isoprenoidal dialkyl glycerol diethers (DAGEs), and Diacylglycerol esters (DGs). The ion µ-scale images of carbonate rocks showed two characteristic styles: (1) high signal intensity of dolomite, halite, and biomarkers, where the biomarkers demonstrate a distinctive co-localization pattern with both dolomite and halite; and (2) a lack of dolomite, halite low signal intensity, and an absence of biomarker co-localization patterns. Our results highlight three remarkable observations. Firstly, the concomitance of dolomite and halite suggests a common source of magnesium and sodium supply, likely from the hypersaline Al-Subiya sabkha. This emphasizes the importance of hypersaline seawater for dolomite formation. Secondly, microbial biomarkers correspond to methane- and sulfate-rich conditions under which dolomite was formed. Lastly, the high intensity of biomarker signals and their association with dolomite and halite indicate that the consortia involved in dolomite formation have preferences for high-salinity conditions. The three observations align with previous studies that have highlighted the importance of methane-sulfate redox, high salinity, and halophilic microbes for dolomite formation. This work is the first to acknowledge ancient microbial biomarkers within Miocene dolomite in Kuwait, which aims to broaden the understanding of the biogeochemical processes triggering dolomite formation in similar environments and ancient geologic settings.

Compositional mapping of Mo-doped ZnO thin films: Mechanical, nano-surface and ToF-SIMS analyses

ZnO and Mo-doped ZnO thin films were grown using the spray pyrolysis process with variations in Mo doping concentrations. The films were characterized with a comprehensive compositional analysis, including electron dispersive X-ray (EDX), X-rays photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS), along with grazing incidence X-ray diffraction(GIXRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and UV–Vis spectroscopy to investigate their structural, morphological, optical and chemical compositions. Micro-hardness analysis was performed on films as a function of the Mo content. GIXRD analysis detected the presence of characteristic peaks of ZnO along the (100), (002) and (101) planes. The presence of Zn, O, and Mo in the synthesized samples was revealed by EDX, XPS, and ToF-SIMS results, which matched the experimental values of a pure and Mo:ZnO-x composition. XPS analysis revealed the Mo6+ oxidation state of molybdenum present in Mo:ZnO films. From UV–Vis absorption spectroscopy, the bang gap was observed to increase with Mo content, up 5 at.%, and located in the 3.18 – 3.24 eV interval. These results will be helpful in the synthesis of Mo:ZnO films for relevant applications, including sensing, optoelectronics and antimicrobial.

Discriminant Principal Component Analysis of ToF-SIMS Spectra for Deciphering Compositional Differences of MSC-Secreted Extracellular Matrices.

Identifying characteristic extracellular matrix (ECM) variants is a key challenge in mechanistic biology, bioengineering, and medical diagnostics. The reported study demonstrates the potential of time-of-flight secondary ion mass spectrometry (ToF-SIMS) to detect subtle differences between human mesenchymal stromal cell (MSC)-secreted ECM types as induced by exogenous stimulation or emerging pathology. ToF-SIMS spectra of decellularized ECM samples are evaluated by discriminant principal component analysis (DPCA), an advanced multivariate analysis technique, to decipher characteristic compositional features. To establish the approach, signatures of major ECM proteins are determined from samples of pre-defined mixtures. Based on that, sets of ECM variants produced by MSCs in vitro are analyzed. Differences in the content of collagen, fibronectin, and laminin in the ECM resulting from the combined supplementation of MSC cultures with polymers that induce macromolecular crowding and with ascorbic acid are detected from the DPCA of ToF-SIMS spectra. The results are verified by immunostaining. Finally, the comparative ToF-SIMS analysis of ECM produced by MSCs of healthy donors and patients suffering from myelodysplastic syndrome display the potential of the novel methodology to reveal disease-associated alterations of the ECM composition.