Search Results (21)

The development of selective and sustainable catalysts is essential to enable the chemical recycling of mixed plastic waste. In this work, calcium-modified biochars derived from cocoa pod husk (CPH) and palm kernel shell (PKS) were prepared for treating a mixture of poly(ethylene terephthalate) (PET) and poly(lactic acid) (PLA). The aim was to separate the mixture through the PLA methanolysis, while maintaining the PET unreacted for a potential physical recycling. Biochar was ex situ modified with calcium precursor using a value-added concentrate recovered from the hydrothermal treatment of Jatropha fruit husk. Subsequently, a pyrolysis step was further applied to convert the calcium species into CaO, which is the active phase for the methanolysis reaction. Structural, microscopic, and spectroscopic analyses revealed that the carbon matrix strongly influences the evolution and stabilization of calcium phases during pyrolysis and post-treatment. CPH-derived biochars promoted the formation of highly dispersed CaO, whereas PKS favored the growth of larger, less reactive Ca(OH)₂ domains. As a result, the CPH_Ca10 (i.e., 10% desired calcium loading based on CPH-biochar mass) catalyst exhibited superior basicity and catalytic activity, achieving near-complete PLA conversion under mild conditions (90–110 °C) depending on the system with only 2 wt.% catalyst. Importantly, under these mild conditions, PET remained chemically intact, demonstrating the process’s high selectivity and applicability to mixed bioplastic–fossil plastic streams. This study highlights a circular, low-carbon route to producing effective Ca-based catalysts from agricultural residues. It establishes a promising strategy for selective depolymerization and separation in complex plastic waste systems. Full article

Aqueous proton batteries (APBs) are promising for safe energy storage, yet their cathode development is hindered by the lack of organic materials with reversible redox activity and long cycling stability in acidic media. Herein, an acceptor-enriched PNZ–TCNQ organic charge-transfer complex was constructed by increasing the TCNQ ratio. Spectroscopic results are consistent with strengthened donor–acceptor interactions and altered local electronic environments. The PNZ–TCNQ cathode delivered ~190 mAh g⁻¹ at 0.6 A g⁻¹ and retained ~85% capacity after 10,000 cycles at 5 A g⁻¹ in acidic three-electrode tests. Kinetic analyses revealed mixed charge storage contributions from pseudocapacitive and diffusion-influenced processes. In situ/ex situ characterizations confirmed reversible redox evolution of the donor–acceptor complex with preserved molecular backbones. This work shows that tuning intermolecular charge-transfer interactions is an effective strategy for improving the cycling stability of organic cathodes in acidic aqueous electrolytes. Full article

This study examines the interfacial and structural evolution of titanium disulfide (TiS₂) during Ca²⁺ intercalation/deintercalation in concentrated aqueous CaCl₂. Electrochemical measurements were combined with ex situ X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy to characterize the solvation structure, potential window, and reversibility in concentrated CaCl₂ electrolytes. Increasing the CaCl₂ concentration from 1.0 to 8.0 M was accompanied by reduced gas evolution and an expanded practical operating window. Stepwise analysis identified the potential range −1.00 to 0.10 V (vs. the saturated calomel electrode) as a practical window that minimized TiO₂/S₈ formation while preserving reversible Ca²⁺ intercalation. Ex situ XRD showed reversible (001) shifts, consistent with interlayer expansion and contraction, and peak broadening was indicative of partial amorphization and defects. XPS revealed CaS and polysulfides (S_z²⁻, 2 ≤ z ≤ 8) to be the prevalent surface species with limited Ca(OH)₂ and CaSO₄; within the detection limits, no chlorine-containing reduction products were observed after charging. The electrochemical and spectroscopic results indicate that intercalation is accompanied by partial sulfur-centered reduction and defect signatures, with associated changes in the interfacial charge-transfer characteristics and reversibility. These findings link the potential, interfacial chemistry, and lattice response, and suggest design considerations for stable aqueous multivalent-ion storage. Full article

Ex situ machine perfusion has emerged as a pivotal technique for organ preservation and pre-transplant viability assessment, where the real-time monitoring of mitochondrial biomarkers—flavin mononucleotide (FMN) and nicotinamide adenine dinucleotide (NADH)—could significantly mitigate ischemia-reperfusion injury risks. This study develops a non-invasive optical method combining fluorescence and UV-visible spectrophotometry to quantify FMN and NADH in hypothermic oxygenated perfusion media. Calibration curves revealed linear responses for both biomarkers in absorption and fluorescence (FMN: λ_ex = 445 nm, λ_em = 530–540 nm; NADH: λ_ex = 340 nm, λ_em = 465 nm) at concentrations < 100 μg mL⁻¹. However, NADH exhibited nonlinear fluorescence above 100 μg mL⁻¹, requiring shifted excitation to 365 nm for reliable detection. Spectroscopic analysis further demonstrated how perfusion solution composition alters FMN/NADH fluorescence properties, with consistent reproducibility across media. The method’s robustness was validated through comparative studies in clinically relevant solutions, proposing a strategy for precise biomarker quantification without invasive sampling. These findings establish a foundation for real-time, optical biosensor development to enhance organ perfusion monitoring. By bridging spectroscopic principles with clinical needs, this work advances translational sensor technologies for transplant medicine, offering a template for future device integration. Full article

Tungsten oxide (WO₃) electrochromic devices are obtaining increasing interest due to their color change and thermal regulation. However, most previous work focuses on the absorption or transmission spectra of materials, rather than the optical parameters evolution in full spectrum in the electrochromic processes. Herein, we developed a systematic protocol of ex situ methods to clarify the evolutions of subtle structure changes, Raman vibration modes, and optical parameters of WO₃ thin films in electrochromic processes as stimulated by dosage-dependent Li⁺ insertion. We obtained the below information by ex situ spectroscopic ellipsometry. (1) Layer-by-layer Li⁺ embedding mechanism demonstrated by individual film thickness analysis. (2) The details of its optical leap in the Brillouin zone in the full spectral. (3) The optical constants varied with the Li⁺ insertion in the ultraviolet, visible, and near-infrared bands, demonstrating the potential for applications in chip fabrication, deep-sea exploration, and optical measurements. (4) Simulated angular modulation laws of WO₃ films for full spectra in different Li⁺ insertion states. This ex situ method to study the optical properties of electrochromic devices are important for monitoring phase transition kinetics, the analysis of optical leaps, and the study of ion diffusion mechanisms and the stoichiometry-dependent changes in optical constants over the full spectral. This work shows that electrochromic films in Li⁺ surface permeation can be applied in the field of zoom lenses, optical phase modulators, and other precision optical components. Our work provides a new solution for the development of zoom lenses and a new application scenario for the application of electrochromic devices. Full article

Hybrid strategies that combine conventional top-down lithography with bottom-up molecular assembly are of interest for a range of applications including nanolithography and sensors. Interest in these strategies stems from the ability to create complex architectures over large areas with molecular-scale control and precision. The molecular-ruler process typifies this approach where the sequential layer-by-layer assembly of mercaptoalkanoic acid molecules and metal ions are combined with conventional top-down lithography to create precise, registered nanogaps. However, the quality of the metal-ligated mercaptoalkanoic acid multilayer is a critical characteristic in generating reproducible and robust nanoscale structures via the molecular-ruler process. Therefore, we explore the assembly of alkanethiolate monolayers, mercaptohexadecanoic acid (MHDA) monolayers, and Cu-ligated MHDA multilayers on Au{111} substrates using atomic force microscopy and in situ dynamic spectroscopic ellipsometry. The chemical film thicknesses in situ dynamic spectroscopic ellipsometry agree with previous ex situ surface analytical methods. Moreover, in situ dynamic spectroscopic ellipsometry provides insight into the assembly process without interrupting the assembly process and potentially altering the characteristics of the resulting chemical film. By following the real-time dynamics of each deposition step, the assembly of the Cu-ligated MHDA multilayers can be optimized to minimize deposition time while having minimal impact to the quality of the chemical film. Full article

Carbon-based materials are one of the ideal negative electrode materials for potassium ion batteries. However, the limited active sites and sluggish diffusion ion kinetics still hinder its commercialization process. To address these problems, we design a novel carbon composite anode, by confining highly reactive short-chain sulfur molecules into nitrogen-doped hollow carbon nanospheres (termed SHC-450). The formation process involves the controlled synthesis of hollow polyaniline (PANI) nanospheres as precursors via an Ostwald ripening mechanism and subsequent sulfuration treatment. The high content of constrained short-chain sulfur molecules (20.94 wt%) and considerable N (7.15 wt%) ensure sufficient active sites for K⁺ storage in SHC-450. Accordingly, the SHC-450 electrode exhibits a high reversible capacity of 472.05 mAh g⁻¹ at 0.1 A g⁻¹ and good rate capability (172 mAh g⁻¹ at 2 A g⁻¹). Thermogravimetric analysis shows that SHC-450 has impressive thermal stability to withstand a high temperature of up to 640 °C. Ex situ spectroscopic characterizations reveal that the short-chain sulfur provides high capacity through reversible formation of K₂S. Moreover, its special hollow structure not only provides ample space for highly active short-chain sulfur reactants but also effectively mitigates volume expansion during the sulfur conversion process. This work offers new perspectives on enhanced K⁺ storage performance from an interesting anode design and the space-limited domain principle. Full article

Delayed atomic layer deposition (ALD) of ZnO, i.e., area selective (AS)-ALD, was successfully achieved on silicon wafers (Si\SiO₂) terminated with tris(dimethylamino)methylsilane (TDMAMS). This resist molecule was deposited in a home-built, near-atmospheric pressure, flow-through, gas-phase reactor. TDMAMS had previously been shown to react with Si\SiO₂ in a single cycle/reaction and to drastically reduce the number of silanols that remain at the surface. ZnO was deposited in a commercial ALD system using dimethylzinc (DMZ) as the zinc precursor and H₂O as the coreactant. Deposition of TDMAMS was confirmed by spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), and wetting. ALD of ZnO, including its selectivity on TDMAMS-terminated Si\SiO₂ (Si\SiO₂\TDMAMS), was confirmed by in situ multi-wavelength ellipsometry, ex situ SE, XPS, and/or high-sensitivity/low-energy ion scattering (HS-LEIS). The thermal stability of the TDMAMS resist layer, which is an important parameter for AS-ALD, was investigated by heating Si\SiO₂\TDMAMS in air and nitrogen at 330 °C. ALD of ZnO takes place more readily on Si\SiO₂\TDMAMS heated in the air than in N₂, suggesting greater damage to the surface heated in the air. To better understand the in situ ALD of ZnO on Si\SiO₂\TDMAMS and modified (thermally stressed) forms of it, the ellipsometry results were plotted as the normalized growth per cycle. Even one short pulse of TDMAMS effectively passivates Si\SiO₂. TDMAMS can be a useful, small-molecule inhibitor of ALD of ZnO on Si\SiO₂ surfaces. Full article

In the present study, we aimed to synthesize (Ag)_1−x(GNPs)_x nanocomposites in variable ratios (25% GNPs–Ag, 50% GNPs–Ag, and 75% GNPs–Ag) via an ex situ approach to investigate the incremental effects of GNPs (graphene nanoparticles) on AgNPs (silver nanoparticles). The prepared nanocomposites were successfully characterized using different microscopic and spectroscopic techniques, including X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, ultraviolet spectroscopy, and Raman spectroscopic analysis. For the evaluation of morphological aspects, shape, and percentage elemental composition, SEM and EDX analyses were employed. The bioactivities of the synthesized nanocomposites were briefly investigated. The antifungal activity of (Ag)_1−x(GNPs)_x nanocomposites was reported to be 25% for AgNPs and 66.25% using 50% GNPs–Ag against Alternaria alternata. The synthesized nanocomposites were further evaluated for cytotoxic potential against U87 cancer cell lines with improved results (for pure AgNPs IC₅₀: ~150 µg/mL, for 50% GNPs–Ag IC₅₀: ~12.5 µg/mL). The photocatalytic properties of the nanocomposites were determined against the toxic dye Congo red, and the percentage degradation was recorded as 38.35% for AgNPs and 98.7% for 50% GNPs–Ag. Hence, from the results, it is concluded that silver nanoparticles with carbon derivatives (graphene) have strong anticancer and antifungal properties. Dye degradation strongly confirmed the photocatalytic potential of Ag-graphene nanocomposites in the removal of toxicity present in organic water pollutants. Full article

Microbial pathogens and bulk amounts of industrial toxic wastes in water are an alarming situation to humans and a continuous threat to aquatic life. In this study, multifunctional silver and graphene nanocomposites (Ag)_1−x(GNPs)_x [25% (x = 0.25), 50% (x = 0.50) and 75% (x = 0.75) of GNPs] were synthesized via ex situ approach. Further, the synthesized nanocomposites were explored for their physicochemical characteristics, such as vibrational modes (Raman spectroscopic analysis), optical properties (UV visible spectroscopic analysis), antibacterial and photocatalytic applications. We investigated the antimicrobial activity of silver and graphene nanocomposites (Ag-GNPs), and the results showed that Ag-GNPs nanocomposites exhibit remarkably improved antimicrobial activity (28.78% (E. coli), 31.34% (S. aureus) and 30.31% (P. aeruginosa) growth inhibition, which might be due to increase in surface area of silver nanoparticles (AgNPs)). Furthermore, we investigated the photocatalytic activity of silver (AgNPs) and graphene (GNPs) nanocomposites in varying ratios. Interestingly, the Ag-GNPs nanocomposites show improved photocatalytic activity (78.55% degradation) as compared to AgNPs (54.35%), which can be an effective candidate for removing the toxicity of dyes. Hence, it is emphatically concluded that Ag-GNPs hold very active behavior towards the decolorization of dyes and could be a potential candidate for the treatment of wastewater and possible pathogenic control over microbes. In the future, we also recommend different other in vitro biological and environmental applications of silver and graphene nanocomposites. Full article

In this work, the melt crystallization behavior and the solid phase transition of isotactic polybutene (PB) were studied in the polybutene/high-density polyethylene (PB/PE) blends covering the whole composition range. For the dynamic cooling crystallization, PE exhibits almost the same crystallization temperature in all blends, whereas PB exhibits a distinct non-monotonic dependence on the composition ratio. Combining the ex situ X-ray diffraction and in situ Fourier transform infrared spectroscope, it was demonstrated that during cooling at 10 °C/min, the presence of at least 70 wt% PE can induce the formation of form I′ directly from the amorphous melt. The detailed relations of polymorphism with temperature were systematically investigated for the PB/PE blends. Different from the formation of the sole tetragonal phase with ≤50 wt% PE, the trigonal form I′ could crystallize directly from amorphous melt with ≥60 wt% PE, which can be further enhanced by elevating the temperature of isothermal crystallization. Interestingly, the critical lowest temperature of obtaining pure form I′ was 85 °C with 70 wt% PE and decreased to 80 °C as the PE fraction was increased to 80 wt%. On the other hand, the spontaneous phase transition from the kinetically favored form II into the thermodynamically stable form I was also explored with X-ray diffraction methods. It was found that at the room temperature, phase transition kinetics can be significantly accelerated by blending at least 70 wt% PE. Full article

TiO₂ thin films deposited by atomic layer deposition (ALD) at low temperatures (<100 °C) are, in general, amorphous and exhibit a smaller refractive index in comparison to their crystalline counterparts. Nonetheless, low-temperature ALD is needed when the substrates or templates are based on polymeric materials, as the deposition has to be performed below their glass transition or melting temperatures. This is the case for photonic crystals generated via ALD infiltration of self-assembled polystyrene templates. When heated up, crystal phase transformations take place in the thin films or photonic structures, and the accompanying volume reduction as well as the burn-out of residual impurities can lead to mechanical instability. The introduction of cation doping (e.g., Al or Nb) in bulk TiO₂ parts is known to alter phase transitions and to stabilize crystalline phases. In this work, we have developed low-temperature ALD super-cycles to introduce Al₂O₃ into TiO₂ thin films and photonic crystals. The aluminum oxide content was adjusted by varying the TiO₂:Al₂O₃ internal loop ratio within the ALD super-cycle. Both thin films and inverse opal photonic crystal structures were subjected to thermal treatments ranging from 200 to 1200 °C and were characterized by in- and ex-situ X-ray diffraction, spectroscopic ellipsometry, and spectroscopic reflectance measurements. The results show that the introduction of alumina affects the crystallization and phase transition temperatures of titania as well as the optical properties of the inverse opal photonic crystals (iPhC). The thermal stability of the titania iPhCs was increased by the alumina introduction, maintaining their photonic bandgap even after heat treatment at 900 °C and outperforming the pure titania, with the best results being achieved with the super-cycles corresponding to an estimated alumina content of 26 wt.%. Full article

Continued downscaling of functional layers for key enabling devices has prompted the development of characterization tools to probe and dynamically control thin film formation stages and ensure the desired film morphology and functionalities in terms of, e.g., layer surface smoothness or electrical properties. In this work, we review the combined use of in situ and real-time optical (wafer curvature, spectroscopic ellipsometry) and electrical probes for gaining insights into the early growth stages of magnetron-sputter-deposited films. Data are reported for a large variety of metals characterized by different atomic mobilities and interface reactivities. For fcc noble-metal films (Ag, Cu, Pd) exhibiting a pronounced three-dimensional growth on weakly-interacting substrates (SiO₂, amorphous carbon (a-C)), wafer curvature, spectroscopic ellipsometry, and resistivity techniques are shown to be complementary in studying the morphological evolution of discontinuous layers, and determining the percolation threshold and the onset of continuous film formation. The influence of growth kinetics (in terms of intrinsic atomic mobility, substrate temperature, deposition rate, deposition flux temporal profile) and the effect of deposited energy (through changes in working pressure or bias voltage) on the various morphological transition thicknesses is critically examined. For bcc transition metals, like Fe and Mo deposited on a-Si, in situ and real-time growth monitoring data exhibit transient features at a critical layer thickness of ~2 nm, which is a fingerprint of an interface-mediated crystalline-to-amorphous phase transition, while such behavior is not observed for Ta films that crystallize into their metastable tetragonal β-Ta allotropic phase. The potential of optical and electrical diagnostic tools is also explored to reveal complex interfacial reactions and their effect on growth of Pd films on a-Si or a-Ge interlayers. For all case studies presented in the article, in situ data are complemented with and benchmarked against ex situ structural and morphological analyses. Full article

This report describes aspects of our previous studies of the mechanochemical synthesis of charge transfer complexes of the electron donor tetrathiafulvalene, which are relevant to the use of laboratory X-ray powder diffraction for ex situ monitoring of mechanochemical reactions toward investigating their mechanisms. In particular, the reaction of tetrathiafulvalene and chloranil was studied under neat mechanochemical conditions and liquid-assisted grinding with diethyl ether (1 μL/mg). The product in both cases is the green tetrathiafulvalene chloranil polymorph and the mechanism of the redox reaction is presumably the same. However, while the kinetic profile of the neat mechanochemical synthesis was fitted with a second-order rate law, that of the overall faster liquid-assisted grinding reaction was fitted with the Ginstling-Brounshtein 3D diffusion-controlled model. Hence, the diffusional processes and mass transfer bringing the reactants together and separating them from products must be different. Diffraction measurements sensitive to crystalline phases and amorphous material, combined with in situ monitoring by spectroscopic techniques, will ultimately afford a better understanding of mechanochemical reaction mechanisms, a hot topic in mechanochemistry. Full article

Direct plasma enhanced-atomic layer deposition (PE-ALD) is adopted for the growth of ZnO on c-Si with native oxide at room temperature. The initial stages of growth both in terms of thickness evolution and crystallization onset are followed ex-situ by a combination of spectroscopic ellipsometry and X-ray based techniques (diffraction, reflectivity, and fluorescence). Differently from the growth mode usually reported for thermal ALD ZnO (i.e., substrate-inhibited island growth), the effect of plasma surface activation resulted in a substrate-enhanced island growth. A transient region of accelerated island formation was found within the first 2 nm of deposition, resulting in the growth of amorphous ZnO as witnessed with grazing incidence X-ray diffraction. After the islands coalesced and a continuous layer formed, the first crystallites were found to grow, starting the layer-by-layer growth mode. High-temperature ALD ZnO layers were also investigated in terms of crystallization onset, showing that layers are amorphous up to a thickness of 3 nm, irrespective of the deposition temperature and growth orientation. Full article