Search Results (149)

The integration of catalytic methane decomposition (CMD) with CO₂ gasification (Reverse Boudouard Reaction) offers a promising chemical looping route for carbon-negative hydrogen and syngas production. This work systematically investigates the gasification reactivity of six carbon morphologies, CNTs, CNFs, activated carbon, graphite, graphene, and CMD-derived carbon, with and without Ni addition. First, activity tests and characterization (XRD, XPS, Raman) revealed that CMD-derived carbon outperformed all other benchmarks due to its highly amorphous nature (sp³/sp² = 0.98), which provides a high density of reactive sites. Second, kinetic analysis showed that the incorporation of 5 wt% Ni on CMD carbon reduced the activation energy (E_a) from 435.3 kJ mol⁻¹ to 114.6 kJ/mol, the lowest among all samples. This 74% reduction confirms that structural defects in CMD carbon act as anchoring sites for Ni, facilitating a strong metal–support interaction (MSI) that promotes CO₂ activation. Third, an investigation into structural synergy revealed that higher Ni loadings (>5 wt%) increased the activation energy (up to 171.2 kJ mol⁻¹). This trend is attributed to Ni agglomeration and weakened MSI, which reduces the active catalytic interface. These findings demonstrate that the efficiency of CO₂ valorization is highly sensitive to carbon morphology, providing a clear optimization strategy for integrated chemical looping methane-to-syngas energy cycles. Full article

This article describes a study on the synthesis and annealing processes of thin-film coatings of vanadium oxide on flat, parallel substrates made of quartz glass, sapphire, and silicon, as well as optical fibers using an organometallic precursor, triisopropoxy vanadium (V) oxide. For the first time, optical constants of nanomaterials were estimated in real time during synthesis and subsequent annealed using the lossy-mode resonance effect. The coatings produced in an inert atmosphere after deposition were amorphous, comprising a mixture of VO₂, V₂O₅, V₆O₁₃, and V₃O₅. This method allowed for accurate determination of the threshold temperature for the transformation of oxide mixtures into a monocomponent phase. Optimal conditions for synthesis and annealing were determined for the production of vanadium dioxide (VO₂) and pentoxide (V₂O₅). Morphological changes in coated surfaces were observed as a result of heat treatment. The composition and properties of these samples were studied using optical, terahertz and Raman spectroscopy, as well as temperature-dependent analysis of electrical resistance. The morphology of the coating surface was determined using a scanning electron microscope and an atomic force microscope. The reduction of VO_x to VO₂ was studied in an atmosphere of hydrogen and argon during annealing after deposition, with its effectiveness being compared. It was shown for the first time that the reduction of higher vanadium oxides is due to the presence of elemental carbon in the volume of the material formed from a metalorganic precursor during growth of vanadium oxide. Coatings obtained by annealing in hydrogen had a smaller hysteresis loop width (~5 °C) during phase transition compared to coatings obtained by argon annealing (~9 °C). Both types of coatings demonstrated a 50–60% increase in transmission at 1 THz frequency and in the IR region, accompanied by a 10³–10⁴-fold change in electrical resistance. Full article

As a novel organic semiconductor derived from biomass, hydrothermal carbonation carbon (HTCC) usually exhibits an amorphous structure due to its well-recognized formation pathway based on 5-hydroxymethylfurfural (HMF), which impedes charge transfer and consequently restricts the photocatalytic activity. Herein, we report a crystalline HTCC photocatalyst produced via an unusual synthesis route applied to cellulose in the presence of an oxidant. Notably, the crystalline structure of cellulose was retained and became highly aromatized during the process, leading to significantly enhanced charge transfer efficiency and an increased density of active sites. Moreover, unlike other reported HTCC photocatalysis, the highly active hydrogen radicals (H•) were identified as the dominant active species governing photocatalytic Cr(VI) reduction over crystalline HTCC. As a result, this crystalline HTCC exhibited dramatically enhanced photocatalytic removal efficiencies of Cr(VI) and microcystin-LR (MC-LR) due to the highly efficient charge transfer, abundant active sites as well as highly active hydrogen radicals. Full article

Diamond-like carbon (DLC) coatings are widely used as protective and self-lubricating surfaces in metal–metal contacts. Their frictional behavior is governed by the formation and evolution of carbon-rich transfer layers (TLs), which can be tailored through functionalization with carbon nanomaterials. Recent studies have shown that graphene sheets (GSs) and nanodiamonds (NDs) act synergistically to achieve ultra-low friction in microrough (~0.2 μm) metal–DLC contacts under dry N₂ at a 1 N load. Here, we probe how this lubrication mechanism evolves with increasing load from 1 to 10 N—corresponding to local contact pressures up to ~11–16 GPa—respectively, in dry N₂ and humid air conditions. Ball-on-disk experiments are performed on an industrial hydrogenated DLC coating sliding against stainless-steel. In dry N₂, GS–ND functionalization yields a low and stable coefficient of friction across the entire load range, reaching a minimum of about 0.05. In humid air, higher friction levels are observed across all loads (CoF ~0.10–0.15), accompanied by oxidation-driven modifications of both wear debris and the counterface contact region, with oxygen content increasing by more than a factor of three compared to dry N₂. Detailed microscopy and spectroscopy analyses indicate that enhanced lubricity in dry N₂ arises from TLs incorporating GSs, NDs, and nanoscroll-like structures, whereas humid air promotes interfacial amorphization and oxidation, leading to load-insensitive friction and boundary lubrication effects through physisorbed water molecules. Full article

Engineering carbon nanostructures directly on carbon fiber fabrics offers an effective route to constructing hierarchical multifunctional coating systems. In this study, methane-based chemical vapor deposition (CVD) was employed to investigate nanocarbon coating formation on woven carbon fabrics supported by electrodeposited Ni catalysts. Catalyst morphology was systematically engineered through surface pretreatment, electric-field configuration, and pulse electrodeposition. At 700 °C, methane activation was insufficient to sustain continuous nanocarbon growth, indicating a temperature-dependent activation threshold. Raising the growth temperature to 900 °C enabled sustained methane decomposition and produced dense nanocarbon coatings; hydrogen assistance suppressed amorphous deposition and promoted more ordered nanofilament features. Pulse electrodeposition refined Ni catalyst dispersion and nucleation density, improving coating uniformity compared with direct-current deposition. Structural ordering was further supported by Raman spectroscopy (D and G bands with an average ID/IG of 0.678 ± 0.068 for methane-grown samples versus 0.798 ± 0.011 for electrodeposition-only controls) and by HRTEM revealing multi-layer graphitic walls (~0.34 nm interlayer spacing). Together, the results support a methane-derived dissolution–diffusion–precipitation growth pathway governed by catalyst morphology, temperature, and gas composition. This controllable, textile-compatible catalyst engineering approach provides a scalable route to hierarchical graphitic coatings for carbon-fabric-based composites, electromagnetic interference shielding, and thermal management applications. Full article

This study investigates the material recycling potential of discarded wind instrument reeds (Arundo donax), which are conventionally incinerated, by compounding them with thermoplastics (thermoplastic polyolefin, TPO; polybutylene succinate, PBS). After recovered reeds were pulverized and injection-molded at 10 and 30 wt% concentrations, their mechanical and interfacial properties were evaluated. Experimentally obtained results indicate that waste reeds function as effective reinforcing agents, particularly when combined with biodegradable PBS. Incorporating 30 wt% reed flour into PBS enhanced flexural strength by approximately 1.7 times and flexural modulus by 2.8 times compared to the neat resin. This superior performance relative to TPO composites is attributed to robust interfacial hydrogen bonding among PBS carbonyl groups and the hydroxyl groups on the reed surface. Additionally, thermal and spectroscopic analyses revealed that these strong interactions elevate the crystallization temperature and generate a “Rigid Amorphous Phase” (RAF) that facilitates efficient stress transfer. These research findings demonstrate the feasibility of creating high-quality, bio-based composites, offering a sustainable method to reduce petroleum reliance and carbon dioxide emissions by upcycling musical waste. Full article

Boron nitride is considered a promising material for solid-state hydrogen storage due to its high thermal and chemical stability up to ~1000 °C, depending on the atmosphere, as well as its ability to form defect-rich structures with enhanced sorption activity. Despite the growing interest in modified BN systems, systematic studies on the effect of multicomponent modification induced by the addition of carbon, titanium, and aluminum on the structural and phase evolution of boron nitride during high-energy mechanical alloying remain limited to date. In this work, the structural-phase and morphological changes in boron nitride-based composites modified by the addition of carbon, titanium, and aluminum, synthesized by high-energy mechanical alloying, were investigated. The structural state and morphology of the materials were analyzed using X-ray diffraction, scanning electron microscopy, particle size analysis, and thermal analysis. It is shown that mechanical alloying leads to a progressive breakdown of the layered hexagonal BN structure and the formation of an amorphous-like, defect-rich state without the formation of new crystalline phases. The main stage of amorphization occurs within 30–60 min, after which structural disordering reaches saturation. Increasing the mechanical alloying time to 120 min does not result in significant changes in the phase state; however, it is accompanied by a reduction in agglomeration and the formation of a more homogeneous powder morphology, characterized by narrower particle size distributions, smoother particle surfaces, and more uniform spatial dispersion of components. It was established that the nature of the added component significantly influences the kinetics of structural transformations: carbon accelerates amorphization, titanium intensifies fragmentation and defect accumulation, whereas aluminum exhibits a stabilizing effect. In multicomponent BN–C–Ti–Al systems, a synergistic combination of these effects is observed, leading to the formation of metastable, partially amorphous structures. Based on a comprehensive analysis of structural and morphological data, the optimal mechanical alloying time was determined to be 120 min, providing a saturated amorphous-like structural state combined with improved microstructural homogeneity. The obtained defect-rich boron nitride structures can be considered a promising basis for further studies in the field of solid-state hydrogen storage. Full article

This study investigates the deposition of amorphous silicon carbon nitride (a-SiCN) films using a microwave sheath–voltage combination plasma (MVP) source under duty-cycle-controlled deposition conditions. Duty ratios of 10, 30, 50, and 70% resulted in substrate temperatures of 180, 600, 980, and 1040 °C, respectively. The deposition rate reached a maximum of approximately 208 μm/h at a duty ratio of 30%. The atomic ratios of C, N, and Si remained nearly constant for duty ratios from 30% to 70%. X-ray diffraction confirmed that all films were amorphous. Raman spectra revealed features characteristic of amorphous carbon (a-C) for duty ratios of 30% or higher, suggesting the incorporation of a-C-like structures into the a-SiCN matrix. The film hardness increased as the duty-cycle-controlled deposition conditions shifted from 10% to 50% (180 to 980 °C), reaching a maximum of 22.65 ± 6.78 GPa at a duty ratio of 50%, and then decreased at 70% (1040 °C). These variations in hardness are suggested to be associated with coupled changes in hydrogen incorporation, C–N bonding, and the evolution of sp²-rich carbon clustering (graphite-like short-range ordering) under elevated temperature and ion-bombardment conditions. Full article

Post-annealing treatments constitute a simple and cost-effective strategy to tailor the structure and photocatalytic performance of polymeric carbon nitride (PCN). In this work, PCNs synthesized from melamine and urea were subjected to post-annealing at 580 °C under air and CO₂ atmospheres to elucidate the role of hydrogen bonding, as well as other structural modifications induced by oxidizing atmospheres, on photocatalytic water splitting. Comprehensive structural, chemical, and textural characterization (XRD, FTIR spectroscopy, XPS, SSNMR, HRTEM, BET, TGA, and UV–Vis DRS) reveals that post-annealing induces markedly different effects depending on the precursor. For melamine-derived PCN, the treatment selectively disrupts hydrogen bonds between melon strands without introducing nitrogen vacancies, amorphization, or framework shortening. This structural rearrangement increases surface area, reduces particle size, slightly widens the band gap, and enhances water–framework interactions, resulting in a twofold improvement in the hydrogen evolution rate (HER), reaching ~3300 µmol h⁻¹ g·cat⁻¹ under visible-light irradiation. In contrast, urea-derived PCN undergoes only minor structural modifications, including slight exfoliation and possible nitrogen deficiency, which do not translate into a measurable enhancement of photocatalytic activity. These results demonstrate that selective hydrogen-bond disruption is a key factor governing charge transport and photocatalytic efficiency in PCN. Importantly, the optimized melamine-derived PCN achieves HER values comparable to those of urea-derived PCN while maintaining a substantially higher synthesis yield, highlighting its potential for scalable solar hydrogen production. Full article

Double complex salts (DCSs) of the composition [Co(NH₃)₆][Fe(CN)₆] are a promising precursor for the preparation of catalysts for the hydrogenation of carbon oxides (CO and CO₂) by Fischer–Tropsch synthesis. The specific surface area is an important parameter for catalysts. Our article investigates the influence of mechanochemical activation (MCA) on this DCS in order to determine the conditions for obtaining the largest specific surface area of the intermetallic compound, a product of the DCS thermolysis. In this work, the effect of MCA on the physicochemical properties of the DCS [Co(NH₃)₆][Fe(CN)₆] and the products of its thermal decomposition in an argon atmosphere were investigated. It was shown that MCA leads to partial reduction of Fe⁺³ to Fe⁺², changes in the coordination of ammonia, amorphization of the structure and a decrease in the thermal stability of DCS. Thermolysis at 650 °C of samples subjected to MCA for 10 min results in the formation of nanocrystalline intermetallic compound Co_0.5Fe_0.5. The results demonstrate the potential of using MCA to control the properties of functional materials based on DCS. Full article

Hydrogenated tetrahedral amorphous carbon (ta-C:H) thin films were modified using 266 nm picosecond laser pulses to investigate structural transformations at low and moderate fluences. Nitrogen-doped hydrogenated tetrahedral amorphous carbon layers 20–40 nm thick were deposited on silicon (Si) and silicon dioxide on silicon (SiO₂/Si) substrates and irradiated with picosecond pulses at 0.5–1.6 J cm⁻² using a raster-scanned beam. Structural changes in morphology, composition, and bonding were evaluated via optical microscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Even below 1.0 J cm⁻², localized color shifts and slight swelling indicated early structural rearrangements without significant material removal. Above 1.0–1.2 J cm⁻², the films were largely ablated, although a persistent 3–6 nm carbon layer remained on both substrate types. XPS showed an increase in sp²-bonded carbon by roughly 15%–20% in optimally modified regions, and Raman spectroscopy revealed defect-activated D-bands and the formation of multilayer defective graphene or reduced-graphene-oxide-like flakes at ablation boundaries. These results indicate that picosecond ultraviolet irradiation enables controllable graphitization and thinning of ta-C:H films while maintaining uniform processing over centimeter-scale areas, providing a route to thin, conductive, partially graphitized carbon coatings for optical and electronic applications. Full article

Sewer corrosion driven by sulfur metabolism threatens infrastructure durability. Current study examined the effect of conductive lining materials on microbial communities and sulfide control under simulated sewer conditions. Three lab-scale reactors (3.5 L total volume, 2.1 L working volume) were prepared with amorphous carbon (SAN-EARTH) and magnetite-black (MTB) linings, while a Portland cement reactor with no coating served as the control. Each reactor was operated for 120 days at room temperature and fed with artificial wastewater. The working volume consisted of 1.4 L of synthetic wastewater mixed with 0.7 L of sewage sludge used as the inoculum source. Sulfate, sulfide, hydrogen sulfide, nitrogen species, pH, and organic carbon were monitored, and microbial dynamics were analyzed via 16S rRNA sequencing and functional annotation. SAN-EARTH and MTB reactors completely suppressed sulfide and hydrogen sulfide, while Portland cement showed the highest accumulation. Both conductive linings maintained alkaline conditions (pH 9.0–10.5), favoring sulfide oxidation. Microbial analysis revealed enrichment of sulfur-oxidizing bacteria (Thiobacillus sp.) and electroactive taxa (Geobacter sp.), alongside syntrophic interactions involving Aminobacterium and Jeotgalibaca. These findings indicate that conductive lining materials reshape microbial communities and sulfur metabolism, offering a promising strategy to mitigate sulfide-driven sewer corrosion. Full article

Lignin is the most structurally complex component of lignocellulosic biomass. Each year, thousands of tons of lignin-rich residues from enzymatic hydrolysis are generated in sugarcane-based cellulosic ethanol biorefineries. The current study specifically utilizes lignin extracted from sugarcane bagasse as the primary feedstock for biochar production, rather than employing the raw bagasse itself. This study investigates, through pyrolytic thermal treatment of two lignin sources, the production of biochars and the evaluation of their potential applications. Kraft commercial lignin and sugarcane bagasse lignin samples, along with their corresponding biochars, were characterized by elemental and proximate analyses, higher heating value determination, spectroscopic techniques, thermogravimetric analysis, X-Ray diffraction, scanning electron microscopy coupled with energy-dispersive spectroscopy, and true density measurements. The results revealed a lower contamination level associated with the extraction process and confirmed the amorphous nature of sugarcane bagasse lignin and its derived biochar. An O/C ratio of approximately 0.3 was obtained for the sugarcane bagasse lignin biochar based on both elemental and Raman spectroscopy analyses. Both elemental composition assessment and Raman spectroscopic analysis indicated that all biochar specimens exhibited hydrogen-to-carbon (H/C) ratios exceeding 0.5. The analyses, therefore, indicated that the biochar derived from sugarcane lignin exhibited higher energy density, moderate stability and a high carbon content. The proposed approach thus provides promising alternatives for the valorizing lignin residues derived from second-generation ethanol production processes. Full article

The fabrication of semiconductor devices with three-dimensional architectures imposes unprecedented demands on advanced plasma dry etching processes. These include the simultaneous requirements of high throughput, high material selectivity, and precise profile control. In conventional reactive ion etching (RIE), fluorocarbon plasma provides both accelerated ion species and reactive neutrals that etch the feature front, while the CF_x radicals promote polymerization that protects sidewalls and enhance selectivity to the amorphous carbon layer (ACL) mask. In this work, we present computational results on the role of CF₄ addition to hydrogen fluoride (HF) plasma for next-generation RIE, specifically cryogenic etching. Simulations were performed by varying the CF₄ concentration in the HF plasma to evaluate its influence on ion densities, neutral species concentration, and electron density. The results show that the densities of CF_x (x = 1–3) ions and radicals increase significantly with CF₄ addition (up to 20%), while the overall plasma density and the excited HF species remain nearly unchanged. The results of plasma density and atomic fluorine density are consistent with the experimental observations of the HF/CF₄ plasma using an absorption probe and the actimetry method. It was verified that the gas-phase reaction model proposed in this study can accurately reproduce the plasma characteristics of the HF/CF₄ system. The coupling of HF-based etchants with CF_x radicals enables polymerization that preserves SiO₂ etching throughput while significantly enhancing etch selectivity against the ACL mask from 1.86 to 5.07, with only a small fraction (~10%) of fluorocarbon gas added. The plasma simulation provides new insights into enhancing the etching performance of HF-based cryogenic plasma etching by controlling the CF₂ radicals and HF reactants through the addition of fluorocarbon gases. Full article

Zeolitic imidazolate frameworks (ZIFs) can provide fascinating stereo morphology and tunable metal active sites, which plays an important role in the synthesis of various catalytic materials. However, it is still a problem to make use of these advantages to design efficient hydrogen evolution reaction (HER) catalysts. Herein, we use covalent coordination strategy to synthesize bimetallic Co_xZn_1−x(2-MeIM)₂ precursors with regular dodecahedral structures for providing uniform active sites and stable carbon skeleton. Furthermore, the ratio of Co and Zn atoms was optimized to balance the electron density and give full play to the synergistic catalytic effect. And then, the subsequent high temperature annealing process is used to construct the amorphous carbon layer, which can improve the overall stability of the material. The gas phase phosphating process realizes the transformation from ZIF material to metal phosphide resulting in enhanced hydrogen evolution activity. Finally, the optimized amorphous nitrogen-doped carbon (NC)-coated Zinc-doped cobalt phosphide (Zn_0.17Co_0.83P@NC) requires only 237.60 mV to reach the current density of 10 mA cm⁻² in alkaline medium, which is 223.22 mV lower than that of CoP, and has a stability of up to 18 h. This work provides a reference for the rational design of efficient and stable compound electrocatalysts for alkaline hydrogen evolution based on the bimetallic ZIF as a precursor. Full article