Search Results (380)

Solar-driven hydrogen production via photocatalytic water splitting represents a promising route toward sustainable and low-carbon energy systems. Among emerging photocatalysts, porphyrin-based framework materials, specifically porphyrinic metal–organic frameworks (PMOFs) and porphyrinic covalent organic frameworks (PCOFs), have attracted increasing attention owing to their strong visible-light absorption, tunable electronic structures, permanent porosity, and well-defined catalytic architectures. In these systems, porphyrins function as versatile photosensitizers whose photophysical properties can be precisely tailored through metalation, peripheral functionalization, and integration into ordered frameworks. This review provides a comprehensive, design-oriented overview of recent advances in PMOFs, PCOFs, and hybrid porphyrinic architectures for photocatalytic H₂ evolution. We discuss key structure–activity relationships governing light harvesting, charge separation, and hydrogen evolution kinetics, with particular emphasis on the roles of porphyrin metal centers, secondary building units, linker functionalization, framework morphology, and cocatalyst integration. Furthermore, we highlight how heterojunction engineering through coupling porphyrinic frameworks with inorganic semiconductors, metal sulfides, or single-atom catalytic sites can overcome intrinsic limitations related to charge recombination and limited spectral response. Current challenges, including long-term stability, reliance on noble metals, and scalability, are critically assessed. Finally, future perspectives are outlined, emphasizing rational molecular design, earth-abundant catalytic motifs, advanced hybrid architectures, and data-driven approaches as key directions for translating porphyrinic frameworks into practical photocatalytic hydrogen-generation technologies. Full article

This study investigated the effect of chickpea flour (CF) on the staling behavior of gluten-free bread (GFB) by comparing a formulation containing 50% rice flour (RF) and 50% CF (CFB) with a control bread based on rice flour supplemented with whey protein (RFB). Bread samples were stored at room temperature for up to 7 days. Changes in color, reflectance, starch and protein structure, specific volume, crumb structure, texture, and staling kinetics were monitored. CFB exhibited a darker and more yellow crumb and crust, with lower reflectance intensity, and showed greater color stability during storage. Fourier-transform infrared (FTIR) spectroscopy revealed higher overall starch crystallinity and more stable relative crystallinity degree (RCD) values in CFB (58.74–59.05%) compared to RFB (46.19–40.52%) throughout storage, indicating early amylose-driven ordering and a more stable molecular organization of starch. Protein secondary structure analysis showed that CFB had a higher β-sheet content (35.05–37.49) than the RFB formulation (30.37–31.16), indicating stronger protein aggregation. In contrast, macroscopic quality parameters showed that CFB had lower specific volume (1.65 vs. 1.93) and porosity (17.17 vs. 21.01 cm³/g) than RFB, resulting in higher hardness (15.92 vs. 6.15 N) and accelerated staling kinetics (k_corr) (0.28 vs. 0.14 day⁻¹), indicating faster crumb firming despite the observed molecular-level stability. Overall, the results demonstrated that CF contributes to enhanced molecular organization of starch and increased nutritional value of GFB, while its technological performance at the macroscopic level remains formulation-dependent. These findings highlight the need for targeted formulation and process optimization to balance molecular stability with desirable textural properties in CFB. Full article

The aim of the study is to assess the effect of diagenesis on the reservoir properties of Carboniferous sandstones in Western Pomerania (NW Poland). The research focuses on Mississippian (Łobżonka Shale, Gozd Arkose, and Drzewiany Sandstone formations) and Pennsylvanian (Wolin, Rega, and Dziwna formations) rocks. A comparative analysis of the sandstones in the individual formations was carried out. The sandstone samples taken from 13 deep boreholes were studied petrographically (using a polarizing microscope, cathodoluminescence, and a scanning electron microscope), and petrophysical features were measured. The Carboniferous sandstones are represented mainly by quartz arenites ranging from very fine- to medium-grained and arkosic and lithic arenites from fine- to coarse-grained. The main diagenetic processes that affected the porosity and permeability of quartz arenites were compaction and cementation. Compaction reduced the primary porosity by an average of about 60% and cementation by about 40% in the Pennsylvanian sandstones. Primary porosity of arkosic and lithic arenites was affected mainly by compaction, cementation, and dissolution. Arkosic arenites have lost an average of 80% of their primary porosity as a result of mechanical compaction. The porosity of these sandstones increased due to the dissolution of mainly feldspar grains and the formation of secondary porosity. Among the Mississippian sandstones, quartz arenites of the Łobżonka Shale Formation exhibit unfavorable reservoir properties (porosity approx. 1%, impermeable). The volcaniclastic arkosic and lithic arenites of the Gozd Arkose Formation have poor reservoir qualities (porosity usually around 5%, mostly impermeable). The quartz arenites of the Drzewiany Sandstone Formation show the best reservoir properties (porosity of about 18%, permeability up to 1000 mD). The Pennsylvanian sandstones, quartz arenites of the Wolin and Rega formations, are characterized by good reservoir qualities (porosity approx. 10%, permeability up to 200 mD), while the Dziwna Formation sandstones show worse properties (porosity approx. 10%, often impermeable). Full article

This study investigates the relationship between apparent electrical resistivity (ER) and key material parameters governing moisture and pore-structure characteristics of concrete. An experimental program was conducted using six concrete mix designs, where ER was continuously measured under controlled wetting and drying cycles to characterize its dependence on the degree of saturation (DS). Results confirmed that ER decreases exponentially with increasing DS across all mixtures, with R² values between 0.896 and 0.997, establishing DS as the dominant factor affecting electrical conduction. To incorporate additional pore-structure parameters, eight input combinations consisting of DS, porosity (P), water–cement ratio (WCR), and compressive strength (f′c) were evaluated using five machine learning models. Gaussian Process Regression and Neural Networks achieved the highest accuracy, particularly when all parameters were included. SHAP analysis revealed that DS accounts for the majority of predictive influence, while porosity and WCR provide secondary but meaningful contributions to ER behavior. Guided by these insights, nonlinear multivariate regression models were formulated, with the exponential model yielding the strongest predictive capability (R² = 0.96). The integrated experimental–computational approach demonstrates that ER is governed by moisture dynamics and pore-structure refinement, offering a physically interpretable and statistically robust framework for nondestructive durability assessment of concrete. Full article

This study examines the influence of sintering temperature on the structural and transport properties of GdBa₂Cu₃O₇ (Gd123) superconductors prepared from nano-sized precursors via the co-precipitation method. The metal-oxalate precursor (average particle size < 50 nm) was calcined at 900 °C for 12 h, and then the prepared pellets were sintered under an oxygen atmosphere in the range of 920–950 °C for 15 h. All samples showed metallic properties and a sharp superconducting transition. Critical temperatures T_C(R=0) were 94–95 K, with higher sintering temperatures steadily boosting critical current density. X-ray diffraction confirmed orthorhombic Gd123 as the dominant phase, with its phase fraction increasing from 92% to 99.8% as the sintering temperature increased. SEM micrographs showed large, densely packed grains, with higher sintering temperatures promoting improved grain connectivity and reduced porosity. The sample sintered at 950 °C exhibited the most favorable transport performance, attributed to enhanced intergranular coupling and the presence of nanoscale secondary phases acting as effective flux-pinning centers. Overall, these results demonstrate that careful control of sintering temperature can significantly optimize the microstructure and superconducting properties of Gd123 materials, supporting their advancement for practical electrical and magnetic applications. Full article

Plastic streams dominated by polyethylene (PE) including PE HD/MD (High Density/Medium Density) and PE LD/LLD (Low Density/Linear Low Density), polypropylene (PP), and polyvinyl chloride (PVC) across Europe demand a design framework that links synthesis with end of life reactivity, supporting circular economic goals and European Union waste management targets. This work integrates polymerization derived chain architecture and depolymerization mechanisms to guide selective valorization of commercial plastic wastes in the European context. Catalytic topologies such as Bronsted or Lewis acidity, framework aluminum siting, micro and mesoporosity, initiators, and strategies for process termination are evaluated under relevant variables including temperature, heating rate, vapor residence time, and pressure as encountered in industrial practice throughout Europe. The analysis demonstrates that polymer chain architecture constrains reaction pathways and attainable product profiles, while additives, catalyst residues, and contaminants in real waste streams can shift radical populations and observed selectivity under otherwise similar operating windows. For example, strong Bronsted acidity and shape selective micropores favor the formation of C₂ to C₄ olefins and Benzene, Toluene, and Xylene (BTX) aromatics, while weaker acidity and hierarchical porosity help preserve chain length, resulting in paraffinic oils and waxes. Increasing mesopore content shortens contact times and limits undesired secondary cracking. The use of suitable initiators lowers the energy threshold and broadens processing options, whereas diffusion management and surface passivation help reduce catalyst deactivation. In the case of PVC, continuous hydrogen chloride removal and the use of basic or redox co catalysts or ionic liquids reduce the dehydrochlorination temperature and improve fraction purity. Staged dechlorination followed by subsequent residue cracking is essential to obtain high quality output and prevent the release of harmful by products within European Union approved processes. Framing process design as a sequence that connects chain architecture, degradation chemistry, and operating windows supports mechanistically informed selection of catalysts, severity, and residence time, while recognizing that reported selectivity varies strongly with reactor configuration and feed heterogeneity and that focused comparative studies are required to validate quantitative structure to selectivity links. In European post consumer sorting chains, PS and PC are frequently handled as separate fractions or appear in residues with distinct processing routes, therefore they are not included in the polymer set analyzed here. Polystyrene and polycarbonate are outside the scope of this review because they are commonly handled as separate fractions and are typically optimized toward different product slates than the gas, oil, and wax focused pathways emphasized here. Full article

Offshore wind farm construction faces significant geotechnical challenges posed by tidal mudflat sediments, including high moisture content, low bearing capacity, and high sensitivity to disturbance. Utilizing MgO—a material characterized by abundant raw materials, low embodied energy, and environmental compatibility—for the stabilization of such soft soils represents a promising and sustainable approach worthy of further investigation. This study elucidates the carbonation-induced stabilization mechanism of coastal mucky soil from Ningbo, Zhejiang Province, through systematic monitoring of reaction temperature and unconfined compressive strength (UCS) testing under varying levels of reactive MgO content, carbonation duration, and initial moisture content. Microstructural characterization was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) to reveal the evolution of mineralogical and pore structure features associated with carbonation. The results indicate that increasing MgO content leads to higher peak reaction temperatures and shorter time-to-peak values. However, the rate of reduction in time-to-peak diminishes beyond 20% MgO. A secondary temperature rise is commonly observed between 3–3.5 h of carbonation in most specimens. When the MgO content is below 30%, UCS peaks within 6–10 h, with the peak time decreasing as MgO content increases. When MgO exceeds 45%, strength deterioration occurs due to structural damage. The correlation between deformation modulus and UCS is found to be comparable to that of conventional cement-stabilized soils. Microstructural analysis reveals that, with increased MgO dosage and prolonged carbonation, carbonation products progressively fill voids and bind soil particles, resulting in reduced total porosity and a refinement of pore size distribution—evidenced by a leftward shift in the most probable pore diameter. Nevertheless, at excessively high MgO levels (e.g., 50%), crystallization pressure from rapid product formation may generate macro-pores, compromising soil fabric integrity. This study presents a low-carbon and efficient ground improvement approach for access road construction in tidal mudflat wind farm developments. Full article

Nitrogen oxides (NO_x) emitted mainly from vehicle exhaust significantly contribute to urban air pollution, leading to photochemical smog and secondary particulate matter. Photocatalytic technology has emerged as a promising solution for continuous NO_x decomposition under ultraviolet (UV) irradiation. This study developed an eco-friendly permeable concrete incorporating activated loess and zeolite to improve roadside air quality. The high porosity and adsorption capability of the concrete provided a suitable substrate for a TiO₂-based photocatalytic coating. A single-component coating system was optimized by introducing colloidal silica to enhance TiO₂ particle dispersibility and adding a binder to secure durable adhesion on the concrete surface. The produced permeable concrete met sidewalk quality standards specified in SPS-F-KSPIC-001-2006. Photocatalytic NO_x removal performance evaluated by ISO 22197-1 showed a maximum removal efficiency of 77.5%. Even after 300 h of accelerated weathering, the activity loss remained within 13.8%, retaining approximately 80% of the initial performance. Additionally, outdoor mock-up testing under natural light confirmed NO_x concentration removal and formation of nitrate by-products, demonstrating practical applicability in real environments. Overall, the integration of permeable concrete and a durable, single-component TiO₂ photocatalytic coating provides a promising approach to simultaneously enhance pavement sustainability and reduce urban NO_x pollution. Full article

The selective removal of trace heteroatomic contaminants from fuel remains a critical challenge for clean combustion and refinery upgrading, particularly due to the chemical stability and structural similarity of sulfur- and nitrogen-containing aromatics. Herein, a surface-engineered graphene oxide aerogel functionalized with cyclodextrin (β-CD-CONH-GO) is developed via covalent grafting to introduce well-defined host–guest recognition sites within a porous framework. Spectroscopic and microscopic characterizations confirm successful functionalization, preserved aerogel morphology, and accessible hybrid interfaces. The removal process for monocyclic, bicyclic, and tricyclic impurities is governed by synergistic molecular inclusion within the cyclodextrin cavity, interfacial hydrogen bonding, and secondary confinement provided by the aerogel porosity. Thus, the β-CD-CONH-GO exhibits efficient adsorption toward representative bicyclic impurities, and the removal performance follows the order of indole > quinoline > benzothiophene. Kinetic analysis demonstrates pseudo-second-order adsorption behavior, indicating chemisorption dominated by cooperative host–guest recognition and hydrogen bonding. It possesses removal selectivity even in mixed systems containing structurally similar aliphatic and aromatic competitors and maintains > 95% efficiency after five regeneration cycles via ethanol extraction, confirming superb durability. This study demonstrates a feasible pathway to design adsorbents for deep fuel refining and highlights cyclodextrin-based graphene hybrid aerogels as promising candidates for separations. Full article

Shale pores and throats are key factors controlling the enrichment and development efficiency of shale oil and gas. However, the characteristics and formation mechanisms of shale pores and throats remain unclear. Taking the Permian continental shales in the Mahu Sag of the Junggar Basin as an example, this paper studies the formation mechanisms of pores and throats in shales of different lithofacies through a series of experiments, such as high-pressure mercury injection and scanning electron microscopy. The results show that the Permian continental shales in the Junggar Basin are mainly composed of five lithofacies: rich siliceous shale (RSS), calcareous–siliceous shale (CSS), argillaceous–siliceous shale (ASS), siliceous–calcareous shale (SCS), and mixed-composition shale (MCS). The pores in shale are dominated by intergranular and intragranular pores. The intergranular pores are mainly primary pores and secondary dissolution pores. The primary pores are mainly slit-like and polygonal, with diameters between 40 and 1000 nm. The secondary dissolution pores formed by dissolution are irregular with serrated edges, and their diameters range from 0.1 to 10 μm. The throats are mainly pore-constriction throats and knot-like throats, with few vessel-like throats, overall exhibiting characteristics of nanometer-scale width. The mineral composition has a significant influence on the development of pores and throats. Siliceous minerals promote the development of macropores, and carbonate minerals promote the development of mesopores. Clay minerals inhibit pore development. Diagenesis regulates the development of pores and throats through mechanical compaction, cementation, and dissolution. Compaction leads to a reduction in porosity, and cementation has varying effects on the preservation of pores and throats. Dissolution is the main factor for increased pores and throats. These findings provide a lithofacies-based geological framework for evaluating effective porosity, seepage capacity, and shale oil development potential in continental shale reservoirs. Full article

A batch of drill pipe joints in a well cracked and failed due to hardbanding. In this study, various experiments were conducted to analyze the reasons for cracking failure, including data verification, macroscopic morphology analysis, mechanical properties, microstructure analysis, and micro-Vickers hardness of cracked areas, as well as macroscopic, metallographic, and energy spectrum analysis of the fracture surface after opening the cracked area. The results indicated that (1) the chemical composition, tensile strength, Charpy impact test, and Brinell hardness results of the joint met the requirements of the order technical conditions. (2) The hardbanding in the cracked area had multiple pores and cracks on its outer surface and inside. The maximum diameter of the internal porosity was about 3.4 mm, and the length of the internal crack was about 1 mm. (3) The main reason for the cracking of a batch of drill pipe joints due to hardbanding is a quality problem of the secondary repair welding of the hardbanding. The cracks in the failed drill pipe originated from the porosity and cracks in the hardbanding of the drill pipe box joint. Under the influence of alternating stress and high-pressure mud erosion underground, the cracks rapidly extended to the inner wall, and the porosity in the hardbanding accelerated crack propagation, ultimately causing the drill pipe to crack and fail. Full article

In shale oil accumulation, the sealing capacity of roof strata is a key factor controlling hydrocarbon retention, primarily governed by pore–throat structures. This study examines the Chang 7₃ sub-member roof in the Ordos Basin using core and drilling samples, combined with SEM, mercury intrusion porosimetry, nitrogen adsorption, and breakthrough pressure tests. The roof rocks are dense and mainly composed of mudstone, silty mudstone, and argillaceous siltstone, which can be further classified into clay-rich and felsic-rich types. The pore system includes organic matter pores, dissolution pores, intergranular pores, clay interlayer pores, intercrystalline pores, and microfractures. Pores are dominated by mesopores (4–10 nm), with few macropores, and display slit-like, plate-, and wedge-shaped morphologies. Breakthrough pressure averages above 20 MPa, reflecting strong sealing capacity. Although dissolution of felsic minerals generates secondary porosity that may weaken sealing, the overall complex pore–throat system, reinforced by compaction and cementation of clay minerals, forms a dense fabric and favorable sealing conditions. These features restrict hydrocarbon migration and enhance the sealing performance of the Chang 7₃ shale oil roof. Full article

Metal casting industries generate substantial quantities of spent foundry sand (SFS), a silica- and alumina-rich by-product that remains underutilized, with recycling rates below 30%. This study explores the incorporation of aluminum SFS as a secondary raw material in aluminosilicate refractory castables to promote sustainable waste valorization and circular economy practices. Refractory mixtures were prepared with bauxite, kyanite, calcium aluminate cement, microsilica, and flint clay, where fine flint clay was partially replaced by aluminum SFS at 0, 5, 10, and 15 wt.%. Samples were dried at 120 °C and sintered at 850, 1050, and 1400 °C for 4 h. Bulk density, apparent porosity, cold crushing strength, and modulus of rupture were measured, while phase and microstructural evolution were examined by XRD and SEM. The 5 wt.% SFS-containing castable exhibited comparable strength and density to the reference formulation, attributed to the formation of secondary mullite and anorthite that improved matrix cohesion. Higher SFS contents (10–15 wt.%) increased porosity and reduced strength due to excess SiO₂ and silica polymorphism. These results demonstrate the technical feasibility of using aluminum SFS in refractory castables, contributing to resource conservation, waste reduction, and the development of environmentally sustainable refractory materials for high-temperature applications. Full article

In this study, a small core diameter single mode fiber laser was applied to weld an 8 mm thick plate of 6061-T6 aluminum alloy. The microstructural evolution and mechanical properties of the laser welded aluminum alloy specimens were investigated in detail. The results indicated that fully penetrated welded specimens, free of welding defects like porosity, melt sagging, and hot cracking could be achieved by optimizing the processing parameters through response surface methodology. The upper part of the fusion zone consisted mainly of fine equiaxed dendrites, with secondary dendrite arm spacing (SDAS) of approximately 3–5 μm. While the lower region of the fusion zone exhibited pronounced microstructural coarsening, made up mostly of coarse columnar grains, along with some localized equiaxed grains, and an SDAS ranging from 8 to 12 μm. Both the fusion zone and heat affected zone (HAZ) were characterized by a “softened” hardness profile. The fusion zone featured a narrow region with the lowest microhardness across the welded joint with the microhardness value reducing to ~72% of the base metal (BM). Meanwhile, the microhardness of the HAZ was ~87.4% of the BM. The ultimate tensile strength of laser welded specimens was ~243.6 MPa, amounting to approximately 78.3% of the base metal. This study provides a fresh approach for welding medium-thick aluminum alloy plate using a high-quality laser beam, even at the kilowatt level with a fiber laser, and it shows a strong promise for applications in light-alloy manufacturing sectors such as automotive, rail transportation, aerospace, and beyond. Full article

Building structures are inherently susceptible to damage from extreme dynamic loads, while conventional concrete exhibits inadequate tensile resistance. While hybrid fibers systems can surpass the limitations of single-fiber reinforcement through their synergistic action, their internal damage mechanisms under impact loading remain inadequately understood. This study investigates the dynamic splitting behavior of hybrid fibers-reinforced cementitious composites combining polyvinyl alcohol (PVA) with either steel (SF) or polyethylene (PE) fibers, using Split Hopkinson Pressure Bar (SHPB) tests at strain rates of 5–31 s⁻¹, along with industrial CT scanning for meso-scale damage analysis. Results indicate that the SF–PVA hybrid improved strength by up to 15.6% compared to mono-PVA, while the PE–PVA hybrid achieved an 11.1% increase. All hybrid systems exhibited improved energy dissipation (which rose 25–45% with strain rate) and displayed secondary stress peaks. Quantitative CT analysis revealed distinct damage patterns: the mono-PVA specimen developed extensive damage networks (porosity: 7.20%; crack ratio: 4.48%), the SF-PVA hybrid system displayed the lowest damage indices (porosity: 3.29%; crack ratio: 1.76%), whereas the PE-PVA hybrid system exhibited the most significant dispersed damage pattern (crack-to-pore ratio: 39.32%). The hybrid systems function via distinct mechanisms: SF–PVA offers multi-scale reinforcement and superior damage suppression, whereas PE–PVA enables sequential energy dissipation, effectively dispersing concentrated damage. These insights support tailored fiber hybridization for impact-resistant structural design. Full article