Search Results (122)

Hydrogen is widely recognized as a key enabler of the clean energy transition, but the lack of safe, efficient, and scalable storage technologies continues to hinder its broad deployment. Conventional hydrogen storage approaches, such as compressed hydrogen storage, cryo-compressed hydrogen storage, and liquid hydrogen storage, face limitations, including high energy consumption, elevated cost, weight, and safety concerns. In contrast, solid-state hydrogen storage using carbon-based adsorbents has gained growing attention due to their chemical tunability, low cost, and potential for modular integration into energy systems. This review provides a comprehensive evaluation of hydrogen storage using carbon-based materials, covering fundamental adsorption mechanisms, classical materials, emerging architectures, and recent advances in computationally AI-guided material design. We first discuss the physicochemical principles driving hydrogen physisorption, chemisorption, Kubas interaction, and spillover effects on carbon surfaces. Classical adsorbents, such as activated carbon, carbon nanotubes, graphene, carbon dots, and biochar, are evaluated in terms of pore structure, dopant effects, and uptake capacity. The review then highlights recent progress in advanced carbon architectures, such as MXenes, three-dimensional architectures, and 3D-printed carbon platforms, with emphasis on their gravimetric and volumetric performance under practical conditions. Importantly, this review introduces a forward-looking perspective on the application of artificial intelligence and machine learning tools for data-driven sorbent design. These methods enable high-throughput screening of materials, prediction of performance metrics, and identification of structure–property relationships. By combining experimental insights with computational advances, carbon-based hydrogen storage platforms are expected to play a pivotal role in the next generation of energy storage systems. The paper concludes with a discussion on remaining challenges, utilization scenarios, and the need for interdisciplinary efforts to realize practical applications. Full article

Highly sensitive real-time detection of hydrogen sulfide (H₂S) is important for human health and environmental protection due to its highly toxic properties. The development of high-performance H₂S sensors remains challenging for poor selectivity, high limit detection and slow recovery from irreversible sulfidation. To solve these problems, we strategically prepared a layered structure of CuO-sensitized WO₃ flower-like hollow spheres with CuO as the sensitizing component. A 15 wt% CuO/WO₃ exhibits an ultra-high response (R_a/R_g = 571) to 10 ppm H₂S (131-times of pure WO₃), excellent selectivity (97-times higher than 100 ppm interference gas), and a low detection limit (100 ppb). Notably, its fast response (4 s) is accompanied by full recovery within 236 s. After 30 days of continuous testing, the response of 15 wt% CuO/WO₃ decreased slightly but maintained the initial response of 90.5%. The improved performance is attributed to (1) the p-n heterojunction formed between CuO and WO₃ optimizes the energy band structure and enriches the chemisorption sites for H₂S; (2) the reaction of H₂S with CuO generates highly conductive CuS, which significantly reduces the interfacial resistance; and (3) the hierarchical flowery hollow microsphere structure, heterojunction, and oxygen vacancy synergistically promote the desorption. This work provides a high-performance H₂S gas sensor that balances response, selectivity, and response/recovery kinetics. Full article

The contamination of aquatic systems by industrial dyes, particularly methylene blue (MB), presents a significant environmental challenge due to their chemical stability and toxicity. In this study, the development and application of a novel magnetic nanohybrid comprising multiwall carbon nanotubes (MWCNTs) functionalized with maghemite (γ-Fe₂O₃) nanoparticles biosynthesized using Eucalyptus globulus extract (denoted MWNT-NPE) is reported. The material was thoroughly characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), Vibrating Sample Magnetometer (VSM), and Fourier-Transform Infrared (FTIR) techniques, revealing high crystallinity, mesoporosity, and superparamagnetic behavior. The MWNT-NPE exhibited exceptional MB adsorption performance under optimized conditions (pH 6, 0.8 g L⁻¹ dose, 40 min equilibrium), achieving a maximum adsorption capacity of 92.9 mg g⁻¹. Kinetic analysis indicated chemisorption and physisorption regimes depending on MB concentration, with the pseudo-second-order and Freundlich isotherm models providing the best fits of experimental data. FTIR spectroscopy demonstrated that the removal mechanism involves π–π stacking, hydrogen bonding, and electrostatic interactions between MB molecules and the composite’s surface functional groups. Notably, the magnetic nanohybrid retained over 98% removal efficiency across five regeneration cycles and successfully removed MB from synthetic effluents with efficiencies exceeding 91%. These findings highlight the synergistic adsorption and magnetic recovery capabilities of the bio-functionalized hybrid system, presenting a sustainable, reusable, and scalable solution for industrial dye remediation. Full article

Biochar-based adsorbents synthesized from agricultural wastes have emerged as economical and environmentally sustainable materials for water purification. In this study, coffee shell-derived biochars were synthesized via pyrolysis at 500 and 700 °C, with and without water washing, and comprehensively characterized to evaluate their potential for removing Rhodamine B (RhB) from aqueous solution. Structural and surface analyses indicated that a higher pyrolysis temperature enhanced pore development and aromaticity, whereas water washing effectively removed inorganic ash, thereby exposing additional active sites. Among all samples, water-washed biochar pyrolyzed at 700 °C (WCB700) exhibited the highest surface area (273.6 m²/g) and adsorption capacity (193.5 mg/g). The adsorption kinetics conformed to a pseudo-second-order model, indicating chemisorption, and the equilibrium data fit the Langmuir model, suggesting monolayer coverage. Mechanism analysis highlighted the roles of π–π stacking, hydrogen bonding, electrostatic interaction, and pore filling. Additionally, WCB700 retained more than 85% of its original capacity after five regeneration cycles, demonstrating excellent stability and reusability. This study presents an economical approach to valorizing coffee waste as well as provides mechanistic insights into optimizing biochar surface chemistry for enhanced dye removal. These findings support the application of engineered biochar in scalable and sustainable wastewater treatment technologies. Full article

Carbon dioxide (CO₂) and hydrogen sulfide (H₂S) as harmful gases are always associated with methane (CH₄) in natural gas, biogas, and landfill gas. Given that chemisorption and physisorption are the key gas separation technologies in industry, selecting appropriate adsorbents is crucial to eliminate these harmful gases. The adsorption of CH₄, CO₂, and H₂S has been studied based on the density functional theory (DFT) in this work to evaluate the feasibility of transition metal (M = Mn, Fe, Co, Ni, Cu, Mo) porphyrin-like moieties embedded in graphene sheets (MN₄-GPs) as adsorbents. It was found that the interactions between gas molecules and MN₄-GPs (M = Mn, Fe, Co, Ni, Cu, Mo) are different. The weaker interactions between CH₄ and MN₄-GPs (M = Co, Ni, Cu, Mo) than those between CO₂ and MN₄-GPs or between H₂S and MN₄-GPs are beneficial to the separation of CH₄ from CO₂ and H₂S. The maximum difference in the interactions between gas molecules and MoN₄-GPs means that MoN₄-GPs have the greatest potential to become adsorbents. The different interfacial interactions are related to the amount of charge transfer, which could promote the formation of bonds between gas molecules and MN₄-GPs to effectively enhance the interfacial interactions. Full article

The co-occurrence of the synthesis of a functionalized magnetic nano iron oxides–biochar composite (MFe@BC) via impregnation–thermal pyrolysis and its use to remove micro-sized poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) microplastics from simulated wastewater was demonstrated in this study. The results showed that PHBV removal efficiency correlated positively with MFe@BC dosage, achieving an adsorption capacity of 13.14 mg/g and a removal efficiency of 98.53% at an optimal dosage of 1.5 g/L. Adsorption kinetics fit a pseudo-second-order model (R² = 0.9999), and the isotherm followed the Langmuir model (R² = 0.8440), yielding a theoretical maximum capacity of 31.96 mg/g. Characterization indicated chemisorption-driven monolayer adsorption via surface complexation and hydrogen bonding. Magnetic nano-iron transfer from MFe@BC to the PHBV surface imparted magnetic properties to PHBV, enabling synergistic adsorption and magnetic separation. Removal efficiency remained above 95% across pH 4–9 and COD 0–500 mg/L. Regeneration experiments indicated that the MFe@BC showed robust reusability, maintaining >92% PHBV removal efficiency after four adsorption–regeneration cycles. The results of this study may provide a feasible pathway for PHBV microplastic removal from secondary effluent, indicating that MFe@BC prepared in this study can be used for the removal of PHBV microplastics in a wide range of water bodies. Full article

Apricot kernel shells were evaluated as a sustainable activated carbon precursor for wastewater treatment using experimental and theoretical methods. Two adsorbents were synthesized: physically activated with CO₂ (AKS-CO₂) and chemically activated with H₃PO₄ (AKS-H₃PO₄). Comprehensive materials characterization and adsorption tests using Pb²⁺ ions and Rhodamine B dye (RhB) as model pollutants revealed that AKS-H₃PO₄ significantly outperformed its physically activated counterpart. With an exceptionally high specific surface area (1159.4 m²/g) enriched with phosphorus-containing functional groups, the chemically activated carbon demonstrated outstanding removal efficiencies of 85.1% for Pb²⁺ and 80.3% for RhB. Kinetic studies showed Pb²⁺ adsorption followed pseudo-second-order kinetics, indicating chemisorption, while RhB adsorption fitted pseudo-first-order kinetics, suggesting intra-particle diffusion control. The thermodynamic analysis confirmed the spontaneity of both processes: Pb²⁺ adsorption was exothermic under standard conditions with positive isosteric heat at higher concentrations, reinforcing its chemisorption nature, whereas RhB adsorption was endothermic, consistent with physisorption. Density Functional Theory (DFT) calculations further elucidated the mechanisms, revealing that Pb²⁺ preferentially binds to oxygen-containing functional groups, while RhB interacts through hydrogen bonding and π–π stacking. These findings establish chemically activated apricot kernel shell carbon as a high-performance adsorbent, exhibiting exceptional removal capacity for both ionic and molecular contaminants through distinct adsorption mechanisms. Full article

UiO-66-NH₂ is a metal–organic framework (MOF) with open metal sites, making it a promising candidate for adsorption and catalysis. However, the powdery texture of MOFs and the use of toxic solvents during synthesis limit their application. A novel solution to this issue is to create a layered porous composite by encasing the MOF within a flexible and structurally robust aerogel substrate using safe, eco-friendly, and green solvents such as ethanol. The fibrous MOF aerogels, characterized by a desirable macroscopic shape of cylindrical block and hierarchical porosity, were synthesized by two approaches: in situ growth of amine-functionalized UiO-66-NH₂ crystals on a TEMPO-oxidized cellulose nanofiber (TOCNF) and ex situ crosslinking of UiO-66-NH₂ crystals onto a TOCNF network to form UiO-66-NH₂/TOCNF. The incorporation of MOF into the cellulose nanofibrils via the in situ method reduces their aggregation potential, alters the nucleation/growth balance to produce smaller MOF crystals, and enhances mechanical flexibility, as evidenced by SEM images. The three adsorbents, including UiO-66-NH₂, ex situ UiO-66-NH₂/TOCNF, and in situ UiO-66-NH₂/TOCNF, were synthesized and used in this study. The effects of pH, time, temperature, and initial concentration were studied. A maximum adsorption capacity (Qmax) of 549.45 mg/g for Congo Red (CR) and 171.23 mg/g for Orange II (ORII) was observed at pH 6, using 10 mg of in situ UiO-66-NH₂/TOCNF at 40 °C with a contact time of 75 min for CR and 2 h for ORII. The adsorption of both dyes primarily occurs through monolayer chemisorption on the in situ UiO-66-NH₂/TOCNF. The main removal mechanisms were hydrogen bonding and surface complexation. The noteworthy adsorption capacity of in situ UiO-66-NH₂/TOCNF coupled with environment-friendly fabrication techniques indicates its potential applications on a large scale in real wastewater systems. Full article

Unlike on Fe and Co catalysts, the CO conversion effect on Ru catalyst performance is little reported. This study is undertaken to explore the issue using a series of Ru/NaY catalysts under 200–230 °C, 2.0 MPa, H₂/CO = 2, and 10–60% CO conversion in a 1 L continuous stirred tank reactor (CSTR). The results are comparatively studied with those of Fe and Co catalysts reported previously. The NaY support and four 1.0%, 2.5%, 5.0%, and 7.5% Ru/NaY catalysts were characterized by BET, H₂ chemisorption, H₂O-TPD, XRD, HRTEM, and XANES/EXAFS techniques. The BET and XRD results suggest a high surface area (730 m²/g), high degree of crystallinity of the NaY support, and high dispersion of Ru, while an hcp Ru structure and well-reduced Ru were reflected in the HR-TEM FFT and XANES/EXAFS results. The reaction results indicate that the CO conversion effect on CH₄ and C₅₊ selectivities on the Ru is the same as that on the Fe and Co catalysts, with CH₄ selectivity decreasing and C₅₊ selectivity increasing with increasing CO conversion. However, the CO conversion effect on olefin formation for the Ru catalyst was found to be opposite to that of the Fe and Co; increasing CO conversion enhanced olefin formation but suppressed secondary reactions of 1-olefins. The H₂O cofeeding experiments showed that H₂O impacted olefin formation by suppressing hydrogen adsorption and hydrogenation. The H₂O-TPD experiment evidenced a much stronger H₂O adsorption capacity (6.8 mmol/g-cat) on Ru followed by Co (1 mmol/g-cat), and then Fe (0.2 mmol/g-cat)., which showed only a very low H₂O adsorption capacity.This finding may explain the opposite CO conversion effect on olefin formation observed on the Ru catalyst, and may also explain why low CH₄ selectivity (i.e., 3%) occurred on the Ru catalyst and high CH₄ selectivity (i.e., 6–8%) occurred on the Co catalyst, both of which possess low water gas shift (WGS) activity. Full article

Metal–organic frameworks (MOFs) have emerged as promising catalysts in the hydrogenation of bicyclopentadiene (DCPD) and furfural. The physical adsorption behaviors of substrate molecules and H₂ within the pore structures of MOFs significantly influence the efficacy of subsequent catalytic reactions. This study employs molecular dynamics (MD) simulations to identify the optimal temperature and pressure conditions for the adsorption of DCPD and H₂, as well as furfural and H₂, within rare-earth-element-based MOFs (RE-MOFs). By analyzing the physical adsorption characteristics of 1538 RE-MOFs, we investigate the correlation between pore structures and adsorption capabilities. This exploration has led to the identification of 10 RE-MOF structures that demonstrate superior physical adsorption performance for both DCPD and furfural. Following this initial evaluation, density functional theory (DFT) calculations were conducted to determine the chemisorption energies of H₂ molecules on these 10 selected RE-MOF structures. Notably, the structure identified as “JALLEQ_clean” exhibited the most optimal overall adsorption performance. This study elucidates the quantitative relationship between the pore structure of RE-MOFs and their physical adsorption performance, clarifying the influence of porosity parameters on adsorption capacity and highlighting the advantages of cluster-type structures in mass transfer and adsorption. The findings provide theoretical guidance for developing high-performance RE-MOF catalysts and offer new insights for the rational design of MOF-based catalytic materials. Full article

Dicyanovinyl (DCV)-substituted oligothiophenes consist of both electron donor and acceptor ligands, which makes them promising materials for organic electronics. Here, we studied the structural and electronic properties of methyl-substituted dicyanovinyl-quinquethiophenes (DCV5T-Me₂) adsorbed on different metal surfaces, namely Au(111), Ag(111), and Cu(111), by using low-temperature scanning tunneling microscopy/spectroscopy (STM/STS). It is found that the assembled structures of DCV5T-Me₂ and the corresponding electronic properties vary depending on the underlying substrates. On Au(111) and Ag(111), compact organic islands are formed through intermolecular hydrogen bonding and electrostatic interactions. The lowest unoccupied molecular orbital (LUMO) and LUMO+1 of DCV5T-Me₂ are lower in energy on Ag(111) than those on Au(111), due to the stronger molecule–surface interaction when adsorbed on Ag(111). Moreover, orbital distributions of the LUMO and LUMO+1 in dI/dV maps on Au(111) and Ag(111) are the same as the DFT-calculated orbital distributions in gas phase, which indicates physisorption. In contrast, chemisorption dominates on Cu(111), where no ordered assemblies of DCV5T-Me₂ could be formed and resonances from the LUMO and LUMO+1 vanish. The present study highlights the key role of molecule–substrate interactions in determining the properties of organic nanostructures and provides valuable insights for designing next-generation organic electronics. Full article

The efficient removal of pharmaceuticals and personal care products (PPCPs) from aqueous solutions using conventional adsorbents is hindered by low adsorption capacity, insufficient selectivity, poor regeneration performance, and limited stability. In this study, a multilayer β-CD/GO membrane was successfully prepared via layer-by-layer coating with β-cyclodextrin (β-CD) and graphene oxide (GO). The multilayer β-CD/GO membrane combines the host–guest complexation ability of β-CD with the abundant oxygen-containing functional groups of GO to enhance the targeted removal of PPCPs (CTD, SMZ, and DCF) from aqueous solutions. The prepared multilayer β-CD/GO membrane adsorbent overcomes the separation difficulties and poor regeneration performance of powdered adsorbents, and the multilayer structure can significantly enhance structural stability and increase the number of adsorption sites. Batch adsorption experiments showed that the optimal adsorption performance of the multilayer β-CD/GO membrane for PPCPs occurred at pH 4 and in the absence of coexisting ions. With increasing pH values in the range of 4–9, the adsorption capacities of CTD, SMZ, and DCF slightly decreased to 14.37, 13.69, and 13.01 mg/g, respectively, and the adsorption capacities decreased slowly to 4.88, 3.51, and 3.26 mg/g as the coexisting ion concentrations increased from 0 to 0.20 mol/L. The adsorption mechanism of the multilayer β-CD/GO membrane for PPCPs was systematically investigated through adsorption kinetics, isotherms, and thermodynamics. The adsorption processes of CTD, SMZ, and DCF by the multilayer β-CD/GO membrane were well described by both pseudo-first-order and pseudo-second-order kinetic models (R² > 0.984), suggesting a hybrid adsorption mechanism involving both physisorption and chemisorption. The isotherm results indicated that the adsorption of CTD by the multilayer β-CD/GO membrane followed the Langmuir model (R² = 0.923), whereas the adsorption of SMZ and DCF was better described by the Freundlich model (R² = 0.984–0.988). The multilayer β-CD/GO membrane exhibited high adsorption capacities for CTD, SMZ, and DCF with maximum capacities of 35.56, 43.29, and 39.49 mg/g, respectively. Thermodynamic analyses indicated that the adsorption of PPCPs was exothermic ($\Delta H^0$ = −86.16 to −218.49 J/mol/K) and non-spontaneous ($\Delta G^0$ = 9.84–11.56, 9.50–12.54, and 10.09–14.46 kJ/mol). The multilayer β-CD/GO membrane maintained a removal efficiency of over 58.45–71.73% for CTD, SMZ, and DCF after five consecutive regeneration cycles, demonstrating high reusability for practical applications. The adsorption mechanisms of the multilayer β-CD/GO membrane include electrostatic interactions, hydrogen bonding, hydrophobic interactions, and π-π EDA interactions. This study offers a promising and environmentally friendly adsorbent for the efficient removal of PPCPs from aqueous solutions. Full article

This study addresses the dual challenges of water pollution and waste management by exploring the valorization of chicken bone biomass in native (NBio) and calcined (CBio) forms as biosorbents for dye removal. Basic fuchsine (BF) and methylene blue (MB) were selected as model pollutants, and adsorption was assessed under varying operational conditions. Characterization using Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) showed that calcination improved crystallinity, eliminated organic impurities, and increased surface area (247 m²/g for NBio vs. 370 m²/g for CBio). Adsorption tests revealed higher performance for CBio, with maximum adsorption capacities of 100 mg/g (BF) and 142.85 mg/g (MB) based on the Langmuir isotherm, while NBio with maximum adsorption capacities of 111 mg/g (BF) and 111.11 mg/g (MB) followed the Freundlich model. Adsorption kinetics indicated pseudo-second-order behavior, suggesting chemisorption. The possible interactions between dyes and the biosorbent are hydrogen bonding, electrostatic interactions, and Lewis acid–base interactions. Thermodynamic analysis highlighted exothermic behavior for NBio and endothermic, entropy-driven adsorption for CBio, with both processes being spontaneous. A decision tree with Least Squares Boosting (DT_LSBOOST) provided accurate predictions (R² = 0.9999, RMSE < 0.003) by integrating key parameters. These findings promote chicken bone biomass as a cost-effective, sustainable biosorbent, offering promising potential in wastewater treatment and environmental remediation. Full article

Addressing aquatic phosphate pollution requires advanced materials that combine high selectivity with recyclability. Here, we present a hierarchically structured composite integrating Mg-Fe layered double hydroxides (LDHs) with magnetic biochar derived from mulberry branches—an abundant agricultural byproduct. Through hydrothermal synthesis, the composite achieves a unique architecture combining Fe₃O₄-enabled magnetic recovery (2.63 emu·g⁻¹ saturation) with LDHs’ anion exchange capacity and biochar’s porous network. Systematic characterization reveals phosphate capture mechanisms dominated by hydrogen bonding through deprotonated carboxyl groups, inner-sphere complexation with metal oxides, and interlayer anion exchange, enabling 99.22% phosphate removal at optimal conditions (pH 6, 25 °C). Crucially, the material demonstrates exceptional selectivity over competing Cl⁻ and NO₃⁻ ions while maintaining 87.83% efficiency after three regeneration cycles via alkaline treatment. Kinetic and thermodynamic analyses confirm chemisorption-driven uptake aligned with pseudo-second-order kinetics (R² > 0.9998) and Langmuir monolayer adsorption (7.72 mg·g⁻¹ capacity). This waste-derived magnetic composite establishes a sustainable paradigm for eutrophication control, merging selective phosphate sequestration with energy-efficient recovery for circular water treatment applications. Full article

Boron nitride nanostructures (BNNs), including nanotubes, nanosheets, and nanoribbons, are renowned for their exceptional thermal stability, chemical inertness, mechanical strength, and high surface area, making them suitable for advanced material applications. Metal–organic frameworks (MOFs), characterized by their porous crystalline structures, high surface area, and tunable porosity, have emerged as excellent candidates for gas adsorption and storage applications, particularly in the context of hydrogen. This paper explores the synthesis and properties of BNNs and MOFs, alongside the innovative approach of integrating BNNs within MOFs to create composite materials with synergistic properties. The integration of BNNs into MOFs enhances the overall thermal and chemical stability of the composite while improving hydrogen sensing and storage performance. Various synthesis methods for both BNNs and MOFs are discussed, including chemical vapor deposition, solvothermal synthesis, and in situ growth, with a focus on their scalability and reproducibility. Furthermore, the mechanisms underlying hydrogen sensing and storage are examined, including physisorption, chemisorption, charge transfer, and work function modulation. Electrochemical characterization techniques, such as cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge, are used to analyze the performance of BNN-MOF systems in hydrogen storage and sensing applications. These methods offer insights into the material’s electrochemical behavior and its potential to store hydrogen efficiently. Potential industrial applications of BNN-MOF composites are highlighted, particularly in fuel cells, hydrogen-powered vehicles, safety monitoring in hydrogen production and distribution networks, and energy storage devices. The integration of these materials can contribute significantly to the development of more efficient hydrogen energy systems. Finally, this study outlines key recommendations for future research, which include optimizing synthesis techniques, improving the hydrogen interaction mechanisms, enhancing the stability and durability of BNN-MOF composites, and performing comprehensive economic and environmental assessments. BNN-MOF composites represent a promising direction in the advancement of hydrogen sensing and storage technologies, offering significant potential to support the transition toward sustainable energy systems and hydrogen-based economies. Full article