Search Results (426)

Although concentrated solar power (CSP) coupled with calcium looping (CaL) offers a promising avenue for efficient thermal chemical energy storage, calcium-based sorbents suffer from accelerated structural degradation and decreased CO₂ capture capacity during multiple cycles. This study used Density Functional Theory (DFT) calculations to investigate the mechanism by which Mg and Ni doping improves the adsorption/desorption performance of CaO. The DFT results indicate that Mg and Ni doping can effectively reduce the formation energy of oxygen vacancies on the CaO surface. Mg–Ni co-doping exhibits a significant synergistic effect, with the formation energy of oxygen vacancies reduced to 5.072 eV. Meanwhile, the O²⁻ diffusion energy barrier in the co-doped system was reduced to 2.692 eV, significantly improving the ion transport efficiency. In terms of CO₂ adsorption, Mg and Ni co-doping enhances the interaction between surface O atoms and CO₂, increasing the adsorption energy to −1.703 eV and forming a more stable CO₃²⁻ structure. For the desorption process, Mg and Ni co-doping restructured the CaCO₃ surface structure, reducing the CO₂ desorption energy barrier to 3.922 eV and significantly promoting carbonate decomposition. This work reveals, at the molecular level, how Mg and Ni doping optimizes adsorption–desorption in calcium-based materials, providing theoretical guidance for designing high-performance sorbents. Full article

The contamination of drinking water by per- and polyfluoroalkyl substances (PFASs) presents a global concern due to their extreme persistence, driven by strong C–F bonds. This study investigated the potential of graphene as a filtration material for PFAS removal, focusing on six key compounds regulated by the U.S. EPA: PFOA, PFNA, GenX, PFBS, PFOS, and PFHxS. Using molecular simulations, adsorption energy, diffusion coefficients, and PFAS-to-graphene distances were analyzed. The results showed that adsorption strength increased with molecular weight; PFOS (500 g/mol) exhibited the strongest adsorption (−171 kcal/mol). Compounds with sulfonic acid head groups (e.g., PFOS) had stronger interactions than those with carboxylate groups (e.g., PFNA), highlighting the importance of head group chemistry. Shorter graphene-to-PFAS distances also aligned with higher adsorption energies. PFOS, for example, had the shortest distance at 8.23 Å (head) and 6.15 Å (tail) from graphene. Diffusion coefficients decreased with increasing molecular weight and carbon chain length, with lower molecules like PFBS (four carbon atoms) diffusing more rapidly than heavier ones like PFOS and PFNA. Interestingly, graphene enhanced PFAS mobility in water, likely by disrupting the water structure and lowering intermolecular resistance. These results highlight graphene’s promise as a high-performance material for PFAS removal and future water purification technologies. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

Per- and polyfluoroalkyl substances (PFASs) are synthetic chemicals widely used in industrial applications and have become persistent environmental contaminants due to their chemical stability. Water-soluble PFASs with fewer than ten carbon atoms, such as perfluorooctanoic acid (PFOA), are particularly concerning because of their high solubility in water, environmental mobility, and resistance to degradation. In this work, we present an eco-friendly Fe₃O₄ magnetic nanoparticle (MNP)-based platform for the detection and removal of PFOA from water. The synthesized iron oxide MNPs exhibit rapid and strong magnetic responsiveness, enabling efficient magnetic separation for both PFOA detection and removal. To optimize surface affinity for PFOA, we functionalized the MNPs with distinctive ligands, including polyethylene glycol (PEG), β-cyclodextrin (βCD), and dopamine (DA). Among these, PEG and DA showed notable binding affinity toward PFOA, as confirmed by infrared spectroscopy and colorimetric assays. After incubation with the functionalized MNPs followed by magnetic retrieval, we achieved over 90% PFOA removal efficiencies, demonstrating the potential for future research in PFAS remediation technologies. Importantly, the system was validated using deionized, tap, and lake water, all of which yielded comparable and promising results. This study provides a promising, eco-friendly, and recyclable nanomaterial platform for investigating the crucial role of surface chemistry in nanoparticle–PFAS interactions through ligand-mediated magnetic separation. Full article

The fundamental chemistries and electronic structures of platinum catalysts over nitrogen-doped carbon supports were examined to determine the subtle yet important roles graphitic defect-based and pyridinic defect-based nitrogen defects have in stabilizing platinum. These roles address and extend previously gathered incomplete knowledge of how combinations of graphitic defect and pyridinic defect affect the local electronic structure, leading to a greater unified understanding of platinum stability. A theoretical study was designed where different atomically sized platinum clusters were investigated over seven different nitrogen defect combinations on graphene carbon support. Differently sized platinum clusters offered parametric insights into the differences in metal–support interactions. Full article

This paper presents a comparative study examining the effects of carbon nanotubes (CNTs) and expanded graphite (EG) on the thermal, mechanical, morphological, electrical, and piezoresistive properties of poly(ethylene-co-methacrylic acid) (EMAA) nanocomposites. To this end, different amounts of carbonaceous fillers (EG and CNTs separately) were added to the EMAA thermoplastic matrix, and the relative electrical percolation thresholds (EPTs) were determined. The effect of filler concentration on thermo-oxidative degradation and the EMAA crystallinity was investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. Dynamic mechanical analysis (DMA) demonstrated that both fillers enhance the Young’s and storage moduli, as well as the glass transition temperature, with a greater improvement for the bidimensional nanofiller, most likely due to the cumulative effect of more extensive EG-matrix interactions. In tensile tests, a very relevant difference was detected in the Gauge Factor (G.F.) and the elongation at break of the two typologies of nanocomposites. The G.F. of EMAA 10% CNT and EMAA 15% EG were found to be 0.5 ± 0.08 and 165 ± 14, respectively, while elongation at break was about 68% for EMAA 10% CNT and 8% for EMAA 15% EG. Emission Scanning Electron Microscopy (FESEM) and Tunneling Atomic Force Microscopy (TUNA) have contributed to explaining the differences between EG- and CNT-based nanocomposites from a morphological point of view, underlying the pivotal role of the filler aspect ratio and its structural features in determining different mechanical and piezoresistive performance. The comprehensive analysis of EMAA-EG and EMAA-CNT nanocomposites provides a guide for selecting the best self-sensing system for the specific application. More specifically, EMAA-CNT nanocomposites with high elongation at break and lower sensitivity to small strains are suitable for movement sensors in the soft robotic field, where high deformation has to be detected. On the other hand, the high sensitivity at a low strain of EMAA-EG systems makes them suitable for integrated sensors in more rigid composite structures, such as aeronautical and automotive components or wind turbines. Full article

Hexagonal boron nitride (h-BN) and boron nitride nanotubes (BNNTs) are emerging advanced nanomaterials with analogous structures to graphene and carbon nanotubes, respectively. However, little is known about what effect replacing carbon atoms with boron and nitrogen will have on the materials’ safety profile. This study’s aim was to first identify if multi-walled nanotubes of BN could produce a hazard profile similar to that evidenced already for multi-walled carbon nanotubes (MWCNTs) and secondly if the material when present in a sheet-like structure increases or decreases the hazard profile. Fish are aquatic organisms sensitive to boron compounds; however, the potential hazard following exposure to BN and especially when present in such nanostructures has not yet been investigated. An in vitro testing platform consisting of multiple cell lines of the rainbow trout, Oncorhynchus mykiss (RTH-149, RTG-2, RTL-W1 and RTgill-W1), was used in a first-hazard screening approach for cytotoxicity and to gain information on material–cellular interaction. Clear differences were evidenced in material uptake, leading to plasma membrane disruption accompanied with a loss in metabolic activity for BNNTs at lower exposure concentrations compared to h-BN. As in the case of carbon nanotubes, close attention must be given to potential interferences with assays based on optical readouts. Full article

The current paper examines the sustainable possibility for recycling unused or expired Metoprolol (MET), a benzodiazepine derivative, as an effective corrosion inhibitor for carbon steel in saline solutions. Repurposing expired medicinal drugs aligns with green chemistry concepts and supports circular economy initiatives by reducing pharmaceutical waste and averting the production of new synthetic inhibitors. The technical benefit of recycling expired MET drugs pertains to the elimination of costs associated with organic inhibitor manufacturing and the decrease in disposal expenses for the expired medication. A combination of electrochemical techniques (potentiodynamic polarization and electrochemical impedance spectroscopy) and quantum chemical calculations was employed to evaluate the inhibitory mechanism and efficacy of MET. At a concentration of 10⁻³ M, MET reduced the corrosion current density from 19.38 to 5.97 μA cm⁻², achieving a maximum IE of 69.1%. Adsorption Gibbs free energy, determined using different adsorption isotherms, revealed that interactions between metal atoms and MET adsorbed molecules have a chemical character with a ∆G^o_ads value of −50.7 kJ·mol⁻¹. Furthermore, quantum chemistry calculations indicate that the investigated drug, owing to its molecular structure (E_HOMO = −9.12 eV, E_LUMO = 0.21 eV, µ = 3.95 D), possesses the capacity to establish an adsorption layer on the metal surface, thereby impeding the diffusion of molecules and ions involved in the overall corrosion process. The results obtained using the different techniques were in good agreement and highlighted the effectiveness of MET in the corrosion inhibition of carbon steel. Full article

Carbon nanotubes (CNTs) functionalized with metal oxides exhibit synergistic properties that enhance their performance across various applications, particularly in electrochemistry. Recent advancements have highlighted the potential of CNT–metal oxide heterostructures, with a specific focus on their electrochemical properties, which are pivotal for applications in sensors, supercapacitors, batteries, and catalytic systems. Among these, nickel oxide (NiO)-modified CNTs have garnered significant attention due to their cost-effectiveness, facile synthesis, and promising gas-sensing capabilities. This study employs quantum-chemical calculations within the framework of density functional theory (DFT) to elucidate the interaction mechanisms between CNTs and NiO. The results demonstrate that the adsorption process leads to the formation of stable CNT-NiO complexes, with detailed analysis of adsorption energies, equilibrium distances, and electronic structure modifications. The single-electron spectra and density of states (DOS) of the optimized complexes reveal significant alterations in the electronic properties, particularly the modulation of the energy gap induced by surface and edge functionalization. Furthermore, the interaction of CNT-NiO composites with acetone (C₃H₆O) and carbon dioxide (CO₂) is modeled, revealing a physisorption-dominated mechanism. The adsorption of these gases induces notable changes in the electronic properties and charge distribution within the system, underscoring the potential of CNT-NiO composites for gas-sensing applications. This investigation provides a foundational understanding of the role of metal oxide modifications in tailoring the sensory activity of CNTs toward trace amounts of diverse substances, including metal atoms, inorganic molecules, and organic compounds. The findings suggest that CNT-NiO systems can serve as highly sensitive and selective sensing elements, with potential applications in medical diagnostics and environmental monitoring, thereby advancing the development of next-generation sensor technologies. Full article

First-principles calculations were conducted to examine the impact of three sulfonamide-containing molecules (H₄N₂O₂S, CH₈N₄O₃S, and C₂H₂N₆O₄S) adsorbed on the FAPbI₃(001) perovskite surface, aiming to establish a significant positive correlation between the molecular structures and their regulatory effects on the perovskite surface. A systematic comparison was conducted to evaluate the adsorption stability of the three molecules on the two distinct surface terminations. The results show that all three molecules exhibit strong adsorption on the FAPbI₃(001) surface, with C₂H₁₂N₆O₄S demonstrating the most favorable binding stability due to its extended frameworks and multiple electron-donating/withdrawing groups. Simpler molecules lacking carbon skeletons exhibit weaker adsorption and less dependence on surface termination. Ab initio molecular dynamics simulations (AIMD) further corroborated the thermal stability of the stable adsorption configurations at elevated temperatures. Electronic structure analysis reveals that molecular adsorption significantly reconstructs the density of states (DOS) on the PbI₂-terminated surface, inducing shifts in band-edge states and enhancing energy-level coupling between molecular orbitals and surface states. In contrast, the FAI-terminated surface shows weaker interactions. Charge density difference (CDD) analysis indicates that the molecules form multiple coordination bonds (e.g., Pb–O, Pb–S, and Pb–N) with uncoordinated Pb atoms, facilitated by –SO₂–NH₂ groups. Bader charge and work function analyses indicate that the PbI₂-terminated surface exhibits more pronounced electronic coupling and interfacial charge transfer. The C₂H₁₂N₆O₄S adsorption system demonstrates the most substantial reduction in work function. Optical property calculations show a distinct red-shift in the absorption edge along both the XX and YY directions for all adsorption systems, accompanied by enhanced absorption intensity and broadened spectral range. These findings suggest that sulfonamide-containing molecules, particularly C₂H₁₂N₆O₄S with extended carbon skeletons, can effectively stabilize the perovskite interface, optimize charge transport pathways, and enhance light-harvesting performance. Full article

Direct methanol fuel cells (DMFCs) represent a promising pathway for energy conversion, yet their reliance on platinum-group metal (PGM)-based anode catalysts poses critical sustainability challenges, which stem from finite mineral reserves, environmentally detrimental extraction processes, and prohibitive lifecycle costs. Current anode catalysts for DMFCs are dominated by platinum materials; therefore, this review systematically evaluates the following three emerging eco-efficient design paradigms using platinum materials as a starting point: (1) the atomic-level optimization of low-Pt alloy surfaces to maximize catalytic efficiency per metal atom, (2) Earth-abundant transition metal compounds (e.g., nitrides and sulfides) and coordination-tunable metal–organic frameworks as viable PGM-free alternatives, and (3) mechanically robust carbon architectures with engineered topological defects that enhance catalyst stability through covalent metal–carbon interactions. Through comparative analysis with pure Pt benchmarks, we critically examine how these strategic material innovations collectively mitigate CO intermediate poisoning risks and improve electrochemical durability. Such fundamental advances in catalyst design not only address immediate technical barriers, but also establish essential material foundations for the development of DMFC technologies compatible with circular economy frameworks and United Nations Sustainable Development Goal 7 targets. Full article

Theoretical calculations were performed to explore the heterogeneous nucleation mechanism of an Mg-Al alloy inoculated by a carbon-containing substance. The valence electron structure and cohesive energy of Al₄C₃ and Al₂C₂Mg crystals were calculated using the empirical electron theory of solids and molecules (EET). The binding energy of Al1-C2 bonds in Al₄C₃ is about 140.6 kJ/mol with a lower number of equivalent bonds. Correspondingly, the binding energy of Al2-C2 bonds is about 129.6 kJ/mol, and the number of equivalent bonds is high. The weak combination of the Al1 and C2 atomic layers might lead to the breaking of Al₄C₃, and then the remaining strong skeleton of the Al2-C2 structure will facilitate the formation of Al₂C₂Mg. Based on the calculating results, the atomic interaction mechanism to account for the heterogeneous nucleation of α-Mg by C inoculation is elaborated, which also provides insights into the essence of the overheating process and the influence of Al and Mn elements on the refinement efficiency of Al₂C₂Mg. Full article

The performance of electrochemical (bio)sensors is fundamentally determined by the precise engineering of interfacial layers that govern (bio)analyte–surface interactions. However, elucidating structure–function relationships remains challenging due to the complex architecture of modern sensors and the irregular nanoscale morphology of many high-performance materials. In this study, we present a strategy for designing custom functional interfaces as well-defined platforms for probing interfacial processes. Focusing on epinephrine (EP) detection as an important representative of catecholamines, we compare the interfacial behavior of two carboxy-functionalized electrodes—grafted with either para-aminobenzoic acid (PAB) or 3,4,5-tricarboxybenzenediazonium (ATA)—against atomically flat highly oriented pyrolytic graphite (HOPG) as a control. While both modifiers introduce carboxyl groups, PAB forms disordered multilayers that inhibit surface responsiveness, whereas ATA yields an ultrathin monolayer with accessible COOH groups. Electrochemical analysis reveals that ATA-HOPG significantly enhances EP detection at sub-micromolar levels, facilitated by electrostatic interactions between surface-bound COO⁻ and protonated EP and its redox products. These results demonstrate that nanoscale control of diazonium grafting is crucial for optimizing bioanalyte recognition. More broadly, this work highlights how molecular-level surface engineering on high-quality carbon substrates can serve as a test-bed platform for the rational design of advanced electrochemical sensing interfaces. Full article

The rational development of single-atom catalysts (SACs) for selective formic acid dehydrogenation (FAD) requires an atomic-scale understanding of metal–support interactions and electronic modulation. In this study, spin-polarized density functional theory (DFT) calculations were performed to systematically examine platinum-group SACs anchored on graphitic carbon nitride (g-C₃N₄). The findings reveal that Pd and Au SACs exhibit superior selectivity toward the dehydrogenation pathway, lowering the free energy barrier by 1.42 eV and 1.39 eV, respectively, compared to the competing dehydration route. Conversely, Rh SACs demonstrate limited selectivity due to nearly equivalent energy barriers for both reaction pathways. Stability assessments indicate robust metal–support interactions driven by d–p orbital hybridization, while a linear correlation is established between the d-band center position relative to the Fermi level and catalytic selectivity. Additionally, charge transfer (ranging from 0.029 to 0.467 e) substantially modulates the electronic structure of the active sites. These insights define a key electronic descriptor for SAC design and offer a mechanistic framework for optimizing selective hydrogen production. Full article

This paper reports several preliminary investigations concerning the relative humidity (RH) detection response of a chemiresistive sensor that uses a novel sensing layer based on pristine carbon nano-onions (CNOs) and polyvinyl alcohol (PVA) at a 1/1 and 2/1 w/w ratio. The sensing device, including a Si/SiO₂ substrate and gold electrodes, is obtained by depositing the CNOs–PVA aqueous suspension on the sensing structure by drop casting. The composition and morphology of the sensing film are explored by means of scanning electron microscopy, Raman spectroscopy, atomic force microscopy, and X-ray diffraction. The manufactured sensor’s room temperature RH detection performance is examined by applying a continuous flow of the electric current between the interdigitated electrodes and measuring the voltage as the RH varies from 5% to 95%. For RH below 82% (sensing layer based on CNOs–PVA at 1/1 w/w ratio) or below 50.5% (sensing layer based on CNOs–PVA at 2/1 w/w ratio), the resistance varies linearly with RH, with a moderate slope. The newly developed sensor, using CNOs–PVA at a 1:1 ratio (w/w), responded as well as or better than the reference sensor. At the same time, the recorded recovery time was about 30 s, which is half the recovery time of the reference sensor. Additionally, the changes in resistance (ΔR/ΔRH) for different humidity levels showed that the CNOs–PVA layer at 1:1 was more sensitive at humidity levels above 80%. The main RH sensing mechanisms considered and discussed are the decrease in the hole concentration in the CNOs during the interaction with an electron donor molecule, such as water, and the swelling of the hydrophilic PVA. The experimental RH detection data are analyzed and compared with the RH sensing results reported in previously published work on RH detectors employing sensing layers based on oxidized carbon nanohorns–polyvinylpirrolidone (PVP), oxidized carbon nanohorns–PVA and CNOs–polyvinylpyrrolidone. Full article