Search Results (3,368)

Global energy de-fossilization requires scalable solutions for extended energy storage and industrial emission reduction. Synthesizing green methane via Power-to-Gas technology offers a viable pathway to store renewable electricity while utilizing captured carbon dioxide. This review evaluates recent advancements in catalytic mechanisms, reactor engineering, artificial intelligence applications, and techno-economic and life cycle assessments of green methane production systems. Analysis shows that advanced reactor configurations effectively manage the exothermic heat of the Sabatier reaction. Furthermore, integrating machine learning algorithms accelerates catalyst discovery and enables dynamic process control under fluctuating renewable energy loads. Economic and environmental assessments indicate that the sustainability of green methane depends strictly on utilizing renewable electricity and sourcing non-fossil carbon. Commercial deployment must focus on improving catalyst stability during transient operations and implementing digital twins to establish green methane as a sustainable carbon backbone for chemical industries. Full article

The continuous increase in atmospheric CO₂ concentration exacerbates global climate change, making carbon reduction an urgent global priority. Carbonic anhydrase (CA), a highly efficient biocatalyst that converts CO₂ into bicarbonate, demonstrates significant potential for carbon capture and resource utilization. However, the stability and catalytic efficiency of native CA in industrial environments are limited, particularly its poor thermal tolerance under flue gas conditions and its sensitivity to impurities, hindering its direct large-scale application. This review systematically summarizes recent advances in modifying microbial CA through protein engineering (e.g., directed evolution, rational design) and immobilization techniques, which have markedly enhanced its thermal stability, adaptability, and reusability. Among these, the integration of machine learning with high-throughput experimentation has emerged as a transformative strategy for CA engineering. Furthermore, we outline CA-driven pathways for CO₂ conversion into high-value chemicals and bioenergy. Finally, future prospects are discussed, including interdisciplinary integration, computational modeling coupled with experimental validation, and comprehensive life-cycle and techno-economic assessments, to facilitate the scaled application of engineered microbial CA in carbon neutrality pathways. Collectively, this review highlights the critical role of engineered CA in bridging biocatalysis with industrial carbon management, offering a viable and sustainable pathway toward carbon neutrality. Full article

The performance and mechanism of heterogeneous catalytic reactions are fundamentally governed by the formation, stability, and reactivity of transient surface intermediates. These species—such as isocyanates, alkyl groups, carboxylates, formates, carbonates, alkoxy and acyl intermediates—often exist at low concentrations and with short lifetimes, making their identification challenging. This review summarizes the current knowledge on the formation, spectroscopic identification, and thermal behavior of these intermediates on metal single crystals, metal nanoparticles, and oxide-supported catalysts. Emphasis is placed on key reactions including CO and NO oxidation–reduction, CO and CO₂ hydrogenation, Fischer–Tropsch-related pathways, and reforming of ethanol. Advanced surface-sensitive techniques (TDS, XPS, UPS, IR, HREELS) are highlighted for their role in elucidating intermediate structures and reaction pathways. The isocyanate surface complex is an existing intermediate in NO reduction with CO, and NCO is responsible for NH₃ formation. Alkyl groups can be prepared from thermal- or photo-induced dissociation of alkyl halogenide. Oxygen-containing intermediates relevant to CO₂ hydrogenation are addressed, with particular attention to formate, carboxylate, and related species. M/CeO₂ (M = Pt, Rh, Ir, Ru) seems to be the best catalyst for hydrogen production from ethanol reforming. The nature of support may affect hydrogen production. The review also discusses how metal–support interactions, particle size, and surface morphology influence intermediate stability and catalytic selectivity. Overall, the work provides a comprehensive framework for understanding how transient surface complexes control technologically important catalytic transformations. Full article

To address the emerging multidrug-resistance crisis caused by Klebsiella pneumoniae, we expressed the endolysin Lys59 derived from phage VB_KpP_HS106 and performed a comprehensive analysis of its antibacterial activity and structural features. Molecular modeling revealed that Lys59 carries a highly positively charged N-terminus and an amphipathic helix at the C-terminus. In vitro antibacterial assays showed that Lys59 exhibited significant bactericidal activity against K. pneumoniae with an approximately 4 log reduction at 50 µg/mL in 2 h. Meanwhile, Lys59 exhibited potent, broad-spectrum activity against both Gram-negative and Gram-positive bacteria. Stability analysis indicated that Lys59 retained high activity over a pH range of 3–9 and a temperature range of 4–55 °C. Notably, the antibacterial activity of Lys59 was found to be regulated by metal ions. Molecular docking indicated that K⁺ can enhance binding stability by interacting with ASN35 and VAL57. In contrast, Mg²⁺ and Ca²⁺ suppressed catalytic function by binding to the essential GLU17 residue. Furthermore, treatment with 200 µg/mL of Lys59 resulted in a 44.6% reduction in K. pneumoniae biofilm biomass. Overall, this study identified a phage-derived endolysin with broad-spectrum antimicrobial activity and demonstrated its potential as an antibacterial agent against multidrug-resistant K. pneumoniae. Full article

To address the critical challenges of sluggish C-C coupling kinetics and the propensity for over hydrogenation to ethane (C₂H₆) in the photocatalytic CO₂ reduction to ethylene (C₂H₄), this study designed a synergistic bimetallic Pt/Co cluster catalyst supported on a covalent organic framework (COF), designated as PtCo-TpBD COF. This catalyst is designed to modulate the adsorption of key intermediates via Co clusters to suppress over-hydrogenation, while leveraging Pt clusters to promote C-C coupling, thereby achieving highly selective C₂H₄ production. Through a series of structural characterization analyses, it was confirmed that Pt/Co clusters were successfully confined within the pores of the COF, and significant electronic interactions were observed. In situ infrared spectroscopy revealed that the introduction of Co clusters effectively weakens the adsorption strength of the CO* intermediate, while the incorporation of Pt clusters promotes C-C coupling. In visible-light-driven gas-phase CO₂ reduction, this catalyst delivered exceptional activity, reaching an C₂H₄ formation rate of 7.54 μmol g⁻¹ h⁻¹ and an C₂H₄ selectivity of 90.1%, along with remarkable inhibition of deep hydrogenation byproducts including C₂H₆. This study not only provides a successful example for constructing efficient bifunctional photocatalysts to achieve highly selective conversion of CO₂ to C₂H₄, but also highlights the great potential of COFs as advanced platforms for integrating multifunctional metal clusters and precisely tuning catalytic selectivity. Full article

A novel citric acid-assisted in situ reduction method has been developed for the synthesis of bimetallic AuPd alloy nanoparticles supported on amine–phosphate-functionalized carbon nanotubes (AuPd/NH₂-P-CNTs). In this strategy, formic acid acts not only as the reducing agent for reducing metal precursors, but also as the hydrogen source for the subsequent catalytic dehydrogenation. The introduction of citric acid significantly accelerates the reduction kinetics and promotes the uniform formation of ultrafine AuPd nanoparticles (∼1.8 nm). As a result, the optimized Au_0.5Pd_0.5/NH₂-P-CNTs exhibit an extraordinary catalytic activity and 100% H₂ selectivity during hydrogen generation from FA with sodium formate as an additive, affording a remarkable initial turnover frequency of 5663.94 mol H₂ mol Pd⁻¹ h⁻¹ at 303 K. The experimental results reveal that the -NH₂ and -P functional groups on the support are crucial for stabilizing and uniformly dispersing the alloy nanoparticles. Furthermore, the enhanced reaction rate can be attributed to the strong metal–support interaction established between AuPd nanoparticles and -NH₂-P-CNT supports. This work provides a new perspective on the design of highly efficient Pd-based catalysts for hydrogen production from formic acid. Full article

Background: PIK3CA-related overgrowth spectrum (PROS) comprises a heterogeneous group of mosaic disorders caused by activating variants in the PIK3CA gene, resulting in dysregulation of the PI3K/AKT/mTOR signaling pathway and abnormal tissue overgrowth. Targeted inhibition of this pathway has recently emerged as a promising therapeutic strategy. Methods: We conducted a literature review to identify published reports describing patients with PROS treated with alpelisib, a selective inhibitor of the p110α catalytic subunit of PI3K. Data regarding patient characteristics, genetic variants, treatment regimens, clinical outcomes, radiological response, and adverse events were extracted and analyzed. Results: Seventeen publications met the inclusion criteria, comprising a total of 114 patients treated with alpelisib. The majority of patients were pediatric (68.4%), with a median age at treatment initiation of 12 years. Clinical manifestations were heterogeneous and included segmental overgrowth, vascular malformations, and soft-tissue hypertrophy. Clinical improvement in at least one disease manifestation was reported in 111 patients (97.3%). Radiological response, defined as reduction ≥20% in lesion volume, was documented in 26 of 60 evaluable cases (47.3%). Adverse events were reported in 64 patients (56.1%) and were generally mild and manageable, with hyperglycemia and diarrhea being the most common. Conclusions: Available real-world evidence suggests that alpelisib provides meaningful clinical benefit across multiple PROS phenotypes, with an acceptable safety profile. However, current data remain limited by small cohort sizes, heterogeneous outcome reporting, and variable follow-up duration. Prospective studies with standardized outcome measures are needed to better define long-term efficacy and safety of PI3K inhibition in PROS. Full article

Molten salt chlorination is a key industrial route for producing titanium tetrachloride (TiCl₄), yet the atomistic catalytic role of iron (Fe) in the carbothermic chlorination of titanium oxides remains unclear. Here, the chlorination behavior of the NaCl–C–Cl₂–FeTiO₃ system was investigated by combining thermodynamic calculations with Ab Initio Molecular Dynamics (AIMD) and Deep Potential Molecular Dynamics (DPMD) simulations. AIMD results show that carbon adjacent to Fe exhibits enhanced reactivity, and that Fe-C synergistic electron transfer promotes both titanium oxide reduction and subsequent titanium chlorination. DPMD results further reveal that Fe not only accelerates these transformations, but also improves interfacial contact among carbon, titanium oxides, and molten salt, thereby enhancing mass transfer and shortening the formation time of TiCl₄. Temperature-dependent analysis indicates that Fe-C and C-O coordination numbers remain high near 1073 K, where TiCl₄ formation is efficient and relatively stable. Although increasing temperature can further enhance diffusion, its effect on reaction acceleration is limited, while excessively high temperatures weaken Fe-C interactions and reduce catalytic efficiency. These findings clarify the catalytic mechanism of Fe in molten salt chlorination at the atomic scale and provide theoretical support for process optimization. Full article

Background/Objectives: Ribosome-inactivating proteins (RIPs) are plant-derived enzymes with potent cytotoxic activity, widely studied as anticancer agents, particularly as toxic payloads in immunoconjugates. Despite numerous encouraging results reported, their clinical application has been limited by their immunogenicity. RIPs from edible plants have been proposed as potentially more suitable candidates due to their possible improved tolerability. However, this aspect still requires validation in vivo in animal models. This study investigated the cytotoxic activity, mechanisms of action and translational potential of sodin 5 (a recently characterized type 1 RIP derived from the edible plant Salsola soda L.) in human colon cancer models, comparing it to the well-known type 1 RIP saporin-S6. Methods: The effects of sodin 5 and saporin-S6 on cell viability, cell death mechanisms and epithelial barrier integrity were assessed on HT29 and Caco-2 cell lines. Sodin 5 cross-reactivity with other anti-type 1 RIP sera was evaluated by ELISA. Finally, its structural characteristics were analyzed. Results: Sodin 5 showed a cytotoxic effect comparable to that of saporin-S6 in HT29 and Caco-2 colon cancer cells, with time- and concentration-dependent reductions in viability. Both type 1 RIPs disrupted the integrity of the intestinal epithelial barrier in mono- and co-culture models and predominantly activated the apoptotic pathway, without inducing necrosis. Sodin 5 exhibited limited immunological cross-reactivity and a conserved catalytic core, supporting its potential relevance as a therapeutic payload for intestinal cancer therapy. Conclusions: Our results indicate that sodin 5 possesses promising characteristics for anticancer applications, particularly in the treatment of intestinal malignancies, where local exposure and repeated administration are often required. Full article

Ventilation air methane (VAM) has an extremely low concentration, making its abatement exceptionally challenging. Catalytic oxidation offers a promising route for VAM treatment, but industrial application requires integrated catalysts with high activity and efficient mass transfer. In this study, a novel straight-channel NiO/CeO₂ ceramic reactor was fabricated via mesh-assisted phase inversion, with NiO content systematically optimized to screen the optimal ratio. The 60 wt% NiO was the optimal composition, exhibiting excellent VAM oxidation performance. Brunauer–Emmett–Teller (BET) analysis confirmed that this optimal ratio yielded the largest specific surface area. Furthermore, H₂-temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) confirmed that this optimal ratio facilitated the formation of abundant NiO–CeO₂ active interfaces, effectively inducing surface Ce³⁺ species and oxygen vacancies. These merits significantly enhanced the reactor’s oxygen adsorption capacity and redox properties, thus realizing efficient methane activation in catalytic oxidation. Moreover, the optimal reactor successfully passed 10 thermal cycle tests, further verifying the thermal stability of the catalytic structure. In addition, it exhibited outstanding long-term stability during a 100 h test, with no carbon deposition or active phase sintering observed. This work develops an optimized straight-channel NiO/CeO₂ ceramic reactor and offers a practical and scalable design strategy for VAM oxidation. Full article

Developing an ultrasensitive electrochemiluminescence (ECL) detection platform remains challenging due to the limited enrichment efficiency of ECL emitters and co-reactants at the electrode interface, as well as the insufficient catalytic enhancement of co-reactant conversion. Moreover, simultaneous in situ analyte enrichment and efficient anti-interference capability are often difficult to achieve in a single sensing interface. Herein, a new ECL platform was developed based on nanocatalyst-supported nanochannel-confined surfactant micelle (SM) system, which integrates an enhanced luminol-dissolved oxygen (DO) ECL response for the ultrasensitive detection of antibiotic rifampicin (RIF). A nanocomposite comprising nitrogen-doped graphene quantum dots and a molybdenum disulfide nanosheet (NGQDs@MoS₂) was modified on an indium tin oxide (ITO) electrode. This nanocomposite layer catalyzed the oxygen reduction reaction (ORR), boosting the co-reactant efficiency of DO. Vertically ordered mesoporous silica film filled with surfactant micelles (SM@VMSF) was subsequently grown in situ on the NGQDs@MoS₂ surface. The hydrophobic micelles enable the simultaneous enrichment of luminol, DO, and RIF. Integrating the triple-enrichment effect of surfactant micelles with the high electrocatalytic effect of NGQDs@MoS₂ nanocomposite results in significant ECL enhancement of the luminol–DO. SM@VMSF also provides an excellent molecular sieving effect, endowing the sensor with high anti-interference capability and stability. RIF quenches the ECL signal by consuming superoxide anion radicals, enabling sensitive detection. Detection of RIF was established with a high sensitivity (2927 a.u. per nM) wide linear range (10 pM to 10 μM) and a low limit of detection (LOD, 2.5 pM). The fabricated sensor exhibits good selectivity and high fabrication reproducibility (relative standard deviation, RSD, of 1.9%). Additionally, the determination of RIF in eye drops and seawater samples was realized. This work offers new insights for the design of high-performance ECL sensing interfaces and sensitive detection of RIF. Full article

Aryl halides are important intermediates for chemical synthesis. However, the negative reduction potential up to −2.7 V (vs. SCE) makes photoredox conversion of aryl halides by reductive dehalogenation to aryl radicals for chemical transformations difficult. Inspired by the outstanding photophysical properties of deazaflavin and triphenylamine, as well as results of theoretical calculations, we attached the diphenylamino group to C8 of deazaflavin, and the resulting compounds look fabricated by “fusing” deazaflavin and triphenylamine (TPA) together by sharing the benzene ring. We also introduced alkyl and aryl moieties to C5 and afforded a series of deazaflavin derivatives (dFLs), namely 10-butyl-8-(diphenylamino)-3,5-dimethylpyrimido[4,5b]quinoline-2,4(3H,10H)-dione (TPAdFlMe), 10-butyl-8-(diphenylamino)-3-methyl-5-(trifluoromethyl)pyrimido[4,5-b]quinoline-2,4(3H,10H)-dione(TPAdFlTF) and 10-butyl-8-(diphenylamino)-3-methyl-5-phenylpyrimido[4,5-b]quinoline-2,4(3H,10H)-dione (TPAdFlPh), and investigated their photophysical properties and performance as sensitizers in the photodehalogenation of aryl halides. We showed that the photophysical properties are significantly improved in these dFLs. The absorption bands of dFLs are redshifted and the absorbance is more than double that of riboflavin tetraacetate (RFTA). The singlet oxygen quantum yields of TPAdFlMe, TPAdFlTF and TPAdFlPh are 0.42, 0.25 and 0.39, respectively, and the corresponding redox potentials are −1.75, −0.75 and −1.71 V vs. Ag/Ag⁺, respectively, comparable to known deazaflavin-based sensitizers. Originating from these properties, TPAdFlMe and TPAdFlPh are capable of sensitizing the full photodehalogenation of 0.038 mmol p-iodoanisole, and the yields of the photodehalogenation of 0.038 mmol p-bromoanisole are 67 and 69%, respectively. They also demonstrate exceptional performance in the photodehalogenation of halides of polycyclic aromatics with yields in the range of 73% for 1-benzhydryl-3-bromobenzene to 100% for 1-bromonapthalene in 18 h runs. The performance of TPAdFlMe and TPAdFlPh in photodehalogenation are already comparable to recently reported deazaflavin-based sensitizers, and we propose the transformation would proceed though the consecutive photo-induced electron transfer (conPET) mechanism with consecutive excitation of charged deazaflavin-based radicals under light irradiation as the key step to generating the aryl radicals, and the vital role of sensitizer-based radicals is further confirmed by mechanistic investigations. We expect the findings will help to design novel flavin-based triplet sensitizers for photoredox catalytic organic transformations. Full article

A ternary CdS–MoS₂–rGO photocathode was developed to enhance visible light-driven hydrogen evolution through interfacial heterostructure engineering. The composite was fabricated via a solution-based deposition method followed by thermal conversion, resulting in crystalline CdS and MoS₂ phases that were uniformly integrated within a conductive reduced graphene oxide (rGO) framework. Structural and surface analyses (XRD and XPS) confirmed the coexistence of Cd²⁺, Mo⁴⁺, and S²⁻ chemical states without detectable secondary phases. Photoelectrochemical measurements revealed that the ternary architecture significantly improves charge separation efficiency and interfacial charge-transfer kinetics compared to binary and single-component films. The CdS–MoS₂–rGO photocathode exhibited the highest photocurrent density, reduced charge-transfer resistance, and favorable Tafel slope under visible-light irradiation (0.25 sun, neutral electrolyte). Gas chromatography measurements verified that these electrochemical enhancements translate into increased hydrogen production rates, following the trend: CdS–MoS₂–rGO > CdS–rGO > MoS₂–rGO >> rGO. Applied bias photon-to-current efficiency (ABPE) analysis further confirmed improved photon utilization efficiency in the ternary system. The enhanced performance is attributed to synergistic integration of CdS (light harvesting), rGO (rapid electron transport), and MoS₂ (catalytic edge sites), which suppresses recombination and accelerates proton reduction kinetics. These findings demonstrate that rational multi-component heterostructure design is an effective strategy for improving hydrogen evolution rate under mild operating conditions. Full article

Monolithic ceramic catalysts are a key technology for the industrial treatment of coal mine ventilation air methane (VAM). The preparation of straight-channel NiO/CeO₂ monolithic ceramic catalysts via phase inversion addresses critical bottlenecks for industrial VAM abatement. However, high-temperature sintering leads to irreversible NiO agglomeration and coarsening, severely reducing catalytic activity. In this study, an in situ reduction–oxidation reconstruction method is developed to regenerate sinter-degraded NiO. The reconstructed catalyst increases methane conversion from below 70% after sintering to over 95% at 550 °C and achieves full conversion at 600 °C. The catalyst maintains near 100% conversion during 400 h of continuous operation at 600 °C and shows no performance degradation over 15 thermal cycles. Moreover, the reconstructed catalyst exhibits excellent steam tolerance with fully reversible deactivation. The reconstructed catalyst presents a refined porous structure with BET surface area rising from 4.5 to 11.4 m² g⁻¹, an elevated Ni³⁺/Ni²⁺ ratio (1.47 to 1.97), a higher surface adsorbed oxygen proportion (36.8% to 48.7%) and significantly strengthened NiO-CeO₂ interfacial interaction. This work provides a facile and efficient in situ regeneration strategy, greatly enhancing the VAM oxidation activity and stability of sinter-degraded monolithic ceramic catalysts. Full article

The efficient on-demand generation of ClO₂ is critical for disinfection and food preservation. However, the development of safe and efficient strategies for gaseous ClO₂ production remains challenging. Herein, we report a stable and efficient electrochemical system for ClO₂ production based on rutile TiO₂ nanorod arrays (TiO₂ NAs). Electrochemical optimization suggests that a cathodic potential of −0.10 V (vs. Ag/AgCl) in an electrolyte solution of 1 M NaClO₃ with 5 M H₂SO₄ achieves the highest ClO₂ production efficiency. Mechanistic studies reveal that ClO₂ generation proceeds via an O₂-induced pathway, in which electrochemically generated H₂O₂ from 2-e⁻ O₂ reduction reacts in situ with ClO₃⁻ to form ClO₂, eliminating the need for external H₂O₂ storage and significantly improving operational safety. Furthermore, when decorated with RuO_x nanoparticles, TiO₂ NA cathodes achieve enhanced catalytic performance and excellent stability. In addition, the generated ClO₂ in the electrolyte solution can be delivered via gas pumping. This ClO₂ atmosphere exhibits antibacterial efficiencies exceeding 99% against Escherichia coli and Staphylococcus aureus, and significantly reduced weight loss and preserved fruit hardness in longan samples during 8 days of storage. Overall, this work presents a safe, efficient approach for ClO₂ generation with strong potential for practical disinfection in the food preservation field. Full article