Search Results (753)

The efficient photocatalytic generation of hydrogen peroxide (H₂O₂) from pure water remains a formidable challenge, primarily due to the rapid recombination of photogenerated electron–hole pairs and insufficient redox potentials inherent in single-component photocatalysts. To address these issues, we designed and synthesized a heterojunction material comprising cadmium sulfide nanoparticles loaded on carbon spheres (CS@CdS). Under conditions utilizing pure water and ambient air, the CS@CdS composite achieves an H₂O₂ production rate of 1305 μmol·g⁻¹·h⁻¹, which is 3.1 and 3.6 times higher than that of pure CdS and CS, respectively, without the need for any sacrificial agents or external oxygen supply. Systematic characterization reveals that CS and CdS form a tightly coupled electronic interface, which significantly accelerates charge carrier separation and effectively prolongs the lifetime of photogenerated carriers, thereby boosting photocatalytic performance. Furthermore, the CS component extends the visible-light absorption range of the composite and functions as an electron acceptor to suppress charge recombination, collectively endowing CS@CdS with enhanced photocatalytic activity. Mechanistic studies indicate that H₂O₂ production over CS@CdS proceeds predominantly via a two-step single-electron oxygen reduction reaction (ORR) pathway. This work offers a viable strategy for constructing CS-based heterojunction photocatalysts for efficient H₂O₂ synthesis. Full article

Solid-contact ion-selective electrodes (SC-ISEs) are typically constructed using ion-selective membrane (ISM)-based configurations. However, such structures often suffer from water-layer formation and the weak mechanical stability of the ISM. Herein, we report an ISM-free K⁺-SC-ISE based on a Prussian blue analogue transducer, KMnFe(CN)₆, eliminating the need for a conventional ionophore-based ISM layer. KMnFe(CN)₆ was synthesized via a one-step citrate-assisted co-precipitation method. The material functions as a bifunctional transducer, in which the open framework structure with ion-transport channels enables selective K⁺ recognition, while the redox-active Mn centers facilitate ion-to-electron transduction. The fabricated KMnFe(CN)₆-based K⁺ sensor exhibits a near-Nernstian response with a sensitivity of 52.3 ± 1.0 mV dec⁻¹ and a rapid response time of 25 s. The linear range and limit of detection were determined to 10⁻⁴ to 10⁻¹ M and 5.8 × 10⁻⁵ M, respectively. The sensor also demonstrates selectivity to representative interfering ions, with log K_ij of −2.39 ± 0.12 (Na⁺), −2.86 ± 0.09 (Li⁺), −3.06 ± 0.09 (Ca²⁺), −2.74 ± 0.12 (Mg²⁺) and −0.95 ± 0.08 (NH₄⁺). By eliminating the ISM layer, the water-layer effect is effectively avoided, resulting in excellent long-term stability with a potential drift of 57.2 ± 6.1 μV h⁻¹ over 7 days. The sensor was further applied to the analysis of K⁺ in real lake water samples, where the measured concentration showed good agreement with ion chromatography results. This work provides an ISM-free SC-ISE strategy for ion analysis in water environments. Full article

In this study, an electrochemical sensor based on magnesium zirconate (MgZrO₃) synthesized using a deep eutectic solvent (DES)-assisted approach was developed for the detection of dopamine. The structural and morphological properties of MgZrO₃ were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy, energy-dispersive spectroscopy, and elemental mapping. The electrochemical performance of the MgZrO₃-modified glassy carbon electrode (GCE) was evaluated using cyclic voltammetry and differential pulse voltammetry. The MgZrO₃/GCE exhibited an enhanced redox response and a reduced oxidation potential for dopamine in phosphate-buffered solution (PBS, pH 7.0), indicating improved electrocatalytic activity compared to the bare electrode. This improvement is attributed to the material’s increased active surface area and facilitated charge transfer kinetics. Under optimized conditions, the sensor showed a linear response over a concentration range of 0.3–80 µM, with a detection limit of 127 nM and quantification limit of 423 nM. The MgZrO₃/GCE also demonstrated good selectivity in the presence of common interfering species and was successfully applied for dopamine detection in biological samples, with satisfactory recovery results. The findings presented here contribute to the growing body of knowledge in the field and open up new possibilities for the development of advanced electrochemical sensors for neurotransmitter detection in clinical and research settings related to Breast Cancer Treatment. Full article

The CO₂ storage–regeneration (CO₂-SR) process represents a promising strategy for integrating CO₂ capture and catalytic conversion within a single cyclic operation using multifunctional catalysts. In this concept, CO₂ is first stored on basic sites and subsequently converted through methane activation, enabling the coupling of CO₂ capture and reforming reactions in a single reactor. In this work, a series of unsupported Ni–Ba catalysts were investigated as model multifunctional materials for the CO₂-SR process. Catalysts with different Ni/Ba ratios were prepared to analyze how the distribution of storage and catalytic sites influences the cyclic CO₂ capture–conversion behavior. In addition, Rh was introduced as a promoter either during synthesis by co-precipitation or ex situ by impregnation, allowing to evaluate the influence of Rh location and surface enrichment on the catalytic properties. Rh incorporation in the NiBa catalyst (Ni/Ba = 10/1 and Ni/Rh = 100/1) increased the specific surface area (BET area 64 m²·g⁻¹ vs. 55 m²·g⁻¹ for NiBa) and reduced the NiO crystallite size from 250.4 Å to 231.5 Å, indicating improved dispersion of the metallic phase. XPS analysis revealed the coexistence of Rh⁰ and Rh³⁺ species, suggesting that Rh acts as a redox mediator that facilitates hydrogen activation and promotes hydrogen spillover to neighboring Ni sites. Raman and CO₂-TPD results show that Ba-derived domains stabilize carbonate species responsible for CO₂ storage, while Rh enhances catalyst reducibility and modifies the kinetics of carbonate decomposition during the regeneration stage. Transient CO₂–CH₄ pulse experiments demonstrate that the CO₂-SR process proceeds through a dynamic surface cycle involving reversible carbonate formation on Ba-derived basic sites coupled with methane activation on Ni-containing interfacial sites. The results indicate that catalyst performance is governed by a hierarchical surface architecture composed of Ni–O–Ba interfacial domains, reversible Ba–O–Ba carbonate storage sites, and more stable Ba-rich domains. The distribution of these domains, controlled by the Ni/Ba ratio and the dispersion of the metallic phase, determines the reversibility of carbonate formation and the efficiency of the cyclic CO₂ storage–regeneration process. Full article

Organic redox-active molecules are promising catholyte materials for aqueous organic redox flow batteries (AORFBs), yet they often suffer from low solubility and poor cycling stability. Herein, we report a series of water-soluble phenothiazine derivatives functionalized with quaternary ammonium groups. The optimized compound, N,N,N-trimethyl-1-(10H-phenothiazin-10-yl) propan-2-aminium chloride (TMiPrPTCl), exhibits exceptional solubility (2.69 M in water) and a high redox potential (0.902 V vs. SHE). A comparative study of four derivatives reveals that side-chain length and branching critically modulate both solubility and degradation pathways: while three-carbon-linked analogs N,N,N-trimethyl-3-(10H-phenothiazin-10-yl)propan-1-aminium chloride (TMPrPTCl) degrade primarily via irreversible oxidation to sulfoxide, two-carbon-linked species (TMiPrPTCl) undergo additional side-chain cleavage, leading to rapid capacity fade. Although the quaternization strategy successfully achieves record solubility, the electrochemical stability remains a key challenge. Post-cycling analysis confirms the loss of redox activity and the formation of inert products. This work highlights the delicate balance between solubility enhancement and molecular stability, providing clear design guidelines for future phenothiazine-based catholytes. Full article

An effective strategy for significantly enhancing photocatalytic activity of composite materials is to construct heterojunctions. Herein, a series of imidazole-modified heterostructured g-C₃N₄/SnO (CNIS) Z-scheme photocatalysts were prepared by calcination methods, leading to superior photocatalytic performance than pure SnO and imidazole-modified g-C₃N₄. Rhodamine B (Rh B) aqueous solution was taken as the target pollutant, and the result presented that both imidazole modification and the Z-scheme heterojunction construction benefited from significant enhancement in photocatalytic activity. Moreover, it is revealed that electrons were transferred from imidazole-modified g-C₃N₄ to SnO through the interface of the composite by XPS analysis. Under visible light (>420 nm) irradiation, the built-in electric field, band edge bending, and Coulomb interaction work synergistically to drive the recombination of relatively useless electrons and holes in the hybrid. As a result, the residual electrons and holes, which possess enhanced reducibility and oxidizability, endow the composite with exceptional redox capability. This research can not only deepen our comprehension of designing and fabricating innovative Z-scheme heterojunction photocatalysts but also presents an effective approach to tackle environmental pollution issues in the future. Full article

Aqueous organic flow batteries are a promising technology for large-scale energy storage, owing to their safety, low cost, and tunable molecular properties. Battery performance is critically governed by the redox potential, solubility, and stability of organic active species, making molecular design a central research priority. Yet, many current systems still rely on inorganic metal-based materials, which face challenges such as high cost and sluggish kinetics. This review outlines a systematic molecular-engineering framework for designing novel redox species, offering strategies to tailor solubility, redox potential, and molecular size in both organic compounds. Recent advances in mechanistic insight, functionalization, and structure-dependent electrochemical performance are summarized. Computational chemistry and machine learning are highlighted for accelerating high-throughput screening and property prediction, speeding up molecular optimization. Small molecules (1–4 rings), including quinones (C=O), alloxazines, phenazines, and indigo derivatives, which undergo reversible redox reactions involving nitrogen and/or carbonyl groups, have been explored as anolytes and/or catholytes in aqueous redox flow batteries. Key challenges remain, including limited electrochemical stability windows, insufficient solubility, and poor molecular stability, leading to low energy density and cycling degradation. Improving anolyte performance by simultaneously lowering redox potential and enhancing solubility and stability is therefore crucial for advancing both organic and broader redox-active battery systems. Computational and machine learning approaches for identifying and refining electrolyte molecules are also addressed, enabling efficient screening and molecular modification toward high-performance flow batteries. Full article

The development of high-performance and sustainable carbon electrodes is increasingly important for next-generation supercapacitors, yet controlling heteroatom doping and hierarchical pore evolution in biomass-derived carbons remains a key challenge. Lignin, as an abundant aromatic biopolymer, offers a structurally rich platform for designing functional carbons, but its rigid cross-linked architecture limits precise pore regulation and efficient nitrogen incorporation. In this work, nitrogen-doped hierarchical porous carbons were engineered from enzymatically treated lignin through a synergistic urea-assisted nitrogen doping and KOH activation strategy. The urea–KOH co-activation drives the coordinated evolution of micropores and mesopores. This approach yields an optimized carbon material possessing a high BET surface area of 2569 m² g⁻¹, an interconnected micro–mesoporous architecture, and a favorable distribution of pyridinic, pyrrolic, and graphitic nitrogen species. The engineered pore hierarchy is correlated with enhanced ion transport kinetics, as evidenced by a high b value of 0.99 and a capacitive contribution of 98.5% at 100 mV s⁻¹; nitrogen functionalities introduce redox-active sites and improve interfacial wettability. As a result, the selected material delivers a high specific capacitance of 221 F g⁻¹ at 0.5 A g⁻¹, strong rate capability with 84.4% retention at 20 A g⁻¹, and excellent cycling durability with 90.7% capacitance retention after 50,000 cycles. This study demonstrates a potentially mechanistically informed, scalable pathway for coupling enzymatic structural regulation with chemical activation, offering a sustainable route for transforming lignin into high-value carbon electrodes suitable for advanced supercapacitor applications. Full article

Nano–bio hybrid catalysts have emerged as a promising platform for sustainable energy conversion by integrating the high selectivity of enzymes with the structural robustness and conductivity of nanomaterials. In recent years, the growing demand for clean energy technologies has driven the development of biohybrid systems capable of efficient electron transfer, enhanced catalytic activity, and improved operational stability. This review comprehensively discusses the design principles, mechanistic foundations, and performance metrics of enzyme–nanomaterial interfaces for energy-related applications. We first outline the fundamentals of enzymatic redox catalysis and the limitations of free enzymes in practical systems. Subsequently, we examine the functional roles of nanomaterials including carbon-based materials, metal and metal oxide nanoparticles, and two-dimensional platforms such as MXenes in facilitating enzyme immobilization and promoting direct or mediated electron transfer. Special emphasis is placed on engineering strategies at the bio–nano interface, including immobilization techniques, surface functionalization, and structural tuning to optimize catalytic efficiency. The review further highlights representative hybrid systems based on laccase, glucose oxidase, peroxidase, and hydrogenase enzymes, and evaluates their applications in biofuel cells, solar–bio hybrid systems, green oxidation reactions, and self-powered biosystems. Stability challenges, deactivation mechanisms, and enhancement strategies such as polymer coatings, cross-linking, and nanoconfinement are critically analyzed. Finally, emerging directions including artificial enzymes, AI-guided catalyst design, and self-healing bioelectrodes are discussed to provide a forward-looking perspective on next-generation sustainable bioelectrocatalytic systems. Full article

Background and Objectives: Tamoxifen, a cornerstone selective estrogen receptor modulator in breast cancer therapy, is increasingly recognized to be associated with retinal toxicity characterized by mitochondrial dysfunction, oxidative stress, lipid peroxidation, and oxidative DNA injury. By targeting mitochondrial bioenergetic dysfunction and redox disequilibrium, adenosine triphosphate (ATP) emerges as a biologically plausible candidate for retinal cytoprotection. This study aimed to evaluate the protective effect of ATP against tamoxifen-induced retinal toxicity in a rat model. Materials and Methods: Twenty-four male albino Wistar rats were randomly assigned to four groups: healthy control (HG), ATP-alone (ATPG, 4 mg/kg, intraperitoneally), tamoxifen-alone (TAMG, 5 mg/kg, orally), and tamoxifen plus ATP-treated (ATAG; ATP, 4 mg/kg, intraperitoneally; tamoxifen, 5 mg/kg, orally). Treatments were administered once daily for 30 days. Oxidative stress markers (malondialdehyde, total glutathione), antioxidant enzyme activities (superoxide dismutase, catalase), and oxidative DNA damage (8-hydroxy-2′-deoxyguanosine) were assessed in ocular tissues. Retinal histopathological evaluation included hematoxylin–eosin staining with semiquantitative assessment of edema, vascular congestion, polymorphonuclear leukocyte infiltration, and cytoplasmic vacuolization, together with quantitative measurements of retinal layer thicknesses and ganglion cell layer (GCL) cell counts. Results: Tamoxifen administration induced marked oxidative stress, antioxidant depletion, and increased oxidative DNA damage in ocular tissues, accompanied by significant thickening of retinal layers, reduced GCL cell counts, and pronounced disruption of retinal architecture. By comparison, ATP co-administration significantly suppressed lipid peroxidation and restored antioxidant defenses, thereby reducing oxidative DNA damage and preserving retinal structural integrity, as reflected by partial normalization of retinal layer thicknesses, preservation of GCL cell counts, and the presence of only mild residual edema. Conclusions: These findings indicate that ATP attenuates tamoxifen-induced retinal toxicity by supporting mitochondrial energy balance and redox homeostasis. Accordingly, ATP administration may represent a promising protective approach for reducing retinal injury associated with long-term tamoxifen therapy. Full article

Aqueous redox flow batteries (ARFBs) are a promising solution for large-scale energy storage; however, the development of organic posolytes that combine high redox potential with long-term stability remains a significant hurdle. This study introduces sodium 3-(10H-phenoxazin-10-yl)propane-1-sulfonate (POZS), a novel sulfonate-functionalized phenoxazine derivative designed to overcome these limitations. By incorporating hydrophilic anionic sulfonic groups, this molecular engineering strategy enhances the structural stability of redox-active phenoxazine materials. Although POZS shows limited solubility in pure water, its solubility increases to 0.98 M (equivalent to a charge capacity of 26.3 Ah L⁻¹) upon the addition of 1.5 M tetraethylammonium chloride (TEAC). This enhancement suggests that the supporting electrolyte optimizes the ionic environment and mitigates intermolecular aggregation, thereby facilitating higher active species concentration. Electrochemical characterization of POZS reveals a highly positive redox potential of 1.51 V (vs. Zn/Zn²⁺) and rapid electron transfer kinetics (2.02 × 10⁻² cm s⁻¹). When tested in a zinc-based hybrid flow cell, the POZS posolyte demonstrates excellent rate capability (up to 50 mA cm⁻²) and a temporal capacity fade rate of 0.335% per hour over 500 cycles—a nearly five-fold improvement over previously reported quaternized phenoxazines. Post-cycling analyses indicate that while the phenoxazine core remains susceptible to nucleophilic ring substitution, the pendant sulfonate groups ensure that any resulting byproducts remain soluble, preventing the catastrophic depletion typically caused by the precipitation of degraded active species. These findings establish a robust molecular framework for the design of high-potential, durable organic posolytes for sustainable energy storage systems. Full article

Organoselenium chemistry has undergone remarkable development over the past five decades, evolving from its initial association with high toxicity into a field with pivotal contributions to materials science, organic synthesis, catalysis, and Medicinal Chemistry. Among the diverse biological activities displayed by organoselenium compounds, their redox behaviour is particularly compelling, as many of these molecules act as efficient mimetics of the antioxidant enzyme glutathione peroxidase (GPx). In this work, we investigated the GPx-like activity of a series of N,N′-diaryl selenoureas toward the depletion of H₂O₂ and cumene hydroperoxide (CumOOH) as model ROS. Their reactivity was correlated with the electronic nature of the aryl substituents using a Hammett-type analysis, revealing a strong dependence of the reaction rate on remote electronic perturbations within the aromatic ring. Combined UV and NMR studies provided mechanistic evidence supporting a catalytic cycle in which selenoureas, operating at sub-stoichiometric loadings (1 mol%) and using a thiol as a cofactor-like molecule, can be used to efficiently scavenge ROS with half-lives of only a few minutes (~10–60 min). Furthermore, these selenoureas exhibited potent antiproliferative activity across several human solid tumour cell lines. Overall, these results offer mechanistic insight into the ROS-eliminating pathways of selenoureas and highlight their potential as chemopreventive or anticancer agents. Full article

Nowadays, organic, inorganic, and microbial pollutants are listed as a substantial threat to the environment as well as public health, leading to water contamination. Green technologies such as photocatalytic and photoelectrocatalytic processes have appeared as favorable tools for water remediation, leading to effective degradation of pollutants under environmentally relevant operating conditions. With the rapid development of photocatalysis in the 21st century, heterogeneous catalysts have been extensively engineered to improve light utilization and promote surface redox reactions. This review presents an overview of recent advances in the synthesis, design, and application of heterogeneous catalysts for water purification. Key reaction mechanisms, material modifications, and hybrid processes are discussed. Also, the growing need for environmentally friendly, sustainable, and cost-effective catalytic materials is underlined. Attention was given to the role of molecular modeling in understanding catalytic mechanisms and guiding the design of efficient and sustainable catalytic materials. By critically analyzing contemporary progress, limitations, and emerging trends, this review directs future research activities towards increasingly efficient and scalable water purification methods. Full article

The development of high-performance electrochemical sensors requires precise integration of electrode active materials that provide both superior electrocatalytic activity and long-term structural stability. Herein, we report a systematically optimized, one-pot electrochemical deposition approach for the fabrication of nanographenide-based nanoarchitectures, incorporating either a conducting polymer (PEDOT-NG) or Prussian blue (PB-NG). Derived from optimization-driven structural refinement—including applied potential, electrodeposition time, and precursor concentration—the robust nanoarchitecture exhibits a hierarchical morphology that provides an expanded electroactive surface area, accelerating charge transfer and enhancing electrochemical catalytic activity. The optimized PEDOT-NG exhibits exceptional sensitivity for the simultaneous determination of ascorbic acid (AA), dopamine (DA), and uric acid (UA), achieving wide linear ranges with low detection limits of 4.1, 0.12, and 0.18 μM, respectively. The PB-NG achieves a limit of detection of 4.39 μM, driven by highly reversible and stable redox kinetics. This performance is underpinned by narrowed peak-to-peak separations (ΔE) and reduced redox potentials. These results underscore the pivotal role of precise parametric control in developing high-performance electrochemical sensors. Furthermore, this work establishes a comprehensive strategy for designing resilient electrode active materials, thereby paving the way for next-generation electrochemical platforms tailored for diverse and robust sensing environments. Full article

Textile wastewater remains one of the most challenging industrial effluents to remediate due to its intense and persistent coloration, high organic load, elevated salinity, and fluctuating pH and the presence of recalcitrant dye structures and auxiliary chemicals. Conventional physicochemical and biological treatments frequently achieve incomplete removal, generate secondary wastes, or fail under high-salt and toxic dye matrices. Advanced oxidation processes (AOPs) provide molecular-level degradation via reactive oxygen species (ROS), yet their deployment is often constrained by narrow operating windows, catalyst instability, chemical/energy demand, and scale-up limitations. In this context, metal–organic frameworks (MOFs) have emerged as tunable porous catalytic platforms that integrate adsorption and oxidation within a single architecture through controllable metal nodes, functional linkers, and engineered pore environments. This critical review reimagines textile effluent treatment through the lens of MOF-based hybrid catalysts, synthesizing progress across Fenton/photo-Fenton catalysis, photocatalytic MOFs, persulfate activation, and MOF-derived/composite systems. Mechanistic pathways are discussed by linking pollutant enrichment, cyclic redox reactions, charge-transfer processes, and ROS-driven degradation toward mineralization, with emphasis on the distinction between rapid decolorization and true organic removal. A critical comparison highlights how hybridization improves charge transport, stability, and catalyst recovery, while persistent gaps remain in hydrolytic robustness, metal leaching control, intermediate toxicity assessment, real-wastewater validation, continuous-flow reactor integration, and techno-economic feasibility. Finally, the review outlines actionable research directions, including water-stable and defect-engineered MOFs, immobilized and structured catalysts, solar-driven operation, standardized performance metrics, and life-cycle-informed design, to accelerate translation toward scalable and sustainable textile wastewater remediation. By bridging material chemistry with reactor-level feasibility and sustainability assessment, this review provides an implementation-oriented perspective for next-generation textile wastewater treatment. Full article