Search Results (760)

The increasing demand for continuous physiological monitoring has accelerated the development of high-sensitivity wearable electrochemical platforms. This study reports the fabrication of a multi-analyte electrochemical sensor based on single-walled carbon nanotubes (SWCNTs) for the detection of sweat-associated metabolites. To facilitate efficient heterogeneous electron transfer, glucose oxidase (Gox), lactate oxidase (Lox), and urease (Ure) were immobilized onto the SWCNT network through π–π interaction using 1-pyrenebutanoic acid succinimidyl ester (PBSE), followed by additional stabilization via 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)/N-hydroxysuccinimide (NHS) coupling. The developed platform exhibited concentration-dependent resistance responses within the ranges of 0.02–0.20 mM for glucose, 20–100 mM for lactate, and 50–400 mM for urea under controlled experimental conditions. The resistance-based configuration enabled stable and reproducible signal modulation across these concentration intervals. Although direct testing with human sweat was not performed, the electrochemical behavior of key sweat-related metabolites was systematically evaluated as a preparatory step toward future wearable integration. Full article

The photoelectrochemical splitting (PEC) of water provides a direct route to converting solar energy into storable chemical fuels. When illuminated, a semiconductor photoelectrode can absorb light and generate electron-hole pairs, which participate in interfacial redox reactions at the semiconductor-electrolyte junction. Therefore, to achieve high-performance PEC, photoelectrodes with optimized optical absorption and charge have been explored. This review analyzes recent fabrication strategies used to design photoelectrodes for the PEC dissociation of water. Physical fabrication techniques, including pulsed laser deposition, magnetron sputtering, and physical vapor deposition, allow for precise control of film thickness, crystallinity, and defect density, critical parameters for efficient charge transport. Typically, in physical methods, reported photocurrent densities span from ~10⁻² to 10¹ mAcm⁻², depending on the semiconductor material, nanostructure design, and interfacial engineering strategies. Chemical synthesis methods, such as hydrothermal growth, successive ion layer adsorption and reaction, and microemulsion techniques, provide greater compositional flexibility and enable controlled doping, surface functionalization, and the formation of nanostructured morphologies. Finally, hybrid fabrication strategies integrate physical and chemical processes within a single synthesis framework to combine structural precision with compositional tuning capabilities. These approaches enable the development of advanced architecture such as heterojunctions, core–shell nanostructures, and catalyst-modified interfaces, which enhance light absorption and optimize interfacial transfer. Furthermore, theoretical and computational tools are here analyzed as complementary approaches that guide the rational design and optimization of photoelectrochemical materials and devices. Full article

Photocatalytic CO₂ reduction to high-value-added C₂+ products is a practical route from an economic viewpoint for advancing the industrialization of CO₂ conversion. Despite significant progress in catalyst modification in recent years (such as defect engineering, heterostructure construction, and single-atom modification), the generation of C₂+ products still faces challenges due to the slow kinetics of multi-electron reactions and the high thermodynamic barrier for C-C coupling. Moreover, the severely imbalanced molar ratio of CO₂ to H₂O in the traditional liquid-phase reaction systems exacerbated the challenge to the unfavorable situation. This article summarizes various strategies to improve the yield of C₂+ products through the regulation of reaction environments, including: (1) increasing the partial pressure of CO₂ to enhance its solubility; (2) using alternative solvents like ionic liquids to reduce water content; (3) transitioning the reaction system from liquid phase to gas phase; (4) designing a three-phase (gas–liquid–solid) interface or floating photocatalysts to optimize reactant transfer and local concentration; (5) utilizing photothermal synergistic effects to enhance the reaction temperature and efficiency under concentrated light. It also discusses the role of different reactor designs in improving the reaction environment. Finally, it emphasizes that future research should pay more attention to the optimization of the reaction environment engineering in addition to catalyst design, providing new perspectives for achieving efficient and highly selective C₂+ products in CO₂ photoreduction. Full article

This study presents the synthesis and electrochemical characterization of meso-tetracyanobutadiene (TCBD)-functionalized diphenylporphyrin (DPP) complexes incorporating copper (Cu) and nickel (Ni) metals. These push–pull metallo diphenylporphyrin–TCBD complexes were synthesized via a [2 + 2] cycloaddition–retroelectrocyclization reaction between 5-bromo-15-formyl-10,20-diphenylporphyrin metal(II) complexes (M = Cu, Ni) and tributyl(phenylethynyl)stannate, followed by tetracyanoethylene (TCNE) addition. The resulting TCBD-functionalized porphyrins were obtained in moderate yields (70–75%) and thoroughly characterized by ¹H and ¹³C NMR, UV-Vis spectroscopy, MALDI-TOF-MS, and single-crystal XRD. Although the single-crystal X-ray structure of NiDPP was solved, DFT calculations were used to determine the structures of the donor–acceptor MDPP-TCBD systems and to visualize their electronic structures. HOMO on the porphyrin π system and LUMO on the TCBD entity were observed, and energy level diagrams clearly laid out the electron donor and acceptor parts of the molecular systems. As expected, these novel donor–acceptor porphyrinoid assemblies exhibited enhanced push–pull properties in both the ground and excited states. Femtosecond transient absorption studies revealed that both NiDPP-TCBD and CuDPP-TCBD populate the charge-transfer state upon photoexcitation, with lifetimes of 383.1 ps and 484.7 ps, respectively, in benzonitrile. The charge-transfer states populated the triplet or doublet states (in the case of CuDPP) before returning to the ground state. Full article

Catalytic ozonation often suffers from a low ozone utilization rate and incomplete mineralization of organic pollutants. To address these challenges, we designed and prepared a novel catalyst via a one-step thermal polymerization method, anchoring single-atom manganese on a glucose-derived carbon network-modified C₃N₅ framework (Mn/C-C₃N₅). Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) on an FEI Titan Themis Z microscope confirmed the atomic dispersion of Mn sites, while Raman spectroscopy using a Renishaw inVia Reflex laser micro-Raman spectrometer verified the successful incorporation of a graphitic carbon network within the C₃N₅ matrix. Moreover, electrochemical analyses, including electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) performed on a Bio-Logic SP-150 electrochemical workstation, demonstrated that the integration of the conductive carbon matrix substantially enhanced the interfacial charge transfer capability. The optimized Mn/C-C₃N₅ catalyst demonstrated exceptional performance in phenol mineralization, achieving a 97% total organic carbon (TOC) removal within 60 min, a remarkable improvement compared to pristine C₃N₅ (30%). Furthermore, the catalyst exhibited excellent operational stability, preserving more than 95% of its original activity over five repeated runs. Mechanistic investigations, including electron paramagnetic resonance (EPR) spectroscopy and radical quenching experiments, revealed that the Mn/C-C₃N₅ system accelerated the generation of multiple oxidizing radicals (•O₂⁻, ¹O₂, and •OH), with •OH identified as the predominant reactive species responsible for complete mineralization. This work establishes an integrated catalytic platform and provides fundamental insights into electronic structure modulation for designing advanced oxidation catalysts. Full article

The continuous increase in power density of electronic devices imposes stringent requirements on the design of lightweight, high-efficiency heat sinks. To overcome the limitations of conventional single-gradient or monomaterial heat sinks—namely, their suboptimal heat-transfer efficiency and poor structural adaptability—this study proposes a dual-gradient, triply periodic minimal surface (TPMS)-based multimaterial heat sink architecture fabricated from CuCrZr and AlSi₇Mg. Thermal performance was quantified experimentally using infrared thermography, while the underlying flow-field mechanisms were investigated numerically via computational fluid dynamics (CFD) simulations employing the standard k–ε turbulence model. With the TPMS material volume ratio fixed at 3:3 (CuCrZr:AlSi₇Mg), the Z-axis gradient configuration P-Z4-5 delivered the best overall thermal performance, achieving a heat-transfer coefficient (HTC) of 1557.63 W·m⁻²·K⁻¹ and a thermal resistance as low as 1.83 K·W⁻¹ at an inlet velocity of 5 m·s⁻¹. In contrast, the Y-axis gradient configuration P-Y3-6 yielded the most uniform temperature distribution, exhibiting a maximum surface temperature difference of only 21.5 °C under the same inlet condition. Velocity and turbulence distribution analyses reveal that the dual-gradient design enhances both the narrow-tube effect and flow-induced disturbances; furthermore, increasing the inlet velocity from 5 m·s⁻¹ to 21.65 m·s⁻¹ significantly intensifies vorticity-driven fluid mixing. Among all configurations evaluated, P-Z4-5 exhibited the highest j/f factor (i.e., the ratio of Colburn j-factor to Fanning friction factor), followed by P-Z3.5-5.5 and P-Z3-6. These findings establish a promising new pathway for the development of high-performance, lightweight heat sinks tailored for next-generation high-power electronics. Full article

To address the inherent limitations of Cu₂Se as a lithium-ion battery (LIB) anode, a Cu₂Se/MnSe@C composite was rationally designed and synthesized via selenization of a CuMn bimetallic metal–organic framework (MOF) precursor. This synthesis strategy integrates carbon composite engineering and heterogeneous structure construction, achieving in situ formation of Cu₂Se/MnSe heterogeneous nanoparticles anchored on amorphous carbon nanosheets. Structural characterizations confirm the successful construction of well-defined Cu₂Se/MnSe interfaces and uniform dispersion of selenide components, with Mn introduction inducing regulated electron transfer between Cu₂Se and MnSe. Electrochemical evaluations demonstrate that the Cu₂Se/MnSe@C composite exhibits a significantly enhanced lithium storage performance compared to single-component Cu₂Se@C, including higher specific capacity and superior rate capability. Mechanistic studies reveal that the synergistic effects of the carbon matrix (enhancing electrical conductivity and mitigating volume expansion) and the Cu₂Se/MnSe heterogeneous interface (lowering charge transfer resistance, accelerating Li⁺ diffusion, and boosting pseudocapacitive contribution) are responsible for the performance enhancement. Moreover, Cu₂Se/MnSe@C||LiFePO₄ full cells deliver a stable average operating voltage and reliable cycling stability, validating the composite’s practical application potential. Full article

3-Acetyl-1-propanol (3-AP) is a key intermediate in the pharmaceutical and pesticide industries, which can be synthesized from the biomass derivative 2-methylfuran (2-MF) through a one-step hydrogenation process with significant economic and environmental benefits. Zeolite-supported metal catalysts showed feasible application, but simply regulating the acidic sites was difficult to break the activity–selectivity balance. Traditional single-metal Pd-based catalysts still suffer from low dispersion. This study constructed the PdZn/TS-1 catalyst for the efficient conversion of 2-MF into 3-AP. The low electronegativity of Zn facilitates the electron transfer from Zn to Pd, forming an electron-rich Pd active center. A small amount of Zn embedded in the Pd lattice causes lattice contraction, optimizing the spatial configuration of active sites. The synergy between the electronic and structural effects significantly improves catalytic performance. Under optimized conditions, the conversion rate of 2-MF reached 80.6%, and the yield of 3-AP reached 69.1%, providing a new paradigm for the design of catalysts for the directed hydrogenation of furan derivatives. Full article

Coffea canephora cultivation areas in Brazil are frequently exposed to successive cycles of water deficit, triggering plant stress responses. In addition to water deficit, increased air temperature can act as a second stress factor. The recurrence of these stress factors may induce plant tolerance mechanisms, potentially mitigating future stress responses even of a different stress nature. We hypothesized that repeated cycles of water deficit can trigger tolerance mechanisms that make C. canephora leaves more resilient to supra-optimal temperatures. To test this hypothesis, young C. canephora plants were grown under non-limited water conditions for seven months (Ψ_mSoil > −20 kPa), after which they were subjected to two consecutive cycles of water deficit (Ψ_mSoil < −300 kPa), followed by rehydration. Two clones were used, ‘A1’ and ‘3V’, previously classified as drought sensitive and tolerant, respectively, considering the dynamics of physiological and architectural responses. After the second cycle, leaf discs were collected from completely expanded leaves formed during the two stress cycles and exposed to heat treatments (35 °C, 40 °C, 45 °C, 50 °C, and 55 °C) for 15 min in a water bath. Chlorophyll a fluorescence emission was then monitored, and the results were analyzed using OJIP transient kinetics and the JIP_Test. High temperatures induced negative changes in both OJIP kinetics and JIP_Test-derived parameters. A significant increase in F₀ and a reduction in F_M were observed mainly at 50 °C and 55 °C, due to changes in the stages of the OJIP curve. These changes impacted the “energy connectivity” and consequently the electron transport along the electron transfer chain (ETC), increasing energy dissipation, as confirmed by the JIP_Test variables. Despite the high temperature impacts, previous water deficit induced heat tolerance in clone ‘A1’, while it increased sensitivity in clone ‘3V’. This study suggests that selecting drought-resistant varieties should consider their subsequent response to short high-temperature stress to avoid cross-sensitivity caused by selecting for a single environmental factor. Full article

High-entropy alloys (HEAs) provide a broad compositional space for tuning phase stability and surface durability. CoCrFeNiMn_x (x = 0.5, 1.0, 1.5, and 2.0) alloys were fabricated by vacuum arc melting and characterized by X-ray diffraction (XRD), optical microscopy (OM), scanning electron microscopy with energy-dispersive spectroscopy (SEM/EDS), microhardness testing, electrochemical testing in 3.5 wt.% NaCl, and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) calculations and first-principles molecular dynamics were further employed to analyze the Mn-dependent electronic structure and oxygen–metal bonding. The XRD results indicate a transition from a single FCC solid solution at x ≤ 1.0 to an FCC + BCC constitution at x ≥ 1.5. With increasing Mn, microstructures evolve from coarse dendrites toward higher fractions of equiaxed grains. Hardness decreases from 163.6 HV (x = 0.5) to 125.1 HV (x = 1.0) and then increases to 162.6 HV (x = 2.0), indicating competing solid-solution and phase/segregation effects. Electrochemical measurements show enhanced corrosion resistance with Mn addition; the x = 2.0 alloy exhibits the lowest fitted corrosion current density (icorr = 0.3482 × 10⁻⁶ μA·cm⁻²) and the most stable passivation response. XPS reveals passive films dominated by Fe₂O₃ together with Mn³⁺ oxides, whose synergistic formation promotes a denser barrier layer. DFT predicts a monotonic decrease in Fermi level and a narrowed conduction band range as Mn increases, consistent with reduced electron transfer activity during anodic dissolution. Interfacial simulations show that O preferentially bonds with Cr and Mn, while Ni–O bonds have the lowest estimated rupture barrier, rationalizing a tendency toward localized corrosion at Ni-associated sites. Full article

Microchannel liquid cooling technology, characterized by high heat-transfer efficiency, represents an effective solution for thermal management in high heat-flux density electronic devices. Existing research has mainly focused on optimizing the structural design of microchannel heat sinks, while neglecting the specific effects of inlet manifold configurations on their heat transfer and flow performance. To obtain more systematic data on microchannel heat transfer performance and internal velocity distribution, this study designed microchannels with single-inlet and triple-inlet configurations. A microchannel cooling performance testing platform was established, and visualization experiments of the internal flow field in straight microchannels were conducted using a particle image velocimetry (PIV) system. The velocity distribution uniformity and heat transfer performance were compared between single-inlet and triple-inlet microchannels with varying channel spacings. The results show that under the same flow conditions, the triple-inlet splitter structure yields a more uniform flow distribution, a lower peak temperature for the heat source chip, and improved heat transfer performance, with its pressure drop reduced to 11.1–26.6% of that of the single-inlet configuration. Furthermore, smaller channel spacings yield improved heat-transfer efficiency in microchannels. Full article

Molecular hydrogen, the basis of hydrogen energy, is formed in many physical and chemical processes, including the absorption of gamma-ray energy by liquid cyclohexane. From the point of view of energy consumption, the stages of gamma radiolytic formation of molecular hydrogen have not been quantified. By means of a new energy method, we analyzed the amounts of released molecular hydrogen during gamma irradiation of liquid cyclohexane in the absence and presence of small additives of bicyclic mono- and dienes RH (initial concentrations of C₀(RH) ≈ 5 × 10⁻³ M/L), depending on the first ionization potentials of the components of solutions determined in the gas phase. Using the new energy method, four primary intermediates—radical anion, electronically excited molecule, radical cation, and superexcited molecule—of liquid cyclohexane gamma radiolysis were identified. Energy, mechanistic, and spin relationships and connections between these four cyclohexane intermediates were established. The experimental value of the adiabatic electron affinity of the cyclohexane molecule is −2.01 eV. The energy of formation of the superexcited cyclohexane molecule is 18 eV (gas phase). Using the energy method, it is shown that an increase in C₀(RH) concentrations from 5 × 10⁻³ to 0.1 M/L leads to a change in the mechanism of RH consumption. Instead of RH activation, as a result of the single electron transfer reaction, RH polymerization begins, which is initiated by cyclohexyl radicals. Full article

Developing efficient and stable electrocatalysts for the hydrogen evolution reaction (HER) is critical for advancing clean and sustainable energy technologies. Herein, a Fe-doped perovskite oxide Ba_0.7Pr_0.3Co_0.8Fe_0.2O_3−δ (BPCF_0.2) was successfully synthesized via the sol–gel method. By regulating the stoichiometric ratio of precursors and calcination temperature, a stable single-phase perovskite structure was achieved. X-ray photoelectron spectroscopy (XPS) analysis indicated that Fe incorporation increased the proportion of high-valent Co species and lattice oxygen content, which respectively reduced the charge transfer resistance of BPCF_0.2, thereby significantly enhancing catalytic performance. Electrochemical measurements revealed that BPCF_0.2 exhibited remarkable HER activity in 1.0 M KOH, achieving an overpotential of 172 mV at a current density of 10 mA cm⁻², with no significant decay during 200 h of continuous HER testing at 100 mA cm⁻². These results demonstrate that the Fe doping strategy can effectively optimize the electronic structure, providing valuable insights for the development of perovskite-based HER catalysts. Full article

Hexavalent chromium (Cr(VI)) is a high-priority environmental pollutant due to its strong oxidizing properties, which cause DNA damage and other severe health effects. Conventional detection methods are often costly and lack real-time monitoring capabilities, creating a strong demand for cost-effective, real-time biosensors that meet industrial requirements. In this study, we developed a novel biosensor for continuous Cr(VI) monitoring using a single-chamber microbial fuel cell (MFC). The biological element is an engineered Escherichia coli strain (ChrA-ChrB-E. coli), constructed by introducing Cr(VI)-resistant (ChrA) and Cr(VI)-reducing (ChrB) genes. The presence of Cr(VI) affects bacterial metabolism and electron transfer within the MFC, generating a measurable signal proportional to the contaminant’s concentration. The biosensor demonstrated robust performance and characteristics. The recombinant strain retained functional activity after 450 days of storage at −20 °C. The system exhibited high sensitivity and excellent linearity (R² ≥ 0.999) across a broad Cr(VI) concentration range of 0.015–200 mg/L. During continuous monitoring of chrome tanning and electroplating wastewater, measurements deviated by less than 2.33% from the standard diphenylcarbazide (DPC) method; electroplating deviation was further reduced to −0.69% with EDTA pretreatment. In fishery water, the deviation was higher (−7.12%) due to dissolved oxygen (DO) interference but was reduced to −0.75% after mechanical stirring to remove DO. The biofilm bacterial community remained highly stable over six months in both wastewater types, with the inoculated ChrA-ChrB-E. coli strain maintaining dominance (>99.6%). These results substantiate the feasibility of using this biosensor for continuous, online, real-time detection of Cr(VI) in actual wastewater environments. Full article

Microbial fuel cells (MFCs) convert the chemical energy of biomass into electricity through microbially driven redox reactions. We evaluated a single-chamber, membrane-less MFC fed with sugarcane molasses and inoculated with a two-member consortium: Saccharomyces cerevisiae (glucose → ethanol fermentation) and Acetobacter aceti (ethanol → acetate oxidation). Three anode–cathode pairs were tested—bronze–Zn, copper–Zn, and graphite–Zn—across 27 units and 20 operating cycles. During ethanol oxidation, A. aceti oxidizes ethanol to acetic acid and, in our configuration, this biocatalytic step is designed to contribute electrons to the bronze, copper, or graphite anodes. These electrons, together with those generated by galvanic reactions in the electrode pair, flow through the external circuit to the zinc cathode, where oxygen reduction closes the circuit. The cells reached open-circuit potentials > 0.8 V, with performance following the hierarchy graphite–Zn > copper–Zn > bronze–Zn, consistent with the superior biocompatibility and lower corrosion of carbonaceous anodes. Multivariate analysis using PLS-SEM confirmed that redox indicators and electrode composition were strong determinants of voltage output (R² = 0.911) and demonstrated high predictive relevance (Q² = 0.906) for the voltage construct. These findings show that coupling yeast fermentation with acetic acid–bacteria oxidation enables synthetic-mediator-free electron transfer in a simple single-chamber configuration and shows that electrode material selection is a primary lever for achieving stable potentials for biomass valorization. Full article