Search Results (3,241)

Formic acid (FA) has emerged as a promising liquid hydrogen storage material, yet efficient photothermal dehydrogenation catalysts with high activity and H₂ selectivity remain challenging. Herein, a polymetallic synergistic PdCu/M-ZNC (where M represents the co-doped In, Sn and Mo species) is fabricated by molten-salt-assisted pyrolysis of ZIF-8 precursors followed by metal incorporation. The unique molten salt environment effectively preserves the porous architecture of ZIF-8, enabling the secure anchoring of PdCu alloy nanoparticles onto the carbonaceous matrix enriched with M-Nₓ coordination sites. Under light irradiation, the PdCu alloy sites kinetically accelerated the overall adsorption and activation of FA molecules. Based on empirical observations and corroborated by the established literature, this alloying effect was inferred to facilitate the C-H bond cleavage and HCOO* desorption processes. Concurrently, the M-Nₓ sites act as efficient electron transfer channels, facilitating the rapid coupling of photogenerated electrons with protons (H⁺) to evolve H₂. Consequently, the optimal catalyst exhibits an enhancement in gaseous product yield (404.46 mmol/g/h) and H₂ selectivity (67.49%) at 75 °C. This work offers a catalyst design that aligns with several principles of green chemistry: it maximizes the atom utilization of precious Pd, incorporates synergistic non-precious metals within MOF-derived frameworks to enhance stability, and leverages solar energy to drive hydrogen production under mild conditions, presenting a more sustainable pathway for hydrogen release from liquid carriers. Full article

Rapid urbanization has intensified challenges regarding urban waterlogging and vehicle exhaust pollution. While permeable asphalt mixtures mitigate waterlogging and nano-TiO₂ offers photocatalytic exhaust degradation capabilities, the direct application of nano-TiO₂ is hindered by agglomeration and low photocatalytic efficiency. This study developed a composite modified nano-TiO₂ via metal ion doping and support treatment to enhance its performance in asphalt pavements. Specifically, nano-TiO₂ was doped with Fe³⁺, Ag⁺, and La³⁺ via the sol–gel method, and supported on activated carbon (AC) or Al₂O₃. The exhaust degradation performance was evaluated using a custom-built system, while dispersion properties were assessed via fluorescence microscopy and UV-Vis spectrophotometry. Furthermore, X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy were conducted to investigate the microstructural mechanisms underlying the doping modification and support treatment. Photocatalytic permeable asphalt mixtures were prepared by partially replacing mineral powder with the composite modified nano-TiO₂ to validate exhaust degradation and pavement performance. The results indicated that metal doping substituted Ti⁴⁺ in the lattice, inducing defects and reducing crystallite size to boost photocatalytic activity. The optimal doping concentrations are determined to be 1.0% for Fe³⁺, 1.5% for Ag⁺, and 1.0% for La³⁺. Among these, Fe³⁺-doped nano-TiO₂ at 1.0% content exhibits superior exhaust degradation, achieving 46.7% efficiency for hydrocarbons (HC) and 33.5% for nitrogen oxides (NO). Regarding dispersion, while AC performs better at low support content, Al₂O₃ at 40% content provides superior dispersion properties by increasing active sites and surface hydroxyl groups. For photocatalytic permeable asphalt mixtures, replacing 40–50% of mineral filler with the composite modifier is recommended. The optimized mixture demonstrates superior exhaust degradation performance while maintaining the required high-temperature stability, low-temperature cracking resistance, water stability, and fatigue life. Specifically, compared to the control group, these indicators for the mixture with 50% of the mineral filler replaced by the composite modifier increases by 7.0%, 12.5%, 13.4%, and 22.9%, respectively. This study presents a viable technical solution for developing multifunctional asphalt mixtures with photocatalytic functionality as the core innovation and mechanical performance as the application baseline. Full article

Conventional powdered biochar encounters severe bottlenecks in practical water treatment, such as difficult separation, easy loss, and potential secondary pollution. This work aimed to develop recyclable and high-performance adsorbents by preparing iron-doped biochar/sodium alginate composite microspheres (BC/MBC500-ALF) through Fe³⁺ cross-linking. Using corn stalk biochar and KMnO₄-modified biochar as adsorbent components and sodium alginate (SA) as a green shaping matrix, SA formed a stable egg-box hydrogel network to convert powdered biochar into uniform microspheres. Batch adsorption experiments revealed that the optimal pH for oxytetracycline (OTC) adsorption was 9, with adsorption capacities of 136.28 mg/g for BC500-ALF and 182.91 mg/g for MBC500-ALF. Kinetic analysis showed that BC500-ALF followed pseudo-first-order kinetics (R² = 0.983) dominated by physisorption, while MBC500-ALF fitted pseudo-second-order kinetics (R² = 0.994) dominated by chemisorption. The maximum Langmuir adsorption capacities at 308 K were 220.75 mg/g and 495.05 mg/g, respectively. Thermodynamic parameters confirmed a spontaneous and endothermic process. The adsorption mechanisms involved hydrogen bonding, π–π stacking, electrostatic attraction, metal-bridging complexation, and Fe–Mn oxide-mediated redox reactions. SA exerted dual functions in structure stabilization and adsorption enhancement. This composite provides an efficient and eco-friendly approach for tetracycline antibiotic pollution control in aqueous environments. Full article

Manganese-based cathodes offer high capacity, low cost, and safety for aqueous zinc-ion batteries (AZIBs), yet suffer from Mn dissolution, Jahn–Teller distortion, and sluggish Zn²⁺ kinetics. Herein, a Zn/Co co-doped MnO nanoporous carbon composite (denoted as ZnCo-MnO@NPC) derived from a bimetallic ZnCoMn metal–organic framework (ZnCoMn-MOF-74) is successfully synthesized and proposed as a high-performance cathode to address these challenges. The introduction of Zn²⁺ increases the initial specific capacity of MnO, while Co doping effectively suppresses the Jahn–Teller distortion and improves the integrity of the structure. Furthermore, the nanoporous carbon matrix facilitates electrolyte infiltration and accelerates ionic transport. To further suppress dendrite growth and enhance cycling stability, a zeolitic imidazolate framework (ZIF-8) protective layer is engineered on the zinc anode (denoted as ZIF-8@Zn), effectively mitigating dendrite formation. The ZnCo-MnO@NPC//ZIF-8@Zn full cell demonstrates superior electrochemical performance, delivering 281.3 mAh g⁻¹ at 0.1 A g⁻¹ and retaining 98.7% of this value after 3500 long-term cycles at 2.0 A g⁻¹, a remarkable finding that underscores its potential for high-performance energy storage. Collectively, this work highlights that transition metal ion doping represents an effective way to design efficient high-performance MOF-derived cathodes of AZIBs. Full article

In this study, a polyethylene glycol (PEG)-based solid electrolyte composite (PEG)₁₀LiClO₄/NaAlOSiO suitable for anodic bonding packaging was successfully fabricated via a combined ball milling and hot pressing process. The micromorphology, ion transport characteristics, and mechanical packaging properties of the composite were systematically investigated using characterization techniques including electrochemical impedance spectroscopy, X-ray diffraction, scanning electron microscopy, and anodic bonding performance tests. The results demonstrate that doping with NaAlOSiO molecular sieve can effectively reduce the crystallinity of the polymer matrix, construct more efficient carrier transport pathways, and simultaneously enhance the ionic conductivity and mechanical properties of the material. When the mass fraction of NaAlOSiO doping is 8 wt.%, the composite exhibits a room temperature ionic conductivity of up to 1.31 × 10⁻⁵ S·cm⁻¹. Under room temperature and a bonding voltage of 800 V, the sample with this doping ratio achieves the optimal anodic bonding with metallic Al, and the tensile strength of the bonding interface reaches 5.93 MPa, showing excellent application prospects in micro–nano-packaging. Full article

Layered double hydroxides (LDH) demonstrate significant potential in flexible superca-pacitors due to their high energy storage capability and adjustable architectures. Never-theless, the practical specific capacitance exhibited by current LDH remains below expec-tations, which is attributed to suboptimal electrode performance and limited active sites. Herein, a novel Fe-doped NiFeCo-LDH/NiFeCoO nanosheet composite supported on car-bon cloth was designed and fabricated as a flexible electrode. In this composite, the Ni-FeCo-LDH supplies numerous reactive centers and accelerates electrochemical kinetics, while the NiFeCoO and carbon cloth significantly improve electrical conductivity and cy-cling stability. Moreover, the heterointerface formed between the LDH and the metal oxide phase further facilitates charge transfer. Owing to such synergistic interactions, the pre-pared NiFeCo-LDH/NiFeCoO@CC electrode demonstrates an excellent areal specific ca-pacitance of 3.282 F cm⁻² at a current density of 1 mA cm⁻², while maintaining a high ca-pacity preservation reaching 88.09% following 5000 cycles. Furthermore, the assembled NiFeCo-LDH/NiFeCoO@CC//AC asymmetric supercapacitor delivers an outstanding en-ergy density reaching 0.302 mWh cm⁻² under a power density of 0.776 mW cm⁻², coupled with an excellent capacitance preservation of 85.29% over 5000 cycles. Meanwhile, it can maintain its initial capacitance under varying bending degrees, rendering it widely ap-plicable for future advanced flexible and wearable electronic devices. Full article

This study aimed to develop a novel fluorescent sensor based on Eu³⁺ complex-doped protein crystal (EC-PC) for the efficient detection of metal ions in blood. By meticulously controlling the crystallization and annealing conditions in the co-crystallization strategy, the crystal growth processes were optimized to obtain doped Eu³⁺ complex-co-protein crystalline (EC-PC) structures. Thus, through co-crystallization of hen egg white lysozyme (HEWL) as a model protein and Eu³⁺ complex as fluorescent center, we successfully prepared Eu³⁺ complex-doped-HEWL co-crystals (EC-HC) with excellent fluorescent properties. Further treatment with 4% glutaraldehyde cross-linking enhanced the structural stability of the co-crystals. Moreover, the characteristic of sensitive, selective quenching of EC-PC fluorescence by biologically relevant cations, such as Cu²⁺, Zn²⁺, Mg²⁺, Ca²⁺ and Fe³⁺ ions, set up a smart sensing system in blood. For example, the fluorescence intensity of the crystals at 610 nm, as measured by a UV–visible spectrophotometer, decreases dose-dependently with the concentration of copper ions, thereby validating the sensor’s high sensitivity to copper ion detection. Significantly, we also found that this hybrid protein-based sensor did not induce hemolysis, at various volume concentrations, confirming good anticoagulation in blood. This research not only provides a new perspective on the application of Eu³⁺ complex-doped protein crystals in the field of biosensing but also offers a new strategy for the detection of biologically relevant cations in blood. Future work will focus on further optimizing the sensor’s performance and exploring its potential applications in clinical sample analysis. Full article

In this study, Zn-doped Co₃O₄ nanorods and nanosheets with controlled Zn/Co molar ratios were synthesized via a hydrothermal strategy to clarify the respective roles of morphology and elemental doping in ethylbenzene sensing. The gas-sensing performance is strongly influenced by morphology, and the radially oriented nanorod structure significantly enhances sensing response compared with nanosheet structures. Zn doping effectively enhances the gas-sensing performance of Co₃O₄. As a result, the optimized Zn-doped nanorod sensor exhibits high sensitivity to ethylbenzene, a low detection limit, rapid response and recovery, and excellent operational stability. Density functional theory calculations reveal that the predominantly exposed facets of the nanorod structure possess stronger adsorption affinity and pronounced charge transfer toward ethylbenzene, providing theoretical support for the morphology-dominated sensing behavior. At the same time, Zn incorporation further adjusts the band structure and surface reactivity. Overall, this work elucidates a morphology-dominated and doping-assisted enhancement mechanism, offering clear design principles for high-performance Co₃O₄-based ethylbenzene sensors. Full article

To address the application requirements of energy storage devices for new energy electric vehicles—including high energy density, high-power density, fast charging and discharging, and long-term cycling stability—traditional symmetric supercapacitors are often limited by low energy density and poor compatibility between the anode and cathode, making it difficult to meet the high-efficiency energy storage demands under the dynamic operating conditions of electric vehicles. This study focuses on the regulation of hierarchical thin-film structures and the innovative heterogeneous coating interface engineering with precise slurry coating and film-forming optimization and designs and fabricates NiCo₂O₄/NiFeO composite thin-film electrodes and Mn-doped porous carbon (Mn-PC) thin-film electrodes. The uniform, compact and stable coating formation on nickel foam substrates via controllable slurry coating facilitates the efficient integration of active materials and conductive supports. The electrode slurries were coated onto conductive nickel foam substrates, and high-performance aqueous supercapacitors were assembled using an asymmetric configuration. A systematic study was conducted covering material preparation, structural characterization, electrochemical testing, and full-device performance evaluation. Using techniques such as XRD, XPS, SEM, TEM, BET, and an electrochemical workstation, the study revealed the structure–activity relationships among material morphology, crystalline phases, pore structure, and electrochemical performance, elucidating the charge storage mechanisms of the composite electrode films and the principles of synergistic adaptation between the anode and cathode. The results indicate that NiCo₂O₄ nanowires decorated with in situ-grown NiFeO nanosheets to form a composite structure; when coated onto nickel foam, this forms a uniform, porous electrode film with a specific surface area of 171.3 m²/g, a specific capacitance as high as 1746 F/g at 1 A/g, and a capacity retention rate of 94.0% after 10,000 cycles. After coating and film formation, the Mn-PC anode introduced pseudocapacitive active sites through uniform Mn doping, resulting in a film electrode specific capacitance of 348 F/g and significantly improved rate and cycling performance. The assembled NiCo₂O₄/NiFeO//Mn-PC asymmetric supercapacitor exhibits a thin-film electrode specific capacitance of 153 F/g at 1 A/g, with a maximum energy density of 52 Wh/kg. Even at a power density of 9000 W/kg, it maintains 45 Wh/kg, and retains 89.5% of its capacity after 10,000 cycles, with overall performance outperforming most previously reported transition metal-based devices. This coating-engineered electrode fabrication strategy breaks through the interface mismatch and structural instability bottlenecks of traditional thin-film electrodes, providing a novel material system and an efficient coating assembly strategy for high-performance supercapacitor thin-film electrodes in new energy electric vehicles, and offers experimental evidence and technical references for the development and application of high-power energy storage coating devices for automotive use, as well as the innovative design of electrode coating engineering in energy storage fields. Full article

Photocatalytic reduction of carbon dioxide (CO₂) into high-value multicarbon products, such as ethylene (C₂H₄), remains a significant challenge due to the difficult C-C coupling process. Potassium poly(heptazine imide) (K-PHI) is a promising photocatalyst, yet efficiently exchanging its interlayer cations to tune catalytic selectivity without causing structural degradation is difficult. Herein, an efficient and green supercritical CO₂ (SC CO₂) assisted ion-exchange strategy was developed to successfully prepare a series of mono-/di-/trivalent cation-doped M-PHI photocatalysts (M = H⁺, Na⁺, Sr⁺, Ca²⁺, Co²⁺, Fe³⁺). Systematic characterizations confirmed that the SC-CO₂ treatment successfully achieved in-depth cation substitution without destroying the intrinsic heptazine framework, effectively regulating the interlayer structure and significantly optimizing the photoelectrochemical charge separation. Among the prepared samples, H-PHI exhibited the optimal photocatalytic CO₂ reduction performance with an outstanding selectivity toward C₂H₄ generation. Under simulated sunlight irradiation for 3 h, the yields of CO, CH₄, and C₂H₄ C₂H₄ C₂H₄ reached 3564.87, 807.32, and 40.00 μmol·g⁻¹, respectively, significantly outperforming pristine K-PHI and other metal-doped samples. Crucially, isotope-tracing experiments utilizing a SC CO₂-DCl treatment detected deuterated CH₄ and C₂H₄ products, providing direct evidence that the hydrogen in the carbon products originates from the introduced protons, thereby elucidating the precise reaction pathway for C-C coupling. This study provides a green and efficient supercritical CO₂ ion exchange strategy for the cation engineering of crystalline carbon nitride, and also offers new ideas and methods for designing high-activity photocatalysts for photocatalytic CO₂ reduction. Full article

With changes in the global energy structure, ammonia has emerged as a favorable hydrogen storage medium due to its excellent properties. This work details the synthesis of a barium-doped cobalt–iron alloy catalyst via subsequent heat treatment. This alloy efficiently catalyzes the decomposition of ammonia into hydrogen. The results showed that using characterization methods such as TEM and XRD indicated that adding Ba to this system could regulate the microstructure of the Co-Fe alloy. After calcination, the barium promoted a reduction in the particle size of Co-Fe nanoparticles, enabling their uniform dispersion on the surface and a more uniform dispersion and improving the accessibility of the exposed surface. The optimized catalyst (0.05Ba-0.25CoFe/CeO₂) achieved an ammonia conversion of 93.2% at 550 °C under a gas hourly space velocity of 30,000 mL·g_cat⁻¹·h⁻¹. Mechanistic analysis based on XPS and CO₂-TPD results indicated that the barium optimized the electronic structure and alkaline sites of Co-Fe, promoted the desorption of nitrogen, and thereby accelerated the reaction kinetics of ammonia decomposition. This research provides a strategic method and theoretical basis for designing high-performance non-precious metal catalysts for ammonia decomposition. Full article

Ammonia is indispensable to the fertilizer and chemical industries, yet its manufacture still relies predominantly on the energy-intensive Haber–Bosch process operated at 400–500 °C and 150–250 bar, with a substantial carbon footprint. Single-atom catalysts (SACs) and sub-nanometric clusters have recently emerged as promising alternatives for thermocatalytic ammonia synthesis under milder conditions because they maximize metal utilization and enable precise control of the active site environment. This review first summarizes how the transition from conventional Fe and Ru nanoparticles to isolated or few-atom sites fundamentally alters the kinetic landscape, favoring associative N₂ activation pathways that lower apparent activation energies and alleviate H₂ poisoning. We then discuss Ru-based SACs and SAAs supported on zeolites, carbons, ceria, and MXenes, highlighting how strong metal–support and promoter interactions, tandem single-atom/nanoparticle motifs, and alloying strategies tune N₂ and H₂ binding to deliver high NH₃ productivities at 200–400 °C and ≤30 bar. In parallel, we review emerging non-noble systems based on Fe and Co, including high-loading Fe–N₄ sites prepared via MOF-derived post-metal-replacement routes and Co single atoms or Co₂ clusters on N-doped carbons, which already rival or surpass Ru benchmarks under similar conditions. Collectively, these studies show that tailoring the number of atom metal sites, coordination, and support polarity around isolated metal sites provides a useful tool to mitigate some aspects of volcano and scaling-relation limitations, indicating that SACs could contribute to low-temperature ammonia synthesis when combined with appropriate process design. Full article

Synthetic dyes frequently persist through conventional wastewater treatment, motivating the use of advanced oxidation processes capable of breaking down these stable molecules. Metal-doped carbon dots (CDs) offer a tuneable platform for catalytic dye degradation in water, although their performance varies strongly with operating conditions. The aim of this work was to determine how temperature, H₂O₂ dosage, and pH influence the catalytic behaviour of Fe-, Cu-, Zn-, and Mg-doped CDs during the degradation of methylene blue (MB) and rhodamine B (RB), optimised using a Taguchi L27 orthogonal array design. Temperature and oxidant loading were the dominant factors: higher temperatures accelerated reactions through Arrhenius-type kinetics, while increasing H₂O₂ availability improved removal until excessive levels began to suppress •OH generation. Across all condition sets, apparent rate constants spanned 7.0 × 10⁻⁴–2.65 × 10⁻² min⁻¹, with t₅₀ values of 26–217 min and t₉₀ extending from ~86 min to >700 min; final decolourisation ranged from ~17% to nearly 100%. pH played a secondary role, mainly affecting dye speciation and surface adsorption. Dopant identity shifted the optimum operating region for each catalyst: Fe- and Cu-CDs achieved complete or near-complete removal of both dyes at pH 7 and 50 °C with relatively low H₂O₂ dosage (0.5–1.0 mL); Zn-CDs reached equivalent performance at pH 7 and 25 °C but required higher oxidant loading (1.5 mL of H₂O₂), reflecting their photo-induced rather than thermally driven activation mechanism; Mg-CDs performed comparably under the same conditions as Fe- and Cu-CDs. The resulting condition–catalyst map highlights the operating regimes that maximise efficiency while minimising chemical input, providing a practical framework for selecting carbon-dot-based catalysts for water treatment applications. Full article

The sluggish kinetics of the hydrogen oxidation reaction (HOR) in alkaline media remain a primary bottleneck for anion exchange membrane fuel cells (AEMFCs), necessitating catalysts that synergistically optimize the adsorption of hydrogen (*H) and hydroxide (*OH) intermediates. Herein, we construct a well-defined heterointerface between Pd clusters and CeO₂ on nitrogen-doped carbon (Pd-CeO₂/NC) to electronically engineer the active sites. Spectroscopic studies and theoretical calculations collectively reveal that CeO₂ acts as an electron acceptor, drawing electrons from Pd via interfacial Pd-O-Ce bridges. This charge transfer induces a downshift of the Pd d-band center, which optimally tunes the adsorption strength of both *H and *OH at the interface, thereby breaking the scaling relationship that limits HOR activity. The resulting Pd-CeO₂/NC catalyst achieves an exceptional exchange current density of 3.66 mA cm⁻², surpassing that of commercial Pt/C by a factor of two and ranking among the best reported noble metal catalysts. Furthermore, it exhibits outstanding long-term stability and remarkable CO tolerance, retaining high activity in an atmosphere containing 1000 ppm CO. This work underscores the profound efficacy of metal–oxide heterointerface engineering in regulating electronic structures for multi-intermediate optimization, offering a viable design principle for advanced alkaline HOR electrocatalysts. Full article

The threshold voltage (Vth) of p-GaN gate enhancement-mode (E-mode) high electron mobility transistors (HEMTs) on silicon substrates grown by metal–organic chemical vapor deposition (MOCVD) is often limited to 1.0–1.5 V. Apart from the low Mg acceptor activation rate, the non-uniform vertical Mg distribution in thin p-GaN layers is also a key bottleneck limiting Vth. This work reveals that the vertical distribution (not only magnitude) of Mg doping fundamentally influences Vth by modulating the charge centroid and electric field coupling to the heterointerface. Through bis(cyclopentadienyl)magnesium (Cp₂Mg) flow modulation, surfactant-assisted growth, and growth rate adjustment, the vertical Mg doping uniformity within the 80 nm p-GaN layer was improved while effectively suppressing Mg out-diffusion. A short-cycle gate-first self-aligned process was used to fabricate the devices, and the results showed that the improved Mg vertical distribution led to a significant Vth enhancement by 0.75 V. Technology Computer-Aided Design (TCAD) simulations further demonstrated that the uniform doping profile builds a stronger negative space charge field beneath the gate, raising the energy band and increasing Vth. This work not only presents practical strategies, but also establishes a direct physical link between vertical Mg doping distribution and Vth in Si-based E-mode HEMTs. Full article