Search Results (1,719)

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

This paper provides a comprehensive overview of research findings concerning the acid catalytic effect (ACE) of hot compressed water and water–alcohol mixtures, along with the applications of these solvents. The ACE observed during reactions can be categorized into three types: inherent, associated, and interfering. These ACE types originate from the solvent, solutes, and reactor, respectively. Distinguishing and evaluating these ACEs is crucial for elucidating reaction mechanisms and developing reaction models. Water exhibits inherent ACE in both its dissociated and undissociated forms under hot compressed conditions. Hot compressed water–alcohol mixtures possess the capability to tune the characteristics of solvents, including ACE, through their composition. The application of hot compressed water and water–alcohol is prevalent in a variety of fields, including the conversion of biomass and biomass-derived materials, extraction, biodiesel production, organic synthesis reactions, recycling via the decomposition of polymers, and inorganic material synthesis. In these applications, the utilization of water–alcohol mixtures resulted in a higher yield of target products and/or superior properties of products compared to the use of pure solvents, such as water alone or alcohol alone. The observed results can be attributed to the optimization of the roles of water and alcohol in the reaction through mixing them. Full article

Electrocatalytic H₂O₂ production via the two-electron oxygen reduction reaction (ORR) is a highly sustainable alternative to industrial methods. To further optimize non-noble catalysts, we report an interfacial engineering strategy to stabilize the metastable P6₃/mmc-La₂O₃ phase on SrTiO₃. This symmetry evolution from the low-symmetry $\mathrm{P}\stackrel{\mathrm{-}}{3}\mathrm{m}1$ (trigonal) to the high-symmetry P6₃/mmc (hexagonal) space group yields a composite with >95% H₂O₂ selectivity. Mechanistic studies demonstrate that the symmetry-regulated interface optimizes *OOH conversion and suppresses O–O bond cleavage. This work offers a robust design principle for high-performance, noble-metal-free H₂O₂ electrosynthesis. Full article

The widespread presence of stable and hazardous organic contaminants, such as synthetic dyes, in industrial effluents necessitates the development of resilient treatment strategies capable of achieving efficient degradation and decolorization of dye pollutants. Conventional treatment processes often fail to remove such recalcitrant compounds, prompting growing interest in integrated advanced systems. Photocatalytic membranes represent a promising solution due to the synergistic combination of physical separation and catalytic degradation. In this study, zinc oxide (ZnO) thin films were deposited by spin coating onto smectite–zeolite ceramic membranes (MS10/Z90), applying one (M1), two (M2), and three (M3) successive coating layers to control catalyst thickness. SEM analysis confirmed that increasing the number of layers resulted in a thicker and more homogeneous ZnO coating, while XRD revealed enhanced crystallinity and larger crystallite size. Water permeability decreased progressively from 623 L·h⁻¹·m⁻²·bar⁻¹ for the uncoated membrane to 506, 439, and 350 L·h⁻¹·m⁻²·bar⁻¹ for M1, M2, and M3, respectively. Photocatalytic performance was evaluated using Rhodamine B (RhB) (10 mg·L⁻¹) under UV irradiation (365 nm, 18 W) for 180 min, achieving degradation efficiencies of 83.0%, 94.6%, and 99.1% for M1, M2, and M3, respectively. The degradation kinetics followed a pseudo-first-order model, with rate constants increasing with catalyst layer thickness. Free radical scavenging assays confirmed that hydroxyl radicals (•OH) were the primary reactive species responsible for RhB degradation. These findings highlight the critical influence of ZnO layer thickness and mass transfer on photocatalytic performance, demonstrating the potential of ZnO-coated ceramic membranes for efficient pollutant degradation and in situ photocatalytic regeneration. Permeability measurements after photocatalytic treatment confirmed effective flux recovery, supporting the operational durability of the developed membranes. Full article

To in situ and efficiently degrade irreversible membrane contaminants under mild conditions, SiC ceramic membranes (CMs) were imparted a catalytic ozonation functionality. A spinel-type CoFe₂O₄ catalyst was fabricated via a citrate-assisted sol–gel method and subsequently impregnated into the macropores of SiC ceramic membranes through a urea-assisted one-step combustion technique. The as-prepared catalytic membranes (CoFe₂O₄-CM) were systematically characterized by SEM, EDS, XRD and XPS techniques, and the catalytic ozonation performance was evaluated in an integrated catalytic ozonation–membrane separation system (CoFe₂O₄-CM/O₃). A flux recovery rate (FRR) of 93.33% was achieved at an ozone concentration of 70.27 mg·L⁻¹ within 30 min, indicating that a catalytic self-cleaning membrane was successfully developed. The possible catalytic reaction mechanism was elucidated by identifying reactive oxygen species generated using free radical quenching tests and electron paramagnetic resonance (EPR) analysis. This study offers a promising and environmentally friendly strategy for ceramic membrane cleaning in various membrane separation fields. Full article

Oxidative catalytic fractionation (OCF) under the lignin-first strategy has emerged as a critical technological approach for biomass refining. To address the inevitable carbohydrate degradation and lignin condensation in conventional OCF, this study designed a cobalt-doped layered double hydroxide oxide (Co-LDO) catalyst compatible with non-alkaline (without Brønsted bases) organic systems, which exhibits excellent performance in poplar biomass OCF. With a straightforward preparation process, the Co-LDO catalyst yields high-content oxidized lignin oligomers while efficiently retaining carbohydrates, providing feedstock rich in carbohydrates (cellulose and hemicellulose) for the subsequent production of bioenergy and biomass-based chemicals. Under optimized conditions screened via systematic reaction condition investigation and metal-doped LDO catalyst evaluation, the process achieved a 94.01 wt% delignification rate, with 72.19 wt% of lignin converted into lignin oligomer oil, supported by detailed product composition and structural characterization. Meanwhile, 74.14 wt% hemicellulose and 98.23 wt% cellulose were recovered in solid residues, with structurally intact hemicellulose retention being 2.3 times higher than in traditional OCF. Mass balance calculation confirmed a total poplar refining yield of 81.58 wt%. In summary, this Co-LDO-catalyzed OCF strategy provides a high-activity non-precious metal system, effectively suppressing lignin condensation while preserving high-yield carbohydrates, realizing the efficient full-component refining of poplar biomass. Full article

Ammonia decomposition represents a promising route for carbon-free hydrogen production, provided that efficient and cost-effective catalysts are developed. In this study, lanthanum-based mixed oxide catalysts (LaNi, LaCo, and LaCe) were synthesized via a controlled co-precipitation method and systematically evaluated for catalytic ammonia decomposition under atmospheric pressure in the temperature range of 350–500 °C. Comprehensive characterization combining N₂ physisorption, XRD, SEM–EDX, TGA–DTG, XPS, and FTIR-pyridine adsorption revealed pronounced structure–property relationships. LaNi exhibited the highest surface area (31.11 m²·g⁻¹), well-developed mesoporosity, and a balanced Lewis/Brønsted acidity (C_L/C_B ≈ 0.82), leading to superior catalytic performance with NH₃ conversion reaching ~48% at 500 °C (GHSV = 50 h⁻¹). LaCo showed intermediate activity (~30% conversion), while LaCe displayed limited performance (<13%), most likely due to its dense morphology and low surface accessibility. Increasing gas hourly space velocity resulted in decreased ammonia conversion for all catalysts, highlighting the critical role of residence time. These findings demonstrate that the catalytic efficiency of lanthanum-based systems is governed by the synergistic interplay between surface area, mesoporous architecture, and acidity distribution, with LaNi emerging as the most promising catalyst among the investigated materials. Full article

A one-pot green combustion route was developed for the synthesis of ashy single-crystalline NiO nanoparticles using date molasses as a biogenic fuel and complexing medium. The obtained DM–NiO showed phase-pure cubic NiO with an average crystallite size of about 18 nm, a mesoporous texture with a BET surface area of 68.9 m² g⁻¹, a pore volume of 0.59 cm³ g⁻¹, an average pore diameter of 17.6 nm, and a mean particle size of 43.6 ± 8.13 nm. Optical characterization revealed defect-mediated light absorption with an energy gap of 3.11 eV, supporting solar-light-driven activity. In the photocatalytic degradation of pyronin Y, the catalyst exhibited strong pH dependence, reaching its best H₂O₂-free performance at pH 11 with a pseudo-first-order rate constant of 0.0072 min⁻¹, nearly six times higher than that at pH 3. The introduction of H₂O₂ markedly intensified the process, and at 9 mM H₂O₂, the rate constant increased to 0.048 min⁻¹, representing more than a sixfold enhancement over photocatalysis alone, while complete disappearance of the main visible absorption band was achieved within 38 min under solar illumination. Radical trapping experiments identified photogenerated holes and hydroxyl radicals as the dominant oxidative species. The catalyst also retained high activity over four successive cycles, with degradation efficiencies decreasing only slightly from 91.8% to 85.7%. These results demonstrate that date-molasses-assisted combustion synthesis provides a sustainable route to defect-active mesoporous NiO with highly enhanced solar photo-Fenton-like performance for dye-contaminated wastewater treatment. Full article

Wheat straw is an abundant agricultural residue with high potential for carbohydrate-based bioconversion, yet its efficient utilization is limited by lignocellulosic recalcitrance. This study systematically investigated Organosolv extraction of wheat straw (Triticum aestivum) with the goal of achieving near-complete enzymatic hydrolysis at minimized process severity and energy demand. Process severity was evaluated using the P-Factor concept. In preliminary screening, acid catalysts and liquor ratios were assessed. Strong acids clearly outperformed weak acids: at comparable severity, 5% (w/w, DM) H₂SO₄ or p-toluenesulfonic acid (PTSA) yielded glucose yields of 83 ± 2.4% and 81 ± 6.2%, respectively, whereas weak acids (phosphoric, lactic, acetic) and a catalyst-free control resulted in only ~20–41% glucose yield. Liquor ratio strongly affected extraction performance; a ratio of 1:19 provided the highest glucose yield (85 ± 1.4%) and robust mixing compared to 1:12–1:15 (67–68%). Two novel pretreatment strategies applied prior to Organosolv extraction, namely Hot-Water Pretreatment (HWP) and Water Pretreatment (WP), significantly increased hydrolysability compared to untreated straw (58 ± 3%), reaching 79 ± 2% for HWP and 86 ± 5% for WP. DoE-based experiments (135–170 °C; P-Factor 3.0–4.0) showed that increasing temperature from 135 to 150 °C markedly improved hydrolysability (e.g., WP: 74 ± 3% to 96 ± 3%), while further increasing to 170 °C provided no additional benefit. Response-surface modeling predicted a maximum hydrolysability of approximately 88% for HWP but complete hydrolysis for WP within 152–170 °C, indicating a broad operational window. Overall, combining simple Water-based Pretreatment with severity-optimized Organosolv extraction enables energy-efficient, near-complete hydrolysis at lower operating temperatures, reducing both energy demand and pressure requirements, and thereby offering advantages in process cost and scalability. Full article

Utilizing the pyrolysis reaction of endothermic hydrocarbon fuels to provide thermal protection for hypersonic vehicles is a feasible approach. The introduction of catalysts or cracking-initiating additives could promote hydrocarbon fuel cracking and increase the reaction heat sink. Catalysts such as ZSM-5 zeolite, Al₂O₃, and precious metals were commonly used for hydrocarbon fuel cracking. By optimizing their pore structure and acidity, their catalytic cracking performance can be effectively improved. These catalysts can function not only as catalytic coatings but also be dispersed in the fuel to act via quasi-homogeneous catalytic cracking. Additionally, small-molecule and macromolecular additives could crack at lower temperatures to generate active free radicals, thereby initiating the cracking of hydrocarbons and increasing the reaction heat sink. Under the conditions of a reaction temperature of 650–750 °C, a pressure of 3–5.5 MPa, and a fuel flow rate of 1 g/s, quasi-homogeneous catalysts can enhance the heat sink of hydrocarbon fuel cracking by 5–21%, while cracking-initiating additives can enhance it by 5.6–8.6%. Therefore, based on the different action modes of catalysts or additives, this review summarizes the recent research on improving the cracking of endothermic hydrocarbons from three aspects: coating catalysts, quasi-homogeneous catalysts, and cracking-initiating additives. Subsequently, the potential challenges of each approach in practical applications are analyzed. Furthermore, based on the current research findings, we outline future research directions with the expectation of facilitating the advancement of efficient cracking technologies for endothermic hydrocarbons. Full article

Gold(I) complexes are particularly useful as catalysts in a variety of reactions including, in particular, the electrophilic activation of alkyne substrates, yet they generally require the addition of a silver salt to activate the gold complex by removing an anionic ligand. This results into higher costs and possible problems related to the non-innocence of the silver additive. In this contribution, we highlight the possibility to proficiently use a dinuclear monocationic gold(I) complex developed in our laboratory as a silver-free catalyst. The complex, featuring a bridging N-phosphanyl-N-heterocyclic carbene (NHCP) ligand, indeed exhibits notable activity and selectivity in standard alkyne hydroamination and hydroalkoxylation reactions, particularly in the case of internal alkynes and secondary aromatic amines as substrates. Full article

Emerging pharmaceutical contaminants, including sulfonamide antibiotics such as sulfamethoxazole (SMX), persist in natural water bodies at ng L⁻¹ to µg L⁻¹ concentrations and are inadequately removed by conventional wastewater treatment technologies, posing significant ecological and public health risks. Porphyrin-based quantum catalysts activated by peroxymonosulfate (PMS) represent a promising advanced oxidation strategy for the remediation of such recalcitrant micro-pollutants. However, the precise molecular mechanisms governing their catalytic activity remain incompletely understood. In this study, we present a comprehensive mechanistic investigation of SMX oxidation catalyzed by Mn (III) meso-tetraphenylporphyrin (Mn-TPP) in the presence of PMS, employing spin-unrestricted density functional theory (DFT) at the Becke, 3-parameter, Lee–Yang–Parr (B3LYP-D3BJ) level of theory with dispersion corrections. Full Gibbs free energy profiles for the catalytic cycle were constructed through geometry optimizations using the LACVP basis set on Mn and 6-31G(d,p) on all non-metal atoms, followed by single-point energy calculation at the 6-311+G(d,p) level, incorporating the SMD implicit solvation model to stimulate aqueous environment conditions. The results demonstrate that the oxidation of Mn TPP by PMS to generate the key high-valent intermediate Mn(V)=O(TPP)⁺ is thermodynamically and kinetically favorable. The activation barrier for Mn(V)=O(TPP)⁺ formation via PMS activation is ΔG† = 17.2 kcal mol⁻¹ (SMD water, 298 K), confirming that this step is kinetically accessible under ambient environmental conditions. Subsequent SMX oxidation processes proceed via concerted radical and non-radical mechanistic pathways, with the most thermodynamically favorable route exhibiting a strongly exergonic reaction-free energy (ΔGr), indicating that significant mineralization of the target pollutant is thermodynamically accessible. The transition state analysis reveals spin density localization characteristic of the Mn-Oxo species, establishing a direct correlation between quantum confinement effects, electronic structure and the observed catalytic selectivity and oxidation stability of the Mn-TPP system. These mechanistic insights provide quantitative molecular-level design parameters, including activation barriers, spin state requirements, and electronic structure descriptors for the rational optimization of next-generation porphyrin-based quantum catalysts capable of efficiently degrading persistent pharmaceutical contaminants in complex aqueous matrices. Full article

The controllable growth of in-plane Ge nanowires provides alternative material foundations for the scalability of Ge-based semiconductor qubit devices. Here, ordered in-plane Ge hut wires with controllable size are grown on the trench-patterned Si substrate by molecular beam epitaxy. By tuning the thickness of the SiGe alloy layer, which acts as strain buffered layer, GeSi mounds with controllable size are achieved. Subsequently, through the deposition of a Ge layer followed by in situ annealing, we realize the size-controllable growth of the Ge nanowire with a height from 1.8 nm to 4.0 nm, as characterized by AFM and TEM techniques. These size-tunable and catalyst-free Ge hut wires provide a promising pathway toward the fabrication of integrated nanowire-based quantum devices. Full article

Efficient charge transfer and effective separation of photo-generated charge carriers are pivotal to the photocatalytic process. In this study, a novel CoAl₂O₄@nitrogen-doped graphitic carbon (CoAl₂O₄@NGC) composite photocatalyst was fabricated via a stepwise hydrothermal method coupled with high-temperature calcination, and its photocatalytic performance for CO₂ reduction was systematically investigated. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and photoelectrochemical measurements were employed to characterize the phase structure, microstructure, surface chemical state and photoelectrochemical properties of the catalyst. Spinel-structured CoAl₂O₄ nanoparticles were uniformly anchored on the NGC substrate, forming a well-integrated composite interface. XPS analysis confirmed the coexistence of Co²⁺/Co³⁺ mixed valence states in CoAl₂O₄ which provides abundant redox sites for CO₂ activation. Photocatalytic tests showed that CoAl₂O₄@NGC exhibits excellent catalytic activity and cycling stability, with CO and CH₄ yields of 27.88 μmol·g⁻¹·h⁻¹ and 23.90 μmol·g⁻¹·h⁻¹, respectively. The narrow bandgap (1.54 eV) enhances visible light absorption, while efficient electron-hole separation and reduced charge transfer resistance improve photocatalytic efficiency. Theoretical calculations further reveal that CoAl₂O₄@NGC lowers the adsorption free energy of CO₂ and the energy barrier for COOH formation, thus facilitating the photocatalytic CO₂ reduction. This work provides insights for the design of efficient and stable photocatalysts for CO₂ reduction and deepens the understanding of the synergistic catalytic mechanism in the spinel/nitrogen-doped carbon composite system. Full article

The PGM-free Fe–Ni–Co trimetallic catalysts developed in this study demonstrated outstanding performance for the oxygen evolution reaction (OER), achieving overpotentials as low as 300 mV at 10 mA cm⁻² in rotating disk electrode (RDE) measurements, a value competitive with the most efficient non-noble electrocatalysts reported in the literature. This study validates the strong catalytic performance of the baseline trimetallic configuration and provides important insights into the relationships among synthesis, structure, and morphology that govern catalyst activity. In particular, the findings highlight that although organic additives can be promising modifiers, the interaction between precursors and transition metals must be carefully controlled to avoid active-site isolation when designing efficient catalysts for sustainable hydrogen production. Actually, to further enhance catalytic activity, the nitrogen-rich precursor melamine was introduced into the supported trimetallic catalyst and then carbonized. However, no improvement in OER performance was observed. During carbonization, melamine promotes the formation of tip-growth carbon nanotubes, which mechanically disrupt the catalyst structure and degrade the supported active phase. Full article