We prepared an alumina-modified carbonized wood composite material by the sol-gel method, achieving the simultaneous improvement in thermal conductivity, self-extinguishing behavior, and bacterial growth inhibition performance. Microscopic and spectroscopic characterizations confirmed the successful incorporation of alumina into the carbonized wood framework, while the deposited particles became more pronounced with increasing alumina loading. In the material weight loss test, at a temperature of 600 degrees C, the weight loss of alumina-modified composites was 2.7%, while that of the unmodified material was 12.5%. The thermal conductivity of the alumina-modified composite is significantly higher than that of the unmodified one, reaching a maximum of 0.825 W m-1 K-1, which is 476.9% higher than that of carbonized wood. For this series of composites, the bacterial growth inhibition is stronger before filtration than after filtration. The apparent bacterial growth inhibition rate of the alumina-modified composite before filtration can reach up to 80.94%, which is 143% higher than that of carbonized wood before filtration. The modified materials obtained in this work overcome the shortcomings of natural wood in terms of poor thermal stability and weak bacterial growth inhibition performance. As a result, they not only extend the service life of wood, expand its application scope, but also make up for the deficiency of traditional carbonized wood in bacterial growth inhibition performance.

Catalytic hydrogenation of CO2 over In2O3 has attracted intense interest due to its exceptionally high methanol selectivity and broad tunability through structural modification. However, the precise formation mechanism of oxygen vacancies (OVs) and exact roles of hydroxyl groups (InOHs), the two most important surface structures, remain poorly understood due to the limited resolution of currently available characterization methods. Here, by employing an advanced 17O labeling strategy combined with high-field solid-state NMR (ssNMR) up to 18.8 T, we achieve exceptionally high spectral resolution of 17O NMR, enabling explicit separation of distinct surface oxygen species. This approach allows tracing the thermal evolution of these species and probing their reactivities toward CO2 activation and hydrogenation. Notably, surface OIn3 sites are identified as the OV precursors, with a formation barrier of approximately 200°C. Unexpectedly, room-temperature oxygen exchange between In2O3 and CO2 is observed, enabled by the high sensitivity of the new 17O NMR method. Further probing with 13CO2 and/or H2, at variable temperatures, we are capable of unraveling the roles between OVs, InOHs and surface lattice oxygen species in CO2/H2 activation and their stepwise conversion into formate intermediates and ultimately methanol, which may prompt rational designs to lower the reaction temperature for In2O3.

Persulfate-based advanced oxidation processes (PS-AOPs) represent a green and sustainable approach for degrading environmental contaminants like bisphenol A (BPA). However, the practical application of conventional heterogeneous iron-based catalysts in PS-AOPs is often hindered by their low atom-utilization efficiency, complex active sites, and suboptimal catalytic performance. To address these limitations, this study reports the successful synthesis of a single-atom iron catalyst anchored on 3D N-doped porous carbon (SAC-Fe) for efficient activation of peroxydisulfate (PDS) to degrade BPA. The SAC-Fe catalyst demonstrated superior performance, achieving 100% BPA degradation with an impressive turnover frequency of 13.62 Lmin-1g-1. The system demonstrated good robustness, maintaining high performance across a broad pH window (3-9) and in the presence of common inorganic anions and complex water matrices. Mechanistic investigations including scavenging tests, probe experiments, and electron paramagnetic resonance (EPR) spectroscopy revealed that the catalytic degradation of BPA by SAC-Fe/PDS follows a synergistic nonradical pathway. In this pathway, PDS first reacts with atomically dispersed Fe-N X active sites on SAC-Fe to generate a surface-bound, high-valent iron-oxo intermediates, which is followed by the degradation of BPA by this active species. Additionally, the NC support in SAC-Fe also participates in PDS activation, promoting BPA degradation synergistically following the electron transfer process. Further investigation indicated this pathway also possesses superior selectivity toward representative emerging contaminants containing electron-donating groups.

As a highly reactive reaction intermediate, surface gallium hydride (Ga-H) has garnered significant attention due to its critical role in various catalytic reactions. However, the detailed experimental characterization of this unique species remains challenging. Recently, we have demonstrated that solid-state NMR can be an effective tool for studying surface Ga-H. In this work, we report a comparative solid-state NMR study on H-2 activation over different Ga2O3 polymorphs, specifically alpha-, beta- and gamma-Ga2O3. H-1 solid-state NMR enabled the identification of Ga-H species formed on all the three samples following high-temperature H-2 treatment. The characteristic H-1 NMR signals of Ga-H species are resolved using J-coupling-based double-resonance NMR methods, revealing highly similar lineshapes of Ga-H for all the Ga2O3 samples. This suggests potentially similar surface Ga-H configurations among different Ga2O3 polymorphs. In addition, the local hydrogen environments on the oxide surfaces are further explored using two-dimensional (2D) H-1-H-1 homonuclear correlation spectra, revealing multiple spatially proximate Ga-H and Ga-H/-OH pairs on different Ga2O3 polymorphs. These findings provide insights into the potential mechanism of H-2 dissociation. Overall, this work offers new perspectives on the local structure of surface Ga-H on Ga2O3, and the analytical approach presented here can be further extended to the study of other Ga-based catalysts and other metal hydride species.

Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O. Herein, a novel Al2O3/C-u hybrid catalyst, composed of N-modified dendritic carbon networks supporting Al2O3 nanoparticles, was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate, Al3+ and urea. The obtained carbon-supported Al2O3 hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state. The introduction of urea enhances the surface N content, the ratio of pyrrolic N, and specific surface area of catalyst, leading to improved adsorption capacity of C=O and the accessibility of active sites. In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor, Al2O3/C-u catalyst achieved a 90% conversion of furfural with 98.0% selectivity to furfuryl alcohol, outperforming that of commercial γ-Al2O3. Moreover, Al2O3/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al2O3 nanoparticles. This work provides an innovative and facile strategy for fabrication of carbon-supported Al2O3 hybrid catalysts with rich AlV species, serving as a high selective hydrogenation catalyst through MPV reaction route.

The emerging oxide–zeolite bifunctional catalysis for direct syngas conversion has drawn extensive interest, both academically and industrially, with further exploration urging a clear mechanistic understanding of this complex catalytic network. Herein, using a specially designed quasi-in situ, solid-state nuclear magnetic resonance-gas chromatography/gas chromatography-mass spectrometry analysis strategy, this reaction is fully monitored from the very early induction period to steady-state conversion under high-pressure flow-reaction conditions, using ZnAlO x /H-ZSM-5 composites as model catalysts. We identify abundant critical and/or transient intermediates in dynamic evolution, including carboxylates, alkoxyls, acid-bounded methyl-cyclopentenones and methyl-cyclopentenyl carbocations, providing direct evidence of vigorous regulation by unique, oxygenate-based pathways of the reaction network. This proposed mechanism overturns the general cognition of oxide–zeolite reactions as simple tandem catalysis, and highlights the many roles (both positive and negative) of CO and H 2 molecules via oxygenate-based routes, thus dictating the final product. The current characterization technology and its mechanistic understanding would benefit further exploration in bifunctional catalysis.

The simultaneous removal of NO and SO2 has always been a challenge in a single reactor instead of process integration. The key of this process is to enhance NO conversion to soluble N-species. Here, a high gravity (HiGee)-enhanced AOP using Fe2+ -catalyzed alkaline H2O2 system is proposed to improve NO oxidation for NO and SO2 simultaneous attenuation within a single Rotating Packed Bed (RPB). We found that an instant mix of FeSO4 and alkaline H2O2 solution shows an excellent capacity in deeply removal NO and SO2 in the RPB. O2˙- is proved to be the dominated radical responsible for NO conversion with ONOO- formed as intermedia. FeSO 4 prompts the NO removal by providing more ˙OH from alkaline H2O2, leading to a higher O2˙- yields. Increased NaOH is conducive to NO removal since it helps O2˙- generation from H2O2. A high gravity level in HiGee process significantly intensifies NO and SO2 capture since the rapid renewal of the liquid film provides more chance for ˙OH, O2˙- and H2O2 to be exposed on the surface of the liquid film. Exploiting this inherent but previously unrecognized mechanism provides theory guide for the HiGee-enhanced AOP technology development in simultaneously removing NO and SO2 .

NMR experiments reveal a mechanism of syngas conversion in which CO reacts with OCH3 on the oxide surface, generating ketene intermediates, which can either form acetate or diffuse into zeolite.

The simultaneous removal of NO and SO2 has always been challenging in a single reactor. The key to solving this problem is to enhance NO conversion to soluble N species. In this study, a high-gravity (HiGee)-enhanced advanced oxidation process (AOP) using a Fe2+-catalyzed alkaline H2O2 system was proposed to improve NO oxidation for simultaneous NO and SO2 attenuation within a single rotating packed bed (RPB). We found that the mixture solution obtained by momentarily mixing FeSO4 and alkaline H2O2 had excellent capacity for thoroughly removing NO and SO2 in the RPB. O2 center dot- has proven to be the dominant radical responsible for NO conversion, with ONOO- acting as an intermediate. FeSO4 promotes NO removal by providing ?OH from alkaline H2O2, resulting in higher O2 center dot-yields. Increased NaOH is conducive to NO removal because it promotes O2 center dot- generation from H2O2. A high gravity level in the HiGee process significantly intensified NO and SO2 capture because the rapid renewal of the liquid film provided more opportunities for?OH, O2 center dot-, and H2O2 to be exposed on the surface of the liquid film. Exploiting this inherent but novel mechanism provides theoretical guidance for developing HiGee-enhanced AOP technology that can simultaneously remove NO and SO2.

Chemotherapy is a primary cancer treatment strategy, the monitoring of which is critical to enhancing the survival rate and quality of life of cancer patients. However, current chemotherapy monitoring mainly relies on imaging tools with inefficient sensitivity and radiation invasiveness. Herein, we develop the bowl-shaped submicroreactor chip of Au-loaded 3-aminophenol formaldehyde resin (denoted as APF-bowl&Au) with a specifically designed structure and Au loading content. The obtained APF-bowl&Au, used as the matrix of laser desorption/ionization mass spectrometry (LDI MS), possesses an enhanced localized electromagnetic field for strengthened small metabolite detection. The APF-bowl&Au enables the extraction of serum metabolic fingerprints (SMFs), and machine learning of the SMFs achieves chemotherapy monitoring of ovarian cancer with area-under-the-curve (AUC) of 0.81-0.98. Furthermore, a serum metabolic biomarker panel is preliminarily identified, exhibiting gradual changes as the chemotherapy cycles proceed. This work provides insights into the development of nanochips and contributes to a universal detection platform for chemotherapy monitoring.

The complex flows under high gravity in intricate advanced oxidation reactions expose a high-gravity advanced oxidation process (HiGee-AOP) modeling and control to uncertainty. Existing methods based on conservation equations cannot describe such a process with sufficient accuracy because of the mismatch between the assumptions and actual system behavior. Here, we propose a fuzzy-logic-based modeling and control scheme for a HiGee-AOP for nitric oxide (NO) attenuation. A hybrid fuzzy model is presented based on the theoretical model and a collection of if-then rules describing the difference between the theoretical model and the real system. Subsequently, the model serves as the internal model, associated with the fuzzy control rules illustrating the recommended actions under various conditions to construct the adaptive fuzzy controller. The results show that the model-simulated values are in good agreement with the experimental data, with a deviation of -0.81 +/- 15.02%, and that the controller has good tracking performance.

Organic and inorganic structure-directing agents (SDAs) impact Al distributions in zeolite, but the insights into how SDAs manipulate Al distribution have not been elucidated yet. Herein, the roles of different SDAs such as cyclohexylamine (CHA), hexamethylenimine (HMI), and Na+ in selective Al substitution of MCM-49 zeolite are investigated comprehensively by multinuclear solid-state NMR. The results demonstrate that MCM-49 synthesized with HMI shows relatively more T6 and T7 Al, while more T2 Al is observed using CHA. The formation of T2 Al in both MCM-49(HMI) and MCM-49(CHA) is derived from Na+, while protonated HMIs show bias in incorporation of T6 and T7 Al. Most HMIs are occluded in protonated status, and about half of CHAs are occluded in nonprotonated status. The close spatial proximity between nonprotonated CHAs and Na+ synergistically promotes the formation of zeolite structure, leading to more Na+ ions occluded in the zeolite channel with preferential T2 Al substitution.

Production of value-added chemicals from oriented methane conversion under mild conditions is of great significance for utilization of the energy resources, which, however, remains a great challenge due to its difficulty in the selective activation of C?H bond. Herein, we report a highly selective and efficient methane conversion to formic acid on atomically dispersed Fe sites confined in the nano-channels of ZSM-5. The turnover frequency for producing C1 liquid oxygenates reaches 84,200 h-1 with a high selectivity of 91% to formic acid at 80 ?C, which outperforms all previously reported catalysts. Electron paramagnetic resonance analysis and density functional theory calculations demonstrate that the ZSM-5-confined Fe-O active centers can facilely dissociate the C?H bonds and catalyze successive oxidation of methane to formic acid via free radical mechanisms under mild conditions. This study opens a new path of engineering the microenvironment of confined Fe sites within nanochannels toward highly selective methane conversion with low energy input.

A novel High-Gravity Advanced Oxidation Process (HiGee-AOP) using basic H2O2 solution as a liquid oxidizing reagent was examined for enhanced NOx removal efficiency in this study. At ambient temperature and optimal conditions, the process achieved a 99% removal of the inlet 1000 ppm NO. Spectroscopic experiments and radical-quenching tests indicated that the nucleophilic hydroperoxyl anion (-OOH) dissociated from H2O2 was the strongest reactive oxygen species (ROS) responsible for NO oxidation in alkaline H2O2, producing peroxynitrite (ONOO-) as detected by Fluorescence Spectroscopy. A mass transfer model coupling the reaction kinetics and gas diffusion under high liquid-film renewal conditions was established to simulate the HiGee-AOP process for NO absorption, and it achieved a model-prediction accuracy of within 10% of experimental data. It is speculated that the improved NO removal efficiency by the HiGee-AOP/alkaline H2O2 process stems from the enhanced mass transfer of NO in the heterogeneous reaction system provided by HiGee and the strong affinity of OOH to NO. Oxidation of NO by OOH may proceed first to form the [NO center dot center dot center dot OOH](-) intermediate due to a strong nucleophile-electrophile interaction, which is followed by an electron transfer within the intermediate producing ONOO- and ultimately as nitrate.

The combustion of fossil fuels has resulted in rapidly increasing emissions of nitrogen oxide (NO x ), which has caused serious human health and environmental problems. NO capture has become a research focus in gas purification because NO accounts for more than 90% of NO x and is difficult to remove. Advanced oxidation processes (AOPs), features the little secondary pollution and the broad-spectrum strong oxidation of hydroxyl radicals ( • OH), are effective and promising strategies for NO removal from coal-fired flue gas. This review provides the state of the art of NO removal by AOPs, highlighting several methods for producing • OH and SO 4 •− . According to the main radicals responsible for NO removal, these processes are classified into two categories: hydroxyl radical-based AOPs (HR-AOPs) and sulfate radical-based AOPs (SR-AOPs). This paper also reviews the mechanisms of NO capture by reactive oxygen species (ROS) and SO 4 •− in various AOPs. A HiGee (high-gravity) enhanced AOP process for improving NO removal, characterized by intensified gas-liquid mass transfer and efficient micro-mixing, is then proposed and discussed in brief. We believe that this review will be useful for workers in this field. Graphical abstract

The combustion of fossil fuels has resulted in rapidly increasing emissions of nitrogen oxide (NOx), which has caused serious human health and environmental problems. NO capture has become a research focus in gas purification because NO accounts for more than 90% of NOx and is difficult to remove. Advanced oxidation processes (AOPs), features the little secondary pollution and the broad-spectrum strong oxidation of hydroxyl radicals (•OH), are effective and promising strategies for NO removal from coal-fired flue gas. This review provides the state of the art of NO removal by AOPs, highlighting several methods for producing •OH and SO4•−. According to the main radicals responsible for NO removal, these processes are classified into two categories: hydroxyl radical-based AOPs (HR-AOPs) and sulfate radical-based AOPs (SR-AOPs). This paper also reviews the mechanisms of NO capture by reactive oxygen species (ROS) and SO4•− in various AOPs. A HiGee (high-gravity) enhanced AOP process for improving NO removal, characterized by intensified gas-liquid mass transfer and efficient micro-mixing, is then proposed and discussed in brief. We believe that this review will be useful for workers in this field.

为了减少工业排放氮氧化物(NOx)对大气造成的污染,需要去除难溶性的NO.活性氧簇(ROS)可以将NO氧化为水溶性NO2,超重力机可以强化气液传质效果.结合二者的优势,文章提出了一种在超重力环境下利用ROS氧化去除NO的方法.研究了吸收液pH值、转速、温度、气液比、气体浓度、吸收液循环对NO脱除率的影响,并对吸收产物进行了测定.结果 表明,在20℃,H2O2浓度为1 mol/L,H2O2溶液pH为13,超重力机转速为1 200 r/min时,NO的脱除效率最好.当NO体积浓度为500×10-6,气液比为100时,NO的脱除效率可达96％.NO最终变为NO3-存在于液相中,且该吸收液可以用于同步脱硫脱硝.

We report a comprehensive understanding of the stereoselective interaction between two opposite enantiomeric polyesters prepared from the regioselective copolymerization of chiral terminal epoxides and cyclic anhydrides. For many of the resultant polyesters, the interactions between polymer chains of opposite chirality are stronger than those of polymer chains with the same chirality, resulting in the formation of a stereocomplex with enhanced melting point (Tm) and crystallinity. The backbone, tacticity, steric hindrance of the pendant group, and molecular weight of the polyesters have significant effects on stereocomplex formation. Bulky substituent groups favor stereocomplexation, resulting in a greater rise in Tm in comparison with the component enantiomeric polymers. Stereocomplex assembly of discrete (R)- and (S)-poly(phenyl glycidyl ether-alt-phthalic anhydride)s oligomers revealed that the minimum degree of polymerization required for stereocomplex formation is five. Raman spectroscopy and solid-state NMR studies indicate that stereocomplex formation significantly restricts the local mobilities of C=O and C-H groups along the backbone of chains. The reduced mobility results in the enhanced spin-lattice relaxation time and both 1H and 13C downfield shifts due to the strong intermolecular interactions between (R)- and (S)-chains.

The effect of the Al 2 O 3 structure on the performance of Pt/Ga/Al 2 O 3 catalysts is investigated for the direct dehydrogenation of propane. The study unveils that the structure of Al 3+ determines the bulk structure of catalysts, particularly a high content of coordinatively unsaturated Al 3+ sites(penta-coordinated Al 3+ ,denoted as Al 3+ penta) could lead to a remarkably improved dehydrogenation activity of the catalyst. The bulk characterization reveals that the sufficient amount of Al 3+ pentain Al 2 O 3 benefit the dispersion of Pt and Ga 2 O 3 on the Al 2 O 3 support. At the same time, TPR results reveal that the presence of Pt facilitates the reduction of Ga 2 O 3 , likely due to the hydrogen spillover between the well dispersed Pt and Ga 2 O 3 ,which consequently enhances the synergistic function between Pt and Ga 2 O 3 in the dehydrogenation of propane. Recyclability tests demonstrate that the dehydrogenation activity stabilizes after three cycles over the Pt/Ga/Al 2 O 3 catalyst.