Search Results (57)

The key to selectively cleaving C–O bonds in lignin to produce high-value aromatic chemicals lies in the development of efficient and stable catalysts. In this study, a heterostructured catalyst with N-doped carbon-supported Co and dual-phase Mo_xC nanoparticles was prepared via the in situ pyrolysis of a Co–Mo–N precursor. The dual-phase α-MoC/β-Mo₂C heterostructure is adjusted by varying the Co:Mo ratio to affect the structure and electronic properties of the catalyst. The heterostructures bring about enhanced electron transfer from Co to Mo, which promotes hydrogen dissociation over the Co sites, significantly improving the catalyst’s hydrogenolysis activity and stability. The optimal catalyst with Co₁Mo_xC@NC exhibits excellent hydrogenolysis activity; under the optimal reaction conditions (260 °C, 1 MPa H₂, 3 h), the yield of aromatic monomers reaches 28.5%. Such prominent performance not only benefits from the numerous α-MoC/β-Mo₂C hetero-interfaces that offer abundant active sites for hydrogen dissociation, but also should be ascribed to the strong synergistic effect between Co and Mo. Full article

Low-molecular-mass gelators (LMMGs) as stabilizers for gel emulsions offer numerous advantages, such as low usage, functionalizability, and insensitivity to phase ratio. Using LMMGs as stabilizers is one of the effective strategies for preparing gel emulsions. Currently, developing LMMGs and stable gel emulsion systems in a rapid and convenient manner remains a challenge. To cope with the challenge, this study aims to develop a simple and efficient gel emulsion preparation method based on LMMGs. In this study, a cholesterol-based star-shaped derivative (CSD) was designed and synthesized as an LMMG. Based on gelation experiments, a high internal phase W/O gel emulsion system (H₂O/CSD-poly(oligo)-dimethylsiloxane/dichloromethane) was successfully developed and stabilized synergistically by the stabilizer (CSD) and the crosslinker (poly(oligo)-dimethylsiloxane with two olefinic bonds at its ends, D-PDMS). The results demonstrate that the synergistic interaction between CSD and D-PDMS is critical for the formation of the gel emulsion. Building on the original gel emulsion system, two novel in situ polymerizable gel emulsion systems (H₂O/CSD-D-PDMS/dichloromethane-tert-butyl methacrylate and H₂O/CSD-D-PDMS/dichloromethane-N-tert-butyl methacrylamide) were successfully developed by introducing suitable amphiphilic (hydrophilic/lipophilic) polymerizable monomers. This study found that changes in the amphiphilicity of the introduced monomers significantly affected the stability and microscopic morphology of the gel emulsion system. The findings indicate that constructing a hydrophilic/lipophilic balanced system via the synergistic action of stabilizers and crosslinkers in a solvent system, followed by the introduction of polymerizable monomers, is a simple and efficient method for rapidly developing novel polymerizable gel emulsions. These new polymerizable gel emulsions lay the foundation for the subsequent preparation of porous organic polymers (POPs). Full article

Despite its widespread application in targeted drug delivery, soft robotics, and smart screens, magnetic hydrogel still faces challenges from lagging mechanical performance to sluggish response times. In this paper, a methodology of in situ generation of magnetic hydrogel based on 3D printing of poly-N-isopropylacrylamide (PNIPAM) is presented. A temperature-responsive PNIPAM hydrogel was prepared by 3D printing, and Fe₂O₃ magnetic particles were generated in situ within the PNIPAM network to generate the magnetic hydrogel. By forming uniformly distributed magnetic particles in situ within the polymer network, 3D printing of customized magnetic hydrogel materials was successfully achieved. The bilayer hydrogel structure was designed according to the different swelling ratios of temperature-sensitive hydrogel and magnetic hydrogel. Combined with the excellent mechanical properties of PNIPAM and printable magnetic hydrogel, 4D-printed remote magnetic field triggered shape morphing of bilayers of five-petal flower-shaped hydrogels was presented, and the deformation process was finished within 300 s. Full article

In this study, CdS/porous g-C₃N₄ heterostructures were successfully synthesized via in situ co-precipitation to efficiently degrade tetracycline hydrochloride (TCH) under visible light. The heterostructures, particularly at a 2:1 mass ratio of CdS to porous g-C₃N₄, demonstrated significant improvements in both adsorption and photocatalytic performance. The adsorption and degradation rates increased 4-fold and 9.64-fold, respectively, compared to pure porous g-C₃N₄, with optimal removal rates achieved at a catalyst dosage of 0.2 g/L. Detailed mechanistic studies revealed that photogenerated holes (h⁺) and superoxide radicals (·O₂⁻) were the primary active species driving the degradation process, while hydroxyl radicals (·OH) played a minimal role. The composite material also maintained over 70% degradation efficiency after five cycles, indicating excellent stability. This research presents a promising route for the photocatalytic treatment of wastewater containing persistent organic pollutants, offering practical insights into dosage optimization, reaction kinetics, and mechanistic pathways that enhance performance. Full article

The construction of transition metal dichalcogenides (TMDs) heterojunctions for high-performance gas sensors has garnered significant attention due to their capacity to operate at low temperatures. Herein, we realize two-dimensional (2D) WS₂ nanosheets in situ grown on one-dimensional (1D) In₂O₃ nanofibers to form heterostructures for formaldehyde (HCHO) gas sensors. Capitalizing on the p-n heterojunctions formed between WS₂ and In₂O₃, coupled with the high surface-to-volume ratio characteristic of 1D nanostructures, the WS₂/In₂O₃ NFs sensor demonstrated an elevated gas response of 12.6 toward 100 ppm HCHO at 140 °C, surpassing the performance of the pristine In₂O₃ sensor by a factor of two. Meanwhile, the sensor presents remarkable repeatability, rapid response/recovery speed, and good long-term stability. The superior sensing capabilities of WS₂/In₂O₃ NFs heterojunction are attributed to the combined impact of the increased charge transfer and the presence of more sites for gas adsorption. The research endows a potent approach for fabricating TMD heterojunctions to significantly enhance the gas sensing properties of gas sensors at relatively low temperatures. Full article

Converting CO₂ into methane is considered a promising and economically viable technology for global transportation and utilization of this greenhouse gas. This study involves the preparation of a Ni-CZ (CeO₂-ZrO₂)/ATP (attapulgite) catalyst through the co-precipitation and impregnation methods. XRD, SEM, TEM, N₂ absorption-desorption isotherms, XPS, H₂-TPR, CO₂-TPD, TG/DSC, and Raman were adapted to characterize the obtained samples. Real-time GC was used to measure the catalytic performances and to intensively study the impact of Ni loading content and ATP to CZ ratio on the catalytic performance of the products. DRIFTs was used to monitor the interstitial radicals in the catalytic reactions and to deduce the catalytic mechanisms. The results indicate that the composite catalytic matrix composed of CZ assembled on ATP demonstrated higher CO₂ methanation stability and better carbon deposition resistance ability than the single CZ or ATP as the carrier, which should be attributed to the improved specific surface area and pore volume of the ATP assembled matrix and the enhanced dispersibility of the CZ and Ni species. The adoption of CZ solid solutions improves the oxygen storage capability of the catalyst, thereby providing continued mobile O²⁻ in the matrix and accelerating the molecular exchange rate in the catalytic reactions. The ideal loading quantity of nickel contents on the CZA matrix is 15%, as the CO₂ conversion decreases at elevated temperatures when the Ni loading content reaches 20%. Among the tested samples, the 15Ni-0.8CZA sample showed the best catalytic performance of 75% CO₂ conversion and 100% CH₄ selectivity at 400 °C. After 50 h of stability tests, the CO₂ conversion rate still remained 70.84%, and the CH₄ selectivity obtained 97.46%. No obvious coke was detected according to the Raman spectra of the used catalyst. The in situ DRIFTS experiment showed that formate is the main intermediate of the CO₂ hydrogenation reaction on the 15Ni-0.8CZA catalyst. Full article

Key long-lived greenhouse gases (CO₂, CH₄, and N₂O) are perhaps among the best-studied components of the Earth’s atmosphere today; however, attempts to predict or explain trends or even shorter-term variations of these trace gases are not always successful. Infrared spectroscopy is a recognized technique for the ground-based long-term monitoring of the gaseous composition of the atmosphere. The current paper is focused on the analysis of new data on CO₂, CH₄, and N₂O total columns (TCs) retrieved from high resolution IR solar spectra acquired during 2009–2022 at the NDACC atmospheric monitoring station of St. Petersburg State University (STP station, 59.88°N, 29.83°E, 20 m asl.). The paper provides information on the FTIR system (Fourier-transform infrared) installed at the STP station, and an overview of techniques used for the CO₂, CH₄, and N₂O retrievals. Trends of key greenhouse gases and their confidence levels were evaluated using an original approach which combines the Lomb–Scargle method with the cross-validation and bootstrapping techniques. As a result, the following fourteen-year (2009–2022) trends of TCs have been revealed: (0.56 ± 0.01) % yr⁻¹ for CO₂; (0.46 ± 0.02) % yr⁻¹ for CH₄; (0.28 ± 0.01) % yr⁻¹ for N₂O. A comparison with trends based on the EMAC numerical modeling data was carried out. The trends of greenhouse gases observed at the STP site are consistent with the results of the in situ monitoring performed at the same geographical location, and with the independent estimates of the global volume mixing ratio growth rates obtained by the GAW network and the NOAA Global Monitoring Laboratory. There is reasonable agreement between the CH₄ and N₂O TC trends for 2009–2019, which have been derived from FTIR measurements at three locations: the STP site, Izaña Observatory and the University of Toronto Atmospheric Observatory. Full article

To investigate the influence of the cubic crystal morphology on the thermal properties and sensitivity of 2,6-bis(picrylamino)-3,5-dinitropyridine (PYX), cubic PYX (CPYX) crystals were prepared using the antisolvent method. Scanning electron microscopy (SEM), laser particle size analysis, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) were used to characterize the morphology, particle size and structure of the prepared products. The thermal behavior, thermal decomposition kinetics, thermal safety parameters and thermal decomposition mechanism of CPYX were investigated by differential scanning calorimetry–thermogravimetry–mass spectrometry–Fourier transform infrared spectrometry (DSC-TG-MS-FT-IR) and in situ FT-IR experiments. Meanwhile, the mechanical sensitivity of CPYX was determined by means of the explosion probability method. The results showed that the product had a smooth cubic morphology and small crystal aspect ratio with an average particle size (d₅₀) of 10.65 μm, but it had no distinct differences from the crystal structure of raw PYX (RPYX). The thermal decomposition peak temperature, the self-accelerating decomposition temperature and the critical temperature of the thermal explosion of CPYX increased by 7.2 °C, 6.1 °C and 10.4 °C, respectively, compared to RPYX. Similarly, the apparent activation energy increased by 15%. Besides these, the impact sensitivity and friction sensitivity of CPYX decreased by 36% and 20%, respectively, compared to RPYX. The decomposition process of CPYX contains two stages. The first stage involves the breakage of N-H bonds and -NO₂ groups with the release of CO₂, N₂O, NO, HCN and H₂O, followed by the thermal decomposition of the resulting intermediate and the release of CO₂, N₂O and HCN in the second stage. Full article

Herein, we present an in-depth investigation into the enhancement of catalytic soot oxidation through cerium-doped three-dimensional ordered macroporous (3DOM) La-Co-Ni-based perovskites synthesized with the colloidal crystal template (CCT) method. The 3DOM structure significantly contributes to the accessibility and interaction efficiency between soot and catalyst. Based on the results of powder X-ray diffraction (XRD), N₂ adsorption-desorption measurements, scanning electron microscopy (SEM), temperature-programmed oxidation of NO (NO-TPO), temperature-programmed reduction of H₂ (H₂-TPR), in situ infrared Fourier transform spectroscopy (In-situ DRIFTS), and temperature-programmed oxidation (TPO) reactions, the role of cerium doping in modifying the structural and catalytic properties of 3DOM perovskite-type La_2−xCe_xCoNiO₆ catalysts was investigated systematically. The optimized cerium doping ratio in La_2−xCe_xCoNiO₆ catalysts can improve the microenvironment for efficient soot-catalyst contact, enhancing the catalytic activity of soot oxidation. Among the catalysts, the 3DOM La_0.8Ce_1.2CoNiO₆ catalyst shows the highest catalytic activity for soot oxidation, whose T₁₀, T₅₀, and T₉₀ values are 306 °C, 356 °C, and 402 °C, respectively. The mechanism of the cerium doping effect for boosting soot oxidation is proposed: The doping of Ce ions can increase the surface oxygen species, which is the main active species for promoting the key step of NO oxidation to NO₂ in catalyzing soot oxidation. This research provides a new strategy to develop high-efficient non-noble metal catalysts for soot oxidation in pollution control and sustainable environmental practices. Full article

In this work, a reliable and robust in situ non-matrix-matched calibration method is proposed for element composition determination in scheelite samples. With external calibration against the silicate glass standard reference material NIST SRM 610, the concentrations of both major elements (Ca and W) and trace elements (Si, Fe, Mo, Y, rare earth elements, etc.) in scheelite are determined using an ArF 193 nm excimer nanosecond laser ablation-inductively coupled plasma mass spectrometer (LA-ICP-MS). Here, the ablation was performed by hole drilling under a helium (He) environment using a laser spot size of 35 μm and a laser repetition of 5 Hz, and the aerosols were then transported to a quadrupole ICP-MS by a mixture of He and make-up gas argon (Ar) with a total gas flow rate of 1.6 L/min. Results showed that there was no apparent matrix effect between the NIST SRM 610 and scheelite by this proposed method. With internal standardization against W, the obtained concentrations of CaO and WO₃ were found to yield an average matrix CaO/WO₃ mass fraction ratio of 0.245 (2σ = 0.003, n = 19), which agreed well with the value of 0.243 (2σ = 0.002, n = 15) from electron probe microanalysis (EPMA). Furthermore, the accuracy of trace element analyses with this proposed non-matrix-matched calibration in situ method was evaluated by comparing the concentration results with those from bulk analysis by solution nebulizer ICP-MS (SN-ICP-MS). It was found that the quantification results from LA-ICP-MS and SN-ICP-MS were comparable, in particular showing a relative concentration bias of the total ∑REE+Y contents of less than 2%. This confirmed that scheelites can be accurately analyzed in situ by LA-ICP-MS without matrix-matched calibration standards. By using this developed in situ method, the element compositions in a series of scheelite samples from different W-associated deposits in China were successfully quantified, promising further genetic process investigation and associated geologic activities of the polymetallic resources. Full article

Non-noble metal electrocatalysts for the oxygen evolution reaction (OER) have recently gained particular attention. In the present work, a facile one-step electrodeposition method is applied in situ to synthesize cobalt sulfide nanostructures on nickel foam (NF) electrodes. For the first time, a systematic study is carried out on the impact of the Co/S molar ratio on the structural, morphological, and electrochemical characteristics of Ni-based OER electrodes by employing Co(NO₃)₂·6 H₂O and CH₄N₂S as Co and S precursors, respectively. The optimum performance was obtained for an equimolar Co:S ratio (1:1), whereas sulfur-rich or Co-rich electrodes resulted in an inferior behavior. In particular, the Co_xS_y@NF electrode with Co/S (1:1) exhibited the lowest overpotential value at 10 mA cm⁻² (0.28 V) and a Tafel slope of 95 mV dec⁻¹, offering, in addition, a high double-layer capacitance (C_DL) of 10.7 mF cm⁻². Electrochemical impedance spectroscopy (EIS) measurements confirmed the crucial effect of the Co/S ratio on the charge-transfer reaction rate, which is maximized for a Co:S molar ratio of 1:1. Moreover, field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and X-ray fluorescence (XRF) were conducted to gain insights into the impact of the Co/S ratio on the structural and morphological characteristics of the electrodes. Notably, the Co_xS_y@NF electrocatalyst with an equimolar Co:S ratio presented a 3D flower-like nanosheet morphology, offering an increased electrochemically active surface area (ESCA) and improved OER kinetics. Full article

Alkali-activated persulfate (PS) is widely used in situ in chemical oxidation processes; however, studies on the innovation of the alkali activation process are very limited. Two supported solid superbases, namely KNO₃/γ-Al₂O₃ (KAl) and KNO₃/SBA-15/MgO (KSM), respectively, were prepared and used to activate persulfate to degrade DCF in this work. The results showed that the superbases elevated the solution pH once added and thus could catalyze persulfate to degrade diclofenac efficiently above pH 10.5. The catalytic efficiency of KAl was close to that of sodium hydroxide, and that of KSM was the highest. The mechanism might be that, in addition to raising the solution pH, some potassium existed as K₂O₂, which had a strong oxidizing effect and was conducive to DCF removal. Hydroxyl, sulfate and superoxide radicals were all found in the reaction system, among which hydroxyl might play the most important role. The material composition ratio, common anion and humic acid all had some influences on the catalytic efficiency. A total of five intermediates were found in the KSM/PS oxidation system, and six oxidation pathways, which were hydroxylation, dehydrogen, dechlorination, dehydration, decarboxylation, and C-N bond breakage, might be involved in the reaction process. Several highly toxic oxidation products that should be paid attention to were also proposed. Full article

In this article, the biocatalytic oxidation of ethanol into acetaldehyde was studied using a catalase entrapped within a monolithic polyampholyte cryogel, p(APTAC-co-AMPS), as catalyst. When an anionic monomer, 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS), was mixed with a cationic monomer, (3-acrylamidopropyl) trimethylammonium chloride (APTAC), under cryo-polymerization conditions at a molar ratio of monomers [APTAC]:[AMPS] = 75:25 mol.% in the presence of 10 mol.% cross-linking agent, N,N-methylenebisacrylamide (MBAA), the macroporous polyampholyte cryogels containing various amounts of catalase were synthesized in situ. The conversion of ethanol into acetaldehyde in good-to-high yields was observed in flow-through and batch-type reactors under optimal conditions: at T = 10–20 °C, pH = 6.9–7.1, [C₂H₅OH]:[H₂O₂] = 50:50 vol.%. According to the SEM images, the pore sizes of the p(AMPS-co-APTAC) cryogel vary from 15 to 55 μm. The catalytic activity of catalase entrapped within a monolithic polyampholyte cryogel in the conversion of ethanol into acetaldehyde was evaluated through the determination of kinetic parameters such as the Michaelis constant (K_m), maximum enzymatic rate (V_max), activation energy (E_a), turnover number (TON) and turnover frequency (TOF). The catalase encapsulated within the monolithic polyampholyte cryogel exhibits a high conversion of ethanol into acetaldehyde. The key parameters of ethanol oxidation in flow and batch reactors in the presence of the cryogel monolith were calculated. Full article

The organic–inorganic composites F70-TiO₂, based on fullerene with carboxyl group derivatives and TiO₂ semiconductor, have been designed and constructed to become an optical-functional photocatalyst via the facile sol–gel method. The composite photocatalyst obtained shows excellent photocatalytic activity for the high-efficiency conversion of benzylamine (BA) to N-benzylidene benzylamine (NBBA) with air pressure at a normal temperature under visible light irradiation. By optimizing the composition, the composites with the 1:15 mass ratio of F70 and TiO₂, denoted as F70-TiO₂(1:15), demonstrated the highest reaction efficiency for benzylamine (>98% conversion) to N-benzylidene benzylamine (>93% selectivity) in this study. However, pure TiO₂ and fullerene derivatives (F70) exhibit decreased conversion (56.3% and 89.7%, respectively) and selectivity (83.8% and 86.0%, respectively). The UV–vis diffuse reflectance spectra (DRS) and Mott–Schottky experiment’s results indicate that the introduction of fullerene derivatives into anatase TiO₂ would greatly broaden the visible light response range and adjust the energy band positions of the composites, enhancing the sunlight utilization and promoting the photogenerated charge (e⁻-h⁺) separation and transfer. Specifically, a series of results on the in situ EPR tests and the photo-electrophysical experiment indicate that the separated charges from the hybrid could effectively activate benzylamine and O₂ to accelerate the formation of active intermediates, and then couple with free BA molecules to form the desired production of N-BBA. The effective combination, on a molecular scale, between fullerene and titanium dioxide has provided a profound understanding of the photocatalysis mechanism. This work elaborates and makes clear the relationship between the structure and the performance of functional photocatalysts. Full article

In this study, an in-situ piezoelectric effect is integrated into a photoactive region to develop a self-powered ultraviolet photodetector based on a p-n junction of ZnO@Polyvinylidene fluoride (PVDF) and poly [9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB). A ZnO@β-PVDF nanocomposite is fabricated using PVDF with the β-phase as the polymer matrix and ZnO nanoparticles as fillers. The strong piezoelectricity of β-PVDF can facilitate the separation and transport of photogenerated electrons in the depletion area and considerably reduce the dark current when the device is polarized with an external bias, resulting in an improvement in the on/off ratio and detectivity. Under 365-nm UV illumination, the as-fabricated device exhibits a high detectivity of 4.99 × 10¹¹ Jones, an excellent on/off ratio (up to 2.75 × 10⁴), and a fast response speed of 46/53 ms (rise/fall times). The device functions stably over approximately 1000 continuous on/off cycles and exhibits extremely long-lasting photostability when exposed to UV light. The findings demonstrate a promising strategy for enhancing the performance of photodetectors for industrial applications. Full article