Tailoring Type III Porous Ionic Liquids for Enhanced Liquid-Liquid Two-Phase Catalysis.

Porous Ionic Liquids (PILs) have gained attention but facing challenges in catalysis, especially in liquid-liquid two-phase reactions due to limited catalytic sites and hydrophilicity control. This work engineered a Type III PILs (PILS-M) using zeolitic imidazolate framework-8 (ZIF-8) confined phosphomolybdic acid (HPMo) as the microporous framework and N-butyl pyridine bis(trifluoromethane sulfonyl) imide ionic liquid ([Bpy][NTf2]) as the solvent. The PILS-M not only combines the advantages of traditional ionic liquids and microporous frameworks, including excellent extraction, high dispersion of catalytically active species, remarkable stability, etc., but also can make the inner surface of ZIF-8 turned to be hydrophilic that favors the contact between aqueous hydrogen peroxide oxidant and catalytically active sites for the promotion of catalytic performance in reactive extractive desulfurization (REDS) processes of fuel oils. This study demonstrates Type III PILs' potential as catalysts for sustainable chemical processes, offering insights into versatile PILs applications in diverse fields.

Crystal-Plane-Engineered TiO2-Anchored Vanadium Single Atoms and Clusters for Boosting Ultradeep Aerobic Oxidative Desulfurization of Diesel.

The crystal plane effect has gained extensive attention in heterogeneous catalysis reactions; however, it is far from being systematically probed in titanium dioxide (TiO2)-supported vanadium catalysts. Herein, a series of vanadium (V) single atoms and clusters anchored on TiO2 with different crystal planes was fabricated by an improved "top-down" protocol. The dispersion state, electronic structure, and redox properties of the V single-atom and VOx cluster-supported catalysts were systematically analyzed by a series of characterization methods, including X-ray absorption near edge structure (XANES) and density functional theory (DFT) calculations, and their catalytic performances were examined for aerobic oxidative desulfurization (AODS) of 4,6-dimethyl-dibenzothiophen (4,6-DMDBT) with O2 as the oxidant. The results unveiled that the synergistic effect between the V single atom and the VOx cluster perceptibly promoted the catalytic performances of VOx/TiO2 samples. Therein, VOx/TiO2-(001) shows the lowest apparent activation energy (Ea) value of 46.3 kJ/mol and the optimal AODS performance with complete 4,6-DMDBT conversion to 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO2) within 60 min at 120 °C as compared with VOx/TiO2-(101) (81.9 kJ/mol and 180 min) and VOx/TiO2-(100) (68.0 kJ/mol and 240 min), which should be attributed to its higher V5+/V4+ ratio, the optimal redox behavior of the V species, the moderate adsorption energy between 4,6-DMDBT and VOx active centers, and the synthetic effect of V single atoms and VOx clusters. Moreover, VOx/TiO2-(001) exhibits robust durability in seven cycles of reuse, showcasing the potential for practical applications in the future.

One-Pot Three-Dimensional Printing of a Hierarchical NiMo/Al2O3 Monolithic Catalyst for 4,6-Dimethyldibenzothiophene Hydrodesulfurization.

The development of a competitive-cost and high-efficiency NiMo/Al2O3 hydrodesulfurization (HDS) catalyst remains challenging in the field of petrochemical industry. Herein, a highly efficient NiMo/Al2O3 monolithic HDS catalyst was elaborately designed and successfully fabricated via a one-pot three-dimensional (3D) printing strategy, and its HDS activity was examined for 4,6-dimethyldibenzothiophene conversion. The results unveil that the NiMo/Al2O3 monolithic catalyst prepared by the 3D printing strategy (3D-NiMo/Al2O3) exhibits hierarchical structure due to the combustion of hydroxymethyl cellulose serving as adhesive, which endows the weaker metal-support-interaction between Mo oxides and Al2O3, remarkably promoting sulfidation of both Mo and Ni species and the formation of "Type II" NiMoS active phase, thereby reducing the apparent activation energy (Ea = 109.2 kJ·mol-1) and increasing the catalytic activity (TOF = 4.0 h-1) and thereafter dramatically boosting the HDS performance of 3D-NiMo/Al2O3 compared with that of NiMo/Al2O3 (Ea = 150.6 kJ·mol-1 and TOF = 2.1 h-1) counterpart synthesized by conventional method with P123 serving as the mesoporous template. Therefore, this study offers a facile and straightforward strategy to fabricate an efficient HDS catalyst with hierarchical structures.

Engineering polyhedral high entropy oxide with high-index facets via mechanochemistry-assisted strategy for efficient oxidative desulfurization.

High entropy oxides are promising catalysts for numerous catalytic oxidation processes with oxygen as the oxidant. However, most of them often show bulk morphologies, which hinders the full exposure of active sites. In this work, a unique 26-faceted polyhedral high entropy oxide MnNiCuZnCoOx-1000 (P-HEO) with highly active site exposure is fabricated via a mechanochemistry-assisted strategy. By employing such a strategy, the supersaturation of P-HEO during the crystal growth process is effectively reduced to form high-index facets, which is proved to be beneficial to the formation of high-index facets. Characterization results indicate that more oxygen vacancies are generated in P-HEO compared with the bulk counterparts. Density functional theory calculations reveal that the high-index facets {-211} can facilitate adsorption and activation of O2 because of the higher adsorption energy -2.23 eV compared with that of (111) surfaces (-1.79 eV), which induces significantly enhanced activity for organic sulfides oxidation. Interestingly, the synthesized P-HEO with high-index facets shows a 98.4% removal rate of dibenzothiophene from model oil within 8 h at 120 °C, which is much higher than that of the bulk counterparts (33.5%).

Gadolinium-doped carbon quantum dots loaded magnetite nanoparticles as a bimodal nanoprobe for both fluorescence and magnetic resonance imaging.

Nowadays, it is highly desired to develop dual-modal fluorescence and magnetic resonance imaging (FI/MRI) probes in medical imaging because it unites the respective advantages of each imaging modality: high sensitivity of FI and superior spatial resolution of MRI. In this study, a facile strategy to fabricate a new bimodal imaging nanoprobe (Gd-CQDs@N-Fe3O4) was reported by integrating the fluorescence ability of carbon quantum dots (CQDs) and T1 and T2 contrast-enhancing functionality of Gd(III) ions and Fe3O4 nanoparticles into a single hybrid nanostructure. The hybrid composites were investigated by FT-IR, XRD, TEM, XPS, VSM, and so on, which confirmed that Gd-CQDs@N-Fe3O4 nanoparticles were successfully obtained and exhibited superparamagnetic property at room temperature. The derived nanoprobes presented an excitation wavelength-independent emission behavior. In addition, r1 and r2 relaxivities of the synthesized imaging nanoprobes were measured to be 5.16 and 115.6 mM-1 s-1, which nominated Gd-CQDs@N-Fe3O4 nanocomposites as a suitable T1-T2 contrast agent. The Gd-CQDs@N-Fe3O4 nanoparticles combining two synergetic imaging modalities showed great potential in FI/MRI dual-modal imaging for a more complementary and accurate detection.

Lattice-Refined Transition-Metal Oxides via Ball Milling for Boosted Catalytic Oxidation Performance.

Surface oxygen vacancy can greatly affect the properties of transition-metal oxides. However, engineering oxygen vacancy-abundant transition-metal oxides with high specific surface area (SSA) remains challenging. At present, the generation of oxygen vacancies in metal oxides is time-consuming and less environmentally friendly by chemical leaching methods that usually require additional waste treatment. Herein, a series of oxygen vacancy-abundant transition-metal oxides with high SSA are constructed via a lattice refining strategy. This strategy is realized by urea-assisted ball milling pyrolysis and is green, efficient, and universal. The oxygen vacancies promote the mobility of oxygen, leading to a boosted catalytic oxidation performance of aromatic sulfides. Such a strategy provides an efficient approach to manufacturing oxygen vacancies on transition-metal oxides, which may be beneficial for various related applications as an effective catalytic material.

Hierarchical FeCo2 S4 Nanotube Arrays Deposited on 3D Carbon Foam as Binder-free Electrodes for High-performance Asymmetric Pseudocapacitors.

The ever-increasing global demand for green energy resources calls for more research attention on the development of cheap and efficient energy storage systems. Herein, we propose the rational design of a 3D carbon foam electrode deposited with perpendicularly oriented FeCo2 S4 nanotubes arrays (FeCo2 S4 /CMF) for high-performance asymmetric supercapacitors. In this work, the macroporous CMF served as conducting backbone not only to enhance the electrical conductivity of the composite, but also to promote the uniform growth of FeCo2 S4 nanotubes. Deposited hierarchical FeCo2 S4 nanotubes arrays with open hollow structures can afford numerous exposed electroactive sites for Faradaic redox reaction and provide short interior channels for fast electrolyte transmission. Due to these unique features, obtained 3D hierarchical FeCo2 S4 /CMF composite foam exhibits a high specific capacitance of 2430 F g-1 (specific capacity of 337.5 mAh g-1 ) at 1 A g-1 , and excellent capacitance retention of 91 % after 5000 cycles at a high current density of 9 A g-1 , which is superior to most of those previously reported binary metal sulfide-based electrodes. Moreover, asymmetric supercapacitor device assembled using the FeCo2 S4 /CMF as positive electrode also delivers a high energy density of 78.7 W h kg-1 at a power density of 800.3 W kg-1 . Therefore, this work provides a new strategy for the low-cost synthesis of 3D foam electrodes towards high-performance supercapacitor devices.

Sorption of copper onto low molecular weight chitosan derivative from aqueous solution.

In this study, sorption of copper onto low molecular weight chitosan derivative was studied. Experimental parameters such as pH of the solution (A), temperature (B), dose of the sorbent (C), and concentration of solution (D) were considered. The statistical results indicated that the dose of sorbent (C) and Cu (II) concentration (D) influenced removal efficiency at 5% significance level. Also, some interactions such as ABCD, ACD, ABC and AC affected the removal process. The sorbent was characterized with FTIR, SEM and TG/DSC. Freundlich isotherm model was the best isotherm model. The kinetic study results correlated well with the pseudo-second-order model. The thermodynamic studies revealed that the nature of copper sorption was spontaneous and endothermic. Strong affinity of the sorbent for copper (II) was revealed by the Isothermal Titration Calorimetry (ITC) technique.

Gd (III) complex conjugate of low-molecular-weight chitosan as a contrast agent for magnetic resonance/fluorescence dual-modal imaging.

The fusion of molecular and anatomical modalities facilitates more reliable and accurate detection in clinic. In this work, we prepared gadolinium (III) complex Gd-DTPA-FITC-CS11 with magnetic resonance (MR) and fluorescence dual-modal imaging modalities. Gd-DTPA-FITC-CS11 consisted of fluorescein isothiocyanate and low-molecular-weight chitosan (CS11) units conjugated with gadolinium diethylenetriamine pentaacetic acid (Gd-DTPA). Gd-DTPA-FITC-CS11 exhibited a higher longitudinal relaxivity (14.09 mM(-1)s(-1)) than the clinical Gd-DTPA (3.85 mM(-1)s(-1)). T1-weighted MR contrast enhancement was also demonstrated the comparability to Gd-DTPA at lower dosage. The binding with bovine serum albumin (BSA) was investigated. The fluorescence of BSA in the presence of Gd-DTPA-FITC-CS11 was weakened due to static quenching mechanism. The conformation of BSA was slightly changed but α-helix was dominant. The binding was entropy-driven and spontaneous and the main contribution was hydrophobic interaction. Our results suggested the potential of Gd-DTPA-FITC-CS11 as an MR/fluorescence dual-modal imaging contrast agent in improving the diagnostic sensitivity and accuracy.

Chitosan oligosaccharide based Gd-DTPA complex as a potential bimodal magnetic resonance imaging contrast agent.

A new gadolinium diethylenetriamine pentaacetic acid (DTPA) complex (Gd-DTPA-DMABA-CS11) as a potential bimodal magnetic resonance imaging (MRI) contrast agent with fluorescence was synthesized. It was synthesized by the incorporation of 4-dimethylaminobenzaldehyde (DMABA) and chitosan oligosaccharide (CSn; n=11) with low polydispersity index to DTPA anhydride and then chelated with gadolinium chloride. The structure was characterized by Fourier transform infrared (FTIR), (1)H NMR, elemental analysis and size exclusion chromatography (SEC). MRI measurements in vitro were evaluated. The results indicated that Gd-DTPA-DMABA-CS11 provided higher molar longitudinal relaxivity (r1) (12.95mM(-1)·s(-1)) than that of commercial Gd-DTPA (3.63mM(-1)·s(-1)) at 0.5T. Gd-DTPA-DMABA-CS11 also emitted fluorescence, and the intensity was much stronger than that of Gd-DTPA. Therefore, it can be meanwhile used in fluorescent imaging for improving the sensitivity in clinic diagnosis. Gd-DTPA-DMABA-CS11 as a potential contrast agent is preliminarily stable in vitro. The results of thermodynamic action between Gd-DTPA-DMABA-CS11 and bovine serum albumin (BSA) illustrated that the binding process was exothermic and spontaneous, and the main force was van der Waals' interaction and hydrogen bond. The preliminary study suggested that Gd-DTPA-DMABA-CS11 could be used in both magnetic resonance and fluorescent imaging as a promising bimodal contrast agent.

Sorption of heavy metal ions onto carboxylate chitosan derivatives--a mini-review.

Chitosan is of importance for the elimination of heavy metals due to their outstanding characteristics such as the presence of NH2 and -OH functional groups, non-toxicity, low cost and, large available quantities. Modifying a chitosan structure with -COOH group improves it in terms of solubility at pH ≤7 without affecting the aforementioned characteristics. Chitosan modified with a carboxylic group possess carboxyl, amino and hydroxyl multifunctional groups which are good for elimination of metal ions. The focal point of this mini-review will be on the preparation and characterization of some carboxylate chitosan derivatives as a sorbent for heavy metal sorption.

Removal of cadmium from aqueous solution using low molecular weight chitosan derivative.

A 2(3) factorial design was used to examine the sorption of Cd(2+) onto cross-linked low molecular weight chitosan pyruvic acid derivative. Three factors and two levels of solution pH (A) (6.0 or 10.0), temperature (B) (45 or 70 °C) and Cd(II) concentration (C) (1 or 3 mg/L) were considered. Batch mode system was employed with 0.05 g of the sorbent and 25 mL of Cd(II) solution. The efficiency of cadmium removal during an exposition time of 4h was then evaluated. The factors and their interaction effect on the cadmium removal efficiency followed the order: Cd(II) concentration > solution pH > interaction between solution pH and Cd(II) concentration>interaction between solution pH, temperature and Cd(II) concentration. Langmuir isotherm model was the best isotherm model. The Pseudo second order fitted well the kinetic data. The thermodynamic studies revealed the nature of the cadmium sorption.

Lead removal onto cross-linked low molecular weight chitosan pyruvic acid derivatives.

Adsorption capacity of cross-linked low molecular weight chitosan pyruvic acid derivatives CSnPA-GLA (n=8, 11) were examined by employing 2(3) factorial design method. Three (3) factors and two (2) levels of adsorbent dose (A) (0.05 and 0.1 g), adsorbent type (B) (CS8PA-GLA and CS11PA-GLA) and concentration of lead solution (C) (1 and 3 mg/L) were considered. From the statistical analysis, all the main parameters (A, B and C) and some interactions of the main parameters (AC and ABC) had influence on the adsorption process at 5% significance level. The adsorption process was greatly influenced by the adsorbent type (B). The adsorption equilibrium results correlated well with the Freundlich isotherm model. The adsorption kinetic data also correlated well with the pseudo second order. The thermodynamic studies also revealed that the nature of lead adsorption was spontaneous and endothermic. The findings suggest that CS8PA-GLA is better than CS11PA-GLA for lead sorption.

Biomimetic catalytic enantioselective decarboxylative aldol reaction of ß-ketoacids with trifluoromethyl ketones.

We disclose an organocatalyzed enantioselective decarboxylative ketone aldol reaction of ß-ketoacids with trifluoromethyl ketones in the presence of biscinchona alkaloid (DHQD)(2)AQN, affording chiral tertiary alcohols in up to 98% yield and 90% ee.

Asymmetric phase-transfer-catalyzed conjugate addition of glycine imine to exocyclic α,ß-unsaturated ketones: construction of polycyclic imines containing three stereocenters.

We developed a facile, one-pot, multistep transformation between glycine imine and exocyclic α,ß-unsaturated ketones in reactions catalyzed by chiral phase-transfer catalysts (PTC). A series of polycyclic imines containing three adjacent stereocenters were obtained in good to high yields with high diastereo- and enantioselectivities. Further transformation of the imines could afford N-fused polycyclic compounds with four adjacent stereocenters.

A powerful synergistic effect for highly efficient diastereo- and enantioselective phase-transfer catalyzed conjugate additions.

An efficient, catalytic, diastereo- and enantioselective conjugate addition of N-(diphenylmethylene)glycine tert-butyl ester to ß-aryl substituted enones was realized in the presence of 1 mol% of newly desired dinuclear N-spiro-ammonium salts, affording functionalized α-amino acid derivatives in 57-98% yields with high diastereoselectivity (up to 99:1 dr) and enantioselectivity (up to 96.5:3.5 er).

Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.