•A core-shell-like Ni-Pd/CB catalyst is prepared via a sequential reduction method.•The catalyst shows excellent activity and generality in Suzuki-Miyaura reaction at 30 °C.•The cost-effective Suzuki-Miyaura reaction can be achieved in green reaction system.A magnetically separable core-shell-like catalyst Ni-Pd/CB is designed and synthesized via a facile sequential reduction strategy. It is found that the Pd nanocrystals with a thickness of ∼1.67 nm and a length of ∼7.92 nm are intimately coupled with the Ni cores and the formed core-shell-like Ni-Pd nanoparticles are well dispersed on the CB surface with much smaller particle size and narrower size distribution as compared with that of unsupported ones. The ligand-free Ni-Pd/CB nanocatalyst is evaluated for Suzuki-Miyaura coupling reaction and exhibits excellent catalytic activity under mild aerobic conditions without using toxic solvents and inert protective atmosphere, achieving green catalysis. The high catalytic performance of Ni-Pd/CB catalyst can be attributed to its unique core-shell-like nanostructure and the concerted effects between the individual components. The introduction of Ni not only makes the catalyst magnetically separable in a suspension system, but also significantly lowers the cost.The Ni core in core-shell-like Ni-Pd/CB catalyst not only endows the catalyst with magnetically separable ability, but also greatly improves the utility of Pd element, leading to enhanced catalytic performances in Suzuki-Miyaura coupling reaction under mild conditions in green system.Download high-res image (198KB)Download full-size image

Chemical sensors are powerful for the fast recognition of chiral compounds. However, the established sensing systems are less effective for chiral tertiary alcohols. The chiral tertiary alcohol group is an important structural unit in natural products and drug molecules, and its enantioselective recognition represents a significant and challenging task. In this paper, a novel type of chiral bisselenourea sensor was first synthesized and used as a strong hydrogen-bonding donor for highly efficient chiral recognition of a diverse range of tertiary alcohols. The obtained sharply split NMR signals are well-distinguishable with a large (up to 0.415 ppm) chemical shift nonequivalence. The NMR signal of the hydroxyl hydrogen atom was first employed for enantiomeric excess determination of tertiary alcohols, giving accurate results with <2% absolute errors. The 2D NOESY spectra and computational studies suggest that the geometrical differentiation of the formed diastereomeric complexes between the sensor and tertiary alcohols enables the chiral discrimination of the hydroxyl hydrogen signals of the tertiary alcohol in the 1H NMR spectrum.

We report a stable palladium/graphene (Pd/G) nanocomposite with differing Pd content for use in the catalytic hydrogenation of nitrophenols and nitrotoluenes. Various microscopic and spectroscopic techniques were employed to characterize the as-prepared catalysts. Catalytic hydrogenation reactions of nitrophenols were conducted in aqueous solution by adding NaBH4, while the nitrotoluene hydrogenation was carried out in methanol in the presence of H2 because of the poor solubility in water. The Pd/G hybrids exhibited much higher activity and higher stability than the commercial Pd/C. Due to the presence of a large excess of NaBH4 compared to p-nitrophenol, the kinetic data can be explained by the assumption of a pseudo-first-order reaction with regard to p-nitrophenol. The resulting high catalytic activity can be attributed to the graphene sheets’ strong dispersion effect for Pd nanoparticles and good adsorption ability for nitrobenzene derivatives via π–π stacking interactions. A plausible mechanism is proposed. Considering inductive and conjugation effects that may affect the reactions, the reactivity of nitrophenols in this study is expected to follow the order m-NP > o-NP > p-NP > 2,4-DNP > 2,4,6-TNP, which is in good agreement with the experimental results.

A rhenium-magnesium cocatalyzed [4+2] annulation of benzamides and alkynes via C-H/N-H functionalization is described. The reaction features a divergent and high level of diastereoselectivities, which are readily switchable by subtle tuning of reaction conditions. Thus, a wide range of both cis- and trans-3,4-dihydroisoquinolinones is expediently synthesized in a highly atom-economical manner. Moreover, mechanistic studies unraveled a tandem mode of action between rhenium and magnesium in the catalytic cycles.

A straightforward strategy is designed for the fabrication of magnetically recyclable ternary titania–cobalt ferrite–polyaniline (P25-CoFe2O4-PANI) photocatalysts with differing P25/CoFe2O4 ratio. The pseudo-second-order and Langmuir models are found to be most suitable for describing the adsorption of methyl orange (MO) onto the photocatalysts. The photocatalytic activity of P25-CoFe2O4-PANI is evaluated by the degradation of various dyes under visible light irradiation, and the results show that the ternary P25-CoFe2O4-PANI photocatalyst exhibits high photocatalytic activity due to the good adsorption capacity of the hybrid and the introduction of P25, which can further improve the separation of the light-induced electron–hole pairs. The degradation of anionic dyes is much more effective than that of cationic dyes due to the negatively charged groups of anionic dyes undergo electrostatic attraction with the positively charged backbone of PANI, and such an effective adsorption helps in promoting the degradation.

A straightforward strategy is designed for the fabrication of CuFe2O4-graphene heteroarchitecture via a one-step hydrothermal route to allow multifunctional properties, i.e., magnetic cycling, high photocatalytic activity under visible light irradiation, and excellent electrochemical behaviors for use as the anode in lithium-ion batteries (LIBs). Transmission electron microscopy (TEM) observations indicate that graphene sheets are exfoliated and decorated with hexagonal CuFe2O4 nanoflakes. The photocatalytic activity measurements demonstrate that the combination of CuFe2O4 and graphene results in a dramatic conversion of the inert CuFe2O4 into a highly active catalyst for the degradation of methylene blue (MB) under visible light irradiation. CuFe2O4 nanoparticles themselves have excellent magnetic properties, which makes the CuFe2O4-graphene heteroarchitecture magnetically recyclable in a suspension system. It should be pointed out that the CuFe2O4-graphene (with 25 wt % graphene) heteroarchitecture as anode material for LIBs shows a high specific reversible capacity up to 1165 mAh g–1 with good cycling stability and rate capability. The superior photocatalytic activity and electrochemical performance of the CuFe2O4-graphene nanocomposite can be attributed to its unique heteroarchitechture, which provides the remarkable synergistic effect between the CuFe2O4 nanoflakes and the graphene sheets.

A simple and straightforward strategy was developed to fabricate magnetically separable MnFe2O4–graphene photocatalysts with differing graphene content. It was found that graphene sheets were fully exfoliated and decorated with MnFe2O4 nanocrystals having an average diameter of 5.65 nm and a narrow particle size distribution. It is very interesting that, although MnFe2O4 alone is photocatalytically inactive under visible light irradiation, the combination of MnFe2O4 nanoparticles with graphene sheets leads to high photocatalytic activity for the degradation of methylene blue under visible light irradiation. The strong magnetic property of MnFe2O4 nanoparticles can be used for magnetic separation in a suspension system, and therefore it does not require additional magnetic components as is the usual case. Consequently, the MnFe2O4–graphene system becomes a dual function photocatalyst. The significant enhancement in photoactivity under visible light irradiation can be ascribed to the reduction of graphene oxide (GO), because the photogenerated electrons of MnFe2O4 can transfer easily from the conduction band to the reduced GO, effectively preventing a direct recombination of electrons and holes. Hydroxyl radicals play the role of main oxidant in the MnFe2O4–graphene system, and the radicals’ oxidation reaction is obviously dominant.

Co3O4@graphene nanocomposite (Co3O4@GE) was prepared by a facile hydrothermal route. X-ray diffraction and transmission electron microscope proved Co3O4 nanoparticles with an average size of 5.8 nm were homogeneously dispersed on sonication-exfoliated graphene sheets. X-ray photoelectron spectra indicated a low oxidation degree of graphene in Co3O4@GE. Small amount of functional groups on graphene sheets not only worked as anchor sites for Co3O4 nanoparticles, but also kept the carbon framework with lower defect density. Electrochemical experiments on Co3O4@GE showed high specific capacitance of 415 F/g at a large current density of 3 A/g in 6 M KOH electrolyte, which is valuable for practical application in supercapacitors.Highlights► Co3O4@GE was prepared with an in situ soft oxidation process. ► Co3O4 nanoparticles had an average size of 5.8 nm. ► The graphene sheets in Co3O4@GE have lower defect density. ► Graphene was exfoliated ultrasonically without severe oxidation/reduction processes. ► Co3O4@GE exhibits an enhanced electrochemical performance at large current density.

A facile and efficient method to synthesize 2- or 4-substituted 1,2-dihydroquinolines and quinolines catalyzed by FeCl3·6H2O (2 mol %) was described. The iron-catalyzed intramolecular allylic amination of 2-aminophenyl-1-en-3-ols proceeded smoothly to afford 13 1,2-dihydroquinoline and 8 quinoline derivatives under mild reaction conditions with good to excellent yields (up to 96%).

A BiVO4–graphene photocatalyst was prepared by a facile one-step hydrothermal method and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray photoelectron spectra (XPS), and transmission electron microscopy (TEM) techniques. The results show that the graphene sheets in this catalyst are exfoliated and decorated by leaf-like BiVO4 lamellas. In comparison with the pure BiVO4 catalyst, the BiVO4–graphene system reveals much higher photocatalytic activity for degradation of methyl orange (MO), methylene blue (MB), Rhodamine B (RhB) and active black BL-G in water under visible light irradiation due to the concerted effects of BiVO4 and graphene sheets or their integrated properties.Graphical abstractHighlights► A facile strategy is designed to deposit leaf-like BiVO4 lamellas on graphene sheet. ► Graphene oxide is reduced to graphene in the hydrothermal reaction process. ► BiVO4–graphene system shows high catalytic effects under visible light irradiation.

A series of novel supramolecular organocatalysts of hydroxyprolinamide based on the upper rim of calix[4]arene scaffold have been developed to catalyze enantioselective multi-component Biginelli reaction. Under the optimal conditions, the reactions occurred with moderate-to-excellent enantioselectivities (up to 98% ee). A plausible transition state constructed by the supramolecular interaction of hydrogen bond and cation-π between catalysts and substrates has been proposed.

We report a stable palladium/graphene (Pd/G) nanocomposite with differing Pd content for use in the catalytic hydrogenation of nitrophenols and nitrotoluenes. Various microscopic and spectroscopic techniques were employed to characterize the as-prepared catalysts. Catalytic hydrogenation reactions of nitrophenols were conducted in aqueous solution by adding NaBH4, while the nitrotoluene hydrogenation was carried out in methanol in the presence of H2 because of the poor solubility in water. The Pd/G hybrids exhibited much higher activity and higher stability than the commercial Pd/C. Due to the presence of a large excess of NaBH4 compared to p-nitrophenol, the kinetic data can be explained by the assumption of a pseudo-first-order reaction with regard to p-nitrophenol. The resulting high catalytic activity can be attributed to the graphene sheets’ strong dispersion effect for Pd nanoparticles and good adsorption ability for nitrobenzene derivatives via π–π stacking interactions. A plausible mechanism is proposed. Considering inductive and conjugation effects that may affect the reactions, the reactivity of nitrophenols in this study is expected to follow the order m-NP > o-NP > p-NP > 2,4-DNP > 2,4,6-TNP, which is in good agreement with the experimental results.