Curvature-Induced Electron Spin Catalysis with Carbon Spheres.

Here, we report curvature-induced electron spin catalysis by using solid carbon spheres as catalysts, which were synthesized using positive curvature molecular hexabromocyclopentadiene as a precursor molecule, following a radical coupling mechanism. The curvature spin of carbon is regarded as an overlapping state of σ- and π-radical, which is identified by the inverse Laplace transform of pulse-electron paramagnetic resonance. The growth mechanism of carbon spheres abiding by Kroto's model, is supported by the density functional theory study of thermodynamics and kinetics calculations. The solid carbon spheres present excellent catalytic behaviour of oxidation coupling of amines to form corresponding imines with the conversion of >99%, selectivity of 98.7%, and yield of 97.7%, which is attributed to the predominantly curvature-induced electron spin catalysis of carbon, supported by the calculation of oxygen adsorption energy. This work proposes a view of curvature-induced spin catalysis of carbon, which opens up a research direction for curvature-induced electron spin catalysis.

Ultrasound-Assisted Hydrothermal Synthesis of Highly Fluorescent Sulfur Quantum Dots for Fe3+ Ion and Ascorbic Acid Detection in Real Samples.

In this work, the ultrasound-assisted hydrothermal synthesis method offers a facile method to synthesize highly efficient photoluminescence sulfur quantum dots (SQDs). Impressively, a switchable fluorescent "on-off-on" sensor was developed using the acquired SQDs, which are capable of sequentially detecting iron ions (Fe3+) and ascorbic acid (AA) with exceptional sensitivity and selectivity. Meanwhile, SQDs and Fe3+ formed complexes through coordination, causing the fluorescence quenching of SQDs because of the static quenching effect. Upon the addition of AA into the SQDs/Fe3+ system, a redox-reaction-mediated mechanism leads to the recovery of fluorescence. The fluorescence intensity of SQDs exhibits a linear relationship with the concentrations of Fe3+ and AA in the ranges 5-30 and 20-100 µM, respectively. Notably, the detection limits achieved are 14.31 nM for Fe3+ and 0.64 µM for AA. Moreover, the chemosensor was successfully employed for monitoring Fe3+ in real water samples and AA in fruits. These results demonstrate the excellent analysis and detection capabilities of SQDs in the complex environment.

Alcohol imination catalyzed by carbon nanostructures synthesized by C(sp2)-C(sp3) free radical coupling.

Imines are important intermediates for synthesizing various fine chemicals, with the disadvantage of requiring the use of expensive metal-containing catalysts. We report that the dehydrogenative cross-coupling of phenylmethanol and benzylamine (or aniline) directly forms the corresponding imine with a yield of up to 98%, and water as the sole by-product, in the presence of a stoichiometric base, using carbon nanostructures as the "green" metal-free carbon catalysts with high spin concentrations, which is synthesized by C(sp2)-C(sp3) free radical coupling reactions. The catalytic mechanism is attributed to the unpaired electrons of carbon catalysts to reduce O2 to O2·-, which triggers the oxidative coupling reaction to form imines, whereas the holes in the carbon catalysts receive electrons from the amine to restore the spin states. This is supported by density functional theory calculations. This work will open up an avenue for synthesizing carbon catalysts and offer great potential for industrial applications.

Electron Spin Catalysis with Graphene Belts.

Here, we report kinetic studies using electron spin resonance spectroscopy on spin catalysis reactions caused by using graphene belts which were synthesized by a radical coupling method. The results show that σ-type free radical species provide the dominant sites for catalytic activity through the spin-spin interaction, although there are some other influencing factors. The spin catalysis mechanism can be applied both in the oxygen reduction reaction (ORR) and in organic synthesis. The graphene belt spin catalyst shows excellent performance with a high ORR half-wave potential of 0.81 V and long-term stability with almost no loss of activity after 50 000 cycles in alkaline media. It also shows excellent performance in a benzylamine coupling with molecular oxygen to generate the corresponding imine at an average conversion of ≈97.7 % and an average yield of ≈97.9 %. This work opens up a new research direction for understanding aerobic processes in the field of spin catalysis.