CaY@C2n: Exploring Molecular Qubits with Ca-Y Metal-Metal Bonds.

Metal-metal bonding is crucial in chemistry for advancing our understanding of the fundamental aspects of chemical bonds. Metal-metal bonds based on alkaline-earth (Ae) elements, especially the heavier Ae elements (Ca, Sr, and Ba), are rarely reported due to their high electropositivity. Herein, we report two heteronuclear di-EMFs CaY@Cs(6)-C82 and CaY@C2v(5)-C80, which contain unprecedented single-electron Ca-Y metal-metal bonds. These compounds were characterized by single-crystal X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, and DFT calculations. The crystallographic study of CaY@Cs(6)-C82 shows that Ca and Y are successfully encapsulated into the carbon cage with a Ca-Y distance of 3.691 Å. The CW-EPR study of both CaY@Cs(6)-C82 and CaY@C2v(5)-C80 exhibits a doublet, suggesting the presence of an unpaired electron located between Ca and Y. The combined experimental and theoretical results confirm the presence of a Ca-Y single-electron metal-metal bond with substantial covalent interaction, attributed to significant overlap between the 4s4p orbitals of Ca and the 5s5p4d orbitals of Y. Furthermore, pulse EPR spectroscopy was used to investigate the quantum coherence of the electron spin within this bond. The unpaired electron, characterized by its s orbital nature, is effectively protected by the carbon cage, resulting in efficient suppression of both spin-lattice relaxation and decoherence. CaY@Cs(6)-C82 behaves as an electron spin qubit, displaying a maximum decoherence time of 7.74 µs at 40 K. This study reveals an unprecedented Ae-rare-earth metal-metal bond stabilized by the fullerene cages and elucidates the molecular qubit properties stemming from their unique bonding character, highlighting their potential in quantum information processing applications.

Substituent Effects of the Nitrogen Heterocycle on Indole and Quinoline HDN Performance: A Combination of Experiments and Theoretical Study.

Hydrodenitrogenation (HDN) experiments and density functional theory (DFT) calculations were combined herein to study the substituent effects of the nitrogen heterocycle on the HDN behaviors of indole and quinoline. Indole (IND), 2-methyl-indole (2-M-IND), 3-methyl-indole (3-M-IND), quinoline (QL), 2-methyl-quinoline (2-M-QL) and 3-methyl-quinoline (3-M-QL) were used as the HDN reactant on the NiMo/γ-Al2O3 catalyst. Some key elementary reactions in the HDN process of these nitrogen compounds on the Ni-Mo-S active nanocluster were calculated. The notable difference between IND and QL in the HDN is that dihydro-indole (DHI) can directly convert to O-ethyl aniline via the C-N bond cleavage, whereas tetrahydro-quinoline (THQ) can only break the C-N single bond via the full hydrogenation saturation of the aromatic ring. The reason for this is that the -NH and C=C groups of DHI can be coplanar and well adsorbed on the Ni-Mo-edge simultaneously during the C-N bond cleavage. In comparison, those of THQ cannot stably simultaneously adsorb on the Ni-Mo-edge because of the non-coplanarity. Whenever the methyl group locates on the α-C or the ß-C atom of indole, the hydrogenation ability of the nitrogen heterocycle will be evidently weakened because the methyl group increases the space requirement of the sp3 carbon, and the impaction of the C=C groups on the Ni-S-edge cannot provide enough space. When the methyl groups are located on the α-C of quinoline, the self-HDN behavior of 2-M-QL is similar to quinoline, whereas the competitive HDN ability of 2-M-QL in the homologs is evidently weakened because the methyl group on the α-C hinders the contact between the N atom of 2-M-QL and the exposed metal atom of the coordinatively unsaturated active sites (CUS). When the methyl group locates on the ß-C of quinoline, the C-N bond cleavage of 3-methyl-quinoline becomes more difficult because the methyl group on the ß-C increases the steric hindrance of the C=C group. However, the competitive HDN ability of 3-M-QL is not evidently influenced because the methyl group on the ß-C does not evidently hinder the adsorption of 3-M-QL on the active sites.

MoS2 decorated on one-dimensional MgFe2O4/MgO/C composites for high-performance microwave absorption.

Advanced microwave absorption (MA) materials have attracted widespread attention to meet the challenges of electromagnetic (EM) pollution. Herein, MgFe2O4/MgO/C fibers were successfully prepared via electrospinning technology and carbonization, and their surfaces were coated by MoS2 via hydrothermal method. The EM wave absorption performance of composites was enhanced due to the introduction of MoS2. The results showed that the EM wave absorption performance of MgFe2O4/MgO/C could not meet the requirements due to low dielectric loss and poor impedance matching. The performance of the composites was improved after coating of MoS2, which showed the strong wave absorption capability and the broad absorption bandwidth. The optimal reflection loss (RL) is -56.94 dB at 9.5 GHz and the effective absorption bandwidth is 3.9 GHz (8.08-11.98 GHz) with a thickness of 2.7 mm. The excellent MA performance can be mainly attributed to excellent synergistic effect between MgFe2O4/MgO/C and MoS2. Furthermore, MoS2 also contributes to dielectric loss and ideal impedance matching. MgFe2O4/MgO/C@MoS2 composites may be utilized for lightweight and high-efficient MA materials.

Reaction Behaviors and Crystal Transformation of Industrial Vanadium-Phosphorus-Oxygen (VPO) Catalysts for n-Butane Oxidation.

A long-time evaluation of n-butane oxidation over an industrial vanadium-phosphorus-oxygen (VPO) catalyst was implemented. The catalytic performances for n-butane oxidation during this period were obtained. It was shown that the conversion of n-butane increased with the evaluation time, but the selectivity of the maleic anhydride (MA) product decreased gradually. To investigate the crystal transformation of the VPO catalyst, the properties of fresh and evaluated VPO catalysts were measured by a series of characterization methods, including X-ray diffraction (XRD), N2 adsorption and desorption, NH3-temperature programmed desorption (TPD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The results showed that the acidities and valence of vanadium increased after evaluation due to the appearance of a ß-VOPO4 phase. The crystal transformation would increase the activity for n-butane oxidation. Meanwhile, during the evaluation period, the decrease in selectivity of the MA product should be related to the decreasing percentage of Lat-O species in the VPO catalyst.