Nitrogen-Anchored Boridene Enables Mg-CO2 Batteries with High Reversibility.

Nanoscale defect engineering plays a crucial role in incorporating extraordinary catalytic properties in two-dimensional materials by varying the surface groups or site interactions. Herein, we synthesized high-loaded nitrogen-doped Boridene (N-Boridene (Mo4/3(BnN1-n)2-mTz), N-doped concentration up to 26.78 at %) nanosheets by chemical exfoliation followed by cyanamide intercalation. Three different nitrogen sites are observed in N-Boridene, wherein the site of boron vacancy substitution mainly accounts for its high chemical activity. Attractively, as a cathode for Mg-CO2 batteries, it delivers a long-term lifetime (305 cycles), high-energy efficiency (93.6%), and ultralow overpotential (∼0.09 V) at a high current of 200 mA g-1, which overwhelms all Mg-CO2 batteries reported so far. Experimental and computational studies suggest that N-Boridene can remarkably change the adsorption energy of the reaction products and lower the energy barrier of the rate-determining step (*MgCO2 → *MgCO3·xH2O), resulting in the rapid reversible formation/decomposition of new MgCO3·5H2O products. The surging Boridene materials with defects provide substantial opportunities to develop other heterogeneous catalysts for efficient capture and converting of CO2.

One-pot noninjection route to CdS quantum dots via hydrothermal synthesis.

Water-dispersible CdS quantum dots (QDs) emitting from 510 to 650 nm were synthesized in a simple one-pot noninjection hydrothermal route using cadmium chloride, thiourea, and 3-mercaptopropionic acid (MPA) as starting materials. All these chemicals were loaded at room temperature in a Teflon sealed tube and the reaction mixture heated at 100 °C. The effects of CdCl(2)/thiourea/MPA feed molar ratios, pH, and concentrations of precursors affecting the growth of the CdS QDs, was monitored via the temporal evolution of the optical properties of the CdS nanocrystals. High concentration of precursors and high MPA/Cd feed molar ratios were found to lead to an increase in the diameter of the resulting CdS nanocrystals and of the trap state emission of the dots. The combination of moderate pH value, low concentration of precursors and slow growth rate plays the crucial role in the good optical properties of the obtained CdS nanocrystals. The highest photoluminescence achieved for CdS@MPA QDs of average size 3.5 nm was 20%. As prepared colloids show rather narrow particle size distribution, although all reactants were mixed at room temperature. CdS@MPA QDs were characterized by UV-vis and photoluminescence spectroscopy, powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectrometry and MALDI TOF mass spectrometry. This noninjection one-pot approach features easy handling and large-scale production with excellent synthetic reproducibility. Surface passivation of CdS@MPA cores by a wider bandgap material, ZnS, led to enhanced luminescence intensity. CdS@MPA and CdS/ZnS@MPA QDs exhibit high photochemical stability and hold a good potential to be applied in optoelectronic devices and biological applications.

Cerium oxyhydroxide clusters: formation, structure, and reactivity.

Cerium oxyhydroxide cluster anions were produced by irradiating ceric oxide particles by using 355 nm laser pulses that were synchronized with pulses of nitrogen gas admitted to the irradiation chamber. The gas pulse stabilized the nascent clusters that are largely anhydrous [Ce(x)O(y)] ions and neutrals. These initially formed species react with water, principally forming oxohydroxy species that are described by the general formula [Ce(x)O(y)(OH)(z)](-) for which all the Ce atoms are in the IV oxidation state. In general, the extent of hydroxylation varies from a value of three OH per Ce atom when x = 1 to a value slightly greater than 1 for x >or= 8. The Ce(3) and Ce(6) species deviate significantly from this trend: the x = 3 cluster accommodates more hydroxyl moieties compared to neighboring congeners at x = 2 and 4. Conversely, the x = 6 cluster is significantly less hydroxylated than its x = 5 and 7 neighbors. Density functional theory (DFT) modeling of the cluster structures shows that the hydrated clusters are hydrolyzed, and contain one-to-multiple hydroxide moieties, but not datively bound water. DFT also predicts an energetic preference for formation of highly symmetric structures as the size of the clusters increases. The calculated structures indicate that the ability of the Ce(3) oxyhydroxide to accommodate more extensive hydroxylation is due to a more open, hexagonal structure in which the Ce atoms can participate in multiple hydrolysis reactions. Conversely the Ce(6) oxyhydroxide has an octahedral structure that is not conducive to hydrolysis. In addition to the fully oxidized (Ce(IV)) oxyhydroxides, reduced oxyhydroxides (containing a Ce(III) center) are also formed. These become more prominent as the size of the clusters increases, suggesting that the larger ceria clusters have an increased ability to accommodate a reduced Ce(III) moiety. In addition, the spectra offer evidence for the formation of superoxide derivatives that may arise from reaction of the reduced oxyhydroxides with dioxygen. The overall intensity of the clusters tends to monotonically decrease as the cluster size increases; however, this trend is interrupted at Ce(13), which is significantly more stable compared to neighboring congeners, suggesting formation of a dehydrated Keggin-type structure.

Study by ESI-FTICRMS and ESI-FTICRMS(n) of zinc and cadmium thiophenolate complexes used as precursors for the synthesis of II-VI nanosemiconductors.

[M(4)(SC(6)H(5))(10)][(CH(3))N](2), [M(10)L(4)(SC(6)H(5))(16)][(CH(3))N](4) and [Cd(17)S(4)(SC(6)H(5))(28)][(CH(3))N](2)(M = Cd or Zn, and L = S or Se) zinc and cadmium thiophenolates have been studied by electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (ESI-FTICRMS) and tandem ESI-FTICRMS (ESI-FTICRMS(n)). ESI-FTICRMS demonstrated its ability to characterize and study such compounds, which may be used as precursors of II-VI nanomaterials. The obtained mass spectrum has been found to be highly relevant of the investigated thiophenolate and the fragmentation behavior of some of the detected ions is indicative of its stability. More specifically, it has been demonstrated that ESI in-source activation or fragmentation experiments conducted in the Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) cell induced the formation of a very stable entity, which corresponds to the general formula M(4)L(4) (M = Zn or Cd and L = S or Se). The elimination of SC(6)H(5)(-) and/or M(SC(6)H(5))(2) moieties by various activation processes from the studied thiophenolates led systematically to this structure.

Investigations of acidity and nucleophilicity of diphenyldithiophosphinate ligands using theory and gas-phase dissociation reactions.

Diphenyldithiophosphinate (DTP) ligands modified with electron-withdrawing trifluoromethyl (TFM) substitutents are of high interest because they have demonstrated potential for exceptional separation of Am (3+) from lanthanide (3+) cations. Specifically, the bis( ortho-TFM) (L 1 (-)) and ( ortho-TFM)( meta-TFM) (L 2 (-)) derivatives have shown excellent separation selectivity, while the bis( meta-TFM) (L 3 (-)) and unmodified DTP (L u (-)) did not. Factors responsible for selective coordination have been investigated using density functional theory (DFT) calculations in concert with competitive dissociation reactions in the gas phase. To evaluate the role of (DTP + H) acidity, density functional calculations were used to predict p K a values of the free acids (HL n ), which followed the trend of HL 3 < HL 2 < HL 1 < HL u. The order of p K a for the TFM-modified (DTP+H) acids was opposite of what would be expected based on the e (-)-withdrawing effects of the TFM group, suggesting that secondary factors influence the p K a and nucleophilicity. The relative nucleophilicities of the DTP anions were evaluated by forming metal-mixed ligand complexes in a trapped ion mass spectrometer and then fragmenting them using competitive collision induced dissociation. On the basis of these experiments, the unmodified L u (-) anion was the strongest nucleophile. Comparing the TFM derivatives, the bis( ortho-TFM) derivative L 1 (-) was found to be the strongest nucleophile, while the bis( meta-TFM) L 3 (-) was the weakest, a trend consistent with the p K a calculations. DFT modeling of the Na (+) complexes suggested that the elevated cation affinity of the L 1 (-) and L 2 (-) anions was due to donation of electron density from fluorine atoms to the metal center, which was occurring in rotational conformers where the TFM moiety was proximate to the Na (+)-dithiophosphinate group. Competitive dissociation experiments were performed with the dithiophosphinate anions complexed with europium nitrate species; ionic dissociation of these complexes always generated the TFM-modified dithiophosphinate anions as the product ion, showing again that the unmodified L u (-) was the strongest nucleophile. The Eu(III) nitrate complexes also underwent redox elimination of radical ligands; the tendency of the ligands to undergo oxidation and be eliminated as neutral radicals followed the same trend as the nucleophilicities for Na (+), viz. L 3 (-) < L 2 (-) < L 1 (-) < L u (-).

Characterization of Ti(6)O(4)(O(2)C(4)H(5))(8)(OCH(2)CH(3))(8) by electrospray time of flight mass spectrometry.

A titanium oxide molecular cluster prepared by hydrolysis of titanium tetraethoxide in the presence of methacrylic acid, can be characterized by electrospray time of flight mass spectrometry (ESMS-TOF). The chemistry of such systems is not well known and ESMS is a powerful technique for studying the reactions of clusters in solution. The fingerprint of the cluster fragmentation suggests formation of Ti(x)O(y) core fragments that represent commonly observed structural constructs in bulk titanium oxide metallates. The fragmentation steps provide insight into the hydrolytic conversion of this molecular sol gel intermediate into bulk TiO(2). While MS has been applied to the study of metal alkoxide hydrolysis mechanisms, mass spectra of isolated individual titanium oxide clusters have not previously been reported.