介孔分子筛MCM-48的氮化与表面胺化及其碱催化反应性能

以介孔分子筛MCM-48为前驱体,通过表面胺化和高温NH3氮化方法制备出两种碱性分子筛.采用X射线衍射(XRD)、N2-吸附脱附、透射电镜(TEM)、红外光谱(FT-IR)、热重分析(TG)和哈密特指示剂法对上述分子筛的结构及表面酸碱性进行了详细表征,并通过苯甲醛与丙二腈的Knoevenagel缩合反应对其碱催化活性及稳定性进行了考察和对比.结果表明,表面胺化和高温氮化的方法均可制备出碱性介孔分子筛,且均在Knoevenagel碱性探针反应中表现出较好的碱催化活性,但与后者相比,前者制备的碱性分子筛具有更强的表面碱性和更好的反应稳定性.     

A New kHz Velocity Map Ion/Electron Imaging Spectrometer for Femtosecond Time-Resolved Molecular Reaction Dynamics Studies

A new velocity map imaging spectrometer is constructed for molecular reaction dynamics studies using time-resolved photoelectron/ion spectroscopy method.By combining a kHz pulsed valve and an ICCD camera,this velocity map imaging spectrometer can be run at a repetition rate of 1 kHz,totally compatible with the fs Ti:Sapphire laser system,facilitating time-resolved studies in gas phase which are usually time-consuming.Time-resolved velocity map imaging study of NH₃ photodissociation at 200 nm was performed and the time-resolved total kinetic energy release spectrum of H+NH₂ products provides rich information about the dissociation dynamics of NH₃.These results show that this new apparatus is a powerful tool for investigating the molecular reaction dynamics using time-resolved methods.     

A new block preconditioner for complex symmetric indefinite linear systems

Using the equivalent block two-by-two real linear systems and relaxing technique, we establish a new block preconditioner for a class of complex symmetric indefinite linear systems. The new preconditioner is much closer to the original block two-by-two coefficient matrix than the Hermitian and skew-Hermitian splitting (HSS) preconditioner. We analyze the spectral properties of the new preconditioned matrix, discuss the eigenvalue distribution and derive an upper bound for the degree of its minimal polynomial. Finally, some numerical examples are provided to show the effectiveness and robustness of our proposed preconditioner.     

Liouville Type Theorems for PDE and IE Systems Involving Fractional Laplacian on a Half Space

In this paper, let α be any real number between 0 and 2, we study the Dirichlet problem for semi-linear elliptic system involving the fractional Laplacian:

$$\left \{\begin {array}{l} (-{\Delta })^{\alpha /2}u(x)=v^{q}(x),\ \ \ x\in \mathbb {R}^{n}_{+},\\ (-{\Delta })^{\alpha /2}v(x)=u^{p}(x),\ \ \ x\in \mathbb {R}^{n}_{+},\\ u(x)=v(x)=0,\ \ \ \ \ \ \ \ \ \ x\notin \mathbb {R}^{n}_{+}. \end {array}\right .\label {elliptic} $$

(1)

We will first establish the equivalence between PDE problem (1) and the corresponding integral equation (IE) system (Lemma 2). Then we use the moving planes method in integral forms to establish our main theorem, a Liouville type theorem for the integral system (Theorem 3). Then we conclude the Liouville type theorem for the above differential system involving the fractional Laplacian (Corollary 4).

     

A Complete Solution to the Existence of ‐Cycle Frames of Type

The existence problem of a ‐cycle frame of type is now solved for any quadruple .     

On Galvin’s theorem for compact Hausdorff right-topological semigroups with dense topological centers

We generalize an important theorem of Fred Galvin from the Stone-Cˇech compactification βT of any discrete semigroup T to any compact Hausdorff right-topological semigroup with a dense topological center;and then apply it to Ellis' semigroups to prove that a point is distal if and only if it is IP*-recurrent, for any semiflow(T, X) with arbitrary compact Hausdorff phase space X not necessarily metrizable and with arbitrary phase semigroup T not necessarily cancelable.     

Electronic Perturbation of Copper Single-Atom CO2 Reduction Catalysts in a Molecular Way

Fine-tuning electronic structures of single-atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron-withdrawing/-donating groups, we show herein the electronic perturbation of Cu single-atom CO₂ reduction catalysts in a molecular way. The elaborately introduced functional groups (−F, −H and −OMe) can regulate the valance state of Cu^δ+, which is found to be directly scaled with the selectivity of the electrochemical CO₂-to-CH₄ conversion. An optimum CH₄ Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F-substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cu^δ+ centers adjusted by the electron-withdrawing group decrease the pK_a of adsorbed H₂O, promoting the hydrogenation of intermediates toward the CH₄ production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.     

Coordinating the Edge Defects of Bismuth with Sulfur for Enhanced CO2 Electroreduction to Formate

Bismuth-based materials have been recognized as promising catalysts for the electrocatalytic CO₂ reduction reaction (ECO₂RR). However, they show poor selectivity due to competing hydrogen evolution reaction (HER). In this study, we have developed an edge defect modulation strategy for Bi by coordinating the edge defects of bismuth (Bi) with sulfur, to promote ECO₂RR selectivity and inhibit the competing HER. The prepared catalysts demonstrate excellent product selectivity, with a high HCOO⁻ Faraday efficiency of ≈95 % and an HCOO⁻ partial current of ≈250 mA cm⁻² under alkaline electrolytes. Density function theory calculations reveal that sulfur tends to bind to the Bi edge defects, reducing the coordination-unsaturated Bi sites (*H adsorption sites), and regulating the charge states of neighboring Bi sites to improve *OCHO adsorption. This work deepens our understanding of ECO₂RR mechanism on bismuth-based catalysts, guiding for the design of advanced ECO₂RR catalysts.     

Ultralow-loss Optical Waveguides through Balancing Deep-Blue TADF and Orange Room Temperature Phosphorescence in Hybrid Antimony Halide Microstructures

Harnessing the potential of thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) is crucial for developing light-emitting diodes (LEDs), lasers, sensors, and many others. However, effective strategies in this domain are still relatively scarce. This study presents a new approach to achieving highly efficient deep-blue TADF (with a PLQY of 25 %) and low-energy orange RTP (with a PLQY of 90 %) through the fabrication of lead-free hybrid halides. This new class of monomeric and dimeric 0D antimony halides can be facilely synthesized using a bottom-up solution process, requiring only a few seconds to minutes, which offer exceptional stability and nontoxicity. By leveraging the highly adaptable molecular arrangement and crystal packing modes, the hybrid antimony halides demonstrate the ability to self-assemble into regular 1D microrod and 2D microplate morphologies. This self-assembly is facilitated by multiple non-covalent interactions between the inorganic cores and organic shells. Notably, these microstructures exhibit outstanding polarized luminescence and function as low-dimensional optical waveguides with remarkably low optical-loss coefficients. Therefore, this work not only presents a pioneering demonstration of deep-blue TADF in hybrid antimony halides, but also introduces 1D and 2D micro/nanostructures that hold promising potential for applications in white LEDs and low-dimensional photonic systems.