Effect of CO2 adsorbents on the Ni-based dual-function materials for CO2 capturing and in situ methanation

The present work studied the effect of different carbon dioxide (CO₂) adsorbents on Ni-based dual-function materials (DFMs) for the development of carbon capture and on-site utilization in a reactor at isothermal condition. The DFMs containing Ni functioning as a methanation catalyst with various CO₂ adsorbents (i.e., CaO, MgO, K₂CO₃, or Na₂CO₃) were prepared on γ-Al₂O₃ through sequential impregnation. The result indicated that Ni-Na₂CO₃/γ-Al₂O₃ had the highest methanation capacity (i.e., 0.1783 mmol/g) and efficiency (i.e., 71.09%) in the CO₂ adsorption–methanation test. The CO₂ uptake and the subsequent methanation capacity of the Ni-Na₂CO₃/γ-Al₂O₃ increased to more than 24 times and more than 17 times, respectively, compared to Ni/γ-Al₂O₃. The high methanation capacity was correlated to its highest amount of weak basic sites, substantial CO₂ capture capacity and capture/release efficiency, and reactivity to H₂ at a lower temperature, supported by CO₂-TPD, TGA analyses for adsorption or adsorption–desorption at the isothermal condition, and H₂-TPRea, respectively. A continuous cyclic CO₂ adsorption–methanation was performed by using the Ni-Na₂CO₃/γ-Al₂O₃ and Ni-CaO/γ-Al₂O₃, showing that the CO₂ adsorption capacity was stabilized from third cycle onward, whereas the methanation capacity was stabilized at all cycles, indicating the high stability of the DFMs for both CO₂ adsorption and subsequent methanation. This work demonstrated successful synthesis of the Ni-based, low-cost, and stable DFMs with the ability to produce methane via the direct capture of CO₂.     

One-Pot Efficient Synthesis of Fully Substituted 1,3,4-Oxadiazole Derivatives from (N-Isocyanimino)triphenylphosphorane,Carboxylic Acids,and Aromatic Bis-Aldehydes

Reactions of (N-isocyanimino)triphenylphosphorane with aromatic bis-aldehydes (isophthalaldehyde and terphthalaldehyde) in the presence of aromatic (or heteroaromatic) carboxylic acids proceed smoothly at room temperature and in neutral conditions to afford sterically congested 1,3,4-oxadiazole derivatives in good yields. The reaction proceeds smoothly and cleanly under mild conditions, and no side reactions were observed.

Divergent Chemistry Paths for 3D and 1D Metallo‐Covalent Organic Frameworks (COFs)

The marriage of dynamic covalent chemistry (DCC) and coordination chemistry is a powerful tool for assembling complex architectures from simple building units. Recently, the synthesis of woven covalent organic frameworks (COFs) with topologically fascinating structures has been achieved using this approach. However, the scope is highly limited and there is a need to discover new pathways that can assemble covalently linked organic threads into crystalline frameworks. Herein, we have identified branching pathways leading to the assembly of three‐dimensional (3D) woven COFs or one‐dimensional (1D) metallo‐COFs (mCOFs), where the mechanism is underpinned by the absence or presence of ligand exchange.     

A simple, high yield method for the synthesis of organic wires from aromatic molecules using nitric acid as the solvent

Using concentrated nitric acid as the solvent, and water as the non-solvent, one-dimensional (1D) organic nanowires can be synthesized in a simple, one-pot process with high yield. The method has broad validity to a wide range of aromatic molecules for the synthesis of derivatized organic wires.     

Scaffolding catalysts: highly enantioselective desymmetrization reactions

Ex-changing places: a highly enantioselective desymmetrization of 1,2-diols has been developed in which the catalyst utilizes reversible covalent bonding to the substrate to achieve both high selectivity and rate acceleration (see scheme, PMP=pentalmethylpiperidine, TBS=tert-butyldimethylsilyl). Induced intramolecularity is responsible for the enhanced rate, thus allowing the reaction to be performed at room temperature.     

Enantioselective hydroformylation of aniline derivatives

We have developed a ligand that reversibly binds to aniline substrates, allowing for the control of regioselectivity and enantioselectivity in hydroformylation. In this paper we address how the electronics of the aniline ring affect both the binding of the substrate to the ligand and the enantioselectivity in this reaction.     

A novel four-component reaction for the synthesis of disubstituted 1,3,4-oxadiazole derivatives

The 1:1 imine intermediate generated by the addition of benzyl amine to cyclobutanone is trapped by (N-isocyanimino)triphenylphosphorane in the presence of an aromatic carboxylic acid leads to the formation of the corresponding iminophosphorane intermediate. Disubstituted 1,3,4-oxadiazole derivatives are formed via intramolecular aza-Wittig reaction of the iminophosphorane intermediate. The reactions were completed in neutral conditions at room temperature. The disubstituted 1,3,4-oxadiazole derivatives, were produced in excellent yields.     

Global uniqueness in an inverse problem for time fractional diffusion equations

Given $(M,g)$, a compact connected Riemannian manifold of dimension $d?2$, with boundary ?M, we consider an initial boundary value problem for a fractional diffusion equation on $(0,T)\times M$, $T>0$, with time-fractional Caputo derivative of order $\alpha \in (0,1)\cup (1,2)$. We prove uniqueness in the inverse problem of determining the smooth manifold $(M,g)$ (up to an isometry), and various time-independent smooth coefficients appearing in this equation, from measurements of the solutions on a subset of ?M at fixed time. In the “flat” case where M is a compact subset of ${\mathbb{R}}^d$, two out the three coefficients ρ (density), a (conductivity) and q (potential) appearing in the equation $\rho {?}_t^{\alpha }u?\mathrm{div}\left(a\mathrm{?}u\right)+qu=0$ on $(0,T)\times M$ are recovered simultaneously.