Efficient Ni₂P/SiO₂ Catalysts with Enhanced Performance for the Hydrogenation of 4,6-Dimethyldibenzothiophene and Phenanthrene

Highly dispersed Ni2P catalysts (Ni2P/SiO2-DPx) were prepared by reducing the passivation-free precursors, which were obtained through the phosphidation of nickel phyllosilicate with sodium hypophosphite. The strong metal–support interaction of nickel phyllosilicate and the mild phosphidation conditions prevented the agglomeration of Ni particles and resulted in a smaller Ni2P particle size. The superior catalytic performance of the as-prepared Ni2P/SiO2-DP catalysts was evaluated in hydrodesulfurization (HDS) of 4,6-dimethyldibenzothiophene and the hydrogenation of phenanthrene, in comparison with Ni2P/SiO2-IM and CoMoS/γ-Al2O3 prepared from a conventional incipient wetness impregnation method. The passivation-free Ni-P/SiO2-DPx precursors showed great storage stability, and Ni2P/SiO2-DP derived from the stored Ni-P/SiO2-DP precursors exhibited negligible loss of HDS activity. This method provides a potential preparation strategy for the industrial applications of transition metal phosphides without the temperature-programmed reduction and the subsequent passivation process

Highly Reproducible Ag NPs/CNT-Intercalated GO Membranes for Enrichment and SERS Detection of Antibiotics

The increasing pollution of aquatic environments by antibiotics makes it necessary to develop efficient enrichment and sensitive detection methods for environmental antibiotics monitoring. In this work, silver nanoparticles and carbon nanotube-intercalated graphene oxide laminar membranes (Ag NPs/CNT-GO membranes) were successfully prepared for enrichment and surface-enhanced Raman scattering (SERS) detection of antibiotics. The prepared Ag NPs/CNT-GO membranes exhibited a high enrichment ability because of the π–π stacking and electrostatic interactions of GO toward antibiotic molecules, which enhanced the sensitivity of SERS measurements and enabled the antibiotics to be determined at sub-nM concentrations. In addition, the nanochannels created by the intercalation of CNTs into GO layers resulted in an 8-fold enhancement in the water permeance of Ag NPs/CNT-GO membranes compared to that of pure GO membranes. More importantly, the Ag NPs/CNT-GO membranes exhibited high reproducibility and long-term stability. The spot-to-spot variation in SERS intensity was less than 15%, and the SERS performance was maintained for at least 70 days. The Ag NPs/CNT-GO membranes were also used for SERS detection of antibiotics in real samples; the results showed that the characteristic peaks of antibiotics were obviously recognizable. Thus, the sensitive SERS detection of antibiotics based on Ag NPs/CNT-GO offers great potential for practical applications in environmental analysis

Bipyridine-Based Nanosized Metal–Organic Framework with Tunable Luminescence by a Postmodification with Eu(III): An Experimental and Theoretical Study

A gallium 2,2′-bipyridine-5,5′-dicarboxylate metal–organic framework, Ga­(OH)­(bpydc), denoted as COMOC-4 (COMOC = Center for Ordered Materials, Organometallics and Catalysis, Ghent University) has been synthesized via solvothermal synthesis procedure. The structure has the topology of an aluminum 2,2′-bipyridine-5,5′-dicarboxylate – the so-called MOF-253. TEM and SEM micrographs show the COMOC-4 crystals are formed in nanoplates with uniform size of 30–50 nm. The UV–vis spectra of COMOC-4 in methanol solution show maximal electronic absorption at 307 nm. This results from linker to linker transitions as elucidated by time-dependent density functional theory simulations on the linker and COMOC-4 cluster models. When excited at 400 nm, COMOC-4 displays an emission band centered at 542 nm. Upon immersion in different solvents, the emission band for the framework is shifted in the range of 525–548 nm depending on the solvent. After incorporating Eu³⁺ cations, the emission band of the framework is shifted to even shorter wavelengths (505 nm). By varying the excitation wavelengths from 250 to 400 nm, we can fine-tune the emission from red to yellowish green in the CIE diagram. The luminescence behavior of Eu³⁺ cations is well preserved and the solid-state luminescence lifetimes of τ₁ = 45 μs (35.4%) and τ₂ = 162 μs (64.6%) are observed

New Functionalized Metal–Organic Frameworks MIL-47‑X (X = −Cl, −Br, −CH₃, −CF₃, −OH, −OCH₃): Synthesis, Characterization, and CO₂ Adsorption Properties

Six new functionalized vanadium hydroxo terephthalates [V^III(OH)­(BDC-X)]·n­(guests) (MIL-47­(V^III)-X-AS) (BDC = 1,4-benzene­di­carboxylate; X = −Cl, −Br, −CH₃, −CF₃, −OH, −OCH₃; AS = as-synthesized) along with the parent MIL-47 were synthesized under rapid microwave-assisted hydrothermal conditions (170 °C, 30 min, 150 W). The unreacted H₂BDC-X and/or occluded solvent molecules can be removed by thermal activation under vacuum, leading to the empty-pore forms of the title compounds (MIL-47­(V^IV)-X). Except pristine MIL-47 (+III oxidation state), the vanadium atoms in all the evacuated functionalized solids stayed in the +IV oxidation state. The phase purity of the compounds was ascertained by X-ray powder diffraction (XRPD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, Raman, thermogravimetric (TG), and elemental analysis. The structural similarity of the filled and empty-pore forms of the functionalized compounds with the respective forms of parent MIL-47 was verified by cell parameter determination from XRPD data. TGA and temperature-dependent XRPD (TDXRPD) experiments in an air atmosphere indicate high thermal stability in the 330–385 °C range. All the thermally activated compounds exhibit significant microporosity (<i>S</i>_BET in the 305–897 m² g^–1 range), as verified by the N₂ and CO₂ sorption analysis. Among the six functionalized compounds, MIL-47­(V^IV)-OCH₃ shows the highest CO₂ uptake, demonstrating the determining role of functional groups on the CO₂ sorption behavior. For this compound and pristine MIL-47­(V^IV), Widom particle insertion simulations were performed based on ab initio calculated crystal structures. The theoretical Henry coefficients show a good agreement with the experimental values, and calculated isosurfaces for the local excess chemical potential indicate the enhanced CO₂ affinity is due to two effects: (i) the interaction between the methoxy group and CO₂ and (ii) the collapse of the MIL-47­(V^IV)-OCH₃ framework

New V^IV-Based Metal–Organic Framework Having Framework Flexibility and High CO₂ Adsorption Capacity

A vanadium based metal–organic framework (MOF), VO­(BPDC) (BPDC^2– = biphenyl-4,4′-dicarboxylate), adopting an expanded MIL-47 structure type, has been synthesized via solvothermal and microwave methods. Its structural and gas/vapor sorption properties have been studied. This compound displays a distinct breathing effect toward certain adsorptives at workable temperatures. The sorption isotherms of CO₂ and CH₄ indicate a different sorption behavior at specific temperatures. In situ synchrotron X-ray powder diffraction measurements and molecular simulations have been utilized to characterize the structural transition. The experimental measurements clearly suggest the existence of both narrow pore and large pore forms. A free energy profile along the pore angle was computationally determined for the empty host framework. Apart from a regular large pore and a regular narrow pore form, an overstretched narrow pore form has also been found. Additionally, a variety of spectroscopic techniques combined with N₂ adsorption/desorption isotherms measured at 77 K demonstrate that the existence of the mixed oxidation states V^III/V^IV in the titled MOF structure compared to pure V^IV increases the difficulty in triggering the flexibility of the framework