RESUMEN
Herein, we report the use of a molecular-defined rhodium(II) coordination polymer (Rh-CP) as a heterogeneous, recyclable catalyst in carbene transfer reactions. We showcase the application of this heterogeneous catalyst in a range of carbene transfer reactions and conclude with the functionalization of natural products and drug molecules.
RESUMEN
As the excessive presence of heavy metals in the environment significantly affects human health, it becomes necessary to develop efficient, selective, and sensitive methods for their detection. In this study, a novel electrochemical sensor for the detection of Pb2+ ions is described. The proposed sensor is based on a glassy carbon electrode (GCE) modified by a thin film of histidine-grafted metal-organic framework (MOF-808-His). The MOF-808 was obtained solvothermally, and then postsynthetically modified by substituting the coordinated acetate with histidinate. By electrochemistry, the MOF-808-His-modified GCE demonstrated high charge selectivity, while electrochemical impedance spectroscopy (EIS) and kinetic studies gave a lower charge transfer resistance (4196 Ω) and a better standard heterogeneous electron transfer rate constant (1.80 × 10-5 cm s-1) on MOF-808-modified GCE. These results indicated a swift and direct electron transfer rate from [Fe(CN)6]3-/4- to the electrode surface. Using square wave anodic stripping voltammetry (SWASV), the rapid and highly sensitive determination of Pb2+ was achieved on MOF-808-His-modified GCE. By optimizing the accumulation-detection parameters including pH of the detection medium, deposition time and potential, and concentration, a remarkable limit of detection (LoD, based on a signal-to-noise ratio of 3) of (1.12 × 10-10 ± 0.10 × 10-10) mol L-1 was obtained, with a sensitivity of (9.6 ± 0.1) µA L µmol-1. After interference and stability studies, the MOF-808-His-modified GCE was applied to the detection of Pb2+ in a tap water sample with a concentration of 10 µmol L-1 Pb2+.
RESUMEN
A newly synthesized series of bimetallic CPM-37(Ni,Fe) metal-organic frameworks with different iron content (Ni/Fe ≈ 2, 1, 0.5, named CPM-37(Ni2Fe), CPM-37(NiFe) and CPM-37(NiFe2)) demonstrated high N2-based specific SBET surface areas of 2039, 1955, and 2378 m2 g-1 for CPM-37(Ni2Fe), CPM-37(NiFe), and CPM-37(NiFe2), having much higher values compared to the monometallic CPM-37(Ni) and CPM-37(Fe) with 87 and 368 m2 g-1 only. It is rationalized that the mixed-metal nature of the materials increases the structural robustness due to the better charge balance at the coordination bonded cluster, which opens interesting application-oriented possibilities for mixed-metal CPM-37 and other less-stable MOFs. In this work, the CPM-37-derived α,ß-Ni(OH)2, γ-NiO(OH), and, plausibly, γ-FeO(OH) phases obtained via decomposition in the alkaline medium demonstrated a potent electrocatalytic activity in the oxygen evolution reaction (OER). The ratio Ni : Fe ≈ 2 from CPM-37(Ni2Fe) showed the best OER activity with a small overpotential of 290 mV at 50 mA cm-2, low Tafel slope of 39 mV dec-1, and more stable OER performance compared to RuO2 after 20 h chronopotentiometry at 50 mA cm-2.
RESUMEN
Two new isostructural semiconducting metal-phosphonate frameworks are reported. Co2 [1,4-NDPA] and Zn2 [1,4-NDPA] (1,4-NDPA4- is 1,4-naphthalenediphosphonate) have optical bandgaps of 1.7â eV and 2.5â eV, respectively. The electrocatalyst derived from Co2 [1,4-NPDA] as a precatalyst generated a low overpotential of 374â mV in the oxygen evolution reaction (OER) with a Tafel slope of 43â mV dec-1 at a current density of 10â mA cm-2 in alkaline electrolyte (1â mol L-1 KOH), which is indicative of remarkably superior reaction kinetics. Benchmarking of the OER of Co2 [1,4-NPDA] material as a precatalyst coupled with nickel foam (NF) showed exceptional long-term stability at a current density of 50â mA cm-2 for water splitting compared to the state-of-the-art Pt/C/RuO2 @NF after 30â h in 1â mol L-1 KOH. In order to further understand the OER mechanism, the transformation of Co2 [1,4-NPDA] into its electrocatalytically active species was investigated.
RESUMEN
Contaminants of emerging concern (CECs), also known as micropollutants, have been recognized in recent years as substantial water pollutants because of the potential threats they pose to the environment and human health. This study was aimed at preparing biochar (BC) based on egusi seed shells (ESS) with well-developed porosity and excellent adsorption capacity towards CECs including ibuprofen (IBP), caffeine (CAF), and bisphenol A (BPA). BC samples were prepared by pyrolysis at different temperatures (400 to 800 °C) and were characterized using nitrogen sorption, FTIR, powder X-ray diffraction (PXRD), SEM/EDS, elemental analysis, and thermal analysis. The nitrogen sorption and SEM results showed that the textural properties were more prominent as the pyrolysis temperature increased. The BC sample obtained at 800 °C which exhibited the largest specific surface area (688 m2/g) and the highest pore volume (0.320 cm3/g) was selected for the adsorption study of CECs. The kinetic study shows that the adsorption equilibrium of CAF and BPA was faster than that of IBP. The pseudo-first- and pseudo-second-order kinetic models best fitted the adsorption data. The Langmuir maximum monolayer adsorption capacities of biochar were found to be ~ 180, 121, and 73 mg/g respectively for IBP, CAF, and BPA. The thermodynamic study shows that the adsorption process was spontaneous and endothermic for the three CECs. The results of the adsorption and the analysis of BC after adsorption showed that hydrogen bonding, van der Waals, π-π, n-π interactions, and pore filling were involved in the adsorption mechanism. The prepared biochar BC from ESS displayed a large surface area and good morphology and significantly promotes adsorption of CECs and good efficiency on synthetic effluent. Finally, it offers a low-cost and cleaner production method.