Mechanistic insights into methylene blue removal via olive stone-activated carbon: A study on surface porosity and characterization

Global attention is increasingly focused on the adverse health and environmental impacts of textile dyes, marking the necessity for effective and sustainable dye remediation strategies in industrial wastewater. This study introduces a novel, eco-friendly activated carbon produced from olive stones (OLS), a readily available by-product of the olive oil industry. The OLS was chemically activated with H₃PO₄ and KOH, creating two materials: OLS-P and OLS-K, respectively. These were then utilized as cost-effective adsorbents for the removal of methylene blue (MB) dye. The activated materials were characterized via X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR), iodine number, and pHpzc analysis, with the zero-point charge determined as approximately pH 1 for OLS-P and pH 8 for OLS-K. Batch adsorption experiments conducted at various temperatures revealed that adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model. Temperature was found to significantly impact adsorption performance, with OLS-K demonstrating a substantial increase in adsorption capacity (q_e) from 6.27 mg/g at 23˚C to 94.7 mg/g at 32 ˚C. Conversely, OLS-P displayed a decrease in q_e from 16.78 mg/g at 23 ˚C to 3.67 mg/g at 32 ˚C as temperature increased. The study highlights the potential of KOH-treated olive stones as a promising, cost-efficient adsorbent for methylene blue remediation from wastewater.     

Modular Synthesis of ortho-Thiolated Aryl Esters Enabled with Thiocarbonate through Catellani Strategy

Herein, we report a palladium/norbornene/copper co-catalyzed single-step approach that merges selective ortho C−H bond esterification with ipso thiolation for construction of synthetically versatile 2-arylthio aryl esters under exceptionally mild conditions. Importantly, this process proceeded in a highly efficient manner, allowing alkoxycarbonyl and thio groups to be installed into one aryl iodides simultaneously by harnessing thiocarbonate as bifunctional reagent. The method has been demonstrated to accommodate good functionalities and features broad substrate scope.     

Rhodium-Catalyzed C8-Alkenylation of Isoquinolones with Maleimides

An efficient Rh(III)-catalyzed C−H alkenylation of N-protected isoquinolone with maleimides is reported. The carbonyl group of isoquinolone acts as an inherent directing group. Various N-substituents in the maleimide, including alkyl, aryl, and even H and −OH, were well tolerated under the developed reaction condition. This protocol showed broad substrate scope, good selectivity, and excellent yields. Hammett plot is also drawn to check the effect of substituents on the reaction progress.     

A Fujiwara-Moritani-Type Alkenylation Using a Traceless Directing Group Strategy: A Rare Example of C−C Bond Formation towards the C2-Carbon of Terminal Alkenes

Herein we report, a rhodium-catalyzed Fujiwara-Moritani-type reaction of unactivated terminal alkenes and benzoic acid derivatives bearing electron donating residues under mild conditions. The acid functionality acts as a traceless directing group delivering products alkenylated in meta-position to the electron donating substituent in contrast to the usually obtained ortho- and para-substitution in Friedel-Crafts-type reactions. Remarkably, the new C−C bond is formed to the C2 of the terminal olefin, in contrast to similar reported transformations. Initially formed mixtures of exo- and endo-double bond isomers can be efficiently isomerized to the more stable endo-products.     

How Ligand Geometry Affects the Reactivity of Co(II) Cyclam Complexes

Cobalt complexes are extensively studied as bioinspired models for non-heme oxygenases as they facilitate both the stabilization and characterization of metal-oxygen intermediates. As an analog to the well-known Co(cyclam) complex Co{N₄} (cyclam=1,4,8,11-tetraazacyclotetradecane), the Co^II complex Co{i-N₄} with the isomeric isocyclam ligand (isocyclam=1,4,7,11-tetraazacyclotetradecane) was synthesized and characterized. Despite the identical N₄ donor set of both complexes, Co{i-N₄} enables the 2e⁻/2H⁺ reduction of O₂ with a lower overpotential (η_eff of 385 mV vs. 540 mV for Co{N₄} ), albeit with a diminished turnover frequency. Characterization of the intermediates formed upon O₂ activation of Co{i-N₄} reveals a structurally identified stable μ-peroxo Co^III dimer as the main product. A superoxo Co^III species is also formed as a minor product, as indicated by EPR spectroscopy. In further reactivity studies, the electrophilicity of these in situ generated Co−O₂ species was demonstrated by the oxidation of the O−H bond of TEMPO−H (2,2,6,6-tetramethylpiperidin-1-ol) via a H atom abstraction process. Unlike the known Co(cyclam), Co{i-N₄} can be employed in oxygen atom transfer reactions oxidizing triphenylphosphine to the corresponding phosphine oxide highlighting the impact of geometrical modifications of the ligand while preserving the ring size and donor atom set on the reactivity of biomimetic oxygen activating complexes.     

A Series of Low-Coordinate Iron Selenido Complexes: Reactivity of a Linear Iron(I) Silylamide towards Selenium

A variety of different low-coordinate iron selenide complexes is reported. These are obtained by reaction of the linear iron(I) silylamide K{18c6}[Fe(N(Dipp)SiMe₃)₂] (Dipp=2,6-diisopropylphenyl) with red selenium. Careful adjustment of the reaction conditions results in the formation of unique low-coordinate selenido iron complexes, namely a monoselenide bridged [2Fe−1Se]²⁺ complex, as well as mononuclear iron per- and triselenides. Further, C−H bond activation of one of the silylamide ligands by a putative terminal iron monoselenide is observed.     

How Doping Affects the Activity of the Aluminum Oxide Support

The performance of heteronuclear clusters [AlXO₃]⁺ (X=Al, AlO₄, AlMg₂O₂, AlZnO, AlAu₂, Mg, Y, VO, NbO, TaO) in activating methane has been explored by a combination of high–level quantum calculations with reported and supplementary gas-phase experiments. With different dopants in [AlXO₃]⁺, the mechanism, reactivity and selectivity towards methane activation varies accordingly. The classic HAT competes with PCET, depending on the composition of intramolecular interactions. Although the existence of terminal oxygen radical is beneficial for classic HAT, the Al_t−C interaction in the [AlXO₃]⁺ clusters as enhanced by the strongly electronegative doping groups (X=Al, AlZnO, Mg, Zn, VO, NbO, TaO) favors the PCET process, facilitating C−H bond breaking. In addition, with different dopants, the destiny of the split methyl group varies accordingly. While strong interaction between Al_t and CH₃ results in the formation of the Al_t−C bond, dopants with variable valance may promote the formation of deep-oxidation products like formaldehyde. It has been discussed in detail how to regulate the activity and selectivity of the active center of the catalyst via rational doping.     

C−F Transformations of Benzotrifluorides by the Activation of Ortho-Hydrosilyl Group

Single C−F transformations of aromatic trifluoromethyl compounds are challenging issues due to the strong C−F bond. We have recently developed selective methods for single C−F transformations such as allylation of o-hydrosilyl-substituted benzotrifluorides through the hydride abstraction with trityl cations. Single C−F thiolation and azidation of o-(hydrosilyl)benzotrifluorides were achieved using trityl sulfides and trityl azide catalyzed by Yb(OTf)₃. Treatment of o-(hydrosilyl)benzotrifluorides with trityl chloride resulted in single C−F chlorination. The resulting fluorosilyl group served in further transformations including protonation, halogenation, and Hiyama cross-coupling with C−Si cleavage. We also synthesized benzyl fluorides by LiAlH₄-reduction of the resulting fluorosilanes and further C−F transformations. These methods enabled us to prepare a broad range of organofluorines from simple benzotrifluorides through C−F and C−Si transformations.     

NHC-Activations on α-, β-, γ-, and Beyond

Over the recent decades, due to the special electronic characteristics and diverse reactivities, N-heterocyclic carbene (NHC) has received significant interest in organocatalyzed reactions. The formation of Breslow intermediates by NHC can convert into acyl anion equivalent, enolates, homoenolate, acyl azolium, and vinyl enolate etc., and the cycloaddition reactions of these species has attracted lots of attention. In this review, we focus on the summry of the development of NHC-activation of carbonyl carbon (or imine carbon) in situ, α-, β-, γ-, and beyond, and the cycloaddition reaction of these species.     

Efficient removal of anionic dye by protonated APTES modified hydrochar: The effect of cold-activation

The study focused on determining the effect of acidic and basic cold activation on hydrochar (HC) for the removal of methyl orange (MO). HC was prepared by hawthorn seeds (HS) under hydrothermal carbonization. HC was cold-activated with HCl and NaOH, respectively, and they were grafted with aminopropyltriethoxysilane (APTES) and protonated to obtain AHC-N⁺ (acid-activated and modified HC) and BHC-N⁺ (base-activated and modified HC) to determine the effect of acidic and basic activation. They were characterized by elemental analysis, IR, thermal analysis, zeta potential, N₂ adsorption–desorption measurements, and SEM–EDX analysis. The prepared adsorbents displayed MO adsorption due to abundant protonated amine groups. BHC-N⁺ showed higher MO adsorption than AHC-N⁺. The result showed that more protonated APTES groups grafted on the surface of HC via NaOH activation. The obtained data had a good fitting with the Langmuir isotherm and pseudo-second-order kinetic. The maximum adsorption capacity of BHC-N⁺ was 250.38 mg g⁻¹. The adsorption mechanism could be attributed to the electrostatic interactions between MO and protonated amine groups of APTES and hydrogen bonding.