Carbocation Mechanism Revelation of Molecular Iodine-Mediated Dehydrogenative Aromatization of Substituted Cyclic Ketones to Phenols.

Dehydrogenative aromatization (DA) of cyclic ketones is central to the development of functionalized aromatic precursors and hydrogen transfer-related technologies. Traditional DA strategies require precious metals with oxidants and are typically performed at high temperatures (100-150 °C) to overcome the high energy barrier of aliphatic C-H bond activation. Recently, a mild alternative approach based on I2 has been proposed to realize DA on substituted unsaturated cyclic ketones under ambient conditions. However, depending on the solvent, the product selectivity may vary between phenol ether and phenol, and the reaction mechanisms remain unclear. Herein, based on time-resolved proton nuclear magnetic resonance, DFT calculation, and mass spectrometric analyses, we established a unified mechanism to account for the product distribution. Through substrate scope and desorption electrospray ionization-mass spectrometry, we discovered the formation of a carbocation, which has been overlooked in previous studies. An expanded substrate scope study coupled with spectroscopic observation provided strong evidence to elucidate the formation mechanism and the location of the carbocation. With a renewed understanding of the mechanism, we achieved a phenolic product yield of 17-96% while controlling the selectivity. Moreover, some reactants could undergo DA in H2O, achieving 95-96% yield at below water-boiling temperature.

One-pot redox cascade paired electrosynthesis of gamma-butyrolactone from furoic acid.

The catalytic valorisation of biomass to afford synthetically useful small molecules is essential for sustainable biorefinery processes. Herein, we present a mild cascaded electrochemical protocol for converting furoic acid, a common biomass-derived feedstock, into a versatile platform chemical, gamma-butyrolactone. In the platinum(+)|nickel(-) electrode paired undivided cell, furoic acid is electrochemically oxidised with 84.2% selectivity to 2(5H)-furanone, the olefin of which is then hydrogenated to yield gamma-butyrolactone with 98.5% selectivity. The final gamma-butyrolactone yield is 69.1% with 38.3% Faradaic efficiency and 80.1% carbon balance when the reaction is performed with 100 mM furoic acid at 80 °C at +2.0 VAg/AgCl. Mechanistic investigation revealed the critical temperature and electrolyte pH conditions that maximise the production and protection of the key intermediate, furan radical, promoting its transition to 2(5H)-furanone rather than self-polymerising. The reaction is scalable, as 2.1 g of 98.1% pure gamma-butyrolactone is isolated through a simple solvent extraction.

Amorphous RuO2 Catalyst for Medium Size Carboxylic Acid to Alkane Dimer Selective Kolbe Electrolysis in an Aqueous Environment.

The catalytic transformation of biomass-derived volatile carboxylic acids in an aqueous environment is crucial to developing a sustainable biorefinery. To date, Kolbe electrolysis remains arguably the most effective means to convert energy-diluted aliphatic carboxylic acids (carboxylate) to alkane for biofuel production. This paper reports the use of a structurally disordered amorphous RuO2 (a-RuO2 ) that is synthesized facilely in a hydrothermal method. The a-RuO2 is highly effective towards electrocatalytic oxidative decarboxylation of hexanoic acid and is able to produce the Kolbe product, decane, with a yield 5.4 times greater than that of commercial RuO2 . A systematic study of the reaction temperature, current intensity, and electrolyte concentration reveals the enhanced Kolbe product yield is attributable to the more efficient oxidation of the carboxylate anions for the alkane dimer formation. Our work showcases a new design idea for establishing an efficient electrocatalysts for decarboxylation coupling reaction, providing a new electrocatalyst candidate for Kolbe electrolysis.

A green slurry electrolysis to recover valuable metals from waste printed circuit board (WPCB) in recyclable pH-neutral ethylene glycol.

The continuous growth of e-waste necessitates an efficient method to recover their metal contents to improve their recycling rate. The successful recovery of the metallic component from Waste Electrical and Electronic Equipment (WEEE) can generate great economic benefits to incentivize the industrial recycling effort. In this study, we report the use of slurry electrolysis (SE) in pH-neutral ethylene glycol (EG) electrolyte to extract and recover the metallic component from waste printed circuit broad (WPCB) powder. The system operates at room temperature and atmospheric pressure, and the electrolyte can be recycled multiple times with no signs of chemical degradation. The EG electrolyte system can oxidize the metallic component without triggering anodic gas evolution, which allowed us to incorporate a reticulated vitreous carbon (RVC) foam anode to maximize the capture and oxidation of the metal content. The system demonstrated up to 99.1% Faraday efficiency for the cathodic metal deposition and could recover Cu from the WPCB powder in a selective manner of 59.7% in the presence of 12 other metals. The SE reaction system was also scalable and displayed no compromises on the Cu recovery selectivity. With the ability to leach and recover metallic content from WPCB in a mild and chemically benign condition, the SE system displayed much promise to be adapted for industrial-scale metal recovery from WPCB.

Superhydrophobic and superoleophilic polydimethylsiloxane-coated cotton for oil-water separation process: An evidence of the relationship between its loading capacity and oil absorption ability.

Developing functional porous materials with highly efficient oil-water separation ability are of great importance due to the global scale of severe water pollution arising from oil spillage and chemical leakage. A solution immersion process was used to fabricate polydimethylsiloxane (PDMS)-coated cotton, which exhibited superhydrophobic and superoleophilic properties. The water contact angle of ∼ 157° and mass of ∼ 1.49 g were retained after 1000 compression cycles, indicating that the PDMS was strongly attached to the cotton fibres. The PDMS-coated cotton absorbed various oils and organic solvents with high selectivity, high absorption capacity (up to 7080 wt.%), and good recyclability (exceeding 500 cycles). Notably, the loading capacity of the PDMS-coated cotton against water exhibited a similar trend to its oil absorption capacity. These findings will further the application of superhydrophobic and superoleophilic porous materials in oil/water separation.

A transition-metal-free, one-pot procedure for the synthesis of α,ß-epoxy ketones by oxidative coupling of alkenes and aldehydes via base catalysis.

A new strategy for the synthesis of epoxides is presented. This process allows the direct synthesis of epoxides from alkenes and aldehydes through C-H functionalization and C-C/C-O bond formation.

Oil/water separation performances of superhydrophobic and superoleophilic sponges.

Superhydrophobic and superoleophilic sponges were fabricated by immersion in an ethanol solution of octadecyltrichlorosilane. The resulting coating strongly adheres to the sponges after curing at 45 °C for 24 h. Absorption capacities of 42-68 times the polymerized octadecylsiloxane sponge weight were obtained for toluene, light petroleum, and methylsilicone oil. These adsorption capacities were maintained after 50 cycles.