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.

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.

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.

Fermentative bioconversion of food waste into biopolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) using Cupriavidus necator.

Dependency on plastic commodities has led to a recurrent increase in their global production every year. Conventionally, plastic products are derived from fossil fuels, leading to severe environmental concerns. The recent coronavirus disease 2019 pandemic has triggered an increase in medical waste. Conversely, it has disrupted the supply chain of personal protective equipment (PPE). Valorisation of food waste was performed to cultivate C. necator for fermentative production of biopolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). The increase in biomass, PHBV yield and molar 3-hydroxy valerate (3HV) content was estimated after feeding volatile fatty acids. The fed-batch fermentation strategy reported in this study produced 15.65 ± 0.14 g/L of biomass with 5.32 g/L of PHBV with 50% molar 3HV content. This is a crucial finding, as molar concentration of 3HV can be modulated to suit the specification of biopolymer (film or fabric). The strategy applied in this study addresses the issue of global food waste burden and subsequently generates biopolymer PHBV, turning waste to wealth.

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.

Modulation of microbial community dynamics by spatial partitioning.

Microbial communities inhabit spatial architectures that divide a global environment into isolated or semi-isolated local environments, which leads to the partitioning of a microbial community into a collection of local communities. Despite its ubiquity and great interest in related processes, how and to what extent spatial partitioning affects the structures and dynamics of microbial communities are poorly understood. Using modeling and quantitative experiments with simple and complex microbial communities, we demonstrate that spatial partitioning modulates the community dynamics by altering the local interaction types and global interaction strength. Partitioning promotes the persistence of populations with negative interactions but suppresses those with positive interactions. For a community consisting of populations with both positive and negative interactions, an intermediate level of partitioning maximizes the overall diversity of the community. Our results reveal a general mechanism underlying the maintenance of microbial diversity and have implications for natural and engineered communities.

Digital Microfluidics for the Detection of Selected Inorganic Ions in Aerosols.

A prototype aerosol detection system is presented that is designed to accurately and quickly measure the concentration of selected inorganic ions in the atmosphere. The aerosol detection system combines digital microfluidics technology, aerosol impaction and chemical detection integrated on the same chip. Target compounds are the major inorganic aerosol constituents: sulfate, nitrate and ammonium. The digital microfluidic system consists of top and bottom plates that sandwich a fluid layer. Nozzles for an inertial impactor are built into the top plate according to known, scaling principles. The deposited air particles are densely concentrated in well-defined deposits on the bottom plate containing droplet actuation electrodes of the chip in fixed areas. The aerosol collection efficiency for particles larger than 100 nm in diameter was higher than 95%. After a collection phase, deposits are dissolved into a scanning droplet. Due to a sub-microliter droplet size, the obtained extract is highly concentrated. Droplets then pass through an air/oil interface on chip for colorimetric analysis by spectrophotometry using optical fibers placed between the two plates of the chip. To create a standard curve for each analyte, six different concentrations of liquid standards were chosen for each assay and dispensed from on-chip reservoirs. The droplet mixing was completed in a few seconds and the final droplet was transported to the detection position as soon as the mixing was finished. Limits of detection (LOD) in the final droplet were determined to be 11 ppm for sulfate and 0.26 ppm for ammonium. For nitrate, it was impossible to get stable measurements. The LOD of the on-chip measurements for sulfate was close to that obtained by an off-chip method using a Tecan spectrometer. LOD of the on-chip method for ammonium was about five times larger than what was obtained with the off-chip method. For the current impactor collection air flow (1 L/min) and 1 hour collection time, the converted LODs in air were: 0.275 for sulfate, 6.5 for ammonium, sufficient for most ambient air monitoring applications.

Tailoring of crystalline structure of carbon nitride for superior photocatalytic hydrogen evolution.

Light absorption and carrier transfer, are two sequential and complementary steps related to photocatalysis performance, whereas the collective integration of these two aspects into graphitic carbon nitride (g-C3N4) photocatalyst through polycondensation optimization have seldom been achieved. Herein, we report on tailoring the crystalline structure of g-C3N4 by avoiding the formation of incompletely reacted N-rich intermediates and selective breaking the hydrogen bonds between the layers of g-C3N4 simultaneously. The obtained layer plane ordered porous carbon nitride (LOP-CN) material shows efficient photocatalytic H2 generation performance. The highest H2 evolution rate achieved is 53.8 µmol under λ ≥ 400 nm light irradiation, which is 7.4 times higher than that of g-C3N4 prepared by convention thermal polycondensation. The substantially boosted photocatalytic activity is mainly ascribed to the efficient charge separation on long-range atomic order layer plane and the extended visible light harvesting ability. This work highlights the importance of crystalline structure tailoring in improving charge separation and light absorption of g-C3N4 photocatalyst for boosting its photocatalytic H2 evolution activity.

Enhanced long-wavelength light utilization with polyaniline/bismuth-rich bismuth oxyhalide composite towards photocatalytic degradation of antibiotics.

Antibiotics in natural waters have posed serious threats to our ecosystem due to its potent biological toxicity. In the present work, a visible-light-driven PANI/Bi4O5Br2 composite photocatalyst was fabricated and used for the degradation of ciprofloxacin (CIP) and tetracycline (TC) antibiotics under visible light (λ ＞ 420 nm). The PANI/Bi4O5Br2 composite presented a significantly improved ability of CIP and TC photodegradation, which is about 2.2 times and 1.6 times to that of Bi4O5Br2, respectively. The promoted photocatalytic activity results from the interface interaction between PANI and Bi4O5Br2, which contributes to the electron-hole separation. The degradation process of CIP was monitored by mass spectrometry, and a possible degradation pathway was proposed based on the analysis of the product. A microbiological antibacterial experiment was designed, proving that the degraded products of CIP and TC have lower toxicity. Furthermore, long wavelength light irradiated (λ ＞ 550 nm) experiment indicated that the introduction of PANI helps to extend the light absorption region and use the long wavelength light more efficiently, thereby promoting the photocatalytic ability. The optimal composite applied for TC degradation was 0.1% PANI/Bi4O5Br2. Its reaction rate constant was 2.8 times to that of Bi4O5Br2 (λ ＞ 550 nm). Eventually, a possible photocatalytic mechanism over PANI/Bi4O5Br2 composite was proposed.

Synthesis of zinc ferrite/silver iodide composite with enhanced photocatalytic antibacterial and pollutant degradation ability.

ZnFe2O4/AgI composites were first prepared successfully with a hydrothermal method, and ZnFe2O4 nanoparticles were uniformly decorated on the surface of AgI particles. The photocatalytic activities of the obtained ZnFe2O4/AgI composites were investigated by the degradation of organic pollutants and the inactivation of bacteria under visible light irradiation. The results showed that the introduction of ZnFe2O4 greatly enhanced the light harvesting ability and improved the separation efficiency of the photogenerated charge carriers, which contributed to the enhanced generation of reactive species and thus promoted the photocatalytic performance. The 5% ZnFe2O4/AgI composite exhibited the optimal photocatalytic disinfection of E. coli (100% removal efficiency in 80 min) as well as the photocatalytic degradation of rhodamine B (RhB) (98.5% removal rate in 40 min). Furthermore, four consecutive cycles also demonstrated the stable photocatalytic activity of the as-prepared ZnFe2O4/AgI composites. In addition, H2O2 was identified as the predominant active species in the photocatalytic inactivation of bacteria. This study indicated that ZnFe2O4/AgI composites are a promising candidate for the treatment of wastewater.