Sustainable Chemistry

The incorporation of Ag nanoparticles onto BiVO₄ (a known H₂O oxidising photocatalyst) through magnetron sputtering to form a composite was studied. ICP-OES results showed that the loading of Ag on BiVO₄ was below 1% in all cases. UV-Vis DRS and CO₂-TPD analyses demonstrated that upon incorporation of Ag onto BiVO₄, an increase in the extent of visible light absorption and CO₂ adsorption was seen. TEM imaging showed the presence of Ag particles on the surface of larger BiVO₄ particles, while XRD analysis provided evidence for some doping of Ag into BiVO₄ lattices. The effect of the composite formation on the activity of the materials in the artificial photosynthesis reaction was significant. BiVO₄ alone produces negligible amounts of gaseous products. However, the Ag-sputtered composites produce both CO and CH₄, with a higher loading of Ag leading to higher levels of product formation. This reactivity is ascribed to the generation of a heterojunction in the composite material. It is suggested that the generation of holes in BiVO₄ following photon absorption is used to provide protons (from H₂O oxidation), and the decay of an SPR response on the Ag NPs provides hot electrons, which together with the protons reduce CO₂ to produce CH₄, CO, and adsorbed hydrocarbonaceous species. Full article

The perovskite oxides CaMnO_3-δ, Ca_0.5Sr_0.5MnO_3-δ, and SrMnO_3-δ were synthesized in air using a solid-state method, and their structural, electrical, and electrocatalytic properties were studied in relation to their oxygen evolution reaction (OER) performance. Iodometric titration showed δ values of 0.05, 0.05, and 0.0, respectively, indicating that Mn is predominantly in the 4+ oxidation state across all materials, consistent with prior reports. Detailed characterization was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), iodometric titration, and variable-temperature conductivity measurements. Four-point probe DC measurements revealed that CaMnO_3-δ (δ = 0.05) has a semiconductive behavior over a temperature range from 25 °C to 300 °C, with its highest conductivity attributed to polaron activity. Cyclic voltammetry (CV) in 0.1 M KOH was employed to assess OER catalytic performance, which correlated with room-temperature conductivity. CaMnO_3-δ exhibited superior catalytic activity, followed by Ca_0.5Sr_0.5MnO_3-δ and SrMnO_3-δ, demonstrating that increased conductivity enhances OER performance. The conductivity trend, CaMnO_3-δ > Ca_0.5Sr_0.5MnO_3-δ > SrMnO_3-δ, aligns with OER activity, underscoring a direct link between electronic transport properties and catalytic efficiency within this series. Full article

This review explores both the positive and negative impacts of chemistry on society, focusing on the intersection between pharmaceutical, natural, and synthetic chemicals. On the one hand, drugs developed through medicinal chemistry have saved lives, improved people’s quality of life, and increased longevity. However, they also pose risks, including fatalities and environmental damage. Pharmaceutical chemistry has revolutionized medical practice by enabling the treatment and cure of fatal or debilitating diseases, significantly contributing to the rise in global life expectancy through the research and development of new bioactive substances. This article also highlights the harmful effects of toxic synthetic substances, which negatively impact human health and the environment, affecting plants, animals, air, water, soil, and food. Full article

The titanium dioxide (TiO₂) photocatalyst is an important semiconducting material that exhibits environmental purification functions when exposed to light. Elemental doping of TiO₂ is considered an important strategy to improve its photocatalytic activity. Herein, we have achieved the low-temperature, atmospheric-pressure synthesis of anatase TiO₂ particles with doping of 3d metals (Fe, Co, Ni and Cu) based on the liquid phase deposition technique. All products prepared by adding 3d metals were found to consist of TiO₂ crystals in the anatase phase with a fine protruding structure of about 40 nm on the surface, as was the case without the addition of metal ions. Iron and copper were observed to be incorporated at higher concentrations than cobalt and nickel, with an elemental addition of up to 4 at% and 1 at%, respectively, when 10 mM iron and copper nitrate were applied. Such doping efficiency could be explained by the difference in ionic radius and chemical stability. A narrowing of the optical band gap with doping elements was also observed, and it was found that optical sensitivity could be imparted down to the visible-light region of 2.4 eV (Fe: 4 at% addition). Furthermore, the 3d metal-doped TiO₂ demonstrated in this study was shown to exhibit photocatalytic methane degradation activity. The amount of methane degradation per unit area of the microparticles was twice as great when iron and copper were added, compared to the undoped counterpart. It has been demonstrated that the strategy of doping TiO₂ with 3d metal ions by low-temperature synthesis methods is effective in enhancing carrier dynamics and introducing surface active sites, thus increasing methane degradation activity. Full article

The well-being of the Earth and its inhabitants is compromised by the energy and climate crisis that has arisen from the prolonged and uncontrolled utilization of fossil fuels, which has caused a tremendous increase in anthropogenic CO₂ and a consistent depletion of natural energy resources [...] Full article

Brewer’s spent grains (BSG) are a by-product of the beer industry and can be used to produce biofuels. In this case, the objective of this study was to obtain reducing sugars from this biomass by subcritical water hydrolysis in a semi-continuous mode after steam explosion. Temperatures of 120–180 °C, reaction times of 1–5 min, and pressures of 15–25 MPa were used for the steam explosion without CO₂. Moistures of 10–50% (w/v), temperatures of 120–180 °C, reaction times of 1–5 min, and pressures of 15–25 MPa were used for the steam explosion with CO₂. Subcritical water hydrolysis of solid-exploded material was developed at 210 °C, 15 MPa, a solid/feed ratio of 16 g/g, and a flow rate of 20 mL/min. The characterization of BSG, reducing sugar yields, kinetic profiles, the composition of monosaccharides and furanic moieties, and the characterization of remaining solid by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) were performed. For steam explosion with CO₂, the significant variables were the temperature and moisture, and the optimized conditions were moisture of 50% (w/v), 120 °C, pretreatment for 1 min, and 15 MPa, with a reducing sugars yield of 18.41 ± 1.02 g/100 g BSG. For steam explosion without CO₂, the significant variables were the time and temperature, and the optimized conditions were 120 °C, pretreatment for 1 min, and 15 MPa, with a reducing sugars yield of 17.05 ± 0.48 g/100 g BSG. The process was successful because the steam explosion ruptured the lignocellulosic matrix, and the subsequent process of subcritical water hydrolysis could dissociate the polymers into low-chain saccharides. Full article

Biochar, produced through the pyrolysis of biomass and green waste, offers significant potential as a soil amendment to enhance soil health and sustainability in agriculture. However, the current Measurement, Reporting, and Verification (MRV) systems for biochar predominantly focus on carbon credits/offsets, neglecting crucial aspects related to its usability and suitability as a soil amendment on agricultural fields. Through an examination of recent findings, this perspective explores the integration of geochemical tracers, functional group (hydroxyl, carboxyl, phenolic, lactonic, etc.) analysis, and nutrient dynamics into MRV procedures/systems to create a more comprehensive framework. By examining the applicability of these indicators, this paper identifies key gaps and proposes a more robust MRV approach. Such a system would not only facilitate better assessment of biochar’s agronomic benefits but also guide its optimal use in various soil types and agricultural practices. Full article

In this study, several professional cleaning products were analyzed for their impact on local air and sewage contamination. The products were first analyzed for their content of potentially harmful ingredients, their biodegradability, and the potential for the mobilization of hazardous substances from the floorings that were cleaned. The contribution of the cleaning products to sewage pollution with environmentally hazardous substances was studied at full scale. All commercially available cleaning products studied were declared to be environmentally friendly (labeled with the EU Ecolabel). However, despite being labeled as “green” products, between 16 and 24 volatile harmful ingredients were identified. An optimized experimental product, produced completely from natural raw materials, also contained several harmful substances originating from the herbal raw materials themselves. During the field study, we identified a range of trace substances in the sewage. Eight of these substances (e.g., p-cymene, butanone, eucalyptol) significantly originated from the cleaning products. Several others may have originated from the cleaning products, but other sources were also possible. The flooring materials that were cleaned contained several harmful substances themselves. The release of some substances (e.g., toluene) into the sewage significantly increased during the cleaning process. Full article

Phosphorus mainly exists in the form of phosphate in water. Excessive phosphorus can cause eutrophication, leading to algae reproduction and the depletion of oxygen in water, destroying aquatic ecology. This study prepared quaternized polyaniline (PN) and quaternized polyaniline with lanthanum hydrate (HLO-PN), and a new nanocomposite for removing phosphate from wastewater was proposed. The results of adsorption experiments show that HLO-PN can effectively remove phosphate in the range of pH 3~7; the maximum adsorption capacity is 92.57 mg/g, and it has excellent anti-interference ability against some common coexisting anions (${\mathrm{F}}^{-},$ ${\mathrm{C}\mathrm{l}}^{-},$ ${\mathrm{NO}}_3^{-},$ ${\mathrm{SO}}_4^{2-}$) other than ${\mathrm{CO}}_3^{2-}$. After five adsorption–desorption cycles, the phosphate adsorption capacity (60 mg/g) was still 74.28% of the initial adsorption capacity (80.85 mg/g), indicating that the HLO-PN nanocomposites had good reusability and recovery of phosphorus. The characterization results show that phosphate adsorption is realized by electrostatic adsorption and ligand exchange. Full article

For a long time, the leather industry has considered the chromium tanning process to be the easiest and fastest way to treat raw hides and transform them into valuable products. In the last few decades, increasing attention has been paid to the potential oxidation of the trivalent chromium in tanned leather. This happens for many reasons, such as the quality of the tanning agent or the adoption of good manufacturing practices. Anyway, the main problem, which is difficult to solve, is the sensibility of the free residual chromium tanned leather, which is high enough for possible harmful activity. Given this scenario, this work proposes a solution to decrease hexavalent chromium formation by using antioxidants during the leather tanning process. In this regard, a screening work was started, to find the worst-case scenario for trivalent chromium oxidation. To do this, commercial tanning products were employed, especially fatliquoring agents, which, in some cases, are the main source that could easily react with ROS (Reactive Oxygen Species) to drive chromium oxidation. After the determination of conditions, different groups of common antioxidants were tested to analyse the antioxidation performances and their possible use in the chromium-based tanning process. The results underline the efficient action of the antioxidants studied, paving the way for some interesting perspectives to limit the drawbacks of chromium tanned leather. Full article

Cross-linked polymers synthesized through inverse vulcanization of unsaturated vegetable oils (biopolymers) were used as matrices for incorporating gentamicin (GEN) to form a biocomposite that can amplify GEN antimicrobial activity against Pseudomonas aeruginosa. Two different biopolymers were synthesized using soybean (PSB) and sunflower (PSF) oils by inverse vulcanization cross-linked with sulfur in a 1:1 weight ratio. The study involves the synthesis and characterization of these biopolymers using FTIR and SEM as well as measurements of density and hydrophobicity. The results reveal the formation of biopolymers, wherein triglyceride molecules undergo cross-linking with sulfur chains through a reaction with the unsaturated groups present in the oil. Additionally, both polymers exhibit a porous structure and display hydrophobic behavior (contact angle higher than 120°). The biopolymers swell more in GEN solution (PSB 127.7% and PSF 174.4%) than in pure water (PSB 88.7% and PSF 109.1%), likely due to hydrophobic interactions. The kinetics of GEN sorption and release within the biopolymer matrices were investigated. The antibacterial efficacy of the resulting biocomposite was observed through the analysis of inhibition growth halos and the assessment of P. aeruginosa viability. A notable enhancement of the growth inhibition halo of GEN (13.1 ± 1.1 mm) compared to encapsulated GEN (PSF-GEN 21.1 ± 1.3 and PSB-GEN 21.45 ± 1.0 mm) is observed. Also, significant bactericidal activity is observed in PSF-GEN and PSB-GEN as a reduction in the number of colonies (CFU/mL), more than 2 log₁₀ compared to control, PSF, and PSB, highlighting the potential of these biopolymers as effective carriers for gentamicin in combating bacterial infections. Full article

The plant-mediated synthesis of therapeutic metal nanoparticles is an intensively exploited field in the last decade. In particular, Salvia officinalis, considered one of these plants, was used in this work to synthesize silver particles. Here, we have used harmless substances to obtain silver particles and common characterization methods for quickly estimating sizes and shapes. Thus, UV–Visible spectroscopy helped us online-monitor and optimize the synthesis of silver particles and estimate the size of metallic particles in the stock solutions. The resulting eco-friendly synthesized silver particles were then separated and re-dispersed in water, to be analyzed by laser light scattering, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) to prove their nanometric size and shape polydispersity. Furthermore, the role of citric acid in stabilizing colloidal solutions of silver nanoparticles was studied. Full article

The aim of this research was to separate the over-the-counter nonsteroidal anti-inflammatory drug (NSAID), ibuprofen, from an aqueous solution using the adsorption method, as this NSAID is one of the most globally consumed. An adsorbent was crafted from the Agave angustifolia bagasse, a byproduct of the bacanora industry (a representative alcoholic beverage of the state of Sonora, in northwestern Mexico). Three bioadsorbents (BCT1, BCT2, and BCT3) were produced via pyrolysis at a temperature of 550 °C, with slight variations in each process for every bioadsorbent. The bioadsorbents achieved material yields of 25.65%, 31.20%, and 38.28% on dry basis respectively. Characterization of the bagasse and adsorbents involved scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The biomass morphology exhibited a cracked surface with holes induced via the bacanora production process, while the surface of the bioadsorbents before ibuprofen adsorption was highly porous, with a substantial surface area. After adsorption, the surface of the bioadsorbents was transformed into a smoother grayish layer. The macromolecules of cellulose, hemicellulose, and lignin were present in the biomass. According to functional groups, cellulose and hemicellulose degraded to form the resulting bioadsorbents, although traces of lignin persisted after the pyrolysis process was applied to the biomass. In an adsorption study, BCT1 and BCT2 bioadsorbents successfully removed 100% of ibuprofen from aqueous solutions with an initial concentration of 62.6 mg/L. In conclusion, the biocarbon derived from Agave angustifolia bagasse exhibited significant potential for removing ibuprofen via adsorption from aqueous solutions. Full article

Ammonia can be considered a relevant compound in the future energy sector, playing a significant role as an energy carrier, storage, or carbon-free fuel. However, the production of this molecule has a high energy demand, and the use of natural gas, which is not free of controversy due to the accidental leakage into the atmosphere produced during extraction and the fact that it is a nonrenewable source, contributes to increasing greenhouse gas emissions. Reducing the process’s energy demand and carbon footprint will be essential to making ammonia a clear alternative for a carbon-free economy. Given the vast research in ammonia production and handling, this gas seems to be the logical step forward in the evolution of the energy sector. However, the current uncertainty in the global market requires cautiousness in decision making. Several factors may impact economic growth and human welfare, thus needing a careful assessment before making any transcendental decisions that could affect worldwide energy prices and raw material availability. Full article

The increasing commercial, industrial, and medical applications of plastics cannot be halted during the coming years. Microplastics are a new class of plastic pollutants which have emerged as escalating environmental threats. The persistence, effects, and removal of MPs present in soil, water, and numerous organisms have become an important research field. However, atmospheric microplastics (AMPs), which are subcategorized into deposited and suspended, remain largely unexplored. This review presents the recent developments and challenges involved in fully understanding suspended and deposited AMPs. The evaluation of indoor suspended MP fibers needs to be critically investigated to understand their implications for human health. Furthermore, the transportation of AMPs to isolated locations, such as cryospheric regions, requires immediate attention. The major challenges associated with AMPs, which have hindered advancement in this field, are inconsistency in the available data, limited knowledge, and the lack of standardized methodologies for the sampling and characterization techniques of AMPs. Full article

Nanochitin, especially in the form of chitin nanowhiskers (ChNWs), represents a significant advance in biopolymer technology due to its high specific surface area, superior tensile strength, and excellent thermal stability. Derived from crustacean waste, which contains 15–40% of chitin, these materials provide a sustainable option that diverts waste from landfills and contributes to environmental conservation. Traditional methods of isolating nanochitin are energy-intensive and generate substantial waste. This study introduces a more sustainable method using inexpensive ionic liquids (ILs) such as [Hmim][HSO₄] and [HN₂₂₂][HSO₄], which bypass the costly and destructive steps of traditional procedures. This study also identified the byproduct in IL-mediated chitin hydrolysis reaction as calcium sulfate dihydrate and presented a solution to circumvent the byproduct formation. The effectiveness of the [HN₂₂₂][HSO₄] IL in producing ChNWs from both purified chitin and crustacean biomass was assessed, showing a high yield and maintaining the purity and structural integrity of chitin, thereby demonstrating a significant reduction in the environmental footprint of ChNW production. Full article