Catalysts

A sequential two-step thermochemical process was studied for spent green tea waste (SGTW), involving an initial pyrolysis step followed by thermal or catalytic cracking. This process was carried out in two bench-scale reactors (fixed bed reactor and tubular reactor) serially coupled. At a fixed pyrolysis temperature of SGTW (550 °C), the application of high cracking temperatures (700 and 800 °C) positively affected both the yield and composition of the gas product. Consequently, it has the potential to be used for the production of diverse biofuels and chemicals, or to be partially recycled to optimize the process efficiency. Moreover, the use of inexpensive catalysts, particularly dolomite, was considered advantageous, since the syngas yield (56.5 wt%) and its potential were greatly enhanced, reaching a H₂/CO ratio of 1.5. The homogenous biochar obtained, with a calorific value of 26.84 MJ/kg, could be harnessed as good-quality fuel for briquette applications and as a biofuel source for generating stationary power. Furthermore, catalytic cracking pyrolysis was examined for different types of coffee waste, revealing that this process is a simple and clean solution to valorize oxygen-rich lignocellulosic biomass and generate valuable gaseous by-products. Full article

In this work, we report the application of Au/WO₃ composite as a photocatalyst for the degradation of dyes under solar light irradiation. Au/WO₃ nanocomposites were synthesized using an acid precipitation method followed by an impregnation/reduction at room temperature. Two composites were obtained by loading gold nanoparticles on two morphologies of nanostructured WO₃, nanoplatelets (NP), and pseudospheres (PS). The elaboration parameters of the nanocomposites were optimized according to the gold mass percentage, the HAuCl₄ precursor concentration, and the impregnation time. The structural, microstructural, and textural characterization were conducted using advanced techniques: XRD, SEM/TEM microscopies, and XPS and DRS spectroscopies. The optimal synthesis parameters are a 48 h impregnation of a five mass percentage of gold from a HAuCl₄ precursor with a concentration of 10⁻³ mol·L⁻¹. The obtained composites were formed with Au nanoparticles of 7 nm in size. The XRD analyses did not reveal any modification of the oxide supports structure after gold grafting, contrary to the sorption analyses, which evidenced a change in the state of the materials surface. XPS analysis revealed the reduction of W⁶⁺ ions into W⁵⁺, favoring the presence of oxygen vacancies. Furthermore, a localized surface plasmon resonance effect was observed in the composite at 540 nm. The photocatalysis results of several dye pollutants have shown a selective degradation efficiency depending on the charge of the polluting molecules, pH medium, and mass loading of the catalysts. At the native pH, the photocatalysis process is highly efficient on a cationic molecule, with a low adsorption capacity. Au/WO₃ PS composite appears to be the most efficient, degrading almost the whole RhB and MB only in 60 min and 90 min, respectively, while, for the MO anionic dye, the degradation is more efficient in acidic medium (80%) than in basic medium (0%). Trap tests of the main active species were investigated and a photodecomposition mechanism is proposed. Full article

Transition metal oxide materials are promising oxygen catalysts that are alternatives to expensive and precious metal-containing catalysts. Integration of transition metal oxides with high activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is an important pathway for good bifunctionality. In contrast to the conventional physical mixing and hybridization strategies, perovskite-type oxide provides an ideal structure for the integration of the transition metal element atoms on an atomic scale. Herein, B-site ordered double-perovskite-type La_1.6Sr_0.4MnCoO₆ nanocrystallites with ultra-small cubic (20–50 nm) morphology and high specific surface areas (25 m² g⁻¹) were proposed. Rational designs were integrated to promote the ORR-OER catalysis, e.g., introducing oxygen vacancies via A-site cation substitution, further increasing surface oxygen vacancies via integration of a small amount of Pt/C and nanosizing of the material via a facile molten-salt method. The batteries with the La_1.6Sr_0.4MnCoO₆ nanocrystallites and an aqueous alkaline electrolyte demonstrate decent discharge−charge voltage gaps of 0.75 and 1.10 V at 1 and 30 mA cm⁻², respectively, and good cycling stability of 250 h (1500 cycles). A coin-type battery with a gel−polymer electrolyte also presents a good performance. Full article

New heterojunction materials (HJs) were synthesized in-situ by molecularly bonding the monomers of a triazine-based covalent organic framework (bulk COF) on the template of exfoliated carbon nitride (g-C₃N₄). The photocatalysts reduced carbon dioxide to carbon monoxide in aqueous dispersions under UV irradiation. The g-C₃N₄ showed production of 6.50 $\mathsf{\mu }$mol CO g⁻¹ h⁻¹ and the bulk COF of 2.77 $\mathsf{\mu }$mol CO g⁻¹ h⁻¹. The CO yield was evaluated in sustainability photoreduction cycles and their CO₂ uptake capacity and isosteric heat of adsorption were estimated. All the heterojunction photocatalysts obtained ameliorated CO production rates compared to the bulk COF. Finally, the influence of the Pt co-catalyst on the photocatalytic activities was determined without the addition of any sacrificial agent, and the COF:g-C₃N₄ heterojunction with the ratio of 1:10 was proven to be a photocatalytic system with an optimum and selective, CO yield of 7.56 $\mathsf{\mu }$mol g⁻¹ h⁻¹. Full article

A novel catalytic system for homocoupling terminal acetylenes was elaborated based on CuCl as a catalyst (10 mol%), TMEDA as a base and CCl₄ as an oxidant. The influence of the solvent, base, amount of catalyst and CCl₄ on the reaction was investigated. Methanol was found to be the solvent of choice. The broad synthetic scope of the reaction was demonstrated. Diynes with various substituents were prepared in up to 92% yields. The possible reaction mechanism is discussed. Full article

A series of NiM/SiO₂ (M = Ce, Co, Cu, Fe, Sn, Zr, Mo) catalysts are prepared and used in the selective hydrodeoxygenation (HDO) of aliphatic acid to produce alkanes with the same number of carbon atoms as the reactant (alkane-Cx). The results indicate the introduction of Mo promotes the hydrodehydration of aliphatic alcohol and suppresses the decarbonylation of aliphatic aldehyde. The selective to alkane-Cx is more than 70% in the case of a complete conversion of aliphatic acid. A mechanism study proves that, due to the higher electronegativity of Mo, electrons transfer from Ni to Mo easily and facilitate the reduction of Mo, and the partially reduced Mo species is favorable for the hydrodehydration of aliphatic alcohol. Meanwhile, the adsorption of alcohol on Mo is more favorable than on the Ni site, and the hydrogen bond between hydroxyl hydrogen and O atoms on the catalyst improves the adsorption stability of aliphatic alcohol. Further COHP analysis indicates that the C-OH bond was activated when alcohol was adsorbed on the Ni₅/MoO₂ surface, which promoted the hydrodehydration of aliphatic alcohols and improved carbon atom utilization. Full article

The development of semiconductor photocatalysts has recently witnessed notable momentum in the photocatalytic degradation of organic pollutants. ZnO is one of the most widely used photocatalysts; however, its activity is limited by the inefficient absorption of visible light and the fast electron–hole recombination. The incorporation of another metal or semiconductor with ZnO boosts its performance. In this present study, a heterostructured ZnO-Bi₂O₃ composite was synthesized via a simple co-precipitation method and was investigated for the UV-driven photocatalytic degradation of the Reactive Orange 16 (RO16), a model textile dye. The successful fabrication of ZnO-Bi₂O₃ microstructures with crystalline nature was characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX). The discoloration of the dye solution was quantified using UV–Vis spectroscopy to determine the photocatalytic efficiency. The photocatalytic activity results demonstrated that the photodegradation at ZnO-Bi₂O₃ heterojunction was more efficient and 300 and 33% faster than individual Bi₂O₃ and ZnO catalysts, respectively, an effect that is indicative of a synergistic effect. In the presence of ZnO-Bi₂O₃ particles, the UV light-driven activity for RO16 degradation was twice as high as in its absence. The influence of adding the oxidant H₂O₂ on the UV-induced photocatalytic degradation was investigated and the results revealed a two-time increase in the photocatalytic activity of ZnO-Bi₂O₃ compared to UV irradiation alone, which could be ascribed to a summative degradative effect between UV and H₂O₂. Hence, this approach holds the potential for environmentally friendly wastewater treatment. Full article

Methyl glycolate was synthesized as a precursor to ethylene glycol from the acid-catalyzed carbonylation of formaldehyde, followed by esterification with methanol. Homogeneous acids and different solid acids (e.g., resins and zeolites) were used as catalysts, and the effect of the solvent was examined. Afterward, a carboxylic acid protection strategy was proposed. With sulfolane and acetic acid as the mixed solvent, the solubility of CO increases, and the reaction rate can be accelerated. The rapid reaction between acetic acid and glycolic acid inhibits glycolic acid polymerization and pulls the reaction balance to promote the carbonylation reaction rate. Under the optimal solvent system (a molar ratio of acetic acid to sulfolane of 1:5) and the appropriate reaction conditions, the selectivity of the target product is higher than 85%. Solid acid catalysts with a −SO₃H or −CF₂SO₃H functional group are supposed to be efficient in the carbonylation of formaldehyde, based on which a supported Nafion catalyst with a high surface area and total acid content was designed and synthesized. The novel supported Nafion catalyst presents a high total acid content and high Brönsted–Lewis acid ratio due to the characteristics of modified zeolite and, thus, leads to the high reactivity and very low selectivity of the by-product. A possible reaction mechanism is proposed to explain the product’s distribution by ascribing the formation of different products to different types of acid sites. Full article

First examples of the reactions of 3-trimethylsilyl-2-propynamides with organic diselenides yielding 3-alkylselanyl-2-propenamides and 3-organylselanyl-2-propynamides were realized. The latter compounds were obtained by the Cu-catalyzed reaction of organic diselenides with 4-propioloylmorpholine. The reaction of 3-trimethylsilyl-2-propynamides with dialkyl diselenides in the system NaBH₄/H₂O/K₂CO₃/THF proceeded in a regio- and stereoselective fashion, affording 3-alkylselanyl-2-propenamides in 90–94% yields. An unsymmetrical divinyl selenide with the cyclic amide groups and a product, containing two selanyl-2-propenamide moieties and three cyclic amide groups, were synthesized. The Cu-catalyzed allylation reaction of 3-trimethylsilyl-2-propynamides was accompanied with desilylation to yield 3-allyl-2-propynamides. Full article

Hydrogen peroxide (H₂O₂) is a clean and mild oxidant that is receiving increasing attention. The photocatalytic H₂O₂ production process utilizes solar energy as an energy source and H₂O and O₂ as material sources, making it a safe and sustainable process. However, the high recombination rate of photogenerated carriers and the low utilization of visible light limit the photocatalytic production of H₂O₂. S-scheme heterojunctions can significantly reduce the recombination rate of photogenerated electron–hole pairs and retain a high reduction and oxidation capacity due to the presence of an internal electric field. Therefore, it is necessary to develop S-scheme heterojunction photocatalysts with simple preparation methods and high performance. After a brief introduction of the basic principles and advantages of photocatalytic H₂O₂ production and S-scheme heterojunctions, this review focuses on the design and application of S-scheme heterojunction photocatalysts in photocatalytic H₂O₂ production. This paper concludes with a challenge and prospect of the application of S-scheme heterojunction photocatalysts in photocatalytic H₂O₂ production. Full article

The adsorption of the lipase B from Candida antarctica (CALB) over polyethylene terephthalate (PET), polypropylene (PP), and derivatives, abundant components of urban solid waste (USW), was investigated. The characterization of the supports and biocatalysts synthesized by SEM-EDS and FTIR is presented. Two immobilization strategies were evaluated, conventional and total adsorption. The adsorbed protein was determined by Bradford and through high-resolution inductively coupled plasma atomic emission spectroscopy (ICP-AES). In this sense, the adsorption of CALB in all the proposed supports was evidenced, obtaining the highest protein loads in bis-(2-hydroxyethyl) terephthalate (BHET). Subsequently, the biocatalysts were applied to the esterification of rac-ibuprofen with ethanol. CALB immobilized in BHET showed remarkable activity, achieving conversions of 30%. In this context, immobilization on this support was optimized, studying the addition of sorbitol-glycerol. Thus, in the presence of 0.91 g of polyols, a catalyst with a protein load of 33.3 mg·g⁻¹ was obtained, achieving productivity of 0.298 mmol min⁻¹ mg⁻¹. Additionally, no differences were found when using BHET from USW bottles of various colors. This research shows the potential of materials derived from PET as enzymatic supports, unreported materials, that we can use as tools to achieve sustainable biotechnological applications. Full article

In the face of the climate change problem caused by fossil fuels, it is essential to seek efficient alternative energies with a lower environmental impact that are derived from renewable resources. Biomass gasification technology continues to generate significant interest in sustainable energy research as an alternative to traditional combustion technology. Gasification involves the thermochemical conversion of raw materials, resulting in a highly valuable gaseous product known as synthesis gas, commonly used as a fuel. Its numerous advantages include the availability of raw materials, the reduction in harmful emission streams, performance, and costs. As this topic gains momentum in the global energy framework, it is imperative to advance the maturity of this technology by addressing its weaknesses, primarily in terms of efficiency. The objective of this project was to investigate the hydrogen production process through the simulation of glucose gasification as a representative compound for biomass. This was achieved by conducting an integrated simulation of glucose gasification, encompassing both the heat transfer in the external system and the conversion of glucose into hydrogen gas, using the results obtained in the external system as initial conditions. Interrelated aspects of this complex process, including heat transfer and the kinetics of the gasification process, were modeled. Glucose was selected as the model compound due to its availability, simplicity, fundamental understanding, reproducibility, comparability, knowledge of reaction pathways, and simplification of mathematical models. The simulation resulted in a H₂:CO ratio of 2.2, and molar fluxes were obtained for H₂, CO, CO₂, CH₄, and H₂O consistent with those typically observed in the gasification process of organic matter. These models were constructed, laying the foundation for the adaptability of subsequent optimization studies. Full article

Proton exchange membrane fuel cells are anticipated to play an important role in decarbonizing the global energy system, but the performance of platinum (Pt) catalysts must be improved to make this technology more economical. Studies have identified non-spherical Pt nanoparticles on carbon supports as promising approaches to address this challenge. However, to realize the full benefits of these strategies, the catalyst synthesis procedures must be successfully simplified and scaled up, and the catalyst must perform well in half and full-cell tests. In this study, a surfactant-free one-pot method is developed to synthesize non-spherical Pt nanoparticles on Ketjen Black carbon, which is either non-treated (Pt/KB), acid-treated (Pt/KB-O), or nitrogen-doped (Pt/KB-N). The catalysts are synthesized in both small and large batches to determine the effect of scaling up the synthesis procedure. The nitrogen-doped carbon support shows a nearly identical morphological structure with uniform distribution of non-spherical Pt nanoparticles for both small and large batches’ synthesis compared with non-treated and acid-treated carbon samples. The comparative oxygen reduction reaction (ORR) activity shows that the Pt/KB-N prepared in small and large batches has better ORR activity, which is likely caused by uniformly distributed non-spherical Pt nanoparticles on the nitrogen-doped carbon support. All three catalysts show similar ORR durability, testing from 0.5–1.0 V, while Pt/KB-O displays slightly better durability from 1.0–1.5 V for carbon corrosion. These results will help inform the implementation of shape-controlled Pt catalysts on modified carbon supports in large scale. Full article

Triclosan (TCS), a broad-spectrum bacteriostatic agent with bactericidal and disinfectant properties, is one of the emerging pollutants of great interest. The electrically activated persulfate-coupled carbon membrane system was studied in this paper. The removal of triclosan achieved 90% within 40 min. Complete degradation can be achieved within 90 min. The electrode was characterized by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The optimal reaction conditions were explored. The catalytic mechanism of the reaction was investigated. It was proved that hydroxyl radicals, sulfate radicals, and singlet oxygen were the main reactive oxygen species in the reaction process by the free radical quenching experiment and electron paramagnetic resonance spectrometer. The degradation path and mechanism of triclosan were investigated. Full article

Membrane separation has been widely utilized to eliminate pollutants from wastewater. Among them, a polyacrylonitrile (PAN) ultrafiltration (UF) membrane has presented outstanding stability, and distinguished chemical and thermal properties. However, UF membranes inevitably incur fouling issues during their operation procedure caused by contaminant adhesion on the membrane surface, which would restrict the operational efficiency and increase the maintenance cost. The conventional physical and chemical cleaning is not an effective technique to reduce the fouling due to the additional chemical addition and inevitable structure damage. Recently, UF membranes combined with photocatalytic materials are suggested to be a useful approach to conquer the membrane fouling issues. Herein, TiO₂ nanoparticles were utilized to blend with a PAN casting solution for fabricating a composite UF membrane via a phase inversion method. With a certain TiO₂ addition, the obtained membranes presented an enhancement of hydrophilicity, which could promote the water permeability and antifouling performance. The optimized M3 membrane prepared with 15.0 wt% PAN and 0.6 wt% TiO₂ exhibited an excellent water permeability up to 207.0 L m⁻² h⁻¹ bar⁻¹ with an outstanding 99.0% BSA rejection and superior antifouling property. In addition, the photocatalytic TiO₂ nanoparticles endowed the M3 membrane with a remarkable self-cleaning ability under the UV irradiation. This facile construction method offered new insight to enhance the UF membrane separation performance with an enhanced antifouling ability. Full article

Rechargeable Zn–air batteries (ZABs) can play a significant role in the transition to a cleaner and more sustainable energy system due to their high theoretical energy density, high cell voltage, and environmental friendliness. ZAB’s air cathode is the principal determinant in predicting the battery’s overall performance, as it is responsible for catalyzing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during the discharging and charging process, respectively. In this work, a detailed optimization study of the architecture of the air cathode was carried out using the benchmark bifunctional oxygen electrocatalyst (Pt/C-RuO₂). The air cathode composition and architecture were optimized regarding the choice of the commercial gas diffusion layer (GDL), the effect of hot pressing the catalyst layer (CL), and the optimum pore size of the current collector. The best cathode from this study shows a maximum power density (PD_max) of 167 mW/cm², with a round trip efficiency and a voltage gap (E_gap) of 59.8% and 0.78 V, respectively, indicating the air cathodes preparation approach proposed in this work as a promising strategy for the improvement of the overall performance of ZABs. Full article

As a natural phospholipid, phosphatidylserine (PS) plays a key role in the food, cosmetic, and pharmaceutical industries. Recently, substantial attention has been focused on the phospholipase D (PLD)-mediated synthesis of PS. However, the application of free PLD is usually limited by high cost, poor reusability, and low stability. In this study, PLD from Streptomyces antibiotics (saPLD) was efficiently immobilized on SiO₂ through physical adsorption to develop saPLD@SiO₂. The stability of the saPLD@SiO₂ was higher than that of the free saPLD over an extensive range of temperature and pH conditions. Furthermore, the PS yield of saPLD@SiO₂ was approximately 41% in the first cycles, and still kept 60% of its initial PS yield after 14 cycles. After a 25-day storage period, the saPLD@SiO₂ retained 62.5% of its initial activity, while the free saPLD retained only 34.3%, suggesting that saPLD@SiO₂ has better stability than free saPLD. A Pickering emulsion was produced by dispersing saPLD@SiO₂ in solutions (ethyl propanoate and acetate/acetic acid buffer) using ultrasound. The engineered Pickering emulsion demonstrated excellent catalytic activity, with a 62% PS yield after 6 h, while free saPLD had only 18%. The results indicated that a high-performance and sustainable biocatalysis method was established for the effective synthesis of PS. Full article

Transition metal selenides have garnered considerable attention in the field of electrocatalytic oxygen evolution reaction (OER). However, their OER performances still lag behind those of Ir-based materials due to limited exposed active sites, inefficient electron transfer and inadequate stability. In this study, we have successfully synthesized nitrogen-doped NiSe₂ nanosheets, which exhibit high efficiency and long-term stability for the OER, requiring only 320 mV to reach a current density of 10 mA cm⁻². The nitrogen doping plays a crucial role in effectively regulating the work function and semiconductor characteristics of NiSe₂, which facilitates the electron transport and optimizes the catalytic sites. Furthermore, the NiSe₂ nanosheets present a larger surface area with more exposed active sites, thus resulting in exceptional OER catalytic activity. The nitrogen-doped NiSe₂ nanosheets also display superior stability, maintaining a sustained current density throughout an 8-h OER operation. Full article

In this work, the LDH approach was used to prepare MnCoAl mixed oxides with various textural and structural frameworks for the purpose of enhancing the total oxidation of ethanol. Our results showed that the catalytic activity of the MnCoAl oxides was influenced by the Mn/Co ratio and the gas atmosphere used during synthesis and thermal treatment. Rietveld refinement was processed to estimate the proportion of phases presented in the prepared materials. Our findings indicated that the generation of Mn₂CoO₄ spinel and Mn₅O₈ lamellar phases improved the redox properties and enhanced the active sites in the MnCoAl oxides. Notably, we observed that the catalytic activity at low temperatures of the catalyst increased with the decrease in the cobalt amount. It was also demonstrated that using an N₂ atmosphere during the preparation of the materials is a promising route to prevent the formation of undesirable phases in the LDHs and their corresponding oxides. The presence of an O₂-free atmosphere during the LDH synthesis positively affects the total ethanol transformation to CO₂ over the oxide catalysts. Full article