Search Results (17,705)

A series of Fe–Ba mixed oxides, including a pure Fe-containing sample as a reference, have been synthesized via a sol–gel process using Fe³⁺ or Fe²⁺ salts and BaSO₄ as raw materials, with Pluronic P123 serving as a template. These oxides have been thoroughly characterized and subsequently utilized as catalysts for the chlorination of various organic molecules. Commercial hydrochloric acid, known for its relative safety, and environmentally friendly aqueous hydrogen peroxide were employed as the chlorine source and oxidant, respectively. The pure Fe-containing catalyst displays excellent thermal stability between 600 and 800 °C and exhibited moderate to high conversions in the chlorination of toluene, benzene, and tert-butyl hydroperoxide, with remarkable ortho-selectivity in chlorination of toluene. The combination of Fe³⁺ salt with BaSO₄ in the sol–gel process results in a Fe–Ba mixed oxide catalyst composed of BaO₂, BaFe₄O₇, and Fe₂O₃, significantly enhancing the chlorination activity compared to that displayed by the pure Fe catalyst. Notably, the chlorination of tert-butyl hydroperoxide (TBHP) does not require additional oxidants such as H₂O₂, and involves both electrophilic substitution and nucleophilic addition. Notably, the chlorination of bromobenzene yields chlorobenzene as the sole product, a transformation that has not been previously reported. Overall, this catalytic chlorination system holds promise for advancing the chlorination industry and enhancing pharmaceutical production. Full article

This study assesses the extent of public goods provision by Brazilian firms and how this behavior has changed over time. We use text data of publicly traded companies’ annual standardized financial declarations from 2010 and 2022 and apply natural language processing techniques to extract ESG (environmental, social, and governance) keywords related to the provision of public goods. Context and sentiment analyses were used to supplement the information extracted from the raw keyword counts; these analyses were conducted using diverse regression techniques. We found a pronounced increase in keyword mentions over time; in particular, “responsibility” and “sustainability” appeared more frequently. Virtually all firms became more dedicated to ESG practices, particularly those that had a low frequency of ESG mentions in a positive context. Overall, it seems that large Brazilian corporations have embedded comprehensive ESG policies into their business practices, thus aligning their strategies with those of pioneering multinationals. Full article

Community drinking water sources are increasingly contaminated by various point and non-point sources, with emerging organic contaminants and microbial strains posing health risks and disrupting ecosystems. This study explores the use of zinc oxide nanoparticles (ZnO-NPs) as a non-specific agent to address groundwater contamination and combat microbial resistance effectively. The ZnO-NPs were synthesized via a green chemistry approach, employing a sol-gel method with lemon peel aqueous extract. The catalyst was characterized using techniques including XRD, ATR-FTIR, SEM-EDAX, UV-DRS, BET, and Raman spectroscopy. ZnO-NPs were then tested for photodegradation of quinoline yellow dye (QY) under sunlight irradiation, as well as for their antibacterial and antioxidant properties. The ZnO-NP photocatalyst showed significant photoactivity, attributed to effective separation of photogenerated charge carriers. The efficiency of sunlight dye photodegradation was influenced by catalyst dosage (0.1–0.6 mg L⁻¹), pH (3–11), and initial QY concentration (10–50 mg L⁻¹). The study developed a first-order kinetic model for ZnO-NPs using the Langmuir–Hinshelwood equation, yielding kinetic constants of equilibrium adsorption and photodegradation of Kc = 6.632 × 10⁻² L mg⁻¹ and kH = 7.104 × 10⁻² mg L⁻¹ min⁻¹, respectively. The results showed that ZnO-NPs were effective against Gram-positive bacterial strains and showed moderate antioxidant activity, suggesting their potential in wastewater disinfection to achieve sustainable development goals. A potential antibacterial mechanism of ZnO-NPs involving interactions with microbial cells is proposed. Additionally, Gaussian Process Regression (GPR) combined with an improved Lévy flight distribution (FDB-LFD) algorithm was used to model QY photodegradation by ZnO-NPs. The ARD-Exponential kernel function provided high accuracy, validated through residue analysis. Finally, an innovative MATLAB-based application was developed to integrate the GPR_FDB-LFD model and FDB-LFD algorithm, streamlining optimization for precise photodegradation rate predictions. The results obtained in this study show that the GPR and FDB-LFD approaches offer efficient and cost-effective methods for predicting dye photodegradation, saving both time and resources. Full article

This study analyzed the operational environment of supply chains involved in the production of eco-friendly plastics, with a particular emphasis on small- and medium-sized businesses worldwide. Qualitative research methods were used to highlight the significance of extended producer responsibility (EPR) regulations and strong recycling programs for the sustainability of small- and medium-sized enterprises (SMEs). Also, this study looked at international regulations affecting the implementation of circular economy strategies and the difficulties in creating sustainable supply chains. It concluded that waste reduction, effective supply chain management, and sustainable practices are crucial aspects of a more effective and sustainable global plastic-manufacturing sector. This research highlighted the significance of government policies in SME revival and used Multiple-Criteria Decision Analysis (MCDA) to help SMEs adopt sustainable supply chain practices that act as a catalyst for industry reform. Full article

Gold-catalyzed propargylic substitution of propargylic alcohols 1 with 1,3-dicarbonyl compounds 2 followed by cycloisomerization in ionic liquid enables the environmentally friendly synthesis of polysubstituted furans 3 in good-to-high yields. The reaction proceeds via the hydrated propargylic substitution product 3″aa. The gold catalyst can be recycled at least three times. Full article

Unique structural and chemical properties, such as ion exchange, developed inner surface, etc., as well as the wide possibilities and flexibility of regulating these properties, cause a keen interest in zeolites. They are widely used in industry as molecular sieves, ion exchangers and catalysts. Current trends in the development of zeolite-based catalysts include the adaptation of their cationic composition, acidity and porosity for a specific catalytic process. Recent studies have shown that mesoporosity is beneficial to the rational design of catalysts with controlled product selectivity and an improved catalyst lifetime due to its efficient mass-transport properties. Nuclear magnetic resonance (NMR) has proven to be a reliable method for studying zeolites. Solid-state NMR spectroscopy allows for the quantification of both Lewis and Brønsted acidity in zeolite catalysts and, nowadays, ²⁷Al and ²⁹Si magic angle spinning NMR spectroscopy has become firmly established in the set of approved methods for characterizing zeolites. The use of probe molecules opens up the possibility for the indirect measurement of the characteristics of acid sites. NMR relaxation is less common, although it is especially informative and enlightening for studying the mobility of guest molecules in the porous matrix. Moreover, the NMR relaxation of guest molecules and NMR cryoporometry can quantify pore size distribution on a broader scale (compared to traditional methods), which is especially important for systems with complex pore organization. Over the last few years, there has been a growing interest in the use of 2D NMR relaxation techniques to probe porous catalysts, such as 2D $T_1$–$T_2$ correlation to study the acidity of the surface of catalysts and 2D $T_2$–$T_2$ exchange to study pore connectivity. This contribution provides a comprehensive review of various NMR relaxation techniques for studying porous media and recent results of their applications in probing micro- and mesoporous zeolites, mainly focused on the mobility of adsorbed molecules, the acidity of the zeolite surface and the pore size distribution and connectivity of zeolites with hierarchical porosity. Full article

The industrial processes used to produce paper and cellulose generate many lignocellulosic residues. These residues are usually burned to produce heat to supply the energy demands of other processes, increasing greenhouse gas emissions and resulting in a high environmental impact. Instead of burning these lignocellulosic residues, they can be converted into saccharides, which are feedstock for high-value products and biofuels. Keggin heteropolyacids are efficient catalysts for obtaining saccharides from cellulose and hemicellulose and converting them into bioproducts or biofuel. Furfural, 5-hydroxymethylfurfural, levulinic acid, and alkyl levulinates are important platform molecules obtained from saccharides and raw materials in the biorefinery processes used to produce fine chemicals and biofuels. This review discusses the significant progress achieved in the development of the processes based on heteropolyacid-catalyzed reactions to convert biomass and their residues into furfural, 5-hydroxymethylfurfural, levulinic acid, and alkyl levulinates in homogeneous and heterogeneous reaction conditions. The different modifications that can be performed to a Keggin HPA structure, such as the replacement of the central atom (P or Si) with B or Al, the doping of the heteropolyanion with metal cations, and a proton exchange with metal or organic cations, as well as their impact on the catalytic activity of HPAs, are detailed and discussed herein. Full article

In green hydrogen production via water electrolysis, catalysts with multiscale nanostructures synthesized by compositing micro-heterojunctions and nanoporous structures exhibit excellent electrocatalytic oxygen evolution reaction (OER) performance. Moreover, they are the most promising non-noble metal catalysts. Herein, FeNi-based aerogels with a three-dimensional nanoporous structure and amorphous matrix embedded with FeNi₃ nanoclusters were synthesized via wet chemical reduction coprecipitation. The FeNi₃ nanoclusters and the FeNi-based amorphous matrix formed a crystalline–amorphous heterojunction. These aerogels exhibited excellent OER performance and electrocatalytic stability in alkaline electrolytes. In 1 mol/L of KOH electrolyte, the as-synthesized aerogel exhibited an overpotential of 262 mV at a current density of 20 mA cm⁻² with a Tafel slope of only 46 mV dec⁻¹. It also demonstrated excellent stability during a 12 h chronopotentiometry test. Full article

Constructing highly efficient catalysts for the degradation of organic pollutants driven by solar light in aquatic environments is a promising and green strategy. In this study, a novel hexagonal sheet-like Pt/SnS₂ heterojunction photocatalyst is successfully designed and fabricated using a hydrothermal method and photodeposition process for photocatalytic tetracycline (TC) degradation. The optimal Pt/SnS₂ hybrid behaves with excellent photocatalytic performance, with a degradation efficiency of 91.27% after 120 min, a reaction rate constant of 0.0187 min⁻¹, and durability, which can be attributed to (i) the formation of a metal/semiconductor interface field caused by loading Pt nanoparticles (NPs) on the surface of SnS₂, facilitating the separation of photo-induced charge carriers; (ii) the local surface plasmon resonance (LSPR) effect of Pt NPs, extending the light absorption range; and (iii) the sheet-like structure of SnS₂, which can shorten the transmission distance of charge carriers, thereby allowing more electrons (e⁻) and holes (h⁺) to transfer to the surface of the catalyst. This work provides new insights with the utilization of sheet-like structured materials for highly active photocatalytic TC degradation in wastewater treatment and environmental remediation. Full article

Catalytic activity, mechanisms, and active sites were determined for methane steam reforming (MSR) over gadolinium-doped ceria (GDC) supported iridium (0.1 wt%) prepared by impregnation of GDC with iridium acetylacetonate. Isothermal steady-state rate measurements followed by micro-gas chromatography analysis were performed at 660 and 760 °C over Ir/GDC samples pretreated in N₂ or H₂ at 900 °C. Transient responses to CH₄ or H₂O step changes in isothermal conditions were carried out at 750 °C over Ir/GDC pretreated in He or H₂ using online quadrupole mass spectrometry. In the proposed mechanism, Ir/GDC proceeds through a dual-type active site associating, as follows: (i) Ir metallic particles surface as active sites for the cracking of CH₄ into reactive C species, and (ii) reducible (Ce⁴⁺) sites at GDC surface responsible for a redox mechanism involving Ce⁴⁺/Ce³⁺ sites, being reduced by reaction with reactive C into CO (or CO₂) depending on the oxidation state of GDC and re-oxidized by H₂O. Full reduction of reducible oxygen species is possible with CH₄ after He treatment, whereas only 80% is reached in CH₄ after H₂ treatment. Full article

We examined the effectiveness of metal-exchanged phosphomolybdic acid salts in converting levulinic acid, derived from biomass, into valuable products (alkyl levulinate). We prepared salts of phosphomolybdic acid using different metals (Fe³⁺, Al³⁺, Zn²⁺, Cu²⁺, Mn²⁺, Ni²⁺, and Co²⁺). The influence of metal cations on the conversion and selectivity of the reactions was assessed. We found that the salts prepared with iron and aluminum phosphomolybdate were the most effective catalysts for the esterification of levulinic acid with methanol, with the conversion and selectivity tending towards 100% after 6 h of reaction at a temperature of 323 K. The effect of catalyst loading and its recovery and reuse was evaluated; the results from the reaction using aluminum phosphomolybdate remained similar for four cycles of use. The influence of temperature on conversion and selectivity was investigated between 298 and 353 K. The reactivity of different alcohols with a carbon chain size of C1-C4 was assessed and conversions above 65% were obtained for all alcohols tested under the conditions evaluated, except for tert-butyl alcohol. These catalysts are a promising alternative to the traditional soluble and corrosive Brønsted acid catalysts. The superior performance of these catalysts was ascribed to the higher pH decline triggered by the hydrolysis of these metal cations. Full article

In the realm of photoelectrocatalytic (PEC) water splitting, the BiVO₄/WO₃ photoanode exhibits high electron–hole pair separation and transport capacity, rendering it a promising avenue for development. However, the charge transport and reaction kinetics at the heterojunction interface are suboptimal. This study uses the hydrothermal–electrodeposition–dip coating–calcination method to prepare a microcrystalline WO₃ photoanode thin film as the substrate material and combines it with nanocrystalline BiVO₄ to form a micro–nano-structured heterojunction photoanode to enhance the intrinsic and surface/interface charge transport properties of the photoanode. Under the condition of 1.23 V vs. RHE, the photoelectric current density reaches 1.09 mA cm⁻², which is twice that of WO₃. Furthermore, by using a simple impregnation–mineralization method to load the amorphous FeOOH catalyst, a noncrystalline–crystalline composite structure is formed to increase the number of active sites on the surface and reduce the overpotential of water oxidation, lowering the onset potential from 0.8 V to 0.6 V (vs. RHE). The photoelectric current density is further increased to 2.04 mA cm⁻² (at 1.23 V vs. RHE). The micro–nano-structure and noncrystalline–crystalline composite structure proposed in this study will provide valuable insights for the design and synthesis of high-efficiency photoelectrocatalysts. Full article

Herein, we synthesized Ti-MOF through a solvothermal method and subsequently calcined it to form anatase TiO₂. We further developed a Bi₂O₃@TiO₂ mixed oxide using impregnation and calcination processes. These oxides showed significant photocatalytic activity for degrading Eriochrome Black T (EBT) dye under visible light irradiation. We characterized the prepared samples using various techniques, including XRD, XPS, FTIR, BET, SEM, EDX, TEM, and UV-DRS analyses. Our results indicated that TiO₂ and 10%Bi₂O₃@TiO₂ achieved 80% and 100% degradation of EBT dye solution (50 ppm) within 30 min in acidic medium with a 50 mg catalyst dose, respectively. The calcination of the Ti-MOF into TiO₂ improved its sensitivity to visible light. The Bi₂O₃@TiO₂ composite was also effective in degrading other organic pollutants, such as Congo Red (degradation ~99%), Malachite Green (degradation ~95%), Methylene Blue (degradation ~81%), and Safranine O (degradation ~69%). The impregnation of Bi₂O₃ increased the surface acidity of TiO₂, enhancing its photocatalytic activity by promoting hydroxyl group formation through increased water adsorption. Additionally, 10%Bi₂O₃@TiO₂ demonstrated excellent chemical stability and reusability, maintaining high degradation efficiency over four cycles. Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) calculations were performed to understand the degradation mechanisms. UV-Vis absorption spectrum simulations suggested that the anionic HEB⁻² (O24) or EB⁻³ forms of the EBT dye are likely to undergo degradation. This study highlights the potential of Bi₂O₃@TiO₂ composites for effective photocatalytic applications in environmental remediation. Full article

In this work, the highly efficient hydrogenation of guaiacol catalyzed by ruthenium supported on Al₂O₃-TiO₂ (Ru/Al₂Ti₁) at very mild conditions was carried out. At temperatures as low as 25 °C and 2 MPa H₂, about 60% of guaiacol could be converted to 2-methoxycyclohexanol (MCH) with a selectivity as high as 94% on the Ru/Al₂Ti₁ catalyst with an appropriate hydrogen pressure. At temperatures above 50 °C, almost all of the guaiacol could be converted with the catalyst of Ru/Al₂Ti₁, mainly into hydrogenated products such as MCH. The surprisingly efficient hydrogenation of guaiacol at low temperatures was most likely due to the ability of Ru particles loaded on the specific complex metal oxide carriers, particularly the reduction of the edge effect of Ru, to activate phenyl and hydrogen and reduce the competition of the dimethoxy process. These findings about the high activity of the Ru/Al₂Ti₁ catalyst at nearly room temperature may be helpful to upgrading the industrial process of the pyrolysis bio-oils. Full article

The use of high catalyst loading is required for most of the organocatalyzed asymmetric aldol reactions in organic synthesis, and this often presents challenges during purification and difficulties in catalyst recovery from the reaction mixture. The immobilization of the catalyst onto gold nanoparticles (AuNPs) can change the structural conformations of the catalyst, thereby improving its catalytic activity and reusability. Herein we report on the synthesis of aldolase mimetic peptide coupled to gold nanoparticles (AuNPs) as efficient organocatalysts for asymmetric aldol reaction. AuNPs were synthesized using the Turkevich method. The conjugation of the peptide to AuNPs was characterized using surface plasmon resonance (SPR), Raman and X-ray photoelectron spectroscopy, and transmission electron microscopy (TEM) was used for particle size determination. The produced nanoparticles, whose sizes depended on the reduction method, were quasi-spherical with a relatively narrow size distribution. The peptide–AuNP conjugates were evaluated for aldol reaction catalytic activity between carbonyls p-nitrobenzaldehyde and cyclohexanone. The products were obtained with good yields (up to 85%) and enantioselectivity (up to 94%). The influence of organic solvents, pH and buffer solutions was also investigated. The results showed that the buffer solutions regulated the colloidal stability of AuNPs, resulting in a significant enhancement in the catalytic rate of the peptide–AuNP conjugate. Full article