Catalysts — Open Access Journal

The present paper reports AC impedance spectroscopic/Tafel polarization and cyclic voltammetry study on the influence of acetonitrile concentration on the kinetics of UPD of H (underpotential deposition of hydrogen) and HER (hydrogen evolution reaction), examined on polycrystalline and polyoriented single-crystal sphere Pt electrode surfaces in 0.5 M H₂SO₄ and 0.1 M NaOH supporting solutions. The resulted data provided confirmation of the destructive role of Pt surface-electrosorbed acetonitrile on the kinetics of underpotentially deposited hydrogen, as well as cathodic hydrogen evolution reaction. The above was exclusively elucidated through evaluation of the associated charge-transfer resistance and capacitance (and complementary exchange current-density and Tafel slope) parameters, derived comparatively on Pt for pure and acetonitrile-modified acidic and alkaline electrolytes. Full article

Novel bimetallic Pd-Mn/Al₂O₃ catalysts are designed by the decomposition of cyclopentadienylmanganese tricarbonyl (cymantrene) on reduced Pd/Al₂O₃ in an H₂ atmosphere. The peculiarities of cymantrene decomposition on palladium and, thus, the formation of bimetallic Pd-Mn catalysts are studied. The catalysts are characterized by N₂ adsorption, H₂ pulse chemisorption, temperature-programmed desorption of hydrogen (TPD-H₂), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The modified catalysts show the changed hydrogen chemisorption properties and the absence of weakly bonded hydrogen. Using an organomanganese precursor provides an uniform Mn distribution on the catalyst surface. Tested in hydrogenation of acetylene, the catalysts show both higher activity and selectivity to ethylene (20% higher) compared to the non-modified Pd/Al₂O₃ catalyst. The influence of the addition of Mn and temperature treatment on catalyst performance is studied. The optimal Mn content and treatment temperature are found. It is established that modification with Mn changes the route of acetylene hydrogenation from a consecutive scheme for Pd/Al₂O₃ to parallel one for the Pd-Mn samples. The reaction rate shows zero overall order by reagents for all tested catalysts. Full article

The catalytic performance of Mn₃O₄ supported on carbon nanotubes (CNTs) in the liquid-phase oxidation of toluene to benzyl alcohol and benzaldehyde was studied. The supported catalysts were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N₂ adsorption–desorption isotherms and ICP-MS. The results demonstrate that Mn₃O₄ nanoparticles loaded on CNTs performed better compared with pristine Mn₃O₄ or CNTs. The main reason for the increased catalytic activity is the dispersion and loading of Mn₃O₄ in CNTs. By optimizing the reaction temperature, reaction time, catalyst quality, oxygen flow rate and initiator dosage, the optimum reaction conditions were obtained. Using tert-butyl hydroperoxide (TBHP) as the initiator and oxygen as the oxidant, the toluene conversion rate was as high as 24.63%, and benzyl alcohol and benzaldehyde selectivity was 90.49%. The good stability of the catalyst was confirmed by repeating the experiment for four cycles and observing no significant changes in its performance. Full article

A series of HZSM-5 catalysts with similar Si/Al_F mole ratio, textual properties and morphology, but different contents of Al_F pairs, were synthesized by controlling the Na/Al molar ratios in the precursor gel and used for propane aromatization. It is shown that the catalyst with a Na/Al molar ratio of 0.8 in the synthetic gel possesses the highest paired Al_F concentration (64.4%) and shows higher propane conversion (38.2%) and aromatics selectivity (19.7 wt.%). Propane pulse experiments, micro reactor activity estimation, Operando diffuse reflectance ultraviolet-visible (DR UV-vis) spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR) analysis of coke species deposited on the catalysts provide evidence that Al_F pairs in the ZSM-5 framework promote oligomerization and cyclization reactions of olefins, and then produce more aromatics. Density Functional Theory (DFT) calculations demonstrate that the cyclization of olefins and hydride transfer reaction occurring on Al_F pairs in HZSM-5 zeolite show a lower free energy barrier and a higher rate constant than those on single Al_F, indicating that the structure of Al_F pairs in the HZSM-5 zeolite has a stronger electrostatic stabilization effect on the transition states than that of single Al_F. Full article

Based on nanotechnology, nanocomposites are synthesized using nanoparticles (NP), which have some advantages in terms of multifunctional, economic, and environmental factors. In this review, we discuss the inorganic applications as well as catalytic applications of NPs. Recently, structural defects, heteroatomic doping, and heterostructures of such efficient ideal catalysts and their application as multifunctional catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. It has been verified that the catalysts used in oxygen reduction reaction and OER can be used effectively in metal/air batteries. Moreover, it has been reported that high-efficiency catalysts are required to implement urea oxidation reaction (UOR), which involves a six-electron reaction, as an electrochemical reaction. We expect that this review can be applied to sustainable and diverse electrochemistry fields. Full article

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) polymerizes rac-lactide (rac-LA) to form highly isotactic polylactide (PLA) with a P_m = 0.88, while meso-LA yields heterotactic PLA (P_m ~ 0.8) at −75 °C. The stereocontrol of the cryogenic-based ring-opening polymerization comes from a perfect imbrication of both chiral LA and the propagating chiral end-group interacting with the achiral TBD catalyst. Full article

In this paper, the effect of cathode configuration on the performance of a membrane-less microbial fuel cell (MFC) was evaluated using three different arrangements: an activated carbon bed exposed to air (MFCE), a wetland immersed in an activated carbon bed (MFCW) and a cathode connected to an aeration tower featuring a water recirculation device (MFCT). To evaluate the MFC performance, the efficiency of the organic matter removal, the generated voltage, the power density and the internal resistance of the systems were properly assessed. The experimental results showed that while the COD removal efficiency was in all cases over 60% (after 40 days), the MFCT arrangement showed the best performance since the average removal value was 82%, compared to close to 70% for MFCE and MFCW. Statistical analysis of the COD removal efficiency confirmed that the performance of MCFT is substantially better than that of MFCE and MFCW. In regard to the other parameters surveyed, no significant influence of the different cathode arrangements explored could be found. Full article

An organic catalyst “(R, R)-1,2-diphenylethylenediamine(DPEN) derivative’’ was devel-oped as a chiral bifunctional organocatalyst and applied for asymmetric Michael additions of aromatic ketones to trans-β-nitroalkene compounds under neutral conditions. The isopropyl-subs-tituted thiourea catalyst in neutral condition provides high chemical yield and enantioselectivities (ee) (up to 96% yield, 98% ee). Full article

Increased interest in the oxidation process of polycrystalline rhodium, observed in recent years, is the result of its application in exhaust catalytic converters. However, most studies have involved sample surfaces with low Miller indices. In our research, we investigated polycrystalline rhodium foil containing crystallographically different, highly stepped, µm-sized crystallites. These crystallites were exposed to identical oxidizing conditions. To determine crystallographic orientation, the electron backscattering diffraction (EBSD) method was used. To investigate the initial stages of oxidation on the individual crystallites of Rh, X-ray photoelectron spectroscopy (XPS) studies were performed. The results obtained for the individual crystallites were compared and analyzed using chemical state quantification of XPS data and multivariate statistical analysis (MVA). Full article

Sulforaphane (SFN) is a health-promoting compound occurring in broccoli. It is formed by action of myrosinase in a two-step reaction that also yields undesirable compounds such as nitriles and isothionitriles. Different techniques affecting enzyme activity and tissue integrity were proposed to increase SFN content in the edible parts and discards of broccoli. Ultrasound processing is an emerging technology that produces these effects in foods, but has been poorly explored in broccoli so far. The aim of this work was to study the effect of ultrasound-assisted blanching on myrosinase activity and SFN content in broccoli florets. Myrosinase showed first-order inactivation kinetics in blanching at different temperatures with and without ultrasound processing. The inactivation rate was faster using ultrasound, with kinetic constants two orders of magnitude higher than without ultrasound. The activation energy (Ea) in traditional blanching (57.3 kJ mol⁻¹) was higher than in ultrasound-assisted blanching (15.8 kJ mol⁻¹). Accordingly, ultrasound accelerates myrosinase inactivation. The blanching time and temperature significantly affected myrosinase activity and SFN content. At 60 °C and 4 min of ultrasound-assisted blanching, myrosinase activity was minimum and SFN content was the highest. These findings may help to design SFN enrichment processes and will contribute to the valorization of agro-industrial wastes. Full article

The objective of the present work is to achieve high yield to 1-propanol (1-POH) by crude glycerol hydrogenolysis in liquid phase and find an alternative to the use of noble metals by employing Ni catalysts. Two Ni catalysts with different supports, alumina (γ-Al₂O₃), and a phosphorous-impregnated carbon composite (CS-P) were studied and characterized in order to determine their acid properties and metallic phases. With the Ni/γ-Al₂O₃ catalyst, which presented small particles of metallic Ni interacting with the acid sites of the support, it was possible to obtain a complete conversion of crude glycerol with high selectivity towards 1,2-propylene glycol (1,2 PG) (87%) at 220 °C whereas with the Ni/CS-P catalyst, the presence of AlPOx species and the Ni₂P metallic phase supplied acidity to the catalyst, which promoted the C-O bond cleavage reaction of the secondary carbon of 1,2 PG to obtain 1-POH with very high selectivity (71%) at 260 °C. It was found that the employment of two consecutive reaction stages (first with Ni/ γ-Al₂O₃ at 220 °C and then with Ni/CS-P at 260 °C) allows reaching levels of selectivity and a yield to 1-POH (79%) comparable to noble metal-based catalysts. Full article

In this study, we prepared cobalt (Co) ion-modified ZnO nanowires using hydrothermal synthesis with zinc acetate dehydrate and Co (II) acetate hydrate precursors in ethanol solutions. Their morphological and optical properties were investigated with varying Co precursor concentration. The morphological changes of the ZnO nanowires depended positively on the concentration of the Co precursor. The ZnO nanowires showed modified crystal orientations and nanostructure shapes depending on the Co concentration in the solutions. Variations in the optical properties of the Co ion-modified ZnO nanowires could be explained by the interaction of the Co ions with the band electrons, oxygen vacancies, and zinc interstitials. The overall growth and characteristics of ZnO nanowires synthesized in solutions containing low levels of Co ions were related to Co doping into the ZnO bulks. In solutions containing high levels of Co ions, these were additionally related to the Co oxide cluster. Full article

To improve the catalytic performance of an active layered double hydroxide (LDH)-derived CuCeMgAlO mixed oxide catalyst in the total oxidation of methane, it was promoted with different transition-metal cations. Thus, two series of multicationic mixed oxides were prepared by the thermal decomposition at 750 °C of their corresponding LDH precursors synthesized by coprecipitation at constant pH of 10 under ambient atmosphere. The first series of catalysts consisted of four M(3)CuCeMgAlO mixed oxides containing 3 at.% M (M = Mn, Fe, Co, Ni), 15 at.% Cu, 10 at.% Ce (at.% with respect to cations), and with Mg/Al atomic ratio fixed to 3. The second series consisted of four Co(x)CuCeMgAlO mixed oxides with x = 1, 3, 6, and 9 at.% Co, while keeping constant the Cu and Ce contents and the Mg/Al atomic ratio. All the mixed oxides were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with X-ray energy dispersion analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption at −196 °C, temperature-programmed reduction under hydrogen (H₂-TPR), and diffuse reflectance UV-VIS spectroscopy (DR UV-VIS), while thermogravimetric and differential thermal analyses (TG-DTG-DTA) together with XRD were used for the LDH precursors. The catalysts were evaluated in the total oxidation of methane, a test reaction for volatile organic compounds (VOC) abatement. Their catalytic performance was explained in correlation with their physicochemical properties and was compared with that of a reference Pd/Al₂O₃ catalyst. Among the mixed oxides studied, Co(3)CuCeMgAlO was found to be the most active catalyst, with a temperature corresponding to 50% methane conversion (T₅₀) of 438 °C, which was only 19 °C higher than that of a reference Pd/Al₂O₃ catalyst. On the other hand, this T₅₀ value was ca. 25 °C lower than that observed for the unpromoted CuCeMgAlO system, accounting for the improved performance of the Co-promoted catalyst, which also showed a good stability on stream. Full article

The application of Fenton-based advanced oxidation processes (AOPs), such as photo-Fenton or electro-Fenton for wastewater treatment have been extensively studied in recent decades due to its high efficiency for the decomposition of persistent organic pollutants. Usually Fenton-based AOPs are used for the degradation of targeted pollutant or group of pollutants, which often leads to the formation of toxic by-products possessing a potential environmental risk. In this work, we have collected and reviewed recent findings regarding the feasibility of Fenton-based AOPs (photo-Fenton, UVC/H₂O₂, electro-Fenton and galvanic Fenton) for the detoxification of real municipal and industrial wastewaters. More specifically, operational conditions, relevance and suitability of different bioassays for the toxicity assessment of various wastewater types, cost estimation, all of which compose current challenges for the application of these AOPs for real wastewater detoxification are discussed. Full article

One of the recent trends in textile wastewater treatment has become catalytic ozonation. The necessity of effective color removal in a short treatment time is a standard during industrial implementation. At the same time, efficient chemical oxygen demand (COD), total organic carbon (TOC), and toxic by-product removal are highly expected. This study presents the results of a catalytic ozonation treatment. Three types of catalysts: a metal oxide (TiO₂ as P25 by Degussa), activated carbon (nano-powder by Sigma, AC), and metal particles (platinum, 1% wt. supported on AC matrix by Sigma, Pt–AC) have been applied. The investigations were conducted for real industrial wastewater originated in textile dyeing with Reactive Black 5 dye (RB5). The experiments ran for the raw wastewater (without pretreatment), exposed blocking of the catalytic action by all used catalysts. The catalytic effect could be observed when catalytic ozonation was used as a polishing step after electrocoagulation (EC). Although the catalytic effect could be observe for all catalysts then, especially in the removal of colorless by-products, the AC was exposed as the most effective. This contributed to 35% and 40% of TOC and COD removal. While only 18% and 23% of TOC and COD were removed in the same process without AC. The decrease in toxicity was 30%. The results of the study revealed the complexity of the issue and resulted in an extensive discussion devoted to the basis of the catalytic activity of each catalyst. Full article

New, more efficient methods of wastewater treatment, which will limit the harmful effects of textile dyes on the natural environment, are still being sought. Significant research work suggests that catalysts based on transition metal complexes can be used in efficient and environmentally friendly processes. In this context, a number of compounds containing manganese have been investigated. A suitable catalyst should have the capacity to activate a selected oxidant or group of oxidants, in order to be used in industrial oxidation reactions. In the present study we investigated the ability of Mn^III(TPPS), where TPPS = 5,10,15,20-tetrakis(4-sulphonatophenyl)-21H,23H-porphyrine, to activate five different oxidants, namely hydrogen peroxide, peracetic acid, sodium hypochlorite, potassium peroxomonosulfate and sodium perborate, via the formation of high valent Mn(TPPS)-oxo complexes. Kinetic and spectroscopic data showed that the oxidation process is highly pH dependent and is strongly accelerated by the presence of carbonate in the reaction mixture for three of the five oxidizing agents. The highest efficiency for the oxidation of Mn^III(TPPS) to high-valent Mn(TPPS)-oxo complexes, was found for peracetic acid at pH ≈ 11 in 0.5 M carbonate solution, which is at least an order of magnitude higher than the rate constants found for the other tested oxidants under similar conditions. Full article

The rapid growth of global biodiesel production requires simultaneous effective utilization of glycerol obtained as a by-product of the transesterification process. Accumulation of the byproduct glycerol from biodiesel industries can lead to considerable environment issues. Hence, there is extensive research focus on the transformation of crude glycerol into value-added products. This paper makes an overview of the nature of crude glycerol and ongoing research on its conversion to value-added products. Both chemical and biological routes of glycerol valorization will be presented. Details of crude glycerol conversion into microbial lipid and subsequent products will also be highlighted. Full article

Rhodium complexes ligated by imidazolium-substituted phosphine were used as catalysts in the hydrosilylation of alkynes (1-heptyne, 1-octyne, and phenylacetylene) with 1,1,1,3,5,5,5-heptamethyltrisiloxane (HMTS) or triethylsilane (TES). In all cases, the above complexes showed higher activity and selectivity compared to their precursors ([Rh(PPh₃)₃Cl] and [{Rh(µ-Cl)(cod)}₂]). In the reactions with aliphatic alkynes (both when HMTS and TES were used as hydrosilylating agents), β(Z) isomer was mainly formed, but, in the reaction of phenylacetylene with TES, the β(E) product was formed. The catalysts are very durable, stable in air and first and foremost insoluble in the reactants which facilitated their isolation and permitted their multiple use in subsequent catalytic runs. They make a very good alternative to the commonly used homogeneous catalysts. Full article

Control of gaseous emissions from livestock operations is needed to ensure compliance with environmental regulations and sustainability of the industry. The focus of this research was to mitigate livestock odor emissions with UV light. Effects of the UV dose, wavelength, TiO₂ catalyst, air temperature, and relative humidity were tested at lab scale on a synthetic mixture of nine odorous volatile organic compounds (VOCs) and real poultry manure offgas. Results show that it was feasible to control odorous VOCs with both photolysis and photocatalysis (synthetic VOCs mixture) and with photocatalysis (manure offgas). The treatment effectiveness R (defined as % conversion), was proportional to the light intensity for synthetic VOCs mixtures and followed an order of UV_185+254 + TiO₂ > UV₂₅₄ + TiO₂ > UV_185+254; no catalyst > UV₂₅₄; no catalyst. VOC conversion R > 80% was achieved when light energy was >~60 J L⁻¹. The use of deep UV (UV_185+254) improved the R, particularly when photolysis was the primary treatment. Odor removal up to ~80% was also observed for a synthetic VOCs mixture, and actual poultry manure offgas. Scale-up studies are warranted. Full article