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Plasma catalysis has recently gained traction as an alternative to ammonia synthesis. The current research is mostly fundamental and little attention has been given to the technical and economic feasibility of plasma-catalytic ammonia synthesis. In this study, the feasibility of plasma-catalytic ammonia is assessed for small-scale ammonia synthesis. A brief summary of the state of the art of plasma catalysis is provided as well as a targets and potential avenues for improvement in the conversion to ammonia, ammonia separation and a higher energy efficiency. A best-case scenario is provided for plasma-catalytic ammonia synthesis and this is compared to the Haber-Bosch ammonia process operated with a synthesis loop. An ammonia outlet concentration of at least 1.0 mol. % is required to limit the recycle size and to allow for efficient product separation. From the analysis, it follows that plasma-catalytic ammonia synthesis cannot compete with the conventional process even in the best-case scenario. Plasma catalysis potentially has a fast response to intermittent renewable electricity, although low pressure absorbent-enhanced Haber-Bosch processes are also expected to have fast responses to load variations. Low-temperature thermochemical ammonia synthesis is expected to be a more feasible alternative to intermittent decentralized ammonia synthesis than plasma-catalytic ammonia synthesis due to its superior energy efficiency.

The BiOI/NH2-MIL-125(Ti) composite photocatalyst with excellent photocatalytic performance was prepared by the solvothermal method. For the BiOI/NH2-MIL-125(Ti) (BNMT) system, the contents of NH2-MIL-125(Ti) in BNMT-4, BNMT-5, BNMT-7, BNMT-9, and BNMT-10 were 4 wt %, 5 wt %, 7 wt %, 9 wt %, and 10 wt %, respectively. XRD, XPS, SEM, and TEM characterizations indicated that BiOI/NH2-MIL-125(Ti) was successfully prepared. Brunauer, Emmett, and Teller (BET) and UV&ndash, vis diffuse reflectance spectra photoelectrochemical analysis indicated that BNMT-9 can make the specific surface area and photo absorption region larger than BiOI. In addition, the separation efficiency of photogenerated carriers was improved, and the recombination efficiency was reduced. The degradation percentages of Rhodamine B (RhB) and p-chlorophenol (P-CP) reached 99% and 90% over BNMT-9 under visible light irradiation. Additionally, the catalysts had high stability. The results of the active spices trapping experiments test indicated that h+ was the main active species. The possible degradation mechanism was proposed.

In this paper, we designed Ag nanoparticles coated with a Cu2O shell, which was successfully decorated on reduced graphene oxide (rGO) via a solid-state self-reduction. The Cu2O, Ag@Cu2O, and Ag@Cu2O-rGO nanocomposites were synthesized and characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV&ndash, Vis, and XPS to evaluate the properties of the composites. In order to compare the chemical catalytic activity, the Cu2O, Ag@Cu2O, and Ag@Cu2O-rGO nanocomposites were employed for the catalytic reduction of p-nitrophenol (4-NP) into p-aminophenol (4-AP) in aqueous solution. The Ag@Cu2O-rGO nanocomposite exhibited excellent catalytic activity due to the intense interaction and high degree of electron transfer among Ag, Cu2O, and rGO. The rGO acted as the platform to bridge the isolated nanoparticles, furthermore, the electrons could quickly transfer from the Ag core to the Cu2O shell, which improved the chemical catalytic efficiency.

With the growing global propylene demand, propane dehydrogenation (PDH) has attracted great attention for on-purpose propylene production. However, its industrial application is limited because catalysts suffer from rapid deactivation due to coke deposition and metal catalyst sintering. To enhance metal catalyst dispersion and coke resistance, Pt-based catalysts have been widely investigated with various porous supports. In particular, zeolite can benefit from large surface area and acid sites, which favors high metal dispersion and promoting catalytic activity. In this work, we investigated the PDH catalytic properties of Beta zeolites as a support for Pt-Sn based catalysts. In comparison with Pt-Sn supported over &theta, Al2O3 and amorphous silica (Q6), Beta zeolite-supported Pt-Sn catalysts exhibited a different reaction trend, achieving the best propylene selectivity after a proper period of reaction time. The different PDH catalytic behavior over Beta zeolite-supported Pt-Sn catalysts has been attributed to their physicochemical properties and reaction mechanism. Although Pt-Sn catalyst supported over Beta zeolite with low acidity showed low Pt dispersion, it formed a relatively lower amount of coke on PDH reaction and maintained a high surface area and active Pt surfaces, resulting in enhanced stability for PDH reaction. This work can provide a better understanding of zeolite-supported Pt-Sn catalysts to improve PDH catalytic activity with high selectivity and low coke formation.

Although the potential and beneficial characteristics of photocatalysis in the degradation of a good number of emerging pollutants have been widely studied and demonstrated, process design and scale-up are restrained by the lack of comprehensive models that correctly describe the performance of photocatalytic reactors. Together with the kinetics of degradation reactions, the distribution of the radiation field in heterogeneous photocatalytic systems is essential to the optimum design of the technology. Both the Local Volumetric Rate of Photon Absorption (LVRPA) and the Overall Volumetric Rate of Photon Absorption (OVRPA) help to understand this purpose. This work develops a Six-lux radiation absorption-scattering model coupled to the Henyey-Greenstein scattering phase function to evaluate the LVRPA profile in a LED-assisted photocatalytic reactor. Moreover, the OVRPA has been calculated and integrated into the kinetic equation, accounting for the influence of the radiation distribution on the reaction rate. The model has been validated with experimental data for the degradation of S-Metolachlor (MTLC), and the set of operating variables that maximize the reactor performance, 0.5 g/L of TiO2 P25 and pH 3, has been determined. This research was funded by the Spanish Ministry of Science, Innovation, and Universities (Grant Numbers: RTI2018-099407-B-I00 and RTI2018-093310-B-I00) (MCIU/AEI/FEDER, UE).

Microbially catalyzed reactions are a powerful and valuable tool for organic synthesis of many compounds with potential biological activity. Herein, we report efficient hydroxylations of the steroidal anabolic-androgenic lactone, oxandrolone, in the cultures of three strains of fungi, Fusarium culmorum, Mortierella isabellina, and Laetiporus sulphureus. These reactions resulted in the production of four metabolites identified as 12β-hydroxyoxandrolone (2), 9α-hydroxyoxandrolone (3), 6α-hydroxyoxandrolone (4), and 15α-hydroxyoxandrolone (5), the latter being a new compound. The high substrate conversion rates and the product yields achieved indicate that these strains offer a new way to generate steroidal hydroxylactones with potential pharmaceutical interest. The structures of the isolated derivatives were characterized on the basis of spectroscopic data. The effect of modification of the A-ring structure of the steroid by the lactone group on the selectivity of hydroxylation in cultures of the tested fungi is also discussed.

Cross-coupling reactions furnishing carbon–carbon (C–C) and carbon–heteroatom (C–X) bond is one of the most challenging tasks in organic syntheses. The early developed reaction protocols by Ullmann, Ullman–Goldberg, Cadiot–Chodkiewicz, Castro–Stephens, and Corey–House, utilizing elemental copper or its salts as catalyst have, for decades, attracted and inspired scientists. However, these reactions were suffering from the range of functional groups tolerated as well as severely restricted by the harsh reaction conditions often required high temperatures (150–200 °C) for extended reaction time. Enormous efforts have been paid to develop and achieve more sustainable reaction conditions by applying the microwave irradiation. The use of controlled microwave heating dramatically reduces the time required and therefore resulting in increase in the yield as well as the efficiency of the reaction. This review is mainly focuses on the recent advances and applications of copper catalyzed cross-coupling generation of carbon–carbon and carbon–heteroatom bond under microwave technology.

The activity and chemoselectivity of the Cp2ZrCl2-XAlBui2 (X = H, Bui) and [Cp2ZrH2]2-ClAlEt2 catalytic systems activated by (Ph3C)[B(C6F5)4] or B(C6F5)3 were studied in reactions with 1-hexene. The activation of the systems by B(C6F5)3 resulted in the selective formation of head-to-tail alkene dimers in up to 93% yields. NMR studies of the reactions of Zr complexes with organoaluminum compounds (OACs) and boron activators showed the formation of Zr,Zr- and Zr,Al-hydride intermediates, for which diffusion coefficients, hydrodynamic radii, and volumes were estimated using the diffusion ordered spectroscopy DOSY. Bis-zirconium hydride clusters of type x[Cp2ZrH2∙Cp2ZrHCl∙ClAlR2]∙yRnAl(C6F5)3&minus, n were found to be the key intermediates of alkene dimerization, whereas cationic Zr,Al-hydrides led to the formation of oligomers.

Novel polymerizations based on alkyne monomers are becoming a powerful tool to construct polymers with unique structures and advanced functions in the areas of polymer and material sciences, and scientists have been attracted to develop a variety of novel polymerizations in recent decades. Therein, catalytic systems play an indispensable role in the influence of polymerization efficiencies and the performances of the resultant polymers. Concerning the shortcomings of metallic catalysts, much of the recent research focus has been on metal-free polymerization systems. In this paper, metal-free catalysts are classified and the corresponding polymerizations are reviewed, including organobase-catalyzed polymerizations, Lewis-acid-catalyzed polymerizations, as well as catalyst-free polymerizations. Moreover, the challenges and perspectives in this area are also briefly discussed.

Enzymatic reaction cascades represent a powerful tool to convert biogenic resources into valuable chemicals for fuel and commodity markets. Sugars and their breakdown products constitute a significant group of possible substrates for such biocatalytic conversion strategies to value-added products. However, one major drawback of sugar cascades is the need for cofactor recycling without using additional enzymes and/or creating unwanted by-products. Here, we describe a novel, multi-enzymatic reaction cascade for the one-pot simultaneous synthesis of L-alanine and L-serine, using the sugar degradation product 2-keto-3-deoxygluconate and ammonium as precursors. To pursue this aim, we used four different, thermostable enzymes, while the necessary cofactor NADH is recycled entirely self-sufficiently. Buffer and pH optimisation in combination with an enzyme titration study yielded an optimised production of 21.3 +/&minus, 1.0 mM L-alanine and 8.9 +/&minus, 0.4 mM L-serine in one pot after 21 h.

Furfural and 5-hydroxymethylfurfural (HMF) have been identified as promising bio-platform furans that have a wide range of potential applications as biofuels, bioplastics, and biochemicals. Furfural and HMF are typically synthesized from the substrates of C5 sugars and C6 sugars, respectively. Furfural can also be produced from C6 sugars, which is technically more challenging owing to the higher energy requirement for carbon&ndash, carbon bond cleavage. In this study, the simultaneous production of furfural and HMF from glucose was conducted over different binary catalyst systems of Br&oslash, nsted acids and Lewis acids using &gamma, valerolactone (GVL) as the solvent. A promising performance was achieved by a SnSO4-H2SO4 coupling catalyst, with an optimized furfural yield of 42% and an HMF yield of 34% at 443 K in GVL. In addition, a kinetics study was performed in order to understand the mechanism of the simultaneous formation of furfural and HMF from glucose at different temperatures and GVL/water ratios. The results showed that the ratio of furfural to HMF production rate at different temperatures (433 to 463 K) or GVL/water ratios (90 to 80%) was constant close to 1, suggesting that the production of furfural and HMF might follow similar reaction pathways. Finally, the reaction pathway of glucose conversion to furfural and HMF was proposed based on the experimental and kinetics studies.

Over the last decades, microalgal biomass has gained a significant role in the development of different high-end (nutraceuticals, colorants, food supplements, and pharmaceuticals) and low-end products (biodiesel, bioethanol, and biogas) due to its rapid growth and high carbon-fixing efficiency. Therefore, microalgae are considered a useful and sustainable resource to attain energy security while reducing our current reliance on fossil fuels. From the technologies available for obtaining biofuels using microalgae biomass, thermochemical processes (pyrolysis, Hydrothermal Liquefaction (HTL), gasification) have proven to be processed with higher viability, because they use all biomass. However, due to the complex structure of the biomass (lipids, carbohydrates, and proteins), the obtained biofuels from direct thermochemical conversion have large amounts of heteroatoms (oxygen, nitrogen, and sulfur). As a solution, catalyst-based processes have emerged as a sustainable solution for the increase in biocrude production. This paper’s objective is to present a comprehensive review of recent developments on the catalyst-mediated conversion of algal biomass. Special attention will be given to operating conditions, strains evaluated, and challenges for the optimal yield of algal-based biofuels through pyrolysis and HTL.

Copper(II) complex of the ligand possessing two enantiomerically pure trans-cyclohexane-1,2-diamine units proved to be an efficient catalyst for the enantioselective Henry reaction of aromatic aldehydes with nitromethane. The effect of various reaction conditions on yield and enantioselectivity of the Henry reaction was studied. The results suggest that only one cyclohexane-1,2-diamine unit is involved in catalysis of the Henry reaction.

The purification of diesel exhaust gas is of great importance to prevent the atmospheric emission of major pollutants such as diesel particulate matter and nitrogen oxides and meet the environmental regulations. The atmospheric-pressure plasma is attracting increasing interest and is a promising after-treatment technology for purifying diesel emission at low temperatures. However, when compared with the numerous publications on nitrogen oxides reduction by non-thermal plasma, using non-thermal plasma to particulate matter treatment have relatively limited. This work provides a comprehensive review of the plasma applications for diesel particulate matter treatment, including self-regenerating diesel particulate filter, diesel particulate matter removal, and simultaneous removal of diesel particulate matter and nitrogen oxides. The treatment of particulate matter from both simulated particulate matter sources and actual diesel engines also discussed in this comprehensive review. The challenge to this technology is limited energy consumption for plasma, which should be less than 5% (~30 J/L) of the overall fuel consumption. Until now, the atmospheric-pressure plasma has been no commercial implementation in diesel exhaust gas treatment, so more research is needed to be done in this field.

I have the honor of writing this editorial note on the top 5 cited papers published in 2018 in the section of Biocatalysis of the Catalyst journal [...]

The storage, utilization, and control of the greenhouse (CO2) gas is a topic of interest for researchers in academia and society. The present review article is dedicating to cover the overall role of ionic liquid-modified hybrid materials in cycloaddition reactions. Special emphasis is on the synthesis of various cyclic carbonate using ionic liquid-based modified catalysts. Catalytic activity studies have discussed with respect to process conditions and their effects on conversion and product selectivity for the reaction of cycloaddition of CO2 with styrene oxide. The reaction temperature and the partial pressure of CO2 have found to play a key role in cyclic carbonate formation. The role of other influential parameter (solvent effect) is also discussed for the conversion of cyclic/aromatic oxides to polycarbonate production. Our own research work that deals with ionic liquid-based halide-modified mesoporous catalyst (MCM-41 type) derived from rice husk waste has also been discussed. Finally, the role of carbon dioxide activation and ring-opening mechanisms involved in the cyclic carbonate product formation from CO2 have been discussed.

The photocatalytic activity of TiO2 depends on numerous factors, such as the chemical potential of electrons, charge transport properties, band-gap energy, and concentration of surface-active sites. A lot of research has been dedicated to determining the properties that have the most significant influence on the photocatalytic activity of semiconductors. Here, we demonstrated that the activity of TiO2 in the gas-phase reduction of CO2 is governed mainly by the desorption rate of the reaction intermediates and final products. This indicates that the specific surface area of TiO2 and binding strength of reaction intermediates and products are the main factors affecting the photocatalytic activity of TiO2 in the investigated process. Additionally, it was shown that rutile exhibits higher photocatalytic activity than anatase/rutile mixtures mainly due to its high efficiency in the visible portion of the electromagnetic spectrum.

Methane reforming is an important potential technology for solving both environmental and energy problems. This technology is important because methane is counted as a greenhouse gas, but on the other hand, it can be reformed into industrially valuable compounds. More research has focused on photocatalytic methane reforming, which has a higher activity than thermal catalysts under dark conditions. The reaction selectivity toward specific products in photocatalytic methane reforming is sometimes different from thermal catalyst systems. Herein, we discuss recent advances in photocatalytic methane reforming to provide various strategies for reforming.

Halogen substituents often lead to a profound effect on the biological activity of organic compounds. Flavin-dependent halogenases offer the possibility of regioselective halogenation at non-activated carbon atoms, while employing only halide salts and molecular oxygen. However, low enzyme activity, instability, and narrow substrate scope compromise the use of enzymatic halogenation as an economical and environmentally friendly process. To overcome these drawbacks, it is of tremendous interest to identify novel halogenases with high enzymatic activity and novel substrate scopes. Previously, Neubauer et al. developed a new hidden Markov model (pHMM) based on the PFAM tryptophan halogenase model, and identified 254 complete and partial putative flavin-dependent halogenase genes in eleven metagenomic data sets. In the present study, the pHMM was used to screen the bacterial associates of the Botryococcus braunii consortia (PRJEB21978), leading to the identification of several putative, flavin-dependent halogenase genes. Two of these new halogenase genes were found in one gene cluster of the Botryococcus braunii symbiont Sphingomonas sp. In vitro activity tests revealed that both heterologously expressed enzymes are active flavin-dependent halogenases able to halogenate indole and indole derivatives, as well as phenol derivatives, while preferring bromination over chlorination. Interestingly, SpH1 catalyses only monohalogenation, while SpH2 can catalyse both mono- and dihalogenation for some substrates.

Here, a simple method was developed to prepare an MgF2-modified hydrotalcite-derived composite, which was used as support for the Pt-In catalyst for isobutane direct dehydrogenation. The catalysts, composites, and their precursors were characterized by numerous characterization techniques. The results provided evidence for the MgF2 promoter effect on the physical–chemical properties and dehydrogenation performance of the supported Pt-In catalysts. The catalyst with MgF2 shows exceptional isobutene selectivity that can be stabilized at 95%, and the conversion increases from 50% to 58% during the reaction process. Moreover, the existence of MgF2 plays an important role in the resistance to coke formation and Pt sintering by improving the Pt dispersion, inhibiting the reduction of the In3+ species, and adjusting the acidity of the catalyst.

The heptyl butanoate ester was synthesized from butanoic acid and heptanol in a heterogeneous medium in the presence of sulfonated activated carbon (AC-SO3H) catalyst particles subjected to microwave irradiation, which led to higher conversion yields (greater product yields) than conventional heating with an oil bath. The advantage of the microwaves appeared only when the moisture content in the butanoic acid batch(es) was high, suggesting that, unlike conventional heating, the reverse reaction caused by the moisture content and/or by the byproduct water was suppressed by the microwaves. This contrasted with the results that were found when carrying out the reaction in a homogeneous medium in the presence of the 2,4,6-trimethylpyridinium-p-toluene sulfonate (TMP-PTS) catalyst, as product yields were not improved by microwave heating relative to conventional heating. The removal of moisture/water content in the reaction solution was more pronounced when the reactor was cooled, as the reaction yields were enhanced via selective heating of the heterogeneous catalyst. A coupled electromagnetic field/heat transfer analysis gave credence to the selective heating of the AC-SO3H catalyst, which was further enhanced by cooling the reactor. It was deduced that unforeseen impurities and local high-temperature fields generated on the surface of small fine catalyst particles may have had an effect on the microwave chemistry such that the associated phenomena could be mistaken as originating from a nonthermal effect of the microwaves. Accordingly, it is highly recommended that impurities and selective heating be taken into consideration when examining and concluding the occurrence of a microwave nonthermal effect.

The greenhouse effect is leading to global warming and destruction of the ecological environment. The conversion of carbon dioxide and methane greenhouse gases into valuable substances has attracted scientists’ attentions. Dry reforming of methane (DRM) alleviates environmental problems and converts CO2 and CH4 into valuable chemical substances; however, due to the high energy input to break the strong chemical bonds in CO2 and CH4, non-thermal plasma (NTP) catalyzed DRM has been promising in activating CO2 at ambient conditions, thus greatly lowering the energy input; moreover, the synergistic effect of the catalyst and plasma improves the reaction efficiency. In this review, the recent developments of catalytic DRM in a dielectric barrier discharge (DBD) plasma reactor on Ni-based catalysts are summarized, including the concept, characteristics, generation, and types of NTP used for catalytic DRM and corresponding mechanisms, the synergy and performance of Ni-based catalysts with DBD plasma, the design of DBD reactor and process parameter optimization, and finally current challenges and future prospects are provided.

In this research work, we reported the synthesis of a spherical-shaped bismuth vanadate (BiVO4) photocatalyst using a cost-effective, simple, chemical hydrothermal method and studied the effect of deposition temperatures on the structural, morphological, optical properties, etc. The XRD result confirmed the monoclinic scheelite phase of BiVO4. An XPS study confirmed the occurrence of Bi, V, and O elements and also found that Bi and V exist in +3 and +5 oxidation states, respectively. SEM micrographs revealed the spherical-shaped morphology of the BiVO4 photocatalyst. Optical investigation showed that the bandgap of the BiVO4 photocatalyst varied between 2.25 and 2.32 eV. The as-synthesized BiVO4 photocatalyst was used to study the photocatalytic degradation of crystal violet (CV) dye under visible light illumination. The photocatalytic degradation experiment showed that the degradation percentage of crystal violet dye using BiVO4 reached 98.21% after 120 min. Mineralization of crystal violet dye was studied using a chemical oxygen demand analysis.

The current work focused on the sunlight-driven thermo-photocatalytic reduction of carbon dioxide (CO2), the primary greenhouse gas, by ethane (C2H6), the second most abundant element in shale gas, aiming at the generation of ethanol (EtOH), a renewable fuel. To promote this process, a hybrid catalyst was prepared and properly characterized, comprising of strontium titanate (SrTiO3) co-doped with ruthenium oxide (RuO2) and nickel oxide (NiO). The photocatalytic activity towards EtOH production was assessed in batch-mode and at gas-phase, under the influence of different conditions: (i) dopant loading, (ii) temperature, (iii) optical radiation wavelength, (vi) consecutive uses, and (v) electron scavenger addition. From the results here obtained, it was found that: (i) the functionalization of the SrTiO3 with RuO2 and NiO allows the visible light harvest and narrows the band gap energy (ca. 14–20%), (ii) the selectivity towards EtOH depends on the presence of Ni and irradiation, (iii) the catalyst photoresponse is mainly due to the visible photons, (iv) the photocatalyst loses &gt, 50% efficiency right after the 2nd use, (v) the reaction mechanism is based on the photogenerated electron-hole pair charge separation, and (vi) a maximum yield of 64 μmol EtOH gcat−1 was obtained after 45-min (85 μmol EtOH gcat−1 h−1) of simulated solar irradiation (1000 W m−2) at 200 °C, using 0.4 g L−1 of SrTiO3:RuO2:NiO (0.8 wt.% Ru) with [CO2]:[C2H6] and [Ru]:[Ni] molar ratios of 1:3 and 1:1, respectively. Notwithstanding, despite its exploratory nature, this study offers an alternative route to solar fuels’ synthesis from the underutilized C2H6 and CO2.

Hydrogen evolution reaction (HER) was investigated on reduced graphene oxide (rGO)-supported Au and PdAu nanoparticles in acid solution. The graphene spread over glassy carbon (rGO/GC) was used as a support for the spontaneous deposition of Au and Pd. The resulting Au/rGO and PdAu/rGO electrodes were characterized using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) techniques. Phase AFM images have shown that the edges of the rGO sheets were active sites for the deposition of both Au and Pd. XPS analysis revealed that the atomic percentages of both Au and PdAu nanoparticles were slightly higher than 1%. The activity of the PdAu/rGO electrode for the HER was remarkably high, with the overpotential close to zero. HER activity was stable over a 3 h testing time, with a low Tafel slope of approx. −46 mV/dec achieved after prolonged hydrogen evolution at a constant potential.

In this study, a Pt/anodized aluminum oxide (AAO) catalyst was prepared by the anodization of an Al alloy (Al6082, 97.5% Al), followed by the incorporation of Pt via an incipient wet impregnation method. Then, the Pt/AAO catalyst was evaluated for autocatalytic hydrogen recombination. The Pt/AAO catalyst’s morphological characteristics were determined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The average Pt particle size was determined to be 3.0 ± 0.6 nm. This Pt/AAO catalyst was tested for the combustion of lean hydrogen (0.5–4 vol% H2 in the air) in a recombiner section testing station. The thermal distribution throughout the catalytic surface was investigated at 3 vol% hydrogen (H2) using an infrared camera. The Al/AAO system had a high thermal conductivity, which prevents the formation of hotspots (areas where localized surface temperature is higher than an average temperature across the entire catalyst surface). In turn, the Pt stability was enhanced during catalytic hydrogen combustion (CHC). A temperature gradient over 70 mm of the Pt/AAO catalyst was 23 °C and 42 °C for catalysts with uniform and nonuniform (worst-case scenario) Pt distributions. The commercial computational fluid dynamics (CFD) code STAR-CCM+ was used to compare the experimentally observed and numerically simulated thermal distribution of the Pt/AAO catalyst. The effect of the initial H2 volume fraction on the combustion temperature and conversion of H2 was investigated. The activation energy for CHC on the Pt/AAO catalyst was 19.2 kJ/mol. Prolonged CHC was performed to assess the durability (reactive metal stability and catalytic activity) of the Pt/AAO catalyst. A stable combustion temperature of 162.8 ± 8.0 °C was maintained over 530 h of CHC. To confirm that Pt aggregation was avoided, the Pt particle size and distribution were determined by TEM before and after prolonged CHC.

This study is dedicated to the comparative investigation of the catalytic activity of layer-like Faujasite-type (FAU) zeolite X obtained from three different synthesis routes (additive-free route, Li2CO3 route, and TPOAC route) in a liquid-phase Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate to ethyl trans-α-cyanocinnamate. It is shown that the charge-balancing cations (Na+ and K+) and the morphological properties have a strong influence on the apparent reaction rate and degree of conversion. The highest initial reaction rate could be found for the layer-like zeolite X synthesised by the additive-free route in the potassium form. In most cases, the potassium-exchanged zeolites enabled higher maximum conversions and higher reaction rates compared to the zeolite X catalysts in sodium form. However, very thin crystal plates (below 100 nm thickness), similar to those obtained in the presence of TPOAC, did not withstand the multiple aqueous ion exchange procedure, with the remaining coarse crystals facilitating less enhancement of the catalytic activity.

In this work, the photocatalytic performance of Ag3PO4, Nb2O5 and Ag3PO4/Nb2O5 hybrid photocatalysts to degrade methyl orange dye, MO, in an aqueous solution under visible light irradiation was evaluated. The Ag3PO4 and Ag3PO4/Nb2O5 photocatalysts, with various Ag to Nb molar ratios, were prepared using a facile precipitation method. The photocatalysts were characterized by X-ray diffraction, UV–Visible, X-ray Photoelectron, and Photoluminescence spectroscopies. Upon the addition of Ag3PO4, the band gap energy of Nb2O5 decreased from 3.0 eV to 2.7 eV, indicating the possible use of the Ag3PO4/Nb2O5 hybrid photocatalysts under visible light irradiation. All of the prepared Ag3PO4/Nb2O5 catalysts exhibited higher photocatalytic performance than Ag3PO4 in degrading methyl orange dye under 23-watt visible light irradiation. The Ag3PO4/Nb2O5 catalyst, with a mole ratio of 2:1, exhibited the fastest MO degradation rate of 7.3 × 10−2 min−1, which is twice faster than that of Ag3PO4. The catalyst also shows better stability, as it is reusable for up to six experimental cycles while maintaining its photocatalytic activity above 60%.

The aim of this study was to promote the Z-isomerization of lycopene in its extraction process from tomato pulp by adding foodstuffs containing Z-isomerization-accelerating compounds. The addition of onion, broccoli, mustard, makonbu (Saccharina japonica), or shiitake mushroom (Lentinus edodes) to the ethyl acetate extraction process significantly accelerated the Z-isomerization of lycopene. For example, when lycopene was extracted from tomato pulp at 70 °C without foodstuffs, the total Z-isomer ratio of lycopene in the extract was 38.4 ± 0.5%, whereas when onion, broccoli, mustard, makonbu, and shiitake mushroom were added to the process and the extraction was performed using the same procedure, the total Z-isomer ratios significantly increased to 53.6 ± 0.4, 47.9 ± 0.3, 48.2 ± 0.1, 41.5 ± 0.9, and 42.0 ± 1.2%, respectively. Since the above foodstuffs contain large amounts of carotenoid Z-isomerization-accelerating catalysts, i.e., polysulfides, isothiocyanates, or iodine, those components would promote Z-isomerization of lycopene in the extraction process. Since lycopene Z-isomers potentially have higher bioavailability and biological effects than the all-E-isomer, lycopene extraction with foodstuffs having a Z-isomerization-promoting effect in ethyl acetate should enhance the health benefits of tomato extracts.

Computational catalysis has been one of the most dynamic research fields over the last decade, and it now represents a critical tool for the analysis of chemical mechanisms and active sites [...]

The present study demonstrates a simple approach to enhancing thermal stability of butyrylcholinesterase (BChE) by using natural polymers. Analysis of thermal inactivation of the tetrameric BChE in starch and gelatin gels at 50–64 °C showed that thermal inactivation followed second-order kinetics and involved two alternating processes of BChE inactivation, which occurred at different rates (fast and slow processes). The activation enthalpy ΔH# and the activation entropy ΔS# for BChE in starch and gelatin gels were evaluated. The values of ΔH# for the fast and the slow thermal inactivation of BChE in starch gel were 61 ± 3, and 22 ± 2 kcal/mol, respectively, and the values of ΔS# were 136 ± 12 and −2.03 ± 0.05 cal∙K−1∙mol−1, respectively. Likewise, the values of ΔH# for BChE in gelatin gel were 58 ± 6 and 109 ± 11 kcal/mol, and the values of ΔS# were 149 ± 16 and 262 ± 21 cal∙K−1∙mol−1, respectively. The values of the activation parameters obtained in this study suggest that starch gel produced a stronger stabilizing effect on BChE exposed to elevated temperatures over long periods compared with gelatin gel.

In the last few years, the development of catalytic carbonylation reactions has increased greatly [...]

The specific roles played by both support and noble metals in light absorption, charge separation, and the formation of ·OH and O2− (ROS) are analyzed for light-triggered oxidation of phenol (Ph) over pristine and over noble metal (Ag, Au, Pt) -loaded TiO2. Experiments show that the supported noble metals act as a light visible absorber, assist the separation of photo-charges and reduction of O2 to O2−. The O2− oxidizes mildly Ph to oxygenated products (hydroquinone, benzoquinone, and 1,2-dihydroxibenzene). In a parallel process, ·OH radicals, yielded by TiO2, mineralize Ph to CO2 by fast reaction sequences. Radical quenching and photo electrochemical measurements (surface photovoltage) confirm independently that the production of ·OH and O2− scale with oxidative conversion of Ph. The selectivity to CO2 and mild oxidation products is the result of the interplay between catalyst activity for ·OH and for O2− production.

The release of methane from vehicles or/and stationary industrial sources must be reduced in order to control the emission of this greenhouse gas into the atmosphere [...]

Electrochemical oxygen evolution reaction (OER) activity was studied on nickel foam-based electrodes. The OER was investigated in 0.1 M NaOH solution at room temperature on as-received and Co- or Mo-modified Ni foam anodes. Corresponding values of charge-transfer resistance, exchange current-density for the OER and other electrochemical parameters for the examined Ni foam composites were recorded. The electrodeposition of Co or Mo on Ni foam base-materials resulted in a significant enhancement of the OER electrocatalytic activity. The quality and extent of Co, and Mo electrodeposition on Ni foam were characterized by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) analysis.

Herein, we report a Pd4L2-type molecular cage (1) and catalyzed reactions of spiroepoxy naphthalenone (2) in water, where selective formation of 2-(hydroxymethyl)naphthalene-1,4-dione (3) via aerobic oxidation, or 1-hydroxy-2-naphthaldehyde (4) via photo-induced rearrangement under N2 have been accomplished. Encapsulation of four molecules of guest 2 within cage 1, i.e., (2)4Ì1, has been confirmed by NMR, and a final host-guest complex of 3Ì1 has also been determined by single crystal X-Ray diffraction study. While the photo-induced ring-opening isomerization from 2 to 4 are known, appearance of charge-transfer absorption on the host-guest complex of (2)4Ì1 allows low-power blue LEDs irradiation to promote this process.

In the present work, the degradation of p-nitrophenol (PNP) and its mineralization by a UV/Vis-based persulphate activation process was investigated. Firstly, a screening of processes as direct photolysis, persulphate alone and persulphate activated by radiation was performed. The incidence of radiation demonstrated to have an important role in the oxidant activation, allowing to achieve the highest PNP and total organic carbon (TOC) removals. The maximum PNP oxidation (100%) and mineralization (61.6%)—both after 2 h of reaction time—were reached when using T = 70 °C, (S2O82−) = 6.4 g/L and I = 500 W/m2. The influence of radiation type (ultraviolet/visible, visible or simulated solar light) was also evaluated, being found that the source with the highest emission of ultraviolet radiation (UV/visible) allowed to achieve the best oxidation efficiency; however, solar radiation also reached very-good performance. According to quenching experiments, the sulphate radical is key in the activated persulphate oxidation process, but the hydroxyl radical also plays an important role.

The β-fructofuranosidase from the yeast Rhodotorula dairenensis (RdINV) produces a mixture of potential prebiotic fructooligosaccharides (FOS) of the levan-, inulin-and neo-FOS series by transfructosylation of sucrose. In this work, the gene responsible for this activity was characterized and its functionality proved in Pichia pastoris. The amino acid sequence of the new protein contained most of the characteristic elements of β-fructofuranosidases included in the family 32 of the glycosyl hydrolases (GH32). The heterologous yeast produced a protein of about 170 kDa, where N-linked and O-linked carbohydrates constituted about 15% and 38% of the total protein mass, respectively. Biochemical and kinetic properties of the heterologous protein were similar to the native enzyme, including its ability to produce prebiotic sugars. The maximum concentration of FOS obtained was 82.2 g/L, of which 6-kestose represented about 59% (w/w) of the total products synthesized. The potential of RdINV to fructosylate 19 hydroxylated compounds was also explored, of which eight sugars and four alditols were modified. The flexibility to recognize diverse fructosyl acceptors makes this protein valuable to produce novel glycosyl-compounds with potential applications in food and pharmaceutical industries., Spanish Ministry of Economy and Competitiveness: BIO2016-76601-C3-2 and of Science and Innovation PID2019-105838RB-C32; Fundación Ramón Areces (XIX Call of Research Grants in Life and Material Sciences); and by institutional grant from Fundación Ramón Areces to the Centro de Biología Molecular Severo Ochoa

Structural design and morphological control of semiconductors is considered to be one of the most effective ways to improve their photocatalytic degradation properties. In the present work, a hexagonal WO3·0.33H2O hierarchical microstructure (HWHMS) composed of nanorods was successfully prepared by the hydrothermal method. The morphology of the HWHMS was confirmed by field-emission scanning electron microscopy, and X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis demonstrated that the synthesized product was orthorhombic WO3·0.33H2O. Owing to the unique hierarchical microstructure, the HWHMS showed larger Brunauer–Emmett–Teller (BET) surface and narrower bandgap (1.53 eV) than the isolated WO3·0.33H2O nanorods. Furthermore, the HWHMS showed enhanced photocatalytic activity for degradation of methylene blue under visible-light irradiation compared with the isolated nanorods, which can be ascribed to the narrower bandgap, larger BET specific surface area, and orthorhombic phase structure of the HWHMS. This work provides a potential protocol for construction of tungsten trioxide counterparts and materials similar to tungsten trioxide for application in gas sensors, photocatalysts, electrochromic devices, field-emission devices, and solar-energy devices.

We report on the highly efficient epoxidation of low-molecular-weight and polymeric olefins catalyzed by a supramolecular manganese porphyrin complex using molecular oxygen as an oxidant and an aldehyde as a co-reductant. At ambient temperature and under optimized reaction conditions, the catalyst showed high activity and stereoselectivity. The efficiency of the supramolecular manganese porphyrin was higher than that of a reference porphyrin catalyst, possibly because it was more stable under the applied reaction conditions. Mechanistic studies suggest that a manganese oxo porphyrin complex may be an intermediate in the epoxidation reaction.

The possibility of wastewater treatment and electricity production using a microbial fuel cell with Cu&ndash, B alloy as the cathode catalyst is presented in this paper. Our research covered the catalyst preparation, measurements of the electroless potential of electrodes with the Cu&ndash, B catalyst, measurements of the influence of anodic charge on the catalytic activity of the Cu&ndash, B alloy, electricity production in a microbial fuel cell (with a Cu&ndash, B cathode), and a comparison of changes in the concentration of chemical oxygen demand (COD), NH4+, and NO3&ndash, in three reactors: one excluding aeration, one with aeration, and during microbial fuel cell operation (with a Cu&ndash, B cathode). During the experiments, electricity production equal to 0.21&ndash, 0.35 mA&middot, cm&minus, 2 was obtained. The use of a microbial fuel cell (MFC) with Cu&ndash, B offers a similar reduction time for COD to that resulting from the application of aeration. The measured reduction of NH4+ was unchanged when compared with cases employing MFCs, and it was found that effectiveness of about 90% can be achieved for NO3&ndash, reduction. From the results of this study, we conclude that Cu&ndash, B can be employed to play the role of a cathode catalyst in applications of microbial fuel cells employed for wastewater treatment and the production of electricity.

Natural zeolite of the heulandite-type framework was modified with iron and tested as a catalyst for the selective catalytic reduction of nitrogen oxides with ammonia (NH3-SCR) in the temperature range of 150–450 °C. The catalyst was prepared at a laboratory scale in a powder form and then the series of experiments of its shaping into tablets was conducted. Physicochemical studies of the catalyst (N2 sorption at −196 °C, FT-IR, XRD, UV-vis) were performed to determine the textural and structural properties and identify the surface functional groups, the crystalline structure of the catalysts and the form and aggregation of the active phase. The activity tests over the shaped catalyst were performed industry-reflecting conditions, using tail gases from the pilot nitric acid plant. The influence of a temperature, catalyst load, and the amount of reducing agent (ammonia) on the NOx reduction process were investigated. The results of catalytic tests that were performed on model gas mixture showed that non-modified clinoptilolite exhibited around 58% conversion of NO at 450 °C. The temperature window of the shaped catalyst shifted to a higher temperature range in comparison to the powder sample. The catalytic performance of the shaped Fe-clinoptilolite in the industry-reflecting conditions was satisfactory, especially at 450 °C. Additionally, it was observed that the ratio of N2O concentration downstream and upstream of the catalytic bed was below 1, which indicated that the catalyst exhibited activity in both DeNOx and DeN2O process.

Ni/oxide-SiO2 (oxide: MgO, CeO2­, La2O3, 10 wt.% target concentration) catalyst samples were prepared by successive impregnation of silica matrix, first with supplementary oxide, and then with Ni (10 wt.% target concentration). The silica matrix with multimodal pore structure was prepared by solvothermal method. The catalyst samples were structurally characterized by N2 adsorption-desorption, XRD, SEM/TEM, and functionally evaluated by temperature programmed reduction (TPR), and temperature programmed desorption of hydrogen (H2-TPD), or carbon dioxide (CO2-TPD). The addition of MgO and La2O3 leads to a better dispersion of Ni on the catalytic surface. Ni/LaSi and Ni/CeSi present a higher proportion of moderate strength basic sites for CO2 activation compared to Ni/Si, while Ni/MgSi lower. CO2 methanation was performed in the temperature range of 150–350 °C and at atmospheric pressure, all silica supported Ni catalysts showing good CO2 conversion and CH4 selectivity. The best catalytic activity was obtained for Ni/LaSi: CO2 conversion of 83% and methane selectivity of 98%, at temperatures as low as 250 °C. The used catalysts preserved the multimodal pore structure with approximately the same pore size for the low and medium mesopores. Except for Ni/CeSi, no particle sintering occurs, and no carbon deposition was observed for any of the tested catalysts.

The influence of the surface chemical properties of the carbon support on the Pd dispersion, activity and stability of Pd(OH)2/C catalyst for the hydrogenolytic debenzylation of tetraacetyldibenzylhexaazaisowurtzitane (TADB) was studied in detail. The flowerlike nanosheet carbon material (NSC) was chosen as the pristine support, meanwhile chemical oxidation with nitric acid and physical calcination at 600 °C treatments were used to modify its surface properties, which were denoted as NSCox-2 (treated with 20 wt% HNO3) and NSC-600, respectively. The three carbon supports and the corresponding catalysts of Pd/NSC, Pd/NSC-600, and Pd/NSCox-2 were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), nitrogen sorption isotherm measurement (BET), powder X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectra (XPS), temperature-programmed desorption (TPD), temperature-programmed reduction (H2-TPR), thermogravimetric analysis (TG), and element analysis. The debenzylation activities of Pd/NSC, Pd/NSC-600, and Pd/NSCox-2, as well as the three catalysts after pre-reduction treatment were also evaluated. It was found that the activity and stability of the Pd(OH)2/C catalysts in the debenzylation reaction highly depended on the content of surface oxygen-containing groups of the carbon support.

Iron-doped titanium dioxide nanoparticles, with Fe/Ti atomic ratios from 0% to 10%, were synthesized by flame spray pyrolysis (FSP), employing a single-step method. Ferrocene, being nontoxic and readily soluble in liquid hydrocarbons, was used as the iron source, while titanium tetraisopropoxide (TTIP) was used as the precursor for TiO2. The general particle characterization and phase description were examined using ICP-OES, XRD, BET, and Raman spectroscopy, whereas the XPS technique was used to study the surface chemistry of the synthesized particles. For particle morphology, HRTEM with EELS and EDS analyses were used. Optical and magnetic properties were examined using UV–vis and SQUID, respectively. Iron doping to TiO2 nanoparticles promoted rutile phase formation, which was minor in the pure TiO2 particles. Iron-doped nanoparticles exhibited a uniform iron distribution within the particles. XPS and UV–vis results revealed that Fe2+ was dominant for lower iron content and Fe3+ was common for higher iron content and the iron-containing particles had a contracted band gap of ~1 eV lower than pure TiO2 particles with higher visible light absorption. SQUID results showed that doping TiO2 with Fe changed the material to be paramagnetic. The generated nanoparticles showed a catalytic effect for dye-degradation under visible light.

The epoxidation of turpentine (technical α-pinene), 3-carene, and limonene with aqueous hydrogen peroxide was studied in a new catalytic system employing manganese sulfate, salicylic acid, sodium bicarbonate, and acetonitrile, as a polar solvent. The proposed approach makes it possible to carry out a “chemical separation” of turpentine components, yielding valuable individual derivatives of monoterpenes without the need to isolate individual monoterpene reagents. Specific methods have been developed for the production of α-pinene epoxide, 3-carene epoxide, limonene diepoxide, as well as for two related compounds: 3-carene-5-one and 3-carene-2,5-dione.

Crystalline porous materials (CPM)-200-In and CPM-200-In/Mg metal-organic frameworks (MOFs) were synthesized by a solvothermal method and were characterized by using powder X-ray diffraction (PXRD), FT-IR, Brunauer–Emmett–Teller (BET), temperature programmed desorption (TPD), TGA, XPS, and SEM-EDS. They were used as heterogeneous catalysts for the cycloaddition of CO2 with epoxides and found to be highly efficient toward the cycloaddition reaction at moderate reaction conditions under solvent-free conditions. The catalyst was easily separated by a simple filtration and can be reused up to five consecutive times without any considerable decrease of its initial activity. CPM-200-In/Mg showed excellent catalytic performance in the cycloaddition reaction due to the synergistic role of the acidic sites and basic sites. A plausible reaction mechanism for the CPM-200-In/Mg MOF catalyzed cycloaddition reaction is proposed based on the experimental results and our previously reported DFT (Density Functional Theory) studies.

A simple and highly efficient protocol for the synthesis of derivatives 7, 7-dimethyl-4-phenyl-2-thioxo-2, 3, 4, 6, 7, 8-hexahydro-1H-quinazoline-5-one from 5, 5-dimethyl cyclohexane-1, 3-dione (4a–4h) (dimedone) has been described. The aryl aldehydes were substituted with thiourea in the presence of synthesized zinc ferrite nanocatalyst, which increased the yield under reflux through condensation, followed by cyclization to give desired products. The other advantages are that it is eco-friendly and economically affordable for large-scale production. Structural validation and characterization of all the newly synthesized compounds were evaluated by spectral analysis (mass spectrometry, proton nuclear magnetic resonance (1HNMR), and Carbon-13 nuclear magnetic resonance(13CNMR)spectroscopies. The structure of antibacterial and antifungal assays was performed with the newly synthesized compounds. The antimicrobial activity of title compounds possessing electron-withdrawing groups such as (4e–4h) (Cl, Br, and cyano group) exhibited more active potential than the electron-donating groups, C6H5,4-C6H4, 3-OC2H5-4OH-C6H3, etc., (4a–4d) containing moiety.

The release of azo dye contaminants from textile industries into the environment is an issue of major concern. Nanoscale zerovalent iron (nZVI) has been extensively studied in the degradation of azo dye pollutants such as methyl orange (MO). In this study, iron was coupled with copper and silver to make trimetallic Fe/Cu/Ag nanoparticles, in order to enhance the degradation of MO and increase reactivity of the catalyst by delaying the rate of oxidation of iron. The synthesis of the trimetallic nanoparticles (Fe/Cu/Ag) was carried out using the sodium borohydride reduction method. The characterization of the particles was performed using XRD, XPS, EDX, and TEM. The analyses confirmed the successful synthesis of the nanoparticles, the TEM images also showed the desired structures and geometry of the nanoscale zerovalent iron particles. The assessment of the nanoparticles in the degradation of methyl orange showed a notable degradation within few minutes into the reaction. The effect of parameters such as nanoparticle dosage, initial MO concentration, and the solution pH on the degradation of MO using the nanoparticles was investigated. Methyl orange degradation efficiency reached 100% within 1 min into the reaction at a low pH, with lower initial MO concentration and higher nanoparticle dosage. The degradation rate of MO using the nanoparticles followed pseudo first-order kinetics and was greatly influenced by the studied parameters. Additionally, LC-MS technique confirmed the degradation of MO within 1 min and that the degradation occurs through the splitting of the azo bond. The Fe/Cu/Ag trimetallic nanoparticles have proven to be an appropriate and efficient alternative for the treatment of dye wastewater.

To upgrade biomass-derived alcohol mixtures to biofuels under solvent-free conditions, MgO–Al2O3 mixed metal oxides (MMO) decorated with Ni nanoparticles (Ni–MgO–Al2O3) are synthesized and characterized. Based on the result, Ni nanoparticles are highly dispersed on the surface of MgAl MMO. As the Ni loading content varies from 2 to 10 wt.%, there is a slight increase in the mean Ni particle size from 6.7 to 8.5 nm. The effects of Ni loading amount, reducing temperature, and Mg/Al ratio on the conversion and product distribution are investigated. With the increase in both the Ni loading amount and reducing temperature, dehydrogenation (the first step of the entire reaction network) is accelerated. This results in an increase in the conversion process and a higher selectivity for the dialkylated compounds. Due to the higher strength and density of basic sites under high Mg/Al ratios, double alkylation is preferred and more long-chain hydrocarbons are obtained. A conversion of 89.2% coupled with a total yield of 79.9% for C5–C15 compounds is acquired by the as-prepared catalyst (prepared with Ni loading of 6 wt.%, reducing temperature of 700 °C, and Mg/Al molar ratio of 3. After four runs, the conversion drops by 17.1%, and this loss in the catalytic activity can be attributed to the decrease in the surface area of the catalyst and the increase in the Ni mean particle size.