The Oscillatory Behaviour of Cu-ZSM-5 Catalysts for N2O Decomposition: Investigation of Cu species by complementary techniques.

Copper-exchanged ZSM-5 (Cu-ZSM-5) is a promising catalyst thanks to the Cu redox pair. A particular feature of this material consists in the presence of spontaneous isothermal oscillations which take place during N2O decomposition reaction, depending on the operating conditions. In the present work, a set of five Cu-ZSM-5 catalysts are synthesised by three procedures and three different copper precursor concentrations: i) wet impregnation, ii) single ion exchange, and iii) double ion exchange. Catalytic tests reveal that the ion-exchanged samples exhibit a low catalytic activity and no oscillatory behaviour, except for the twice-exchanged sample which achieves an average N2O conversion of 26% at 400 °C. Conversely, the impregnated samples reach higher levels of N2O conversion (66% for Cu5ZSM5_WI and 72% for Cu10ZSM5_WI) and demonstrate a similar oscillating pattern. Further investigations disclosed that the most active catalysts, characterised by the presence of oscillatory behaviour, have more abundant and easily reducible copper specis (ICP, EDX and H2-TPR) which interacts better with the zeolitic support (FT-IR). Catalytic tests under a long time on stream (TOS) suggest that either self-organised patterns or deterministic chaos can be achieved during the reaction, depending on the operating conditions, such as temperature and contact time.

Preparation of a Mesoporous Biosensor for Human Lactate Dehydrogenase for Potential Anticancer Inhibitor Screening.

Cancer is the second leading cause of death worldwide, with a dramatic impact due to the acquired resistance of cancers to used chemotherapeutic drugs and treatments. The enzyme lactate dehydrogenase (LDH-A) is responsible for cancer cell proliferation. Recently the development of selective LDH-A inhibitors as drugs for cancer treatment has been reported to be an efficient strategy aiming to decrease cancer cell proliferation and increase the sensitivity to traditional chemotherapeutics. This study aims to obtain a stable and active biocatalyst that can be utilized for such drug screening purposes. It is conceived by adopting human LDH-A enzyme (hLDH-A) and investigating different immobilization techniques on porous supports to achieve a stable and reproducible biosensor for anticancer drugs. The hLDH-A enzyme is covalently immobilized on mesoporous silica (MCM-41) functionalized with amino and aldehyde groups following two different methods. The mesoporous support is characterized by complementary techniques to evaluate the surface chemistry and the porous structure. Fluorescence microscopy analysis confirms the presence of the enzyme on the support surface. The tested immobilizations achieve yields of ≥80%, and the best retained activity of the enzyme is as high as 24.2%. The optimal pH and temperature of the best immobilized hLDH-A are pH 5 and 45 °C for the reduction of pyruvate into lactate, while those for the free enzyme are pH 8 and 45 °C. The stability test carried out at 45 °C on the immobilized enzyme shows a residual activity close to 40% for an extended time. The inhibition caused by NHI-2 is similar for free and immobilized hLDH-A, 48% and 47%, respectively. These findings are significant for those interested in immobilizing enzymes through covalent attachment on inorganic porous supports and pave the way to develop stable and active biocatalyst-based sensors for drug screenings that are useful to propose drug-based cancer treatments.

Natural Zeolite Clinoptilolite Application in Wastewater Treatment: Methylene Blue, Zinc and Cadmium Abatement Tests and Kinetic Studies.

In recent decades, several abatement techniques have been proposed for organic dyes and metal cations. In this scenario, adsorption is the most known and studied. Clinoptilolite was considered, since it is a zeolite with a relatively low cost (200-600 $ tons-1) compared to the most well-known adsorbent used in wastewater treatment. In this work, Clinoptilolite was used for the adsorption of Methylene Blue (MB) at three different concentrations, namely, 100, 200, and 250 ppm. Furthermore, the adsorption capacity of the natural zeolite was compared with that of Activated Charcoal (250 ppm of MB). The two adsorbents were characterized by complementary techniques, such as N2 physisorption at -196 °C, X-ray diffraction, and field emission scanning electron microscopy. During the adsorption tests, Clinoptilolite exhibited the best adsorption capacities at 100 ppm: the abatement reached 98% (t = 15 min). Both Clinoptilolite and Activated Charcoal, at 250 ppm, exhibited the same adsorption capacities, namely, 96%. Finally, at 250 ppm MB, the adsorption capacity of Clinoptilolite was analyzed with the copresence of Zn2+ and Cd2+ (10 ppm), and the adsorption capacities were compared with those of Activated Charcoal. The results showed that both adsorbents achieved 100% MB abatement (t = 40 min). However, cation adsorption reached a plateau after 120 min (Zn2+ = 86% and 57%; Cd2+ = 53% and 50%, for Activated Charcoal and Clinoptilolite, respectively) due to the preferential adsorption of MB molecules. Furthermore, kinetic studies were performed to fully investigate the adsorption mechanism. It was evidenced that the pseudo-second-order kinetic model is effective in describing the adsorption mechanism of both adsorbents, highlighting the chemical interaction between the adsorbent and adsorbate.

Simultaneous CO2 reduction and NADH regeneration using formate and glycerol dehydrogenase enzymes co-immobilized on modified natural zeolite.

In this work, the co-immobilization of formate dehydrogenase (FDH) and glycerol dehydrogenase (GlyDH) enzymes is proposed to reduce CO2 into formic acid, an important chemical intermediate. The reduction of carbon dioxide is carried out by FDH to obtain formic acid, simultaneously, the GlyDH regenerated the nicotinamide cofactor in the reduced form (NADH) by the oxidation of glycerol into dihydroxyacetone. Natural zeolite was selected as immobilization support given its good properties and low cost. The natural zeolite was modified with subsequent acid-alkaline attacks to obtain a mesostructurization of the clinoptilolite. The two enzymes were co-immobilized on clinoptilolite, previously hetero-functionalized with amino and glyoxyl groups. The distribution of the enzymes was confirmed by fluorescence microscopy analysis. Furthermore, a great increase in the retained activity for the formate dehydrogenase enzyme was noted, passing from 18% to 89%, when the mesostructured clinoptilolite was used as support. The immobilization yield of formate dehydrogenase and glycerol dehydrogenase is around 100% with all the supports studied. The promising results suggest a possible development of this procedure in enzyme immobilization and biocatalysis. The biocatalysts were characterized to find the optimal pH and temperature. Furthermore, a thermal stability test at 50 °C was carried out on both enzymes, in free and immobilized forms. Finally, it was shown that the biocatalyst is effective in reducing CO2, both by using the cofactor in the reduced form (NADH) or the oxidized form (NAD+), obtaining NADH through the regeneration with glycerol in this latter case.

Catalytic Abatement of Volatile Organic Compounds and Soot over Manganese Oxide Catalysts.

A set of manganese oxide catalysts was synthesized via two preparation techniques: solution combustion synthesis (Mn3O4/Mn2O3-SCS and Mn2O3-SCS) and sol-gel synthesis (Mn2O3-SG550 and Mn2O3-SG650). The physicochemical properties of the catalysts were studied by means of N2-physisorption at -196 °C, X-ray powder diffraction, H2 temperature-programmed reduction (H2-TPR), soot-TPR, X-ray photoelectron spectroscopy (XPS) and field-emission scanning electron microscopy (FESEM). The high catalytic performance of the catalysts was verified in the oxidation of Volatile Organic Compounds (VOC) probe molecules (ethene and propene) and carbon soot in a temperature-programmed oxidation setup. The best catalytic performances in soot abatement were observed for the Mn2O3-SG550 and the Mn3O4/Mn2O3-SCS catalysts. The catalytic activity in VOC total oxidation was effectively correlated to the enhanced low-temperature reducibility of the catalysts and the abundant surface Oα-species. Likewise, low-temperature oxidation of soot in tight contact occurred over the Mn2O3-SG550 catalyst and was attributed to high amounts of surface Oα-species and better surface reducibility. For the soot oxidation in loose contact, the improved catalytic performance of the Mn3O4/Mn2O3-SCS catalyst was attributed to the beneficial effects of both the morphological structure that-like a filter-enhanced the capture of soot particles and to a probable high amount of surface acid-sites, which is characteristic of Mn3O4 catalysts.

Synthesis and characterization of ordered mesoporous silicas for the immobilization of formate dehydrogenase (FDH).

This work studied the influence of the pore size and morphology of the mesoporous silica as support for formate dehydrogenase (FDH), the first enzyme of a multi-enzymatic cascade system to produce methanol, which catalyzes the reduction of carbon dioxide to formic acid. Specifically, a set of mesoporous silicas was modified with glyoxyl groups to immobilize covalently the FDH obtained from Candida boidinii. Three types of mesoporous silicas with different textural properties were synthesized and used as supports: i) SBA-15 (DP = 4 nm); ii) MCF with 0.5 wt% mesitylene/pluronic ratio (DP = 20 nm) and iii) MCF with 0.75 wt% mesitylene/pluronic ratio (DP = 25 nm). As a whole, the immobilized FDH on MCF0.75 exhibited higher thermal stability than the free enzyme, with 75% of residual activity after 24 h at 50 °C. FDH/MCF0.5 exhibited the best immobilization yields: 69.4% of the enzyme supplied was covalently bound to the support. Interestingly, the specific activity increased as a function of the pore size of support and then the FDH/MCF0.75 exhibited the highest specific activity (namely, 1.05 IU/gMCF0.75) with an immobilization yield of 52.1%. Furthermore, it was noted that the immobilization yield and the specific activity of the FDH/MCF0.75 varied as a function of the supported enzyme: as the enzyme loading increased the immobilization yield decreased while the specific activity increased. Finally, the reuse test has been carried out, and a residual activity greater than 70% was found after 5 cycles of reaction.

Immobilization strategies of photolyases: Challenges and perspectives for DNA repairing application.

Photolyases are enzymes that repair DNA damage caused by solar radiation. Due to their photorepair potential, photolyases added in topical creams and used in medical treatments has allowed to reverse skin damage and prevent the development of different diseases, including actinic keratosis, premature photoaging and cancer. For this reason, research has been oriented to the study of new photolyases performing in extreme environments, where high doses of UV radiation may be a key factor for these enzymes to have perfected their photorepair potential. Generally, the extracted enzymes are first encapsulated and then added to the topical creams to increase their stability. However, other well consolidated immobilization methods are interesting strategies to be studied that may improve the biocatalyst performance. This review aims to go through the different Antarctic organisms that have exhibited photoreactivation activity, explaining the main mechanisms of photolyase DNA photorepair. The challenges of immobilizing these enzymes on porous and nanostructured supports is also discussed. The comparison of the most reported immobilization methods with respect to the structure of photolyases show that both covalent and ionic immobilization methods produced an increase in their stability. Moreover, the use of nanosized materials as photolyase support would permit the incorporation of the biocatalyst into the target cell, which is a technological requirement that photolyase based biocatalysts must fulfill.

Photocatalytic Abatement of Volatile Organic Compounds by TiO2 Nanoparticles Doped with Either Phosphorous or Zirconium.

The aim of this work is to study the activity of novel TiO2-based photocatalysts doped with either phosphorus or zirconium under a UV-Vis source. A set of mesoporous catalysts was prepared by the direct synthesis: TiO2_A and TiO2_B (titanium oxide synthesized by two different procedures), P-TiO2 and Zr-TiO2 (binary oxides with either nonmetal or metal into the TiO2 framework). Complementary characterizations (N2 physisorption at 77 K, X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) analysis, X-ray Photoelectron Spectroscopy (XPS), and (DR)UV-Vis spectroscopy) were used to investigate the physicochemical properties of the prepared catalysts. Then, the photocatalysts were tested for the oxidation of propylene and ethylene under UV-Vis light. As a result, the most promising catalyst for both the propylene and ethylene oxidation reactions was the P-TiO2 (propylene conversion = 27.8% and ethylene conversion = 13%, TOS = 3 h), thus confirming the beneficial effect of P-doping into the TiO2 framework on the photocatalytic activity.

In situ Raman analyses of the soot oxidation reaction over nanostructured ceria-based catalysts.

To reduce the emissions of internal combustion engines, ceria-based catalysts have been widely investigated as possible alternatives to the more expensive noble metals. In the present work, a set of four different ceria-based materials was prepared via hydrothermal synthesis, studying the effect of Cu and Mn as dopants both in binary and ternary oxides. In situ Raman analyses were carried out to monitor the behaviour of defect sites throughout thermal cycles and during the soot oxidation reaction. Despite ceria doped with 5% of Cu featured the highest specific surface area, reducibility and amount of intrinsic and extrinsic defects, a poor soot oxidation activity was observed through the standard activity tests. This result was confirmed by the calculation of soot conversion curves obtained through a newly proposed procedure, starting from the Raman spectra collected during the in situ tests. Moreover, Raman analyses highlighted that new defectiveness was produced on the Cu-doped catalyst at high temperature, especially after soot conversion, while a slight increase of the defect band and a total reversibility were observed in case of the ternary oxide and pure/Mn-doped ceria, respectively. The major increment was related to the extrinsic defects component; tests carried out in different atmospheres suggested the assignment of this feature to vacancy-free sites containing oxidized doping cations. Its increase at the end of the tests can be an evidence of peroxides and superoxides deactivation on catalysts presenting excessive oxygen vacancy concentrations. Instead, ceria doped with 5% of Mn exhibited the best soot oxidation activity, thanks to an intermediate density of oxygen vacancies and to its well-defined morphology.

Study of Ce-Cu mixed oxide catalysts by in situ electrical conductivity measurements.

Three Ce-Cu mixed oxides, namely Ce0.95Cu0.05, Ce0.6Cu0.4 and Ce0.15Cu0.85, along with pure CeO2 and CuO were characterized by in situ electrical conductivity measurements. Their electrical conductivity was studied as a function of temperature and oxygen partial pressure, and was followed with time during successive exposure to air, nitrogen and different gaseous mixtures containing propane as a VOC model molecule, under conditions close to those of their catalytic applications. CeO2 and CuO appeared to be n-type and p-type semiconductors, respectively, while the semiconducting behavior of the Ce-Cu mixed oxides depended on the oxide composition. The semiconductive and redox properties of the samples were correlated with their catalytic behavior in CO oxidation, ethene total oxidation and soot combustion.

Catalytic Oxidation of CO and Soot over Ce-Zr-Pr Mixed Oxides Synthesized in a Multi-Inlet Vortex Reactor: Effect of Structural Defects on the Catalytic Activity.

In the present work, ceria, ceria-zirconia (Ce = 80 at.%, Zr = 20 at.%), ceria praseodymia (Ce = 80 at.%, Pr = 20 at.%) and ceria-zirconia-praseodymia catalysts (Ce = 80 at.%, Zr = 10 at.% and Pr = 10 at.%) have been prepared by the multi-inlet vortex reactor (MIVR). For each set of samples, two inlet flow rates have been used during the synthesis (namely, 2 ml min-1, and 20 ml min-1) in order to obtain different particle sizes. Catalytic activity of the prepared materials has been investigated for CO and soot oxidation reactions. As a result, when the catalysts exhibit similar crystallite sizes (in the 7.7-8.8 nm range), it is possible to observe a direct correlation between the Ov/F2g vibrational band intensity ratios and the catalytic performance for the CO oxidation. This means that structural (superficial) defects play a key role for this process. The incorporation of Zr and Pr species into the ceria lattice increases the population of structural defects, as measured by Raman spectroscopy, according to the order: CeO2 < Ce80Zr20 < Ce80Zr10Pr10 < Ce80Pr20. On the other hand, the presence of zirconium and praseodymium into the ceria lattice does not have a direct beneficial effect on the soot oxidation activity for these catalysts, in contrast with nanostructured ones (e.g., Ce-Zr-O nanopolyhedra, Ce-Pr-O nanocubes) described elsewhere (Andana et al. Appl. Catal. B 197: 125-137, 2016; Piumetti et al., Appl Catal B 180: 271-282, 2016).

CO and Soot Oxidation over Ce-Zr-Pr Oxide Catalysts.

A set of ceria, ceria-zirconia (Ce 80 at.%, Zr 20 at.%), ceria-praseodymia (Ce 80 at.%, Pr 20 at.%) and ceria-zirconia-praseodymia (Ce 80 at.%, Zr 10 at.% and Pr 10 at.%) catalysts has been prepared by the solution combustion synthesis (SCS). The effects of Zr and Pr as dopants on ceria have been studied in CO and soot oxidation reactions. All the prepared catalysts have been characterized by complementary techniques, including XRD, FESEM, N2 physisorption at -196 °C, H2-temperature-programmed reduction, and X-ray photoelectron spectroscopy to investigate the relationships between the structure and composition of materials and their catalytic performance. Better results for CO oxidation have been obtained with mixed oxides (performance scale, Ce80Zr10Pr10 > Ce80Zr20 > Ce80Pr20) rather than pure ceria, thus confirming the beneficial role of multicomponent catalysts for this prototypical reaction. Since CO oxidation occurs via a Mars-van Krevelen (MvK)-type mechanism over ceria-based catalysts, it appears that the presence of both Zr and Pr species into the ceria framework improves the oxidation activity, via collective properties, such as electrical conductivity and surface or bulk oxygen anion mobility. On the other hand, this positive effect becomes less prominent in soot oxidation, since the effect of catalyst morphology prevails.

Study on the CO Oxidation over Ceria-Based Nanocatalysts.

A series of ceria nanocatalysts have been prepared to study the structure dependency of the CO oxidation reaction. The ceria samples with well-defined nanostructures (nanocubes/Ce-NC and nanorods/Ce-NR) have been prepared using the hydrothermal method. Mesoporous ceria (Ce-MES) and ceria synthesized with solution combustion technique (Ce-SCS) have also been prepared for comparison. The lowest CO oxidation temperature has been reached by using ceria nanocubes (Ce-NC). This high activity draws immense contributions from the highly reactive (100) and (110) surfaces of the truncated nanocubes. The Ce-MES and Ce-SCS samples, despite their high surface areas, are unable to outdo the activity of Ce-NC and Ce-NR due to the abundant presence of (111) crystalline planes. This finding confirms the structure sensitivity of CO oxidation reaction catalyzed with ceria.