Catalysts, Volume 10, Issue 3 (March 2020) – 90 articles

This study presents a multi-residue method for simultaneous qualitative and quantitative analysis of eight antibiotics from some common classes, including beta-lactam, tetracyclines, lincosamides, glycopeptides, and sulfonamides in 39 aquaculture and river water samples from the Mekong Delta (Vietnam) using liquid chromatography-tandem mass spectrometry (LC-MS/MS). As a result, doxycycline (DXC), oxytetracycline (OTC), lincomycin (LCM), sulfamethoxazole (SMX), and sulfamethazine (SMZ) were detected with high frequency over 65% and an average concentration of 22.6–76.8 ng·mL⁻¹. The result suggests that antibiotic residues in the aquaculture and river waters are considered as an emerging environmental problem of the region. To address this issue, we fabricated the well-defined TiO₂ nanotube arrays (TNAs) and nanowires on nanotube arrays (TNWs/TNAs) using the anodization method. The TNAs had an inner tube diameter of ~95 nm and a wall thickness of ~25 nm. Meanwhile, the TNWs/TNAs had a layer of TiO₂ nanowires with a length of ~6 µm partially covering the TNAs. In addition, both TNAs and TNWs/TNAs had pure anatase phase TiO₂ with (101) and (112) dominant preferred orientations. Moreover, the TNAs and TNWs/TNAs effectively and rapidly degraded the antibiotic residues under UV-VIS irradiation at 120 mW/cm² and obtained over 95% removal at 20 min. Indeed, the photocatalytic reaction rate constants (k) were in the range of 0.14–0.36 min⁻¹ for TNAs, and 0.15–0.38 min⁻¹ for TNWs/TNAs. Noticeably, the k values of TNWs/TNAs were slightly higher than those of TNAs for LCM, DXC, OTC, SMZ, and SMX that could be attributed to the larger surface area of TNWs/TNAs than TNAs when TNWs/TNAs had an additional ~6μm TNWs top layer. Full article

SrF₂ promotes the dehydrochlorination (DeHCl) of 1,1-difluoro-1-chloroethane, which is the key process for the manufacture of VDF (vinylidene fluoride), one of the most typical fluorinated monomers. However, the selectivity is low as dehydrofluorination (DeHF) to VCF (vinylidene chlorofluoride) competes with the formation of VDF. In this study, SrF₂@C (SrF₂ embedded in carbon) and SrF₂@NC (N-doped carbon) catalysts were fabricated following calcination in N₂ with SrC₂O₄, PVDF (poly vinylidene fluoride) and urea as the precursors. The catalysts were characterized by XRD, SEM, TEM, and XPS. The results show that both the calcination temperature and N-doping play an important role in the conversion of HCFC-142b and the selectivity to VDF and VCF. Calcination at elevated temperatures enhances the Sr-C interaction. For SrF₂@C, improved interaction facilitates withdrawing electrons from Sr by the carbon support. By contrast, the strong interaction of Sr with N-doped carbon supply electrons from N species to Sr. The electron deficiency of Sr is favorable for the adsorption of F with higher electronegativity and consequently, DeHF reaction forming VCF. The supply of electrons to Sr by the support improves the formation of VDF (DeHCl). The present work provides a potential strategy for the improvement of selectivity to the target product. Full article

In this work, molybdena-promoted Li/MgO is studied as a catalyst for the oxidative conversion of n-hexane. The structure of the catalysts is investigated with X-ray Diffraction (XRD) and Raman spectroscopy. The MoO₃/Li/MgO catalyst contains three types of molybdena-containing species, the presence of which depend on molybdena loading. At low Mo/Li ratios (i) isolated dispersed [MoO₄]²⁻ anionic species are observed. At high Mo/Li ratios, the formation of crystalline lithium molybdate phases such as (ii) monomeric Li₂MoO₄ and tentatively (iii) polymeric Li₂Mo₄O₁₃ are concluded. The presence of these lithium molybdates diminishes the formation of Li₂CO₃ in the catalyst. Subsequently, the catalyst maintains high surface area and stability with time-on-stream during oxidative conversion. Molybdena loading as low as 0.5 wt % is sufficient to induce these improvements, maintaining the non-redox characteristics of the catalyst, whereas higher loadings enhance deep oxidation and oxidative dehydrogenation reactions. Promoting a Li/MgO catalyst with 0.5 wt % MoO₃ is thus efficient for selective conversion of n-hexane to alkenes, giving alkene yield up to 24% as well as good stability. Full article

In this communication, we report a biomass-derived nitrogen-doped porous carbon (named as NC-800) as an electrocatalyst for the ambient conversion of N₂ to NH₃. The catalyst NC-800 was prepared from naturally renewable and easily available bamboo shoots, with inherently an approximate 8 wt % of N-containing components, such as the N source, in a cost-effective and environmentally benign manner. This exhibited remarkable catalytic activity with a large NH₃ yield and a Faradaic efficiency as high as 16.3 μg h⁻mg^-1_cat and 27.5%, respectively, at −0.35 V versus a reversible hydrogen electrode (RHE) in 0.1 M HCl solution at ambient conditions. More importantly, the catalyst NC-800 demonstrated excellent electrochemical selectivity and stability. Full article

Hydrogen is an important raw material in chemical industries, and the steam reforming of light hydrocarbons (such as methane) is the most used process for its production. In this process, the use of a catalyst is mandatory and, if compared to precious metal-based catalysts, Ni-based catalysts assure an acceptable high activity and a lower cost. The aim of a distributed hydrogen production, for example, through an on-site type hydrogen station, is only reachable if a novel reforming system is developed, with some unique properties that are not present in the large-scale reforming system. These properties include, among the others, (i) daily startup and shutdown (DSS) operation ability, (ii) rapid response to load fluctuation, (iii) compactness of device, and (iv) excellent thermal exchange. In this sense, the catalyst has an important role. There is vast amount of information in the literature regarding the performance of catalysts in methane steam reforming. In this short review, an overview on the most recent advances in Ni based catalysts for methane steam reforming is given, also regarding the use of innovative structured catalysts. Full article

A series of cobalt spinel catalysts doped with bismuth in a broad range of 0–15.4 wt % was prepared by the co-precipitation method. The catalysts were thoroughly characterized by several physicochemical methods (X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), Raman spectroscopy (µRS), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption analyzed with Brunaer-Emmett-Teller theory (N₂-BET), work function measurements (WF)), as well as aberration-corrected scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS). The optimal bismuth promoter content was found to be 6.6 wt %, which remarkably enhanced the performance of the cobalt spinel catalyst, shifting the N₂O decomposition (deN₂O) temperature window (T_50%) down from approximately 400 °C (for Co₃O₄) to 240 °C (for the 6.6 wt % Bi-Co₃O₄ catalyst). The high-resolution STEM images revealed that the high activity of the 6.6 wt % Bi-Co₃O₄ catalyst can be associated with an even, atomic-level dispersion (3.5 at. nm⁻²) of bismuth over the surface of cobalt spinel nanocrystals. The improvement in catalytic activity was accompanied by an observed increase in the work function. We concluded that Bi promoted mostly the oxygen recombination step of a deN₂O reaction, thus demonstrating for the first time the key role of the atomic-level dispersion of a surface promoter in deN₂O reactions. Full article

Recent rapid development in homogeneous gold catalysis affords an alternative and particularly thriving strategy for the generation of gold carbenes through gold-catalyzed oxidation/amination/cycloaddition of alkynes, while it avoids the employment of hazardous and potentially explosive diazo compounds as starting materials for carbene generation. In addition to facile and secure operation, gold carbenes generated in this strategy display good chemoselectivity distinct from other metal carbenes produced from the related diazo approach. N-heterocyclic carbene (NHC) gold is a special metal complex that can be used as ancillary ligands, which provides enhanced stability and can also act as an efficient chiral directing group. In this review, we will present an overview of these recent advances in alkyne oxidation/amination/cycloaddition by highlighting their specificity and applicability, aiming to facilitate progress in this very exciting area of research. Full article

The intrinsic mechanism of Ni-catalyzed methanol steam reforming (MSR) is examined by considering 54 elementary reaction steps involved in MSR over Ni(111). Density functional theory computations and transition state theory analyses are performed on the elementary reaction network. A microkinetic model is constructed by combining the quantum chemical results with a continuous stirring tank reactor model. MSR rates deduced from the microkinetic model agree with the available experimental data. The microkinetic model is used to identify the main reaction pathway, the rate determining step, and the coverages of surface species. An analytical expression of MSR rate is derived based on the dominant reaction pathway and the coverages of surface species. The analytical rate equation is easy to use and should be very helpful for the design and optimization of the operating conditions of MSR. Full article

In this work, flexible ternary composites of cobalt-doped cadmium selenide/electrospun carbon nanofibers (Co-CdSe@ECNFs) for photocatalytic applications were fabricated successfully via electrospinning, followed by carbonization. For the fabrication of the proposed photocatalysts, Co-CdSe nanoparticles were grown in situ on the surface of ECNFs during the carbonization of precursor electrospun nanofibers obtained by dispersing Se powder in the electrospinning solution of polyacrylonitrile/N,N-Dimethylformamide (PAN/DMF) containing Cd²⁺ and Co²⁺. The photocatalytic performance of synthesized samples is investigated in the photodegradation of methylene blue (MB) and rhodamine B (RhB) dyes. Experimental results revealed the superior photocatalytic efficiency of Co-CdSe@ECNFs over undoped samples (CdSe@ECNFs) due to the doping effect of cobalt, which is able to capture the photogenerated electrons to prevent electron–hole recombination, thereby improving photocatalytic performance. Moreover, ECNFs could play an important role in enhancing electron transfer and optical absorption of the photocatalyst. This type of fabrication strategy may be a new avenue for the synthesis of other ECNF-based ternary composites. Full article

A series of Pd-TiO₂/Pd-Ce/TiO₂ catalysts were prepared by an equal volume impregnation method. The effects of different Pd loadings on the catalytic activity of chlorobenzene (CB) were investigated, and the results showed that the activity of the 0.2%-0.3% Pd/TiO₂ catalyst was optimal. The effect of Ce doping enhanced the catalytic activity of the 0.2% Pd-0.5% Ce/TiO₂ catalyst. The characterization of the catalysts using BET, TEM, H₂-TPR, and O₂-TPD showed that the oxidation capacity was enhanced, and the catalytic oxidation efficiency was improved due to the addition of Ce. Ion chromatography and Gas Chromatography-Mass Spectrometer results showed that small amounts of dichlorobenzene (DCB) and trichlorobenzene (TCB) were formed during the decomposition of CB. The results also indicated that the calcination temperature greatly influenced the catalyst activity and a calcination temperature of 550 °C was the best. The concentration of CB affected its decomposition, but gas hourly space velocity had little effect. H₂-TPR indicated strong metal–support interactions and increased dispersion of PdO in the presence of Ce. HRTEM data showed PdO with a characteristic spacing of 0.26 nm in both 0.2% Pd /TiO₂ and 0.2% Pd-0.5% Ce/TiO₂ catalysts. The average sizes of PdO nanoparticles in the 0.2% Pd/TiO₂ and 0.2% Pd-0.5% Ce/TiO₂ samples were 5.8 and 4.7 nm, respectively. The PdO particles were also deposited on the support and they were separated from each other in both catalysts. Full article

Ni catalysts supported on ZrO₂, 5%CeO₂-ZrO₂, and 5%La₂O₃-ZrO₂ were prepared via the impregnation method and tested in the oxy-steam reforming of methane and liquified natural gas (LNG). All tested catalysts exhibited high catalytic activity in the studied process at 700 and 900 °C. The improvement of the stability of Ni catalysts after the addition of CeO₂ oxide in the studied oxy-steam reforming of LNG process was confirmed. In addition, high activity and selectivity towards hydrogen was proven in the oxy-steam reforming process at 900 °C over a 20%Ni/5%CeO₂-ZrO₂ catalyst. It was also proved that the addition of CeO₂ onto a ZrO₂ carrier leads to a decrease in the NiO and metallic Ni crystallite sizes that were detected by the X-Ray diffraction (XRD) technique. The solid solution formation between NiO and ZrO₂ and/or NiO and CeO₂ was proved. Superior reactivity in the oxy-steam reforming of CH₄ and the LNG process exhibited a 20%Ni/ZrO₂ catalyst, which showed the highest methane conversions at 500 and 600 °C, equal to 63% and 89%, respectively. In addition, also in the case of the LNG reforming reaction, the most active catalyst was the 20%Ni/ZrO₂ system, which demonstrated 46.3% and 76.9% of the methane conversion value at 500 and 600 °C and the total conversion of others hydrocarbons (ethane, propane and butane). In addition, this catalytic system exhibited the highest selectivity towards hydrogen formation in the oxy-steam reforming of the LNG reaction equal to 71.2% and 71.3% at 500 and 600 °C, respectively. The highest activity of this system can be explained by the uniform distributions of Ni species and their highest concentration compared to the rest of the monometallic Ni catalysts. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) results also confirmed a strong interaction of NiO with ZrO₂ in the case of the 20%Ni/ZrO₂ catalysts. The presence of selected NiZrO⁺ ions emitted from the investigated surface of the 20%Ni/ZrO₂ system was detected. Full article

The poisoning effect of single elements on commercial V₂O₅-WO₃/TiO₂ catalysts has been studied in the past decades. In this study, the combined effects of two multi-element systems (phosphorus-potassium and phosphorus-lead) on V₂O₅-WO₃/TiO₂ catalysts were studied by diverse characterizations. The results show that potassium and lead can result in the deactivation of catalysts to different degrees by reacting with active acid sites and reducing the amount of V⁵⁺. However, phosphorus displays slight negative influence on the NO_x conversion of the catalyst due to the comprehensive effect of reducing V⁵⁺ amount and generating new acid sites. The samples poisoned by phosphorus–potassium and phosphorus–lead have higher NO_x conversion than that by potassium or lead, because doped potassium or lead atoms may react with new acid sites generated by phosphate, which liberates more V–OH on the surface of catalysts and reduces the poisoning effects of potassium or lead on vanadium species and active oxygen species. Full article

Meropenem (MER), a carbapenem, is considered a last-resort antibiotic. Its presence in water bodies, together with other antibiotics, has brought about environmental problems related to the destruction of natural microorganisms and the development of antibiotic-resistant bacteria. Herein, the degradation of MER by heterogeneous photocatalysis using TiO₂ immobilized on fiberglass substrates is reported. Morphological characterization of the substrates was performed by Scanning Electron Microscopy (SEM). Three pH values (4.0, 5.7, and 7.9) were tested for the treatment of MER solutions (100 mg/L). The best rate constants and MER removals were obtained at pH 4.0 (0.032 min⁻¹; 83.79%) and 5.7 (0.032 min⁻¹; 83.48%). Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) removals of 25.80% and 29.60% were achieved for the treatment at a pH value of 5.7. The reuse and regeneration of the plates were also tested. The activity of the substrates was maintained until the fourth cycle of reuse, nonetheless, a decrease in MER removal was observed for the 5th cycle. After the fourth cycle of reuse, the activity of the substrates was recovered by a regeneration procedure involving a wash stage of the substrates with a 1% H₂O₂ solution in an ultrasonic bath. Full article

For the production of chemicals from biomass, new selective processes are required. The selective oxidation of 5-(Hydroxymethyl)furfural (HMF), a promising platform molecule in fine chemistry, to 2,5-furandicarboxylic acid (FDCA) is considered a promising approach and requires the oxidation of two functional groups. In this study, Au/ZrO₂ catalysts with different mean particle sizes were prepared by a chemical reduction method using tetrakis(hydroxymethyl)phosphonium chloride (THPC) and tested in HMF oxidation. The catalyst with the smallest mean particle size (2.1 nm) and the narrowest particle size distribution was highly active in the oxidation of the aldehyde moiety of HMF, but less active in alcohol oxidation. On the other hand, increased activity in FDCA synthesis up to 92% yield was observed over catalysts with a larger mean particle size (2.7 nm), which had a large fraction of small and some larger particles. A decreasing FDCA yield over the catalyst with the largest mean particle size (2.9 nm) indicates that the oxidation of both functional groups require different particle sizes and hint at the presence of an optimal particle size for both oxidation steps. The activity of Au particles seems to be influenced by surface steps and H bonding strength, the latter particularly in aldehyde oxidation. Therefore, the presence of both small and some larger Au particles seem to give catalysts with the highest catalytic activity. Full article

Following biennial meetings held since 1968, the Iberoamerican Federation of Catalysis Societies (FISoCat), the Portuguese Chemical Society (SPQ) and the University of Coimbra jointly organized the XXVI Iberoamerican Congress on Catalysis (CICat 2018), which took place in the historic city of Coimbra, Portugal, between the 9th and 14th of September 2018 [...] Full article

Teraryl-based alpha-helix mimetics have resulted in efficient inhibitors of protein-protein interactions (PPIs). Extending the concept to even longer oligoarene systems would allow for the mimicking of even larger interaction sites. We present a highly efficient synthetic modular access to quateraryl alpha-helix mimetics, in which, at first, two phenols undergo electrooxidative dehydrogenative cross-coupling. The resulting 4,4′-biphenol is then activated by conversion to nonaflates, which serve as leaving groups for iterative Pd-catalyzed Suzuki-cross-coupling reactions with suitably substituted pyridine boronic acids. This work, for the first time, demonstrates the synthetic efficiency of using both electroorganic as well as transition-metal catalyzed cross-coupling in the assembly of oligoarene structures. Full article

Baeyer-Villiger monooxygenases (BVMOs) are flavin-dependent enzymes that primarily convert ketones to esters, but can also catalyze heteroatom oxidation. Several structural studies have highlighted the importance of the ‘control loop’ in BVMOs, which adopts different conformations during catalysis. Central to the ‘control loop’ is a conserved tryptophan that has been implicated in NADP(H) binding. BVMO_AFL210 from Aspergillus flavus, however, contains a threonine in the equivalent position. Here, we report the structure of BVMO_AFL210 in complex with NADP⁺ in both the ‘open’ and ‘closed’ conformations. In neither conformation does Thr513 contact the NADP⁺. Although mutagenesis of Thr513 did not significantly alter the substrate scope, changes in peroxyflavin stability and reaction rates were observed. Mutation of this position also brought about changes in the regio- and enantioselectivity of the enzyme. Moreover, lower rates of overoxidation during sulfoxidation of thioanisole were also observed. Full article

Owing to their unique physicochemical properties and comparable size to biomacromolecules, functional nanostructures have served as powerful supports to construct enzyme-nanostructure biocatalysts (nanobiocatalysts). Of particular importance, recent years have witnessed the development of novel nanobiocatalysts with remarkably increased enzyme activities. This review provides a comprehensive description of recent advances in the field of nanobiocatalysts, with systematic elaboration of the underlying mechanisms of activity enhancement, including metal ion activation, electron transfer, morphology effects, mass transfer limitations, and conformation changes. The nanobiocatalysts highlighted here are expected to provide an insight into enzyme–nanostructure interaction, and provide a guideline for future design of high-efficiency nanobiocatalysts in both fundamental research and practical applications. Full article

Eucalyptus globulus wood samples were treated with hot, compressed water (autohydrolysis) in consecutive stages under non-isothermal conditions in order to convert the hemicellulose fraction into soluble compounds through reactions catalyzed by in situ generated acids. The first stage was a conventional autohydrolysis, and liquid phase obtained under conditions leading to an optimal recovery of soluble saccharides was employed in a new reaction (second crossflow stage) using a fresh wood lot, in order to increase the concentrations of soluble saccharides. In the third crossflow stage, the best liquid phase from the second stage was employed to solubilize the hemicelluloses from a fresh wood lot. The concentration profiles determined for the soluble saccharides, acids, and furans present in the liquid phases from the diverse crossflow stages were employed for kinetic modeling, based on pseudohomogeneous reactions and Arrhenius-type dependence of the kinetic coefficients on temperature. Additional characterization of the reaction products by High Pressure Size Exclusion Chromatography, High Performance Anion Exchange Chromatography with Pulsed Amperometric Detection, and Matrix Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry provided further insight on the properties of the soluble saccharides present in the various reaction media. Full article

Lanthanide (La, Ce, Nd, Gd, Tb, Ho or Lu)-doped Cu-SAPO-18 samples were prepared using the ion-exchange method. Physicochemical properties of the samples were systematically characterized by a number of analytical techniques, and the effects of lanthanide doping on catalytic activity and hydrothermal stability of the Cu-SAPO-18 catalysts for the NH₃-SCR reaction were examined. It is shown that the doping of lanthanide elements could affect the interaction between the active components (copper ions) and the AEI-structured SAPO-18 support. The inclusion of some lanthanides significantly slowed down hydrolysis of the catalyst during hydrothermal aging treatment process, leading to an enhanced catalytic activity at both low and high temperatures and hydrothermal stability. In particular, Ce doping promoted the Cu²⁺ ions to migrate to the energetically favorable sites for enhancement in catalytic activity, whereas the other lanthanide ions exerted little or an opposite effect on the migration of Cu²⁺ ions. Additionally, Ce doping could improve hydrothermal stability of the Cu-SAPO-18 catalyst by weakening hydrolysis of the catalyst during the hydrothermal aging treatment process. Ce doping increased the catalytic activity of Cu-SAPO-18 at low and high temperatures, which was attributed to modifications of the redox and/or isolated Cu²⁺ active centers. Full article

Hydrogen is considered to be an ideal energy carrier to achieve low-carbon economy and sustainable energy supply. Production of hydrogen by catalytic reforming of organic compounds is one of the most important commercial processes. With the rapid development of photocatalysis in recent years, the applications of photocatalysis have been extended to the area of reforming hydrogen evolution. This research area has attracted extensive attention and exhibited potential for wide application in practice. Photocatalytic reforming for hydrogen evolution is a sustainable process to convert the solar energy stored in hydrogen into chemical energy. This review comprehensively summarized the reported works in relevant areas, categorized by the reforming precursor (organic compound) such as methanol, ethanol and biomass. Mechanisms and characteristics for each category were deeply discussed. In addition, recommendations for future work were suggested. Full article

The effect of cobalt substitution with nickel was investigated for the Fischer–Tropsch synthesis reaction. Catalysts having different Ni/Co ratios were prepared by aqueous incipient wetness co-impregnation, characterized, and tested using a continuously stirred tank reactor (CSTR) for more than 200 h. The addition of nickel did not significantly modify the morphological properties measured. XRD, STEM, and TPR-XANES results showed intimate contact between nickel and cobalt, strongly suggesting the formation of a Co-Ni solid oxide solution in each case. Moreover, TPR-XANES indicated that nickel addition improves the cobalt reducibility. This may be due to H₂ dissociation and spillover, but is more likely the results of a chemical effect of intimate contact between Co and Ni resulting in Co-Ni alloying after activation. FTS testing revealed a lower initial activity when nickel was added. However, CO conversion continuously increased with time on-stream until a steady-state value (34%–37% depending on Ni/Co ratio) was achieved, which was very close to the value observed for undoped Co/Al₂O₃. This trend suggests nickel can stabilize cobalt nanoparticles even at a lower weight percentage of Co. Currently, the cobalt price is 2.13 times the price of nickel. Thus, comparing the activity/price, the catalyst with a Ni/Co ratio of 25/75 has better performance than the unpromoted catalyst. Finally, nickel-promoted catalysts exhibited slightly higher initial selectivity for light hydrocarbons, but this difference typically diminished with time on-stream; once leveling off in conversion was achieved, the C₅+ selectivities were similar (≈ 80%) for Ni/Co ratios up to 10/90, and only slightly lower (≈ 77%) at Ni/Co of 25/75. Full article

The transformation of glucose represents a topic of great interest at different levels. In the first place, glucose is currently conceived as a green feedstock for the sustainable production of chemicals. Secondly, the depletion of glucose at the cellular level is currently envisioned as a promising strategy to treat and alter the erratic metabolism of tumoral cells. The use of natural enzymes offers multiple advantages in terms of specificity towards the glucose substrate but may lack sufficient robustness and recyclability beyond the optimal operating conditions of these natural systems. In the present work, we have evaluated the potential use of an inorganic based nanohybrid containing gold nanoparticles supported onto ordered mesoporous supports. We have performed different assays that corroborate the enzyme-mimicking response of these inorganic surrogates towards the selective conversion of glucose into gluconic acid and hydrogen peroxide. Moreover, we conclude that these enzyme-like mimicking surrogates can operate at different pH ranges and under mild reaction conditions, can be recycled multiple times and maintain excellent catalytic response in comparison with other gold-based catalysts. Full article

The selective oxidation of veratryl alcohol as lignin-derived compound was studied under mild conditions, using Au-Cu catalysts synthesized from pre-formed nanoparticles with different Au:Cu molar ratios. Bimetallic catalysts show higher activity compared to monometallic counterparts, highlighting a clear synergistic effect. By comparing the physico-chemical surface properties of catalysts supported on carbon and Al₂O₃, we were able to establish a strong support effect, with alumina-based catalysts being more active than carbon-supported ones. Moreover, TEM and X-ray photoelectron spectroscopy (XPS) analyses showed a different composition of nanoparticles (NPs) and metal exposure, and we established that Au is the active phase of the reaction. The co-presence of Au and Cu species, and their different interaction with the support, enabled obtaining more than 70% conversion of veratryl alcohol to veratryl aldehyde as a unique product. Moreover, the Au₁Cu₁ supported on alumina catalyst was recovered by filtration and reused without significant loss of activity and selectivity up to four times. Full article

The fiber-like bis-(dimethylglyoximato) nickel(II) complex, Ni(DMG)₂ was successfully synthesized. The obtained samples were characterized by SEM-EDS, FT-IR, XRD, and XPS. The TG-DSC-FTIR-MS coupling technique was used to characterize the thermal decomposition behavior and evolved gas analysis of Ni(DMG)₂. The non-isothermal decomposition reaction kinetic parameters were obtained by both combined kinetic analysis and isoconversional Vyazovkin methods. It was found that Ni(DMG)₂ begins to decompose at around 280 °C, and a sharp exothermic peak is observed in the DSC curve at about 308.2 °C at a heating rate of 10 °C·min⁻¹. The main gaseous products are H₂O, NH₃, N₂O, CO, and HCN, and the content of H₂O is significantly higher than that of the others. The activation energy obtained by the combined kinetic analysis method is 170.61 ± 0.65 kJ·mol⁻¹. The decomposition process can be described by the random nucleation and growth of the nuclei model. However, it was challenging to attempt to evaluate the reaction mechanism precisely by one ideal kinetic model. Full article

Palladium nanoparticles (Pd NPs) synthesized by the metal vapor synthesis technique were supported on poly(4-vinylpyridine) 2% cross-linked with divinylbenzene (Pd/PVPy). Transmission electron microscopy revealed the presence of small metal nanoparticles (d_m = 2.9 nm) highly dispersed on the PVPy. The Pd/PVPy system showed high catalytic efficiency in Suzuki-Miyaura carbon–carbon coupling reactions of both non-activated and deactivated aromatic iodides and bromides with aryl boronic acids, carried out under an air atmosphere. The high turnover of the catalyst and the ability of the PVPy resin to retain active Pd species are highlighted. By comparing the catalytic performances of Pd/PVPy with those observed by using commercially available Pd-based supported catalysts, the reported system showed higher selectivity and lower Pd leaching. Full article

Flavin-dependent monooxygenases (FMOs) are ancient enzymes present in all kingdoms of life. FMOs typically catalyze the incorporation of an oxygen atom from molecular oxygen into small molecules. To date, the majority of functional characterization studies have been performed on mammalian, fungal and bacterial FMOs, showing that they play fundamental roles in drug and xenobiotic metabolism. By contrast, our understanding of FMOs across the plant kingdom is very limited, despite plants possessing far greater FMO diversity compared to both bacteria and other multicellular organisms. Here, we review the progress of plant FMO research, with a focus on FMO diversity and functionality. Significantly, of the FMOs characterized to date, they all perform oxygenation reactions that are crucial steps within hormone metabolism, pathogen resistance, signaling and chemical defense. This demonstrates the fundamental role FMOs have within plant metabolism, and presents significant opportunities for future research pursuits and downstream applications. Full article

The sodium-treated sepiolite (NaSep)-supported rare earth oxide (RE/NaSep; RE = La, Eu, Dy, and Tm) samples were prepared using the rotary evaporation method. Physicochemical properties of these materials were characterized by XRD, SEM, BET, FTIR, XPS, H₂–TPR, NH₃–TPD, and in situ DRIFTS, and their catalytic activities for formaldehyde (HCHO) (2000 ppm) oxidation were evaluated. The results show that loading of the rare earth oxide on NaSep improved its catalytic performance. Among all the samples, Eu/NaSep performed the best, and complete HCHO conversion was achieved at a temperature of 150 °C and a gas hourly space velocity of 240,000 mL/(g h); a good catalytic activity was still maintained after 45 h of stability test. The catalytic oxidation mechanism of HCHO was studied using the in situ DRIFTS technique. As a result, the effective and stable catalytic performance of the Eu/NaSep sample was mainly due to the presence of hydroxyl groups on the sepiolite surface and the doped rare earth oxides, which contributed to its high performance. HCHO oxidation underwent via the steps of HCHO + O₂ → HCOO⁻ + OH⁻ → H₂O + CO₂. It is concluded that the optimal catalytic activity of Eu/NaSep was associated with the highest O_ads/O_latt atomic ratio, the largest amount of hydroxyl groups, the highest acidity, and the best reducibility. The present work may provide new insights into the application in the removal of high-concentration HCHO over the rare earth oxides supported on natural low-cost clays. Full article

Delignified rice husk waste (25.66% (wt) cellulose) was converted to levulinic acid using three types of manganese catalysts, i.e., the Mn₃O₄/hierarchical ZSM-5 zeolite and Mn₃O₄ heterogenous catalysts, as well as Mn(II) ion homogeneous counterpart. The hierarchical ZSM-5 zeolite was prepared using the double template method and modified with Mn₃O₄ through wet-impregnation method. The structure and physicochemical properties of the catalyst materials were determined using several solid-state characterization techniques. The reaction was conducted in a 200 mL-three neck-round bottom flask at 100 °C and 130 °C for a certain reaction time in the presence of 10% (v/v) phosphoric acid and 2% (v/v) H₂O₂ aqueous solution, and the product was analyzed using HPLC. In general, 5-hydroxymethyl furfural (5-HMF) as the intermediate product was produced after 2 h and decreased after 4 h reaction time. To conclude, the Mn₃O₄/hierarchical ZSM-5 heterogenous catalyst gave the highest yield (wt %) of levulinic acid (39.75% and 27.60%, respectively) as the main product, after 8 h reaction time. Full article