Catalysts, Volume 6, Issue 6 (June 2016) – 16 articles

This study aimed to investigate TiO₂ photocatalytic degradation of synthetically-prepared greywater samples with differing compositional contents of organic matter (OM), anion concentration, and microbiological consortium. Treatment efficiency was followed through removal of organic matter content in terms of dissolved organic carbon (DOC), specific spectroscopic parameters, and bacterial inactivation. Photocatalytic degradation kinetics were expressed by pseudo first-order kinetic modeling. The best DOC removal rates were attained for greywater samples containing OM with lower molecular size fractions. In addition, either enhancing or reducing the effect of common anions as radical scavengers were observed depending on the composition and concentration of variables in the greywater matrix. Moreover, possibility of a photocatalytic disinfection process was found to be of a bacteria type specific in OM-loaded synthetic greywater samples. Photocatalytic destruction of fecal streptococci required longer irradiation periods under all conditions. Bacterial removal rates were found to be in the order of total coliform > fecal coliform > fecal streptococci, for low organic load greywater, and fecal coliform > total coliform > fecal streptococci, for high organic load greywater. Full article

New gold catalysts supported on CeO₂, ZrO₂ and TiO₂ were synthesized by two different techniques: deposition-precipitation and colloidal method. The role of the surfactant (PVA, PVP, THPC) was also investigated. The catalysts were tested in the oxidation of glucose to gluconic acid, in aqueous environment and under mild conditions (60 °C and atmospheric pressure). TEM and SEM analyses have shown that the small size of gold nanoparticles is a necessary condition, but not sufficient for a good conversion. In fact, for an active sample, we have verified that the excess of surfactant must be removed because it would coat the surface of the catalyst. The surfactant, however, should not be completely eliminated, since it has the fundamental role of stabilizing the sample preventing nanoparticles from aggregation. It was evidenced that both the synthetic approach and the kind of support affect the catalysts’ activity. In fact, by focusing on the three different supports, with all the preparation methods, the ceria has proved to be the best support. This is due to its ability to obtain small gold nanoparticles and to its ability to accumulate oxygen. The most appropriate synthesis methodology proved to be the colloidal method with PVA. Recyclability issue was investigated too. Full article

Organic and inorganic compounds utilised at different stages of various industrial processes are lost into effluent water and eventually find their way into fresh water sources where they cause devastating effects on the ecosystem due to their stability, toxicity, and non-biodegradable nature. Semiconductor photocatalysis has been highlighted as a promising technology for the treatment of water laden with organic, inorganic, and microbial pollutants. However, these semiconductor photocatalysts are applied in powdered form, which makes separation and recycling after treatment extremely difficult. This not only leads to loss of the photocatalyst but also to secondary pollution by the photocatalyst particles. The introduction of various magnetic nanoparticles such as magnetite, maghemite, ferrites, etc. into the photocatalyst matrix has recently become an area of intense research because it allows for the easy separation of the photocatalyst from the treated water using an external magnetic field. Herein, we discuss the recent developments in terms of synthesis and photocatalytic properties of magnetically separable nanocomposites towards water treatment. The influence of the magnetic nanoparticles in the optical properties, charge transfer mechanism, and overall photocatalytic activity is deliberated based on selected results. We conclude the review by providing summary remarks on the successes of magnetic photocatalysts and present some of the future challenges regarding the exploitation of these materials in water treatment. Full article

The discovery and generation of biocatalysts with extended catalytic versatilities are of immense relevance in both chemistry and biotechnology. An enhanced atomistic understanding of enzyme promiscuity, a mechanism through which living systems acquire novel catalytic functions and specificities by evolution, would thus be of central interest. Using esterase-catalyzed amide bond hydrolysis as a model system, we pursued a simplistic in silico discovery program aiming for the identification of enzymes with an internal backbone hydrogen bond acceptor that could act as a reaction specificity shifter in hydrolytic enzymes. Focusing on stabilization of the rate limiting transition state of nitrogen inversion, our mechanism-guided approach predicted that the acyl hydrolase patatin of the α/β phospholipase fold would display reaction promiscuity. Experimental analysis confirmed previously unknown high amidase over esterase activity displayed by the first described esterase machinery with a protein backbone hydrogen bond acceptor to the reacting NH-group of amides. The present work highlights the importance of a fundamental understanding of enzymatic reactions and its potential for predicting enzyme scaffolds displaying alternative chemistries amenable to further evolution by enzyme engineering. Full article

Rh(III)-catalyzed regioselective alkylation of indoles with diazo compounds as a highly efficient and atom-economic protocol for the synthesis of alkyl substituted indoles has been developed. The reaction could proceed under mild conditions and afford a series of desired products in good to excellent yields. Full article

The development of thermodynamically stable supported bimetallic catalysts for high-temperature reaction is significant and highly desirable but remains a grand challenge. In this work, we report a novel approach that relies on the interaction of metal nanoparticles with the support material to form unique bimetallic nanoparticles, which epitaxially anchor onto the support surface. Such unique nanostructured systems are catalytically active and ultrastable during selected catalytic reactions. In this paper, we describe the synthesis processes of ultrastable PtZn nanoparticles epitaxially anchored onto ZnO nanowires, which primarily consist of {10−10} nanoscale facets. Such anchored PtZn nanoparticles demonstrated good stability during high temperature treatments and selected catalytic reactions. The synthesis approach reported in this work provides a new strategy to develop thermodynamically stable supported bimetallic catalysts. Full article

Aimed at developing a highly active and stable non-precious metal electrocatalyst for oxygen reduction reaction (ORR), a novel Fe_xN_y/NC nanocomposite—that is composed of highly dispersed iron nitride nanoparticles supported on nitrogen-doped carbon (NC)—was prepared by pyrolyzing carbon black with an iron-containing precursor in an NH₃ atmosphere. The influence of the various synthetic parameters such as the Fe precursor, Fe content, pyrolysis temperature and pyrolysis time on ORR performance of the prepared iron nitride nanoparticles was investigated. The formed phases were determined by experimental and simulated X-ray diffraction (XRD) of numerous iron nitride species. We found that Fe₃N phase creates superactive non-metallic catalytic sites for ORR that are more active than those of the constituents. The optimized Fe₃N/NC nanocomposite exhibited excellent ORR activity and a direct four-electron pathway in alkaline solution. Furthermore, the hybrid material showed outstanding catalytic durability in alkaline electrolyte, even after 4,000 potential cycles. Full article

Bio-oil can be obtained via fast pyrolysis of biomass, and typically contains acetic acid (~30 mass %). The acetic acid has often been tested as a model compound for hydrogen production via reforming bio-oil, in which catalysts are a key factor for stable hydrogen production. However, deactivation of catalysts by coking and oxidation hinders the application of the reforming process. Dolomite-derived Ni-based catalysts with Fe additive, MgNi_0.2Ca_0.8−xFe_xO_2±δ (x = 0–0.8), were successfully synthesized by the hydrothermal synthesis method, and then tested in auto-thermal reforming (ATR) of acetic acid (AC). The MgNi_0.2Ca_0.5Fe_0.3O_2±δ catalyst performed a stable reactivity in ATR: the conversion of AC reached 100%, and the H₂ yield remained stable around 2.6 mol-H₂/mol-AC. The catalysts were characterized by X-ray diffraction (XRD), N₂ physisorption, X-ray photoelectron spectra (XPS), H₂-temperature-programmed reduction (TPR), inductively coupled plasma- atomic emission spectroscopy (ICP-AES) and Thermogravimetry (TG); the results show that a periclase-like solid solution of Mg(Ni,Fe)O and lime were formed via the precursors of dolomite and hydrotalcite, and then transformed into Fe-rich Ni-Fe alloy with basic support of MgO-CaO after reduction. The stable Ni⁰ spices with basic support can explain the stability and resistance to coking during ATR of AC. Full article

The simultaneous adsorption and visible light photodegradation of Alizarin Red S in water solutions were studied in real time mode by using nano-TiO₂, such as Anatase and Aeroxide P-25, supported on polypropylene strips. Kinetic results of the overall process were compared with those obtained from separated steps of adsorption and photodegradation previously studied; kinetic advantages were evidenced with the simultaneous approach. From the study of different dye concentrations, a kinetic model has been proposed which describes the overall process. This model considered two consecutive processes: The adsorption of dye on TiO₂ surface and its photodegradation. The obtained results were in good agreement with experimental data and can predict the profiles of free dye, dye adsorbed on TiO₂ and photoproduct concentrations during the total process. Full article

Carbon-supported bimetallic Pt-Co cathode catalysts have been previously identified as higher activity alternatives to conventional Pt/C catalysts for fuel cells. In this work, a series of Pt-Co/C catalysts were synthesized using electroless deposition (ED) of Pt on a Co/C catalyst prepared by modified charge enhanced dry impregnation. X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) characterization of the base catalyst showed highly dispersed particles. A basic ED bath containing PtCl₆²⁻ as the Pt precursor, dimethylamine borane as reducing agent, and ethylenediamine as stabilizing agent successfully targeted deposition of Pt on Co particles. Simultaneous action of galvanic displacement and ED resulted in Pt-Co alloy formation observed in XRD and energy dispersive X-ray spectroscopy (XEDS) mapping. In addition, fast deposition kinetics resulted in hollow shell Pt-Co alloy particles while particles with Pt-rich shell and Co-rich cores formed with controlled Pt deposition. Electrochemical evaluation of the Pt-Co/C catalysts showed lower active surface but much higher mass and surface activities for oxygen reduction reaction compared to a commercial Pt/C fuel cell catalyst. Full article

This review discusses the use of molecular modeling tools, together with existing experimental findings, to provide a complete atomic-level description of enzyme dynamics and function. We focus on functionally relevant conformational dynamics of enzymes and the protonation states of substrates. The conformational fluctuations of enzymes usually play a crucial role in substrate recognition and catalysis. Protein dynamics can be altered by a tiny change in a molecular system such as different protonation states of various intermediates or by a significant perturbation such as a ligand association. Here we review recent advances in applying atomistic molecular dynamics (MD) simulations to investigate allosteric and network regulation of tryptophan synthase (TRPS) and protonation states of its intermediates and catalysis. In addition, we review studies using quantum mechanics/molecular mechanics (QM/MM) methods to investigate the protonation states of catalytic residues of β-Ketoacyl ACP synthase I (KasA). We also discuss modeling of large-scale protein motions for HIV-1 protease with coarse-grained Brownian dynamics (BD) simulations. Full article

Technical-grade oleic acid esters of sucrose and fructose were prepared using solvent-free biocatalysis at 65 °C, without any downstream purification applied, and their physicochemical and bioactivity-related properties were evaluated and compared to a commercially available sucrose laurate emulsifier. To increase the conversion of sucrose and fructose oleate, prepared previously using solvent-free lipase-catalyzed esterification catalyzed by Rhizomucor miehei lipase (81% and 83% ester, respectively), the enzymatic reaction conditions was continued using CaSO₄ to control the reactor’s air headspace and a lipase (from Candida antarctica B) with a hydrophobic immobilization matrix to provide an ultralow water activity, and high-pressure homogenation, to form metastable suspensions of 2.0–3.3 micron sized saccharide particles in liquid-phase reaction media. These measures led to increased ester content of 89% and 96% for reactions involving sucrose and fructose, respectively. The monoester content among the esters decreased from 90% to <70% due to differences in regioselectivity between the lipases. The resultant technical-grade sucrose and fructose lowered the surface tension to <30 mN/m, and possessed excellent emulsification capability and stability over 36 h using hexadecane and dodecane as oils, comparable to that of sucrose laurate and Tween^® 80). The technical-grade sugar esters, particularly fructose oleate, more effectively inhibited gram-positive foodborne pathogens (Lactobacillus plantarum, Pediococcus pentosaceus and Bacillus subtilis). Furthermore, all three sugar esters displayed antitumor activity, particularly the two sucrose esters. This study demonstrates the importance of controlling the biocatalysts’ water activity to achieve high conversion, the impact of a lipase’s regioselectivity in dictating product distribution, and the use of solvent-free biocatalysis to important biobased surfactants useful in foods, cosmetics, personal care products, and medicine. Full article

A novel generic method of silica supported catalyst system generation from a fluid state is presented. The technique is based on the combined flow and radiation (such as microwave, thermal or UV) induced co-assembly of the support and catalyst precursors forming nano-reactors, followed by catalyst precursor decomposition. The transformation from the precursor to supported catalyst oxide state can be controlled from a few seconds to several minutes. The resulting nano-structured micro-porous silica supported catalyst system has a surface area approaching 300 m²/g and X-ray Diffraction (XRD)-based catalyst size controlled in the range of 1–10 nm in which the catalyst structure appears as lamellar sheets sandwiched between the catalyst support. These catalyst characteristics are dependent primarily on the processing history as well as the catalyst (Fe, Co and Ni studied) when the catalyst/support molar ratio is typically 0.1–2. In addition, Ca, Mn and Cu were used as co-catalysts with Fe and Co in the evaluation of the mechanism of catalyst generation. Based on extensive XRD, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) studies, the micro- and nano-structure of the catalyst system were evaluated. It was found that the catalyst and silica support form extensive 0.6–2 nm thick lamellar sheets of 10–100 nm planar dimensions. In these lamellae, the alternate silica support and catalyst layer appear in the form of a bar-code structure. When these lamellae structures pack, they form the walls of a micro-porous catalyst system which typically has a density of 0.2 g/cm³. A tentative mechanism of catalyst nano-structure formation is provided based on the rheology and fluid mechanics of the catalyst/support precursor fluid as well as co-assembly nano-reactor formation during processing. In order to achieve these structures and characteristics, catalyst support must be in the form of silane coated silica nano-particles dispersed in water which also contains the catalyst precursor nitrate salt. This support-catalyst precursor fluid must have a sufficiently low viscosity but high elastic modulus (high extensional viscosity) to form films and bubbles when exposed to processing energy sources such as microwave, thermal, ultra-sound or UV-radiation or their combination. The micro-to-nano structures of the catalyst system are essentially formed at an early stage of energy input. It is shown that the primary particles of silica are transformed to a proto-silica particle state and form lamellar structures with the catalyst precursor. While the nano-structure is forming, water is evaporated leaving a highly porous solid support-catalyst precursor which then undergoes decomposition to form a silica-catalyst oxide system. The final catalyst system is obtained after catalyst oxide reduction. Although the XRD-based catalyst size changes slightly during the subsequent heat treatments, the nano-structure of the catalyst system remains substantially unaltered as evaluated through TEM images. However, if the catalyst preparation is carried out without film formation, the XRD-based catalyst size increases substantially by a factor of 2–8, with no significant alteration in surface area. Full article

It is now common knowledge that enzymes are mobile entities relying on complex atomic-scale dynamics and coordinated conformational events for proper ligand recognition and catalysis. However, the exact role of protein dynamics in enzyme function remains either poorly understood or difficult to interpret. This mini-review intends to reconcile biophysical observations and biological significance by first describing a number of common experimental and computational methodologies employed to characterize atomic-scale residue motions on various timescales in enzymes, and second by illustrating how the knowledge of these motions can be used to describe the functional behavior of enzymes and even act upon it. Two biologically relevant examples will be highlighted, namely the HIV-1 protease and DNA polymerase β enzyme systems. Full article

In this paper glucoamylase from Aspergillus niger was immobilized by using a modified version of cross-linked enzyme aggregates (CLEA). The co-aggregates were cross-linked with glutaraldehyde; meanwhile dextrin and xanthan gum as protecting agents were added, which provides high affinity with the enzyme molecules. The immobilized glucoamylase was stable over a broad range of pH (3.0–8.0) and temperature (55–75 °C); dependence shows more catalytic activity than a free enzyme. The thermostability, kinetic behavior, and first-order inactivation rate constant (k_i) were investigated. The two types of protector made the immobilized glucoamylase more robust than the free form. Both of the immobilized enzymes have excellent recyclability, retaining over 45% of the relative activity after 24 runs. In addition, immobilized enzymes reduced only 40% of the initial activity after three months by the storability measure, indicating high activity. Full article

Hybrid multi-functional nanomaterials comprising two or more disparate materials have become a powerful approach to obtain advanced materials for environmental remediation applications. In this work, an Ag-Ag₂O/TiO₂@polypyrrole (Ag/TiO₂@PPy) heterojunction has been synthesized by assembling a self-stabilized Ag-Ag₂O (p type) semiconductor (denoted as Ag) and polypyrrole (π-conjugated polymer) on the surface of rutile TiO₂ (n type). Ag/TiO₂@PPy was synthesized through simultaneous oxidation of pyrrole monomers and reduction of AgNO₃ in an aqueous solution containing well-dispersed TiO₂ particles. Thus synthesized Ag/TiO₂@PPy was characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and UV-Vis diffuse reflectance spectroscopy (UV-vis DSR). The photocatalytic activity of synthesized heterojunction was investigated for the decomposition of methylene blue (MB) dye under UV and visible light irradiation. The results revealed that π-conjugated p-n heterojunction formed in the case of Ag/TiO₂@PPy significantly enhanced the photodecomposition of MB compared to the p-n type Ag/TiO₂ and TiO₂@PPy (n-π) heterojunctions. A synergistic effect between Ag-Ag₂O and PPy leads to higher photostability and a better electron/hole separation leads to an enhanced photocatalytic activity of Ag/TiO₂@PPy under both UV and visible light irradiations. Full article