Non-selective Oxidation Research Articles

Influence of Phosphorus Poisoning of Cu/SSZ‐13 Zeolite Catalysts on the SCR Performance

AbstractHerein, the influence of phosphorus poisoning on the catalytic performance of Cu/SSZ‐13 zeolite catalysts for NOx emission decrease was studied. We conducted a detailed analysis of catalyst activity and N₂ selectivity in both fresh and P‐poisoned states, employing a range of advanced physicochemical characterization methods and in situ analyses. Our findings reveal a dual effect of phosphorus addition: Although it decreases the free Cu2+ species and specific surface area, leading to diminished SCR activity at low temperatures, it simultaneously reduces CuOx content, inhibiting nonselective NH3 oxidation at high temperatures and ultimately enhancing SCR activity under those conditions. These insights highlight the complex role of phosphorus in moderating catalyst behavior.

Modulating NH3 oxidation and inhibiting sulfate deposition to improve NH3-SCR denitration performance by controlling Mn/Nb ratio over MnaNbTi2Ox (a = 0.6-0.9) catalysts

The MnaNbTi2Ox (a = 0.6–0.9) catalysts for NH3 selective catalytic reduction denitration were prepared using the co-precipitation method. Among them, Mn0.7NbTi2Ox exhibits well low-temperature catalytic performance, wide activity temperature range (180–480 ℃), and worthy resistance to SO2 even with H2O. XRD was used to investigate the structure of MnaNbTi2Ox, in which Mn and Nb oxides highly dispersed in the MnaNbTi2Ox catalysts and Nb can dope into the crystal lattice of TiO2. XRF and XPS results show Nb can affect the transfer of electrons to Mn4+, and changing the Mn/Nb ratio can regulate the Mn4+ content on the MnaNbTi2Ox catalysts. H2-TPR, NH3 and NO oxidation results verify that Nb inhibits the oxidation capacity of MnaNbTi2Ox, and altering the Mn/Nb ratio can get appropriate oxidation property, which facilitates low-temperature NH3 activation and limit non-selective oxidation for NH3. In-situ DRIFTS results show Nb-OH bonds can provide new Brønsted acid sites, and both Lewis and Brønsted acid sites are active. Furthermore, Nb addition prevents sulphate deposition on the catalyst. The effect of Mn/Nb on catalytic performance, N2O formation and inhibition, SO2 poisoning, SO2 effect on NH3-SCR, and the enhancement of SO2 tolerance are also analyzed.

Surface engineering of TeOx modification on MoVTeNbO creates a high-performance catalyst for oxidation of toluene homologues to aldehydes

The heterogeneous catalytic oxidation of toluene by O2 is an inherently safe and green route for production of benzaldehyde, but after more than fifty years of effort, it remains a great challenge. Here, we report the best heterogeneous catalyst, TeOx/MoVTeNbO, up to now for the green oxidation of toluene by O2 to benzaldehyde, balancing the catalyst activity, selectivity, and stability. The deposition of TeOx endows the MoVTeNbO composite oxide with entirely new property for toluene oxidation and the surface engineering mechanism has been fully explained. The discrete TeOx clusters on the surface, shielding the nonselective oxidation sites that interact strongly with the benzene ring of toluene molecule, allows toluene molecule to chemically adsorb to the surface perpendicularly and the methyl is then prone to oxidation to aldehyde on the reshaped selective oxidation sites, where V=O is the main active species responsible for continuously extracting hydrogen from methyl and implanting oxygen to form benzaldehyde. The TeOx clusters participate in this reaction through variable valences and stabilize benzaldehyde by couple interaction with the –CHO group of benzaldehyde, thereby achieving high selectivity to benzaldehyde (>95%). The extended works indicate that the catalytic mechanism is effective in a series of selective oxidation of toluene homologues to corresponding aldehydes.

Promoting effect of Cu as electron transfer medium on NH3-SCO reaction in asymmetric Ag-Ov-Ti-Sm-Cu ring active site

Selective catalytic oxidation of ammonia (NH3-SCO) has become an effective method to reduce ammonia (NH3) emissions, and is a key part to solve the problem of NH3 pollution. Nevertheless, the optimization of this technology’s performance relies heavily on innovation and the development of catalyst design. In this study, a SmCuAgTiOx catalyst with an asymmetric Ag-Ov-Ti-Sm-Cu ring active site was prepared and applied to the NH3-SCO reaction. The low conversion of Cu-based catalysts in NH3 at low temperature and the inherent low N₂ selectivity of Ag-based catalysts were solved. The successful creation of the asymmetric ring active site improved the catalyst’s reduction performance. Additionally, Cu, acting as an electron transfer medium, plays a crucial role in enhancing electron transfer within the asymmetric ring active site, thus increasing the redox cycle of the catalyst during the reaction. In addition, some lattice oxygen is lost in the catalyst, resulting in the formation of a large number of oxygen vacancies. This process stimulates the adsorption and activation of surface-adsorbed oxygen, facilitating the conversion of NH3 to an amide (NH2) intermediate during the reaction and reducing non-selective oxidation. The N2 selectivity was improved without significantly affecting the performance of Ag-based catalyst. In-situ diffuse reflectance fourier transform infrared spectroscopy (In-situ DRIFTS) analysis reveals that the SmCuAgTiOx catalyst primarily follows an “internal” selective catalytic reduction (iSCR) mechanism in the NH3-SCO reaction, complemented by the imide mechanism. The asymmetric Ag-Ov-Ti-Sm-Cu ring active site developed in this study provides a new perspective for efficiently solving NH3 pollution in the future.

Oxidation-induced starch molecular degradation: A comprehensive kinetic investigation using NaClO/NaBr/TEMPO system

Starch degradation often coincides with its chemical modification, and understanding how chemical modification influences starch degradation is vital for determining the properties of the resultant modified products. This work investigates the effect of oxidation on starch molecular degradation, examining factors such as oxidation degree, reaction kinetics, and degradation patterns during 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated starch oxidation under varying conditions, including reaction time, pH, temperature, and concentrations of NaBr, TEMPO, and NaClO. Results emphasize that extended reaction durations primarily lead to β-elimination, causing α-1,4 linkage cleavages. pH 8.5 favored non-selective oxidation, while pH 11 enhanced β-elimination, both slowing the reaction rate and severely damaging starch chains (Mw of 8.8 × 105 g/mol and 7.2 × 105 g/mol, respectively). Elevated temperature from 0 to 30 °C significantly expedited both selective and non-selective oxidation, dramatically reducing molecular mass to 8.1 × 105 g/mol. Increasing concentrations of NaBr and TEMPO boost the reaction rate with minimal impact on molecular mass. Meanwhile, increasing NaClO concentration from 0.2 to 2.2 mmol/g-starch not only affects the reaction rate but also reinforces β-elimination, enhancing molecular degradation. This study is insightful for starch modification to achieve desired oxidation levels and chain lengths by controlling reaction conditions, offering potential advancements in oxidized starch-based materials like nano micelles.

Modulating the Microstructure and Surface Acidity of MnO2 by Doping-Induced Phase Transition for Simultaneous Removal of Toluene and NOx at Low Temperature.

It is a great challenge to remove VOCs and NOx simultaneously from flue gas in nonelectric industries. This study focuses on the construction of Fe-MnO2 catalysts that perform well in the simultaneous removal of toluene and NOx at low temperatures. Utilizing the Fe-induced phase transition of MnO2, Fe-MnO2-F&R catalysts with a composite morphology of nanoflowers and nanorods were successfully prepared that provided an abundant microporous structure to facilitate the diffusion of molecules of different sizes. Through in-depth investigation of the active sites and reaction mechanism, we discovered that Fe-induced phase transition could modulate the surface acidity of Fe-MnO2-F&R. The higher concentration of surface Mn4+ provided numerous Brønsted acid sites, which effectively promoted the activation of toluene to reactive intermediates, such as benzyl alcohol/benzoate/maleic acid. Simultaneously, Fe provided a large number of Lewis acid sites that anchor and activate NH3 species, thereby inhibiting NH3 nonselective oxidation. Furthermore, additional Brønsted acid sites were generated during the simultaneous reaction process, enhancing toluene activation. Consequently, the simultaneous removal of toluene and NOx was achieved through regulation of the physical structure and the concentration of acidic sites. The present work provides new insights into the rational design of bifunctional catalysts for the synergistic control of VOCs and NOx emissions.

Photocatalytic Transformation of Organics to Valuable Chemicals - Quo Vadis?

Recent development in photocatalysis is increasingly focused on transforming organic compounds toward producing fine chemicals. Simple, non-selective oxidation reactions (degradation of pollutants) and very demanding solar-to-chemical energy conversion processes (production of solar fuels) face severe economic limitations influenced by still low efficiency and insufficient stability of the systems. Synthesis of fine chemicals, including reductive and oxidative selective transformations, as well as C-C and C-N coupling reactions, can utilise the power of photocatalysis. Herein, we present the recent progress in photocatalytic systems designed to synthesise fine chemicals. In particular, we discuss the factors influencing the efficiency and selectivity of the organic transformations, dividing them into intrinsic (related to individual properties of photocatalysts) and extrinsic (originating from the reaction environment). A rational design of the photocatalytic systems, based on a deep understanding of these factors, opens new perspectives for applied photocatalysis.

High-efficiency ternary CeO2/WO3/AC photocatalyst supported by biomass waste-derived activated carbon for efficient doxycycline photodegradation: Optimization of synthesis conditions and operational parameters

Herein, a stable and reusable photocatalyst based on activated carbon (AC) with varying CeO2/WO3 loadings is synthesized and optimized using Central Composite Design (CCD) with the intention of Doxycycline (DOX) degrading as an organic pollutant. Prepared optimum photocatalyst have been characterized through XRD, BET, FE-SEM, EDS-Mapping, TEM, FT-IR, and UV–Vis band gap analyses. Additionally, the effect of operational parameters including catalyst dosage (0.2–1.4 g.L−1), DOX concentration (10–50 ppm), irradiation time (20–140 min), and pH (2–10) on DOX degradation is investigated by CCD in order to highly-efficient DOX degradation. The best working condition shows an experimental degradation efficiency of 97.23%. Moreover, selected CeO2/WO3/AC photocatalyst remove 83.11% of COD from DOX solution. The h+ and •O2− radicals are found to be essential for the destruction of the DOX due to heir strong and nonselective oxidation characteristics. Furthermore, the stability of the selected photocatalyst observed after undergoing five degradation cycles.

Electrochemical oxidation of glucose in alkaline environment—A comparative study of Ni and Au electrodes

The glucose oxidation reaction (GOR) was studied on Au and Ni electrodes by cyclic voltammetry (CV), rotating disk electrode (RDE) measurements coupled with Koutecky–Levich analysis, Differential Electrochemical Mass Spectrometry (DEMS), in situ Fourier Transform Infrared spectroscopy (FTIRS) and High Performance Liquid Chromatography (HPLC) analysis of the reaction products after electrolysis in potentiostatic mode under continuous flow conditions. This study allowed to identify the reaction products and propose tentative reaction mechanisms. On gold, glucose is adsorbed on metallic sites through its anomeric function (C1) resulting in the formation of gluconate as the main GOR product at potentials close to 0.6 V vs. RHE, with a selectivity towards gluconate close to 100% and a projected faradaic efficiency of ca. 70%. The conversion rate is rather low, close to 20%, due to poisoning of the surface, leading to a strong deactivation. At potentials above 0.7 V vs. RHE, the selectivity towards gluconate decreases and non-selective GOR oxidation proceeds through CC bond cleavage. On nickel, the GOR occurs at high potentials (close to 1.2 V vs. RHE) on Ni(OH)2 and NiOOH sites, and proceeds through C1C2 bond breaking, resulting in arabinose and formate. At higher potentials, the selectivity towards arabinose decreases, formate being the main reaction product.

Synthesis of Chiral Sulfoxides by A Cyclic Oxidation-Reduction Multi-Enzymatic Cascade Biocatalysis.

Optically pure sulfoxides are valuable organosulfur compounds extensively employed in medicinal and organic synthesis. In this study, we present a biocatalytic oxidation-reduction cascade system designed for the preparation of enantiopure sulfoxides. The system involves the cooperation of a low-enantioselective chimeric oxidase SMO (styrene monooxygenase) with a high-enantioselective reductase MsrA (methionine sulfoxide reductase A), facilitating "non-selective oxidation and selective reduction" cycles for prochiral sulfide oxidation. The regeneration of requisite cofactors for MsrA and SMO was achieved via a cascade catalysis process involving three auxiliary enzymes, sustained by cost-effective D-glucose. Under the optimal reaction conditions, a series of heteroaryl alkyl, aryl alkyl and dialkyl sulfoxides in R configuration were synthesized through this "one-pot, one step" cascade reaction. The obtained compounds exhibited high yields of >90 % and demonstrated enantiomeric excess (ee) values exceeding 90 %. This study represents an unconventional and efficient biocatalytic way in utilizing the low-enantioselective oxidase for the synthesis of enantiopure sulfoxides.

A novel Z-scheme heterojunction photocatalyst CeO2@WO3 nanocomposite with enhanced visible-light photocatalytic performance for wastewater treatment by cephalexin antibiotic degradation: Process optimization

Considering growing global environmental concerns, there is a heightened focus on expediting the synthesis of highly efficient catalytic materials to address these challenges effectively. Herein, a novel CeO2@WO3 heterojunction photocatalyst was synthesized using an ultrasonic-assisted method for the environmentally friendly degradation of cephalexin (CPX) under visible light. The optimized photocatalyst synthesis condition was achieved by assessing the influence of effective parameters, including the CeO2 content (5–25 wt%) and calcination temperature (300–600 °C), employing the RSM method. The synthesized photocatalysts were comprehensively characterized through XRD, SEM, TEM, EDS-mapping, BET, FTIR, and UV–Vis band gap analysis. Using optimal photocatalyst (CeO2 content: 15.78 %, calcination temperature: 440.59 °C, and ultrasonic power: 80 W), the influence of four critical variables on CPX degradation was thoroughly investigated via RSM-CCD. The maximum CPX degradation efficiency of 98.8 % was attained under the following optimal conditions: CPX concentration: 20.00 mg/L, solution pH: 6.79, photocatalyst dosage: 0.019 g/L, and visible light time: 94.82 min. Statistical analysis confirmed the accuracy of the regression model based on empirical data. The CeO2@WO3 heterojunction demonstrated substantial Chemical Oxygen Demand (COD) removal, reaching 73.26 % during the mineralization of CPX, surpassing the outcomes of previous studies. Trapping experiments and EPR analysis indicated the crucial involvement of hydroxyl radicals and superoxide radicals as highly active species due to their non-selective oxidation capabilities. Furthermore, a Z-scheme charge transfer mechanism was proposed to elucidate the enhanced photocatalytic activity. Identifying degradation intermediates was accomplished through HPLC-MS analysis, leading to a plausible pathway for CPX degradation. Overall, CeO2@WO3 exhibited excellent stability and could endure five cycles with minimal cerium leaching, highlighting its effectiveness in decomposing organic contaminants.

Induction of Extracellular Hydroxyl Radicals Production in the White-Rot Fungus Pleurotus eryngii for Dyes Degradation: An Advanced Bio-oxidation Process.

Among pollution remediation technologies, advanced oxidation processes (AOPs) are genuinely efficient since they are based on the production of strong, non-selective oxidants, mainly hydroxyl radicals (·OH), by a set of physicochemical methods. The biological counterparts of AOPs, which may be referred to as advanced bio-oxidation processes (ABOPs), have begun to be investigated since the mechanisms of induction of ·OH production in fungi are known. To contribute to the development of ABOPs, advanced oxidation of a wide number of dyes by the white-rot fungus Pleurotus eryngii, via a quinone redox cycling (QRC) process based on Fenton's reagent formation, has been described for the first time. The fungus was incubated with 2,6-dimethoxy-1,4-benzoquinone (DBQ) and Fe3+-oxalate, with and without Mn2+, leading to different ·OH production rates, around twice higher with Mn2+. Thanks to this process, the degradative capacity of the fungus increased, not only oxidising dyes it was not otherwise able to, but also increasing the decolorization rate of 20 dyes by more than 7 times in Mn2+ incubations. In terms of process efficacy, it is noteworthy that with Mn2+ the degradation of the dyes reached values of 90-100% in 2-4 h, which are like those described in some AOPs based on the Fenton reaction.

Catalysts Based on Iron Oxides for Wastewater Purification from Phenolic Compounds: Synthesis, Physicochemical Analysis, Determination of Catalytic Activity

In this work, the synthesis of magnetite nanoparticles and catalysts based on it stabilized with silicon and aluminum oxides was carried out. It is revealed that the stabilization of the magnetite surface by using aluminum and silicon oxides leads to a decrease in the size of magnetite nanocrystals in nanocomposites (particle diameter less than ~10 nm). The catalytic activity of the obtained catalysts was evaluated during the oxidation reaction of phenol, pyrocatechin and cresol with oxygen. It is well known that phenolic compounds are among the most dangerous water pollutants. The effect of phenol concentration and the effect of temperature (303–333 K) on the rate of oxidation of phenol to Fe3O4/SiO2 has been studied. It has been determined that the dependence of the oxidation rate of phenol on the initial concentration of phenol in solution is described by a first-order equation. At temperatures of 303–313 K, incomplete absorption of the calculated amount of oxygen is observed, and the analysis data indicate the non-selective oxidation of phenol. Intermediate products, such as catechin, hydroquinone, formic acid, oxidation products, were found. The results of UV and IR spectroscopy showed that catalysts based on magnetite Fe3O4 are effective in the oxidation of phenol with oxygen. In the UV spectrum of the product in the wavelength range 190–1100 nm, there is an absorption band at a wavelength of 240–245 nm and a weak band at 430 nm, which is characteristic of benzoquinone. In the IR spectrum of the product, absorption bands were detected in the region of 1644 cm−1, which is characteristic of the oscillations of the C=O bonds of the carbonyl group of benzoquinone. The peaks also found at 1353 cm−1 and 1229 cm−1 may be due to vibrations of the C-H and C-C bonds of the quinone ring. It was found that among the synthesized catalysts, the Fe3O4/SiO2 catalyst demonstrated the greatest activity in the reaction of liquid-phase oxidation of phenol.

Selective catalytic reduction of NOX with CH4 over In/SSZ-13 zeolites: The enhancement of high-temperature catalytic activity by Ce modification

The selective catalytic reduction of nitrogen oxides by methane (CH4/NOX-SCR) is a potential technique for the abatement of the NOX emissions from lean-burn GDI engines, due to the excellent thermal stability of CH4. This work focuses on the promotion of In/SSZ-13 catalysts by Ce modification for the CH4/NOX-SCR performance at high temperatures. A series of In/SSZ-13 and Ce-In/SSZ-13 catalysts were prepared using the wetness impregnation method. The effects of Ce modification on the catalytic performance were analysed in detail using the scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectrum and temperature-programmed desorption/reduction techniques. The results show that the Ce modification significantly enhances the high-temperature activity of the In/SSZ-13 catalysts for the NOX-SCR reaction, especially for the 5 wt% Ce-15 wt% In/SSZ-13 sample which has more than 75% NOX conversion at 390–700 °C. In addition, the Ce modification enhances the water vapor tolerance of the catalyst sample. The Ce modification increases not only the concentration of surface chemisorption oxygen species, but also the relative amount of InO+ species which serve as the main active sites for CH4 activation. Furthermore, the incorporation of Ce into In/SSZ-13 greatly promotes NOX adsorption on the catalyst surface. Most importantly, the Ce modification makes In species well-dispersed on the catalyst surface and thus suppresses the formation of bulk In2O3 species which are more active for the CH4 non-selective oxidation. The combination of all these effects results in the Ce-In/SSZ-13 samples with the superior catalytic activity.

A Numerical Study of the Efficiency of the Sono Galvano-Fenton Process as a Tertiary Treatment Technique for the Wastewater Reuse in Agriculture

In the present study, the Sono-Galvano-Fenton process is studied numerically as a tertiary treatment process for treated wastewater reuse in irrigation, with in situ generation of the Fenton’s reagent and catalyst, i.e., H2O2 and Fe2+. The sonochemical pathway is examined as a source of hydrogen peroxide under the pre-optimized condition of acoustic frequency, 200 kHz. The macroscopic model accounting for the performance of the single acoustic cavitation bubble and the bubble population density is combined with the Fe/Cu galvanic cell operating in acidic conditions (pH 3), following a cumulative and instantaneous production approach in terms of Fenton’s reagent. The combination is optimized based on the rate of hydroxyl radicals generated by the Galvano-Fenton process, as a non-selective powerful oxidant against recalcitrant pollutants, then considering the synergetic effect of the hybrid process in terms of HO● pumped sonochemically and via the Fenton based pathway, treated using simulations of the isolated processes then their combined configuration following both aforementioned approaches.

Electrochemical oxidation of tetrahydrofurfuryl acohol on boron-doped diamond anode: Influence of current density and electrolyte solution

Tetrahydrofurfuryl alcohol (THFA), a widely applied raw materials, intermediate and solvent in the fields of agricultural, industry (especially in nuclear industry), is a potentially hazardous and non-biodegradable pollutant in wastewater. In this study, the electrochemical degradation pathways of THFA by a boron-doped diamond (BDD) anode with different current density (jappl = 20, 40 and 60 mA cm−2) and electrolyte solution (KNO3, KCl and K2SO4) was carefully investigated. The results exhibit that high chemical oxygen demand (COD) removal and mineralization rates were achieved by rapid non-selective oxidation in electrolyte solutions mediated by hydroxyl radicals (∙OH) and active chlorine (sulfate) under constant current electrolysis. In-depth data analysis using the high performance liquid chromatography and liquid chromatography/mass spectroscopy, the underlying removal pathways of THFA in KNO3, KCl and K2SO4 electrolyte solutions are proposed according to the effect of different mineralization mechanisms.

Preparation of PANI modified TiO2 and characterization under pre- and post- photocatalytic conditions.

Polyaniline (PANI) is a promising conducting polymer for surface modification of TiO2 to overcome limitations of the use of visible light and attain increased photocatalytic efficiency for the removal of organic contaminants. In this study, a series of polyaniline modified TiO2 (PANI-TiO2) composites were prepared by using "in-situ" chemical oxidation polymerization method. The composites were systematically characterized by Fourier transform infrared spectroscopy (equipped with an attenuated total reflection accessory, FTIR-ATR), Raman spectroscopy, X-ray diffractometry (XRD), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDAX), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-DRS), photoluminescence spectroscopy (PL), nitrogen (N2) physisorption (Brunauer - Emmett - Teller surface area (SBET) and Barrett-Joyner-Halenda (BJH) pore size analysis), thermogravimetry-derivative thermogravimetry (TG-DTG) techniques. XRD patterns of PANI-TiO2 composites confirmed both the amorphous phase of PANI and the crystalline character of TiO2. TG/DTG analysis complemented the XRD profiles that the interactions between PANI and TiO2 resulted in a more stable PANI-TiO2 matrix. SEM images displayed the dominant morphology as dandelion-like shapes of PANI being more pronounced with increasing PANI ratios in PANI-TiO2 composites. UV-DRS profiles revealed that the band gap energies of the composites were lower than bare TiO2 expressing a shift to the visible light region. Both PL and UV-DRS analyses confirmed the band-gap reduction phenomenon of PANI modification of TiO2. The incorporation of PANI into TiO2 resulted in a reduction of the surface area of TiO2. The composites were subsequently subjected to photocatalytic activity assessment tests using humic acid (HA) as a model of refractory organic matter (RfOM) under simulated solar irradiation (Uyguner-Demirel et al. Environ Sci Pollut Res 30 85626-85638, 2023). The morphological and structural changes attained upon application of photocatalysis were also evaluated by FTIR-ATR, Raman spectroscopy, XRD, and SEM-EDAX methods in a comparable manner. The FTIR-ATR spectral features of PANI, RfOM and all composites displayed peaks with slight shifts under pre- and post- photocatalytic conditions as well as following dark surface interactions. Besides exhibiting noticeable photocatalytic performance, PANI-TiO2 composites were also proven to maintain stability under non-selective oxidation conditions in the presence of a complex organic matrix. The prepared PANI-TiO2 composites overcoming the limitations of UVA light active bare TiO2 photocatalysis could possibly find a beneficial use as potential catalysts in solar photocatalytic applications.

Hydrodynamics and Energy Analysis in Suspended Catalyst Photocatalytic Membrane Reactors

Photocatalysis is a non-selective advanced oxidation process (AOP) that can be effective for degradation of toxic compounds. Its main drawback however has been high processing costs compared to other AOPs. Suspended catalyst photocatalytic membrane reactors (SPMR) are promising design configuration for implementation of the technology. This work involves experimental and theoretically analysis of the hydrodynamics and energy consumption in a SPMR under crossflow and oscillatory shear conditions. An optimization approach is presented for intensification of the reactor performance that considers the coupling effects of the applied shear and the transmembrane pressure on the hydrodynamics and the specific energy consumption (kWh/m3). The results showed that the optimum shear rate decreases with increasing the membrane area due to the relatively high contribution of the permeate pumping power to the energy consumption which makes the advantages of operating at higher shear rate relevant. This trend changes for larger membranes areas where the energy consumption due to higher shear outweighs the advantage of its performance enhancement resulting in increasing the system specific energy consumption. In general, the latter was found to be higher for a crossflow system compared to an oscillatory membrane design, which in addition to its smaller footprints, can make such design an attractive option for confined and/or limited space applications.

Molecular comparison of organic matter removal from shale gas flowback wastewater: Ozonation versus Fenton process

Shale gas extraction process generates a large amount of shale gas flowback wastewater (SGFW) containing refractory organic compounds, which can pose serious environmental threats if not properly treated. However, the extremely complex compositions of organics in SGFW are still unknown and their transformation pathways in O3- and •OH-dominated systems are not well recognized, which restrain the selection of treatment technology and optimization of operational parameters. The removal characteristics and reaction mechanism of dissolved organic matter (DOM) in SGFW treated by ozonation and Fenton processes were comparatively investigated using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The results showed that both processes could degrade low-oxygen highly unsaturated and phenolic organics, polyphenolics and polycyclic aromatics, and transform them into aliphatic organics and high-oxygen highly unsaturated and phenolic organics. With increasing action of reactive oxygen species (O3 for ozonation and •OH for Fenton process), the degradation products (mainly aliphatic organics) increased during ozonation. However, in Fenton process, a wider range of DOM was removed without aliphatic organics accumulation. The degradation mechanisms of DOM during ozonation and Fenton processes included oxygen addition reactions (+3O, +H2O2, and +2O) as dominant pathways. However, ozonation showed more violent oxygenation, hydroxylation, and carboxylation, while Fenton process presented more violent chain-breaking reactions. These results revealed the selective oxidation of ozone and nonselective oxidation of •OH during SGFW treatment, and provided theoretical support for selecting SGFW treatment approaches.

Carbonyl Migration in Uronates Affords a Potential Prebiotic Pathway for Pentose Production.

Carbohydrate biosynthesis is fundamental to modern terrestrial biochemistry, but how this collection of metabolic pathways originated remains an open question. Prebiotic sugar synthesis has focused primarily on the formose reaction and Kiliani-Fischer homologation; however, how they can transition to extant biochemical pathways has not been studied. Herein, a nonenzymatic pathway for pentose production with similar chemical transformations as those of the pentose phosphate pathway is demonstrated. Starting from a C6 aldonate, namely, gluconate, nonselective chemical oxidation yields a mixture of 2-oxo-, 4-oxo-, 5-oxo-, and 6-oxo-uronate regioisomers. Regardless at which carbinol the oxidation takes place, carbonyl migration enables β-decarboxylation to yield pentoses. In comparison, the pentose phosphate pathway selectively oxidizes 6-phosphogluconate to afford the 3-oxo-uronate derivative, which undergoes facile subsequent β-decarboxylation and carbonyl migration to afford ribose 5-phosphate. The similarities between these two pathways and the potential implications for prebiotic chemistry and protometabolism are discussed.