Kinetic Reaction Rate Research Articles

Green‐Synthesized SnO2 Derived From Kombucha Tea and Assessment of Its Photocatalytic Activity for the Degradation of Procion Red MX‐5B

AbstractThis study introduces a green synthesis approach for producing tin dioxide (SnO2) nanoparticles (NPs) using Kombucha tea and evaluates their photocatalytic effectiveness in degrading the Procion Red MX‐5B (PR) dye. Characterization techniques, including UV–vis, FTIR, XRD, and TEM, confirmed the successful synthesis of SnO2 NPs with appropriate optical and structural properties. For instance; the absorption peak at 526 cm−1 in FT‐IR diagram is attributed to Sn–O which indicates the successful synthesis of SnO2. Photocatalytic tests under optimized conditions showed a notable degradation efficiency of PR dye, with the highest observed degradation efficiency reaching 97.60% at a catalyst loading of 30 mg, pH 6, in 90 min. A kinetic study was performed and the PR degradation followed first‐order reaction kinetics. For this process, the reaction kinetic rate constants were found to be 0.0589, 0.078, 0.1367, and 0.1389 min−1 for 25, 35, 45, and 55 °C, respectively. Moreover, the activation energy for the degradation process was calculated to be 25.75 kJ/mol, indicating a chemisorption mechanism. The reusability of SnO2 NPs was tested and after five subsequent usages, it still showed high degradation efficiency (95.7%). These results demonstrate the potential of Kombucha‐derived SnO2 nanoparticles as an efficient, low‐cost, reusable, and environmentally friendly photocatalyst for wastewater treatment applications.

Peroxymonosulfate Activation by Rice-Husk-Derived Biochar (RBC) for the Degradation of Sulfamethoxazole: The Key Role of Hydroxyl Groups.

In this work, rice-husk-derived biochar (RBC) was synthesized by using simple one-step pyrolysis strategies and served as catalysts to activate peroxymonosulfate (PMS) for degrading sulfamethoxazole (SMX). When the annealing temperature (T) = 800 °C, RBC800 exhibits the typical hardwood structure with several micropores and mesoporous. Furthermore, RBC800 obtains more defect sites than RBC600, RBC700, and RBC900. In the RBC800/PMS system, the removal rate of the SMX reached 92.0% under optimal conditions. The kinetic reaction rate constant (kobs) of the RBC800/PMS system was 0.009 min-1, which was about 1.50, 1.28, and 4.50 times that of the RBC600/PMS (kobs = 0.006 min-1), RBC700/PMS (kobs = 0.007 min-1), and RBC900/PMS (kobs = 0.002 min-1) systems, respectively. In the RBC800/PMS system, sulfate radical (SO4•-) is the main active species. Compared with other active sites, the hydroxyl group (C-OH) on the surface of RBC800 interacts more strongly with PMS, which is more likely to promote the stretching of the O-O bond of the PMS, thus breaking into the activated state and significantly reducing the activation energy required for reaction. The degradation intermediates of SMX were speculated, and the toxicity analysis was conducted. Generally, this work reveals in depth the interaction between reactive sites of biochar-based catalysts and PMS at the molecular level.

Hydrogen bonding network in the electrical double layer mediates fast proton skipping to Get Rid of Fenton reaction pH dependence enables highly efficient alkaline water purification

A fundamental scientific quandary in environmental has always been the pH dependence in Fenton reaction, that is, the reaction kinetics decreases by approximately 1–3 orders of magnitude upon transitioning from an acidic to an alkaline state. Here, we discovered that protons significantly contribute to the Fenton reaction through an examination of the reaction's interfacial behavior characteristics. Proton transfer mediated by hydrogen bond network connectivity in the electric double layer is responsible for the pH dependence of Fenton reaction kinetics. On this basis, the surface potential of Fenton reaction catalyst was modified to optimize the distribution of H2O in the electrical double layer, enhancing the connectivity of the interfacial hydrogen bond network and providing a fast channel for rapid proton transfer. The consecutive hydrogen bond network mediates rapid proton hopping, increasing the proton concentration in the Helmholtz layer, and consequently promoting the proton conductivity from 5.38×10−7 S·cm−2 to 4.35×10−6 S·cm−2 in alkaline conditions for Fenton reaction. Meanwhile, the kinetics reaction rate was improved 20 times, and the pH dependence was reduced from 70.9 % to 12.6 %. This discovery clarifies the key role of the interfacial hydrogen bond network and proton transfer in Fenton reaction kinetics pH dependence. It provides new theories and methods for achieving alkaline high Fenton reaction kinetics.

Effects of nickel substitution on structural, magnetic and optical properties of Sillenite bismuth ferrite nanoparticles

The Ni-doped Bi25FeO40 nanoparticles [Bi25 NixFe(1-x)O40, x = 0.1, 0.3, and 0.5] were synthesized by the hydrothermal method at a temperature of 180 °C. The effects of the Ni substitute on the structural, optical, magnetic, and photocatalytic performance have been investigated. The successful synthesis of the materials was confirmed by Rietveld's refined powder X-ray diffraction and Fourier transform infrared spectroscopy. Scanning electron microscopy together with energy dispersive X-ray spectroscopy (EDS) revealed the morphology of the synthesized nanomaterials as well as its chemical composition. The studied materials exhibited anomalous magnetic properties as evident from the vibrating sample magnetometry (VSM) analysis. These features display a weak ferromagnetic nature and demonstrate increased magnetization when doping elements are incorporated. Furthermore, Optical analysis revealed that bandgaps of Bi25NixFe(1-x)O40 were found to be increased from 2.06 eV to 2.31 eV with increasing Ni content. Additionally, the expansion of sillenite bismuth nickel ferrite's optical bandgap was further confirmed by the photocatalytic degradation of methylene blue as a model dye under the low-power white LED illumination. Lower bandgap undoped nanoparticles showed the highest photocatalytic efficiency, with a degradation rate of ∼43.11 % compared to higher bandgap doped nanoparticles, without adjustment of any reaction conditions such as pH or catalyst amount. The kinetic reaction rate of undoped Bi25FeO40 was roughly twice as fast as that of the material doped with 50 % Ni.

Homogeneous reactive distillation: The influence of pressure drop on separation and reaction kinetics

This study investigates the Total Annual Cost (TAC) optimization of a reactive distillation (RD) process for methyl acetate (MA) production as a function of tray pressure drop, focusing on the trade-off between chemical reaction kinetics and separation efficiency. The analysis examines how variations in column diameter and weir height influence the TAC across different liquid hold-ups with and without incorporating a tray pressure drop in the simulations. Results indicate that for larger liquid hold-ups, the decrease in separation efficiency predominates over kinetic advantages, leading to higher energy costs when pressure drop is considered. Despite the loss in separation efficiency with a high weir height, a pressure drop-incorporated column design featuring a high weir height and small diameter is shown to achieve lower TAC due to the comparatively lower installed costs. A reduction of tray liquid hold-up of more than 50 % is found for the optimal column design in the considered case study when the tray pressure drop is considered. A sensitivity analysis towards a hypothetical infinite fast reaction is conducted to illustrate how the energy costs are affected by the kinetic rate of the chemical reaction.

Phosphorus heteroatom doped BiOCl as efficient catalyst for photo-piezocatalytic degradation of organic pollutant and unveiling the mechanism: Experiment and DFT calculation

A novel phosphorus heteroatom doped bismuth oxychloride (P-BiOCl) catalyst was synthesized and the photo-piezocatalytic degradation of rhodamine B dye performances were explored under the ultrasound vibration and light illumination. The P-BiOCl exhibited excellent photo-piezocatalytic degradation activity, such as an ultra-high reaction kinetic rate constant of 0.3961 min−1, efficient degradation efficiency (94.7 % within 8 min) and excellent stability compared to solely piezocatalysis and photocatalysis. More impressively, these outstanding performances of P-BiOCl exceeded pure BiOCl and most other catalytic materials systems. The relevant experimental and density functional theory (DFT) calculation results were exhibited to clarify enhanced photo-piezocatalytic mechanism. The introduction of P heteroatom could reduce the bandgap of BiOCl, modulate electronic structure and charge redistribution, provide novel electron channel to promote electron transfer and restrain charge carriers recombination. Additionally, P-doped could also enhance the adsorption of oxygen and water molecules, promote intrinsic catalytic activity, leading to the increased production of active free radicals ·O2– and ·OH, thus significantly boosting the efficiency of organic pollutant degradation. This work provides a comprehensive understanding of heteroatom doping enhancing photo-piezocatalytic activity and presents a potential new strategy for designing highly efficient catalysts for wastewater treatment.

Mass Transfer Resistance and Reaction Rate Kinetics for Carbohydrate Digestion with Cell Wall Degradation by Cellulase.

This paper introduces an enzymatic approach to estimate internal mass-transfer resistances during food digestion studies. Cellulase has been used to degrade starch cell walls (where cellulose is a significant component) and reduce the internal mass-transfer resistance, so that the starch granules are released and hydrolysed by amylase, increasing the starch hydrolysis rates, as a technique for measuring the internal mass-transfer resistance of cell walls. The estimated internal mass-transfer resistances for granular starch hydrolysis in a beaker and stirrer system for simulating the food digestion range from 2.2 × 107 m-1 s at a stirrer speed of 100 rpm to 6.6 × 107 m-1 s at 200 rpm. The reaction rate constants for cellulase-treated starch are about three to eight times as great as those for starch powder. The beaker and stirrer system provides an in vitro model to quantitatively understand external mass-transfer resistance and compare mass-transfer and reaction rate kinetics in starch hydrolysis during food digestion. Particle size analysis indicates that starch cell wall degradation reduces starch granule adhesion (compared with soaked starch samples), though the primary particle sizes are similar, and increases the interfacial surface area, reducing internal mass-transfer resistance and overall mass-transfer resistance. Dimensional analysis (such as the Damköhler numbers, Da, 0.3-0.5) from this in vitro system shows that mass-transfer rates are greater than reaction rates. At the same time, SEM (scanning electron microscopy) images of starch particles indicate significant morphology changes due to the cell wall degradation.

CTAB-crafted ZnO nanostructures for environmental remediation and pathogen control

This study addresses the critical need for efficient and sustainable methods to tackle organic pollutants and microbial contamination in water. The present work aim was to investigate the potential of multi-structured zinc oxide nanoparticles (ZnO NPs) for the combined photocatalytic degradation of organic pollutants and antimicrobial activity. A unique fusion of precipitation-cum-hydrothermal approaches was precisely employed to synthesize the ZnO NPs, resulting in remarkable outcomes. The synthesized CTAB/ZnO NPs demonstrated exceptional properties: they were multi-structured and crystalline with a size of 40 nm and possessed a narrow band gap energy of 2.82 eV, enhancing light absorption for photocatalysis. These nanoparticles achieved an impressive degradation efficiency of 91.75% for Reactive Blue-81 dye within 105 min under UV irradiation. Furthermore, their photocatalytic performance metrics were outstanding, including a quantum yield of 1.73 × 10–4 Φ, a kinetic reaction rate of 3.89 × 102 µmol g–1 h–1, a space–time yield of 8.64 × 10–6 molecules photon–1 mg–1, and a figure-of-merit of 1.03 × 10–9 mol L J–1 g–1 h–1. Notably, the energy consumption was low at 1.73 × 10–4 J mol–1, compared to other systems. Additionally, the ZnO NPs exhibited effective antimicrobial activity against S. aureus and P. aeruginosa. This research underscores the potential of tailored ZnO NPs as a versatile solution for addressing both organic pollution and microbial contamination in water treatment processes. The low energy consumption further enhances its attractiveness as a sustainable solution.

CFD-DEM study on the raceway transport phenomena and thermo-chemical behaviors in a three-dimensional blast furnace: Effects of process parameters

An in-depth exploration of the kinetic behaviors of the raceway can provide practical insights for optimizing blast furnace (BF) operations. In this study, the transport phenomena and thermo-chemical behaviors in the raceway of a three-dimensional BF were simulated from particulate scale by using the discrete element method-computational fluid dynamics (DEM-CFD) approach. The effects of process parameters (blast velocity, oxygen concentration, blast temperature, coke size and distribution, tuyere insertion depth, and tuyere inclination) on coke combustion characteristics (mass fraction distributions of gas species and reaction kinetics rate) and thermo-chemical behaviors (particle volume fraction, raceway size, mass loss, and coke temperature) were investigated. Meanwhile, microstructures of coke bed were analyzed, and correlations were established for raceway size prediction. The results indicate that the mass fraction distributions of O2 and CO are similar, both showing balloon-like shapes. The distributions of both the CO2 mass fraction and the kinetic rates of reactions exhibit annular shapes. The raceway size increases or even overlaps with increasing blast velocity/oxygen concentration/PSD standard deviation of coke and decreasing blast temperature/coke size. Too large or too small tuyere insertion depth or tuyere inclination is not conducive to the formation of the raceway. Besides, the mass loss, temperature, and microstructures also vary with the process parameters. RSM model can well predict the raceway depth, width, and height. This study extends the particle-scale model by considering transport phenomena towards the global perspective of a real BF, and the obtained new findings on the complex reacting behaviors in the raceway will provide better insights into the optimization of the BF process.

Effect of Metal Work Function on Electron Transfer Kinetics in Electrochemical Reactions

The longstanding problem of explaining the observed dependence of the kinetic rates of electrochemical reactions on the work function of the electrode material (metal) is revisited, based on a recent paper.1 It was proposed that this dependence could be explained in terms of the effect of the work function of the metal on the free energies of activation of the forward and backward electron transfer reactions. In this presentation, we will explore details of the proposed mechanism.In essence, the mechanism is based on the effect of work function on the Galvani potential of the metal at any given applied potential. Even though the total electron energy (Fermi level) of an electron in the electrode must be the same, regardless of the metal, when it is at equilibrium with a given electrolyte, the manner in which that energy is partitioned between the effect of work function and the effect of potential is significantly different for different electrode materials. A higher work function leads to more stabilization of an electron in the metal (lower free energy) and, since the total free energy must remain the same, this lower free energy due to work function must be compensated by a more negative Galvani potential.The classical analysis of the effect of a more negative potential is based on the theory that a change in potential has a greater effect on the initial (reactant) free energy than it does on the free energy of the transition state. Consequently, the activation energy of the forward (cathodic) reaction is decreased by some fraction α of the corresponding increase in electron energy in the metal. This type of analysis is generally used to quantify the effect of changes in applied voltage and derive current-voltage relationships. In this paper we extend the analysis to take account of changes in the (Galvani) potential ϕm of the metal due to changes in work function Φm.It is reasonable to assume that a change in ϕm will have a similar effect whether it occurs due to a change in applied voltage or due to a change in the work function of the metal. This implies that an increase in work function with a corresponding negative shift in Galvani potential can lead to a lowering of activation energy and so to faster kinetics. However, we must also consider a possible change in activation energy arising from the decreased electron energy (increased stabilization) due to higher work function. If this caused a change in activation energy it would be expected to be in the opposite direction to the change due to Galvani potential, since it would be expected to lower the initial free energy by a greater amount than that of the transition state.The presentation will consider in detail the interplay of these effects and the consequent implications for modelling electrode kinetics. K. S. R. Dadallagei, D. L. Parr IV, J. R. Coduto, A. Lazicki, S. DeBie, C. D. Haas, and J. Leddy, J. Electrochem. Soc. 170, 086508 (2023)

Exploiting the efficiency of narrow band gap S-doped g-C3N4/Expanded Perlite/Red Ocher nanocomposite for high-level eliminating halogenated dye in Cool‐White‐SMD/H2O2 system

Hitherto, constructing prominent visible-light-driven g-C3N4/soil composites still suffers from several intricacies, including low specific surface area, inadequate charge separation, and a high band gap energy (Eg >2.7 eV). To address these drawbacks, sulfur atoms were introduced into g-C3N4 (S-doped g-C3N4 or SCN); thereby, Red Ocher (RO) and Expanded Perlite (EP) were grafted to SCN, which the engineered SCN/10EP/20RO nanocomposite divulged a higher specific surface area, further light-harvesting capability, narrower Eg, prolonged charge recombination process, lower the charge transfer resistance, and higher photocurrent density than bulk g-C3N4 (CN). Additionally, the formed S-scheme charge migration mechanism and the hole-trapping role of the hydroxyl functional groups synergistically engendered robust visible-light-driven catalytic performances under visible-light exposure. By enabling the heterogeneous photo-Fenton-like process, the Methylene Blue removal efficiency (MBRE) and the Total Organic Carbon (TOC) decontamination promptly elevated to 99.6% and 87.7% within 90 min under Cool-White-SMD/H2O2 condition, respectively. Manifestly, the kinetic reaction rate of the photo-Fenton-like process was 7.5 times higher than the primary photocatalysis, showcasing HO•had a determining role towards decent decomposing MB. After overviewing, our detailed findings straightforwardly corroborated that SCN/10EP/20RO nanocomposite would be an efficient, long-lasting, and green photocatalyst for eradicating halogenated organic pollution.

Reactive adsorption and catalytic oxidation of gaseous hydrogen sulfide using a prototype air purifier built with bismuth-doped titanium dioxide

A prototype air purifier (AP) module has been constructed using bismuth-doped titanium dioxide (Bix-P25: x(%) as Bi/Ti molar ratios of 1.1, 2.1, 3.3, 5.3, and 8.7). The reactive adsorption property of Bix-P25 materials is evaluated against H2S gas at a recirculation rate of 160 L min−1 in a 17 L closed chamber. The AP (Bi5.3-P25) exhibits superior performance against 10 ppm H2S in dry air under dark conditions (i.e., without light irradiation), with a removal efficiency (XH2S)= 99% in 5 mins, reaction kinetic rate (r (at X = 10%))= 7.3 mmol h−1g−1, and partition coefficient= 0.18 mol kg−1 Pa−1. As such, its superiority is evident over the reference AP (P25) filter with XH2S < 10%. The clean air delivery rate (CADR) of AP (Bi5.3-P25) increases noticeably from 9.9 to 17.8 L min−1 with increasing relative humidity (RH) from 0 to 80%, respectively. In contrast, the CADR decreases from 9.9 to 5.8 L min−1 as the H2S increases from 10 to 20 ppm. According to density functional theory (DFT), the presence of H2O vapor enhances the hydroxylation of Bix-P25 surface to promote H2S mineralization through the formation of TiS3 (i.e., thermodynamic reaction of S atom with the catalytic surface). Complete removal of H2S on the Bi5.3-P25 surface is also confirmed consistently through gas chromatography-mass spectrometry (GC-MS), in-situ diffuse reflection infrared spectroscopy (in-situ DRIFTS), and elemental analysis (EA). This work represents the first utilization of Bix-P25 materials fabricated on an AP platform toward the desulfurization of H2S at room temperature (RT). The practical utility of Bix-P25 is overall validated by its eminent role in reactive adsorption and catalytic oxidation (RACO) of H2S from the air.

Rational design and construction of direct Z-scheme ternary heterojunction photocatalyst AgBr/CoWO4/Ag for efficient environmental remediation

The indiscriminate discharge of micropollutants (e.g., dyes, antibiotics, industrial additives, etc.) represents a significant risk to human health, and the removal of these substances from water bodies has become a prominent area of research within the field of environmental remediation. A simple hydrothermal-precipitation-photoreduction method was employed to synthesize novel Z-scheme heterojunction photocatalysts of AgBr/CoWO4/Ag. The catalysts demonstrated remarkable degradation capabilities with regard to a range of micropollutants present in wastewater. Of the catalysts tested, 5AgBr/CoWO4/Ag exhibited the highest degradation rates, reaching 98.58% for Rhodamine B, 86.82% for tetracycline hydrochloride, and 95.60% for 2-mercaptobenzothiazole within 60 min. In particular, the reaction kinetic rate of 5AgBr/CoWO4/Ag towards Rhodamine B degradation (k2 = 0.26278 L mg−1·min−1) is 9 times that of AgBr (k2 = 0.02953 L mg−1·min−1) and 113 times that of CoWO4 (k2 = 0.00233 L mg−1·min−1), which serves to highlight the exceptional photocatalytic activity of the material. The experimental data and subsequent analysis indicated that the enhanced photocatalytic performance can be attributed to two factors: firstly, the electron mediation by Ag nanoparticles leading to improved charge separation efficiency, and secondly, the formation of Z-scheme heterojunctions between AgBr and CoWO4. The cyclic tests provided confirmation of the excellent stability and recyclability of the AgBr/CoWO4/Ag photocatalysts. It is anticipated that this study will facilitate the development of novel methods for the degradation of refractory micropollutants and provide insights into environmental remediation, thereby contributing to the sustainable development of society.

Room temperature thermocatalytic removal of formaldehyde in air using a copper manganite spinel-supported palladium catalyst with ultralow noble metal content

The room temperature (RT)-catalytic oxidation of gaseous formaldehyde (FA) in the dark is regarded as one of the most viable technical options for its removal from indoor air. Herein, the copper manganite spinel (CuMn2O4) supported palladium (Pd) catalysts are firstly synthesized for the thermocatalytic oxidation of FA in air. In particular, 0.05% Pd-CuMn2O4-R (‘R’ denotes high-temperature reduction pre-treatment using hydrogen) achieves 100% conversion (XFA) of 50 ppm FA at RT (gas hourly space velocity of 4342 h−1). The performance of 0.05% Pd-CuMn2O4-R against FA, if assessed in terms of the reaction kinetic rate (r at 10% XFA), is estimated as 3.01E−02 mmol g−1h−1. The lowering of XFA with the increases in FA concentration, flow rate, and relative humidity indicates the detrimental effects of such variables on the catalytic activity. FA oxidation kinetics predominantly follows the Mars van Krevelen mechanism. In-situ diffuse reflectance infrared Fourier transform spectroscopy shows that FA oxidation proceeds through multiple reaction intermediates (e.g., dioxymethylene and formate). The density functional theory simulations indicate that the catalytic oxidation efficacy of FA over CuMn2O4 increases by the synergy between Pd loading and surface reduction. The present study represents the first report on the synthesis of CuMn2O4-supported Pd catalysts and their application for the RT oxidative removal of FA in air under dark conditions. The findings of the present work offer valuable insights into the construction of efficient and cost-effective catalysts with ultra-low noble metal content for the RT oxidative removal of VOCs in indoor environment.

The important role of diatomite on multifunctional modified separator of Li-S battery

The commercial applications of lithium-sulfur (Li-S) batteries are limited by decreased cycling performance caused by the shuttle effect of polysulfides, slower kinetic reaction rates, and lithium anode dendrites. This study demonstrates the important role of diatomite (DT) in regulating cycle performance of modified separator for Li-S batteries. A multifunctional separator (Co/NC/DT) with DT as a carrier assembled high loading cobalt nanocluster is prepared. The N-doped carbon is immobilized via Si-N bond between DT and N-doped carbon. The depth profiles of XPS indicate that the ratio of pyrrolic N to pyridinic N of Co/NC/DT reaches 5.31 at the etching of 100 nm versus 0.83 for Co/NC at surface, which suggesting that mainly N species is pyrrolic N after the addition of DT. Theoretical calculations confirm that cobalt nanoclusters grown on pyrrolic N-doped carbon have a lower adsorption energy for active materials compared to that on pyridinic N-doped carbon and can reduce the energy barrier, especially only 0.09 eV for reduction from Li2S6 to Li2S4. In-situ X-ray diffraction analysis confirms Co/NC/DT can effectively promote formation of Li2S. Lithium anode in-situ optical microscopy observation shows the modified separator could reduce lithium dendrites effectively. Li-S battery assembled with the modified separator can reach an initial capacity of 1331.3 mAh g−1 at 0.2 C and cycle 1500 cycles at 1.0 C with a decay of only 0.039% per cycle. Through regulation of DT, Co/NC/DT accelerates the conversion from long-chain sulfur to short-chain sulfur and Li+ transfer rate, resulting in improving cycling performance.

Surface crystallized supramolecular to achieve highly dispersed ultrafine nano-palladium in-situ deposition to promote thermal/electrocatalytic reduction

To promote the greening and economization of industrial production, the development of advanced catalyst manufacturing technology with high activity and low cost is an indispensable part. In this study, nitrogen-doped hollow carbon spheres (NHCSs) were used as anchors to construct a supramolecular coating formed by the self-assembly of boron clusters and β-cyclodextrin by surface crystallization strategy, with the help of the weak reducing agent characteristics of boron clusters, highly dispersed ultra-small nano-palladium particles were in-situ embedded on the surface of NHCSs. The deoxygenation hydrogenation of nitroaromatics and the reduction of nitrate to ammonia were used as the representatives of thermal catalytic reduction and electrocatalytic reduction respectively. The excellent properties of the constructed Pd/NHCSs were proved by the probe reaction. In the catalytic hydrogenation of nitroaromatics to aminoaromatics, the reaction kinetic rate and activation energy are at the leading level. At the same time, the constructed Pd/NHCSs can also electrocatalytically reduce nitrate to high value-added ammonia with high activity and selectivity, and the behavior of Pd/NHCSs high selectivity driving nitrate conversion was revealed by density functional theory and in situ attenuated total reflection Fourier transform infrared (ATRFTIR) technique. These results all reflect the feasibility and superiority of in-situ anchoring ultra-small nano-metals as catalysts by surface crystallization to build a supramolecular cladding with reducing properties, which is an effective way to construct high-activity and low-cost advanced catalysts.

Isolated auto-citrullinated regions of PADI4 associate to the intact protein without altering their disordered conformation

PADI4 is one of the human isoforms of a group of enzymes intervening in the conversion of arginine to citrulline. It is involved in the development of several types of tumors, as well as other immunological illnesses, such as psoriasis, multiple sclerosis, or rheumatoid arthritis. PADI4 auto-citrullinates in several regions of its sequence, namely in correspondence of residues Arg205, Arg212, Arg218, and Arg383. We wanted to study whether the citrullinated moiety affects the conformation of nearby regions and its binding to intact PADI4. We designed two series of synthetic peptides comprising either the wild-type or the relative citrullinated versions of such regions – i.e., a first series of peptides comprising the first three arginines, and a second series comprising Arg383. We studied their conformational properties in isolation by using fluorescence, far-ultraviolet (UV) circular dichroism (CD), and 2D1H NMR. Furthermore, we characterized the binding of the wild-type and citrullinated peptides in the two series to the intact PADI4, by using isothermal titration calorimetry (ITC), fluorescence, and biolayer interferometry (BLI), as well as by molecular docking simulations. We observed that citrullination did not alter the local conformational propensities of the isolated peptides. Nevertheless, for all the peptides in the two series, citrullination slowed down the kinetic koff rates of the binding reaction to PADI4, probably due to differences in electrostatic effects compared to the presence of arginine. The affinities of PADI4 for unmodified peptides were slightly larger than those of the corresponding citrullinated ones in the two series, but they were all within the same range, indicating that there were no relevant variations in the thermodynamics of binding due to sequence effects. These results highlight details of the self-citrullination of PADI4 and, more generally, of possible auto-catalytic mechanisms taking place in vivo for other citrullinating enzymes or, alternatively, in proteins undergoing citrullination passively.

Reusable MIL-100(Fe)-polyacrylonitrile-TiO2 nanofiber webs for adsorption and decomposition of toluene

Due to rapid industrialization and urbanization, addressing the pressing issue of environmental pollution, particularly indoor air quality, demands innovative solutions. Volatile organic compounds (VOCs), notably toluene, are prevalent indoor pollutants that necessitate effective adsorption and removal strategies due to their adverse health impacts. Here, we propose a novel method for crafting a multifunctional air-filter membrane capable of simultaneous toluene adsorption and photocatalytic degradation across diverse light conditions, thus facilitating the development of a reusable air filtration system. This study outlines the successful synthesis of an air filter membrane by illustrating the in-situ growth of MIL-100(Fe) particles on polyacrylonitrile (PAN) nanofibers loaded with TiO2 nanoparticles, resulting in the formation of a PTF membrane. The PTF membrane exhibits an exceptional toluene adsorption efficiency of 98 % and a high toluene capacity of 383.94 mg g−1 (4.166 mmol/g), with a corresponding partition coefficient (PC) of 38.39 L/g ± 1.41. Notably, its design enables functionality, demonstrating impressive photocatalytic degradation efficiencies of 62.3 %, 71.3 %, and 80.2 % under UV, visible, and combined UV–visible light, respectively. This high efficiency is attributed to the PTF membrane’s reduced bandgap and enhanced light-absorption capabilities. Under the combined light conditions, the PTF membrane achieved the highest space–time yield (STY) of 0.197 mol/g/h and the highest reaction kinetic rate for toluene degradation, determined to be 6.34 × 10-8, surpassing the performance observed under individual UV and visible light sources. Moreover, the regeneration cycle of the PTF membrane demonstrates minimal efficiency loss, ensuring prolonged performance. The developed PTF membranes demonstrate notable stability and resilience even under the most extreme humid conditions, suggesting their strong potential for future applications in air filtration. This innovative approach offers a straightforward and environmentally friendly method for fabricating metal–organic framework (MOF)-based photocatalytic filters tailored to indoor VOC purification systems. This study is expected to significantly advance efforts aimed at improving and managing air quality, thereby fostering a healthier and more sustainable environment.

Resource utilization of medical waste incineration fly ash to activate peroxydisulfate for tetracycline degradation: Synergy between adsorption and PDS activation

Medical waste incineration fly ash (MWI FA) is classified as a hazardous solid waste. Therefore, the development of recycling technologies to convert MWI FA into useful products is necessary and challenging. In this study, we developed a sustainable approach for preparing a catalyst through the pyrolysis of water-washed MWI FA (WW FA-x, where x corresponds to the pyrolysis temperature). Subsequently, it was applied as a potent peroxydisulfate (PDS) activator to remove tetracycline (TC) from water. The results showed that the WW FA-800 exhibited remarkable adsorption performance as well as highly efficient catalytic activation of PDS, with a 115 mg/g maximum TC adsorption capacity and 93.5% (reaction kinetic rate = 315 μmol/g/h) TC removal within 60 min. A synergistic effect was achieved by adsorption and PDS activation. TC degradation was primarily driven by non-radical (1O2 and electron transfer) processes. WW FA-800 possesses multiple active sites, including defects, π–π*, O–CO groups, Fe0, and Cu(I). Three possible pathways for TC decomposition have been proposed, with the majority of intermediates exhibiting less toxicity than TC. Furthermore, the WW FA/PDS system exhibited an excellent anti-interference ability, and universality in the degradation of various organic contaminants. Notably, energy consumption was minimal, approximately 2.80 kWh/(g·TC), and the leachability of heavy metals in the WW FA-800 was within acceptable limits. This study provides a MWI FA recycling route for the development of highly active catalysts.

Study on interdigital flow field structure and two phase flow characteristics of PEM electrolyzer

Proton exchange membrane (PEM) electrolytic hydrogen production has the advantages of high current density, high operating pressure, wide power regulation range and so on. It has good adaptability to wind and photovoltaic power with high volatility and recognized as an important way to solve the effective utilization of renewable energy. In PEM electrolyzer cell (PEMEC), anode flow field plate plays a crucial role in the process of water electrolysis to produce oxygen, which affects the of gas and liquid transfer. Among them, the channel blockage caused by bubble retention is an important factor limiting the performance of PEMEC. In this paper, an interdigital flow field plate is designed based on the plant leaf vein system. The two-phase flow behaviors within the interdigital flow field channel are studied. The results show that the interdigital flow field plate is superior to the traditional serpentine flow field in terms of electrolytic efficiency and voltage loss. The reaction kinetics rate is accelerated, the overall ohmic resistance is reduced by about 4.8 %, and the hydrogen production is increased by about 9.1 %. The above research can provide guidance for the structural improvement and performance improvement of PEMEC.