Fe3O4 Surface Research Articles

Recovery of Chlorella biomass using Fe3O4 and Fe3O4@SiO2 magnetic nanoparticles: isotherm and thermodynamic characteristics of adsorption

AbstractHarvesting microalgae by centrifugation and filtration is very costly, affecting technical and economical feasibility of downstream processing of algal biomas to bioproducts. Flocculation is a potential technique for recovery of algae biomass. Particularly, flocculation using magnetic nanoparticles offers high separation efficiency due to their high surface area and magnetic properties. In this work, the synthesized magnetic nanoparticles including Fe3O4 and Fe3O4@SiO2 were used to harvest C. sorokiniana TH01 from aqueous suspension. The effects of pH, adsorbent dosage, algal biomass concentration, temperature and reaction time on harvesting performance were investigated. It was revealed that the optimal C. sorokiniana TH01 harvesting conditions for Fe3O4 were pH of 5, adsorbent dosage of 0.5 g/L, biomass concentration of 2‐2.5 g/L, temperature 25oC and reaction time 20‐30 min. For Fe3O4@SiO2, the optimal conditions were pH of 7, adsorbent dosage of 0.6 g/L, with the same biomass concentration, temperature and reaction time as Fe3O4. Under the optimal conditions, Fe3O4 and Fe3O4@SiO2 can be regenerated up to three cycles with harvesting efficiency till remained over 55%. Adsorption of C. sorokiniana TH01 on Fe3O4 and Fe3O4@SiO2 exhibited the best fitness with Langmuir isortherm with R2 and maximal adsorption capacity estimated of 0.995 and 6.55 g/g and 0.9971 and 9.53 g/g, respectively. Thermodynamics study revealed that an adsorption of C. sorokiniana TH01 on Fe3O4 and Fe3O4@SiO2 was exothermic process. Furthermore, XRD, EDS, SEM, TGA and FT‐IR data confirmed the successful binding of microalgae cells on surfaces of Fe3O4 and Fe3O4@SiO2. The super‐magnetization intensities (> 22 emu/g) of the synthesized materials demonstrated an excellent separation capability with external magnetic devices.

Metal cation cross-linked 3D frameworks of Fe3O4 nanospheres encapsulated in graphene nanomesh with enhanced anode performance for lithium-ion batteries

Transition metal oxide (TMO) particles encapsulated in graphene shell has been reported to be an ideal lithium-ion batteries (LIBs) anode due to its well TMO particles volumetric adaptability upon cycling. In this paper, to further enhance the structural stability as well as electrochemical performance of Fe3O4-based electrodes for LIBs, 3D composite structures of Fe3O4 nanospheres (NSs) encapsulated in interconnected holey graphene nanosheets (Ca2+/p-rGO@Fe3O4) were fabricated by facile hydrothermal process using Ca2+ as crosslinker and hydrogen peroxide (H2O2) as etching agent. The composite was characterized by X-ray diffractometer (XRD), Scanning electron microscope (SEM), Transmission electron microscope (TEM), Fourier Transform Infrared Spectrometer (FTIR), and other test methods. The morphological and structural tests show that Fe3O4 NSs are homogenously embedded in the 3D framework of interconnected graphene nanomesh aerogels. Based on its unique structure, the Ca2+/p-rGO@Fe3O4 composite electrode delivers an initial discharge and charge capacities of 1288 and 783 mA h g−1, respectively, remarkable rate capability at current densities from 0.1 to 2 A g−1 and excellent cyclic stability with respect to that of its counterparts Ca2+/rGO@Fe3O4 electrode, p-rGO@Fe3O4 electrode and rGO@Fe3O4 electrode, which are prepared using a similar synthetic procedure but without the addition of H2O2 or CaCl2 or neither. It is proved that the synergistic effects of Ca2+-induced crosslinking reaction at the edge of GO nanosheets and in-plane pores on graphene coated on the surface of Fe3O4 can enhance the whole electrochemical performance of anode for LIBs.

A microfluidic device for enhanced capture and high activity release of heterogeneous CTCs from whole blood

Circulating tumor cells (CTCs) are tumor cells that spontaneously detach from the primary focus, and early detection and characterization of CTCs is vital for cancer diagnosis and appropriate treatment. Current methods commonly use EpCAM to capture CTCs, but this results in a loss of information on other CTC subsets (EpCAM-negative cells) due to the heterogeneity of CTCs. Here, we report a novel microfluidic device that integrates the capture and release of heterogeneous CTCs directly from whole blood. A spiral chip was designed for the separation of differently sized cells, and larger CTCs were effectively separated from smaller blood cells with a 98% recovery rate. CD146-containing magnetic beads were used to complement the EpCAM-based CTC capture methods, and the capture efficiency of Fe3O4@Gelatin@CD146/EpCAM increased by 20% over Fe3O4@Gelatin@EpCAM. Finally, MMP-9 was employed to release CTCs with high efficiency and less damage by degrading gelatins on the surface of Fe3O4. The established method was successfully applied to CTC capture and release in a simulated patient's whole blood. The developed method achieved enhanced capture and high activity release of heterogeneous CTCs with less interference by blood cells, which contributes to the early detection and clinical downstream analysis of CTCs.

Immobilization-free dual-aptamer-based photoelectrochemical platform for ultrasensitive exosome assay

Exosomes, involved in cancer-specific biological processes, are promising noninvasive biomarkers for early diagnosis of cancer. Herein, an immobilization-free dual-aptamer-based photoelectrochemical (PEC) biosensor was proposed for the enrichment and quantification of cancer exosome based on photoactive bismuch oxyiodide/gold/cadmium sulfide (BiOI/Au/CdS) composites, nucleic acid-based recognition and signal amplification. In this biosensor, the recognition of exosome by two aptamers would trigger the deoxyribonucleotidyl transferase (TdT) enzyme-aided polymerization, leading to the enrichment of alkaline phosphatase (ALP) on Fe3O4 surface. After magnetic separation, ALP could catalyze the generation of ascorbic acid (AA) as electron donor and initiate the following redox cycle reaction for further signal amplification. Furthermore, all the above processes were performed in solution, the recognition and signal amplification efficiency would be superior than the heterogeneous strategy owing to the avoidance of steric hindrance effect. As a result, the proposed PEC biosensor was capable of enriching and detecting of cancer exosomes with high sensitivity and selectivity. The linear range of the biosensor was from 1.0 × 102 particles·μL−1 to 1.0 × 106 particles·μL−1 and the detection limit was estimated to be 21 particles·μL−1. Therefore, the proposed PEC biosensor holds great promise in quantifying tumor exosome for nondestructive early clinical cancer diagnosis and various other bioassay applications.

Facile fabrication of naphthalene-functionalized magnetic nanoparticles for efficient extraction of polycyclic aromatic hydrocarbons from environmental water and fish samples

In this study, naphthalene-modified magnetic nanoparticles (Fe3O4@Nap) were simply prepared based on specific chelation interaction between phosphate groups and metal ions on Fe3O4 surface. The resultant Fe3O4@Nap were characterized by FTIR, BET, SEM, TEM, NAM, TGA, and VSM techniques. With Fe3O4@Nap as adsorbent, the polycyclic aromatic hydrocarbons (PAHs) were efficiently extracted by magnetic solid-phase extraction (MSPE) from environmental water and fish samples through the π-π interaction between modified naphthalene groups and PAHs, followed by their determination by GC–MS/MS. The key parameters influencing the extraction efficiency were investigated. Under the optimized conditions, the Fe3O4@Nap-based MSPE/GC-MS/MS method proposed in this paper was evaluated and applied for analyzing PAHs in environmental water and fish samples. And the proposed MSPE/GC-MS/MS method exhibited good linearities for water samples (in the range of 0.1–10 ng/mL, R2 >0.9945) and for fish samples (in the range of 1–100 ng/g, R2 > 0.9905). The limits of detection (LODs) for water and fish samples were 0.004–0.031 ng/mL and 0.07–0.28 ng/g, respectively. Additionally, this method exhibited desirable accuracy and precision. The PAH recovery values from water and fish samples ranged from 81.5% to 109.6% with inter- and intra-day relative standard deviations (RSDs) of less than 12.8%. The MSPE/GC-MS/MS method was successfully applied to the analysis of real environmental water and fish samples. Overall, the newly synthesized Fe3O4@Nap exhibited high sensitivity, specificity, reusability, repeatability, and it could efficiently extract PAHs from environmental water and fish samples by MSPE.

The Adsorption Mechanism of Hydrogen on FeO Crystal Surfaces: A Density Functional Theory Study.

The hydrogen-based direct reduction of iron ores is a disruptive routine used to mitigate the large amount of CO2 emissions produced by the steel industry. The reduction of iron oxides by H2 involves a variety of physicochemical phenomena from macroscopic to atomistic scales. Particularly at the atomistic scale, the underlying mechanisms of the interaction of hydrogen and iron oxides is not yet fully understood. In this study, density functional theory (DFT) was employed to investigate the adsorption behavior of hydrogen atoms and H2 on different crystal FeO surfaces to gain a fundamental understanding of the associated interfacial adsorption mechanisms. It was found that H2 molecules tend to be physically adsorbed on the top site of Fe atoms, while Fe atoms on the FeO surface act as active sites to catalyze H2 dissociation. The dissociated H atoms were found to prefer to be chemically bonded with surface O atoms. These results provide a new insight into the catalytic effect of the studied FeO surfaces, by showing that both Fe (catalytic site) and O (binding site) atoms contribute to the interaction between H2 and FeO surfaces.

Fast Procedure for Removing Silver Species in Waters Using a Simple Magnetic Nanomaterial

The increase in the production and use of disinfectants containing silver atoms (in both its ionic and nanomeric forms) in their formulation, due to the global pandemic situation caused by COVID-19, has increased the presence of silver species in wastewater. Moreover, silver atoms are now considered as emerging pollutants in water. In this work, we propose a novel method for the instantaneous and simultaneous removal of ionic and nanomeric silver in water samples, using a previously unpublished methodology consisting of the in situ formation of magnetic nanoparticles in the aqueous samples to be treated. While the nanoparticle precursors react to form them, the silver atoms present in the sample are adsorbed onto them due to a strong electrostatic interaction. As the final nanoparticles are magnetic, they can be easily removed from the aqueous medium using a magnet, leaving the samples free of silver species. The innovative feature of the method is that the adsorbent is synthesized in situ, within the sample to be treated, making the approach a low-cost, easy-to-perform solution. Temperature, contact time, dose of Fe3O4, and concentration of nanomeric and ionic silver were investigated. The results showed that at 50 °C, 100% of both silver species were removed from the water samples simultaneously. The surface of Fe3O4 was characterized before and after the application of the removal process using energy-dispersive X-ray spectroscopy and Field Emission scanning electron microscopy. Adsorption kinetics and equilibrium isotherms studied reveal a Langmuir-type physicochemical process. The procedure has been applied to different water samples (river and drinking water) with excellent results, making the method a new standard for the removal of ionic and nanomeric silver. In addition, the nanoparticles formed could be recycled and reused for other analytical and decontamination purposes.

Effective removal of cesium by ammonium molybdophosphate–polyethylene glycol magnetic nanoparticles

This study synthesizes a new adsorbent composite for the removal of Cs ions from waste effluents. The adsorbent is composed of polyethylene glycol-decorated ammonium molybdophosphate magnetic Fe3O4 nanoparticles (PEG–AMP MNs) and is prepared via coprecipitation by grafting ammonium phosphomolybdate onto the surface of Fe3O4 and coprecipitation with polyethylene glycol. The physical and chemical structure of the PEG–AMP MNs was investigated using various spectroscopic and analytical techniques, revealing that Fe3O4 was tightly bound to the AMP particles and that the composites exhibited superparamagnetic behavior. The Cs+ adsorption behavior of the adsorbent was investigated in a wide range of pH values and temperatures, using multiple Cs+ contact times and initial Cs+ concentration, and with interference from additional ionic species. The adsorbent achieved 99.8% removal of Cs+ in the solution pH range of 1–12 and maintained its stability after adsorption. Interfering ions had little effect on the amount of Cs+ adsorbed. The experimental data were fitted using Langmuir, Freundlich, Redlich-Peterson and Sips isotherms pseudo-first-order and pseudo-second-order kinetic models. The results showed that the adsorption data fitted well with pseudo-second-order kinetics and the Langmuir isotherm model, with a maximum adsorption capacity of 53.89 mg g−1 and equilibrium reached within 20 min. Thermodynamic experiments showed the adsorption process to be inherently endothermic. The mechanism of Cs+ adsorption by PEG–AMP MNs is proposed to primarily be a combination of weak electrostatic attraction and ion exchange between NH4+ and Cs+. More importantly, the encapsulation of a magnetic carrier allows for the efficient separation and recovery of Cs+ after adsorption.

Dual interfaces and confinements on Fe2N@Fe3O4/VN heterojunction toward high-efficient lithium storage

Ferroferric oxide (Fe3O4) as an anode material of lithium-ion battery has been widely investigated due to its high theoretical capacity, environmental friendliness, natural abundance, and low cost. However, it suffers from severe aggregation and volume expansion during energy storage. Herein, we rationally construct an advanced Fe2N@Fe3O4/VN heterostructure via a hydrothermal and followed nitridation process, where the wrapping of conductive Fe2N on the surface of Fe3O4 effectively improves the electron conductivity and alleviates the volume expansion, and VN inhibits the agglomeration of Fe2N@Fe3O4. Benefiting from the dual conductive confinements and promoted interfacial charge transfer, the Fe2N@Fe3O4/VN heterojunction exhibits excellent rate capability and cycling stability. It possesses the highest reversible capacity of 420.8 mAh g−1 at 1 A g−1 after 600 cycles, which is three times that of Fe3O4. Furthermore, a full cell based on a Fe2N@Fe3O4/VN anode and a LiFePO4 cathode delivers considerable electrochemical performance. This work demonstrates that Fe2N@Fe3O4/VN is a potential anode material and provides a model in constructing other high-performance electrode materials.

β-Cyclodextrin-Functionalized Fe3O4-Supported Pd-Nanocatalyst for the Reduction of Nitroarenes in Water at Mild Conditions.

In this study, a novel heterogeneous catalyst (Fe3O4@β-CD@Pd) has been developed by the deposition of palladium nanoparticles on the β-cyclodextrin-functionalized surface of magnetic Fe3O4. The catalyst was prepared by a simple chemical co-precipitation method and characterized extensively by using Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma-optical emission spectrometry (ICP-OES) analyses. Herein, the applicability of the prepared material was evaluated for the catalytic reduction of environmentally toxic nitroarenes to the corresponding anilines. The catalyst Fe3O4@β-CD@Pd showed excellent efficiency for the reduction of nitroarenes in water under mild conditions. A low catalyst loading of 0.3 mol % Pd is found to be efficient for reducing nitroarenes in excellent to good (99-95%) yields along with high TON values (up to 330). Nevertheless, the catalyst was recycled and reused up to the 5th cycle of reduction of nitroarene without any loss of significant catalytic activity.

Insights into the selectivity of metallic oxides for arsenic and phosphate from EXAFS and DFT calculations

Phosphate is the biggest competitor for arsenic removal. Nanoscale metal oxides (NMOs) are commonly used to treat arsenic-contaminated water, yet their selective adsorption mechanisms for arsenic and phosphate are poorly understood. We quantified the selectivity of iron oxide (Fe2O3), zinc oxide (ZnO), and titanium dioxide (TiO2) nanosheets for arsenic in systems containing arsenic and phosphate, and determined the interaction of phosphate and arsenate/arsenite on metal oxide surfaces through batch experiments, spectroscopic techniques, and DFT calculations. We found that Fe2O3, TiO2, and ZnO nanosheets exhibit selectivity for arsenate/arsenite in the presence of phosphate, with Fe2O3 the most selective, followed by TiO2 and ZnO. The bonding mechanism on these metallic oxide surfaces dominates the selectivity. The more stable inner-sphere complexes of arsenate on the surfaces of Fe2O3 (bidentate binuclear), TiO2 (bidentate binuclear), and ZnO nanosheets (tridentate trinuclear) contribute to their preference for arsenate over phosphate. This difference in arsenate selectivity can be reflected in the difference in adsorption energy, net electron transfer number, and M − O bond length of the most stable inner sphere complexes. Overall, our study elucidated the selective adsorption mechanisms of arsenate/arsenite on Fe2O3, TiO2, and ZnO surfaces and highlighted the need to consider the competition between arsenate and phosphate during their removal from contaminated water.

A smart material: Multi-stimulus-responsive composite microspheres prepared via RAFT polymerization as recyclable pickering emulsifiers and their application in stabilizing real oil phases

The development of smart composites to sustainably separate and recover oil from oily water had attracted much attention. In this study, tri-block (P(LMA-b-NIPAM-b-AA)) polymer brushes were controllably “grown on” the Fe3O4 surface by three-step surface-initiated reversible addition fragmentation chain transfer (SI-RAFT) polymerization to prepare Fe3O4-P(LMA-b-NIPAM-b-AA) (MNPLNA) magnetic nanospheres with interfacial activity. The MNPLNA nanospheres were characterized to demonstrate the triple response of pH, temperature and magnetism. Meanwhile, the comparison experiments showed that the MNPLNA nanospheres with tri-block structure had excellent interfacial activity. Then, the O/W type of Pickering emulsion was prepared by using MNPLNA nanospheres as the particle emulsifier. The size variation pattern of Pickering emulsion was comprehensively investigated by adjusting the concentration of nanospheres, oil-water ratio, electrolyte concentration and polarity of oil phase. Pickering emulsions were controllably separated by the action of an external magnetic field, and could be reversibly switched at least 10 cycles between emulsified and broken states under the trigger of pH and temperature. In addition, MNPLNA nanospheres exhibited excellent emulsification properties for stabilizing variety of real oil phases (e.g., canola oil, kerosene, diesel and crude oil). Based on this, MNPLNA nanospheres were applied as smart multifunctional materials in simulated kerosene-containing wastewater separation. MNPLNA nanospheres could be used to recover kerosene with high recovery rate after 10 separation cycles under the stepwise action of pH, temperature and magnetic field.

Reductive Photodegradation of 4,4'-Isopropylidenebis(2,6-dibromophenol) on Fe3O4 Surface.

Advanced Oxidation Processes (AOPs) are the water treatment techniques that are commonly used forthe decomposition of the non-biodegradable organic pollutants. However, some pollutants are electron deficient and thus resistant to attack by reactive oxygen species (e.g., polyhalogenated compounds) but they may be degraded under reductive conditions. Therefore, reductive methods are alternative or supplementary methods to the well-known oxidative degradation ones. In this paper, the degradation of 4,4'-isopropylidenebis(2,6-dibromophenol) (TBBPA, tetrabromobisphenol A) using two Fe3O4 magnetic photocatalyst (F1 and F2) is presented. The morphological, structural and surface properties of catalysts were studied. Their catalytic efficiency was evaluated based on reactions under reductive and oxidative conditions. Quantum chemical calculations were used to analyse early steps of degradation mechanism. The studied photocatalytic degradation reactions undergo pseudo-first order kinetics. The photocatalytic reduction process follows the Eley-Rideal mechanism rather than the commonly used Langmuir-Hinshelwood mechanism. The study confirms that both magnetic photocatalyst are effective and assure reductive degradation of TBBPA.

Construction of Fe3O4/xSiO2/ySiO2 Nanoparticles for Pesticide Removal from Water: Improved Dispersion Stability and Adsorption Capacity.

Highly efficient and reusable adsorbents for pesticide removal from wastewater have received increasing attention. In this study, Fe3O4 was synthesized using the solvothermal method. Fe3O4/xSiO2 and Fe3O4/xSiO2/ySiO2 were obtained through layer-by-layer silica (SiO2) coating on the surface of Fe3O4. SiO2 coating improved the dispersibility of the adsorbent, which can be separated from water rapidly under the action of the external magnetic field. The adsorption capacity of the adsorbent was investigated through removing pyraclostrobin from synthetic wastewater. The adsorbent showed the highest adsorption effect at the adsorbent concentration of 1 mg mL-1, at a pH of 7, and the adsorbent time of 110 min. The fitting model of the adsorption process conformed to the second-order kinetic model and the Langmuir model. The maximum adsorption capacity of Fe3O4/xSiO2/ySiO2 nanoparticles was 94.89 mg g-1, and the removal efficiency was about 96% at adsorption equilibrium. Acetone as the eluent can effectively desorb the adsorbent, and the desorbed adsorbent had high reusability. Particularly, the removal efficiency was still greater than 86% after 9 times of reuse. These results provide a reference for designing reusable nanoparticles to effectively absorb pesticides in wastewater.

Strongly coupled Fe3O4 quantum dots-3D N-enriched carbon aerogel towards boosting peroxydisulfate activation by electron redistribution of multiple active sites

Simultaneous regulation of electronic environment of active sites and engineering architectures with efficient exposed active sites are crucial to realize efficient persulfate activation for pollutants degradation, which remains a great challenge. This study demonstrated an ingenious platform of 0D/3D nanofibrous N-enriched carbon hybrid with incorporated ultrafine metal oxide quantum dots (QDs, ≈ 3 nm) with abundant oxygen vacancies that enabled efficient PDS activation for pollutants degradation via integrating electron density regulation and morphology modulation. The favorable structure configuration and intimate coupling action between QDs and N-doped carbon matrix promoted PDS activation on the surface of Fe3O4 QDs@NC and simultaneously modified pollutant absorption property towards catalyst, synergistically resulting in excellent TC degradation efficiency. More importantly, electron-rich Fe sites derived from electron redistribution and highly-conductive N-doped carbon matrix synergistically directed PDS activation by non-radical pathway with generation of 1O2. This work provides a fresh insight into improving persulfate activation by engineering architectures and regulating local electronic density of multiple active sites.

RETRACTED: Mixed matrix membrane O2/N2 selectivity enhancement by intercalation of iron-ferrite nanoparticles under moderate external magnetic fields; DFT assisted study

Magnetic field-induced mixed matrix membranes (MMMs) were used for separation of O2 and N2 gas according to their different magnetic properties. The double-layered MMMs were made of polyethersulfone (PES) and Pebax-1657 and super-paramagnetic Fe3O4 nanoparticles (NPs) by simultaneous co-casting method. The PES served as the supporting layer while the Pebax layer (intercalated by the Fe3O4 NPs) acted as the selective parts of the MMMs. An external magnetic field (0–0.5 T) was applied to avoid the demagnetizing effects between the polymeric (because of monomer chains mobility) and the magnetic NPs components of the MMMs. In the presence of an external magnetic field (H = 0.4 T), the ideal selectivity of the fabricated MMMs (∼25 µm in thickness) was tested for O2/N2 separation, considering different concentrations of the NPs. The results indicated a substantial improvement up to 3.59 at room temperature for the sample containing 24 wt% Fe3O4 NPs under the gas feeding of 10 bar, whereas the selectivity for non-magnetic MMMs was ∼ 1.87. The results showed that the external magnetic field could facilitate the formation of magnetic channels by loosen hydrogen bonds of the carbonyl groups in the polymer and also alignment of the super-paramagnetic NPs.As a complimentary study, for better understanding of the rule of the magnetic NPs, Density Functional Theory (DFT) simulation was employed to investigate the general behavior of the O2 and N2 molecules near the Fe3O4 (magnetite) surface. Based on the results, the magnetic interactions between the NPs and O2 molecules could form a layered structure for oxygen accumulation, which in turn affects the gas flow rate within the pores and channels of the MMMs near the magnetic NPs.

Synthesis of magnetic NaY zeolite for plasma proteomics application

Magnetically modified NaY zeolite has shown advantages in high-throughput and large-scale clinical plasma proteomic studies. In this study, magnetic NaY zeolite was prepared via an improved method, "layer by layer adhesion", using epoxy adhesive. The morphology, structure, and magnetic properties of magnetic NaY zeolite were characterized and tested by scanning electron microscope (SEM), fourier transform infrared spectrometer (FT-IR), X-ray diffractometer (XRD), and vibrating sample magnetometer (VSM), and using sodium dodecyl sulfonate-polyacrylamide gelelectrophoresis (SDS-PAGE) and liquid chromatography-tandem mass spectrometry (LC-MS) for plasma proteomics studies. The results showed that NaY zeolite was coated on the surface of Fe3O4 by epoxy adhesive, and such coating did not affect the surface properties of the magnetic zeolite. The saturation magnetization of magnetic NaY zeolite was measured as 9.964 emu g−1. Approximately 2929 proteins could be identified from plasma protein corona formed on magnetic NaY zeolite, reaching 97.6 % of the identification number of pure NaY zeolite. Furthermore, compared with NaY zeolite, the solid-liquid separation processes of magnetic zeolite during plasma proteomics studies were significantly reduced from half an hour to few minutes. Due to excellent plasma protein adsorption performance and rapid magnetic separation property, magnetic NaY zeolite is expected to become a powerful tool for the large-scale adsorption of low-abundant plasma proteins and high-throughput proteomic studies.

Reaction mechanism of selective catalytic reduction of NO with NH3 on Fe3O4 (1 1 1) surface: Experimental and DFT studies

Iron-based catalysts have vast potential for application prospect in selective catalytic reduction of NOx with NH3 (NH3-SCR). These catalysts offer excellent SCR activity at medium and high temperatures, N2 selectivity and environmental performance. Among these catalysts, Fe3O4 catalyst is highly active and significant in the denitration reaction due to the presence of both ferrous and ferric ions. This study utilized density functional theory (DFT) in combination with experimental measurements to investigate the reaction pathway of NH3-SCR on the Fe3O4(111) surface. The research found that the surface was favorable for the adsorption of NO molecules and followed the NO activation mechanism. Upon activation of NO at the Feoct site, it reacted with NH3 to form NH2NO, This compound then underwent decomposition into N2 and H2O. The presence of O2 on the catalyst facilitated the surface dehydrogenation reaction and completed the SCR cycle reaction. Based on the DFT results, the formation of NH2NO intermediate was the rate-determining step of SCR reaction. The Fe3O4(111) surface followed the L-H mechanism, which was in line with the experimental results. This study provided novel insights into the SCR reaction process and can be useful in developing new iron-based SCR catalysts.

Multiple redox mechanisms for water-gas shift reaction on Fe3O4 (1 1 1) surface: A density functional theory and mean-field microkinetic modeling study

We investigated redox mechanisms for the high temperature (HT) water–gas shift reaction (WGSR) on the Fe3O4 (111) surface using density functional theory (DFT) calculations and mean-field microkinetic modeling (MKM). The redox pathways branched into three Langmuir-Hinshelwood processes (LH1, LH2 and LH3) and one Mars-van-Krevelen (MVK) process (in the presence of oxygen vacancy) from multidentate binding of CO and CO2 over four available reactive sites (Feoct2, Fetet1, Fe bridge, and O1). We found that the LH1 and LH2 processes have CO adsorption at a single iron site (Feoct2 or Fetet1), while the LH3 and MVK processes have stronger chemisorption of CO or CO2 by both the Feoct2 site and the O1 site. From the mechanistic study of these reaction path, we recognized that availability of O1 sites was key to proceed to either CO oxidation by the single site (LH1, LH2) or by the dual site (LH3, MVK). We observed that the reaction energetics were significantly different in the CO oxidation steps, where the single or dual site results in markedly different apparent activation energy (73–281 kJ/mol) and reaction rates (10−3–10−10 mol⋅m−2⋅s−1) among the four reaction mechanisms. The utilization of mean field MKM with DFT reaction energetics helps explain the experimental debates for the catalytic reaction details as well as providing a possible direction to engineer the catalyst with higher activity.

Synthesis of core–shell magnetic nanocomposite bearing phosphonic acid ligand for uranium extraction from strong HNO3 solution

Recovery of uranium from strong acid media using magnetic nanomaterials as sorbents is vital for sustainable nuclear energy, due to their superparamagnetism and large specific surface energy. However, it remains a huge challenge to develop magnetic nanomaterials for extracting uranium from strong acid media, since magnetic nanomaterials often suffer from poor structural stability and low uranium adsorption performance in strong acid media. Herein, a novel core–shell magnetic nanocomposite Fe3O4@SiO2/P (MBA-VPA) bearing phosphonic acid was fabricated by distillation-precipitation polymerization of N, N'-methylene diacrylamide (MBA) with vinylphosphonic acid (VPA) around the surface of Fe3O4 decorated by SiO2 (Fe3O4@SiO2). By optimizing the polymerization system, high concentration of phosphonic acid with high free movement degree was led into the surface of the sorbent. Under applied conditions (c(H+) = 4 mol L−1, T = 298 K and t = 3 h), the sorbent showed a record-breaking maximum adsorption capacity (qmax) of 262.5 mg g−1 with an excellent selectivity for uranium in the presence of multi-ions. The adsorption capacity of the sorbent in strong HNO3 increased remarkably with increase of the concentration and free movement degree of phosphonic acid. By coating Fe3O4 with an inert SiO2, the sorbent exhibited excellent acidic resistance in strong HNO3. The sorbent could also be magnetically recovered within 15 s, and repeated at least six times without obvious reduction in adsorption capacity. The excellent adsorption performance in strong HNO3 media was primarily assigned to the abundant accessible PO groups, evidenced by X-ray photoelectron spectroscopy (XPS), control experiments and density functional theory (DFT). Most importantly, this work provides a new perspective for developing highly active, excellent acidic resistance, and recyclable magnetic nanomaterials for extracting uranium from strong acid media.