Large Surface Area Research Articles

Gd and Ni co-doped BiFeO3 ferrite/r-GO nanocomposite for photocatalytic environmental remediation applications

Synergistic effects of the co-doping of rare earth and transition metals on the structural, electrical and optical, in multi-ferroic BiFeO3 nanoferrites (NFs) combined with reduced graphene oxide (r-GO) nanosheets, photocatalytic degradation properties can be boosted. In this current study gadolinium and nickel-co-doped Bi1-xGdxFe1-yNiyO3 were synthesised via the tartaric acid-assisted sol-gel method and their composite Bi1-xGdxFe1-yNiyO3/r-GO with 10 % reduced graphene oxide (r-GO) via the ultra-sonication route. Phase and structural investigation were carried out using x-ray diffraction (P-XRD), Raman scattering, and Fourier transform infrared (FTIR) analysis, which confirms the successful fabrication of co-doping in the rhombohedral geometry of the perovskite-type Bi1-xGdxFe1-yNiyO3. Electrical conductivity of the fabricated composite material was observed to increase because of the co-doping and the addition of r-GO. Photoluminescence (PL) spectra of co-doped and r-GO composite material exhibited a decline in PL intensity because optical bandgap energies exhibited narrowing of 1.99 eV and 1.91 eV respectively, which indicates the excellent separation and stabilization of photo-excited charge pairs. Special conduction properties of r-GO nanosheets improved electrical and optical properties, a well-porous nature, large surface area, lower bandgap, and increased dye degradation in the Bi1-xGdxFe1-yNiyO3/r-GO photocatalyst showing excellent photo-degradation of cationic malachite green (M.G.) dye, achieving a degradation efficiency of 96.4 % under natural solar light. Hence, the photocatalyst shows excellent stability where quenching of radicals using selective scavengers shows that OH* radicals and e−/h+ pairs are primarily involved in the mechanism of photo-degradation in a basic pH medium, making the as-fabricated material a potential material for photo-catalytic environmental remediation.

Preparation of solution blow spinning nanofibers and its application in the food field: a review

Abstract Solution blow spinning is a technology that uses high-pressure gas to prepare spinning solution into nanofibers. It has the advantages of high production efficiency and easy operation, and the prepared nanofibers have a large specific surface area, high porosity, and flexible surface functionalization. Therefore, solution blow spinning has received more and more attention in the food field. This paper first introduces the principle of solution blow spinning, the influence of spinning liquid properties, process parameters, and environmental factors on the spinning process. Secondly, it introduces the materials and ways of applying solution blow-spun nanofibers in the food field, such as bacteriostatic food packaging, slow-release food packaging, and intelligent sensors. Finally, the application of solution blow spinning technology in food is summarized and prospected. This paper provides a reference for further research and application of solution blow spinning in the food field at a later stage.

Nanocomposites with polyurethane polymer matrix/ particulate material

The environment is currently considered one of the main concerns of the industrial sector and society. In the particular case of the oil industry, one of the biggest environmental catastrophes that can happen are large oil spills, where to reduce or minimize the environmental damage caused, various cleaning methods are used. Thus, nanocomposites aim to change the mechanical, physical and chemical properties of polymer matrices. The main focus of modifying Polyurethanes has been directed to materials science, the objective of which is to obtain particulate materials, allowing surfaces to be differentiated, reducing surface energy and increasing interlayer spacing for polymer intercalation. This particulate material, produced and modified, interspersed with the Polymer, allows us to absorb crude oil, as it is hydrophobic and, consequently, organophilic. The factors that define the degree of sorption of organic compounds are: hydrophobicity, porosity, molecular structure and volume, and the volume of the surface area of the sorbent material. Therefore, the sorbent must be wettable by the hydrophobic compound and non-wettable or slightly wettable by water. Sorbent materials must have characteristics such as a large surface area, high porosity, good oleophilic character, as well as good oil retention capacity and ease of application. Polyurethane presents several of these characteristics, making it an interesting sorbent for the oil sector. The present work studies the obtaining of these nanocomposites, using a particulate material to combat leaks or spills of hydrocarbons.

Pore Fractal Characteristics between Marine and Marine–Continental Transitional Black Shales: A Case Study of Niutitang Formation and Longtan Formation

Marine shales from the Niutitang Formation and marine–continental transitional shales from the Longtan Formation are two sets of extremely important hydrocarbon source rocks in South China. In order to quantitatively compare the pore complexity characteristics between marine and marine–continental transitional shales, the shale and kerogen of the Niutitang Formation and the Longtan Formation are taken as our research subjects. Based on organic petrology, geochemistry, and low-temperature gas adsorption analyses, the fractal dimension of their pores is calculated by the Frenkel–Halsey–Hill (FHH) and Sierpinski models, and the influences of total organic carbon (TOC), vitrinite reflectance (Ro), and mineral composition on the pore fractals of the shale and kerogen are discussed. Our results show the following: (1) Marine shale predominantly has wedge-shaped and slit pores, while marine–continental transitional shale has inkpot-shaped and slit pores. (2) Cylindrical pores are common in organic matter of both shale types, with marine shale having a greater gas storage space (CRV) from organic matter pores, while marine–continental transitional shale relies more on inorganic pores, especially interlayer clay mineral pores, for gas storage due to their large specific surface area and high adsorption capacity (CRA). (3) The fractal characteristics of marine and marine–continental transitional shale pores are influenced differently. In marine shale, TOC positively correlates with fractal dimensions, while in marine–continental shale, Ro and clay minerals have a stronger influence. Ro is the primary factor affecting organic matter pore complexity. (4) Our two pore fractal models show that the complexity of the shale in the Longtan Formation surpasses that of the shale in the Niutitang Formation, and type I kerogen has more complex organic matter pores than type III, aiding in evaluating pore connectivity and flow effectiveness in shale reservoirs.

Application of Graphdiyne Confined Gold Nanoparticles Modified Electrode as A Robust Sensing Platform for The Detection of 7-Hydroxy-6-methoxy-hydrocoumarin

Abstract A graphdiyne (GDY) and gold nanoparticles (AuNPs) nanocomposite was formed with AuNPs growing on the surface and between the layers of GDY, which was used as the sensing interface on carbon ionic liquid electrode (CILE) to detect 7-hydroxy-6-methoxy-hydrocoumarin (7-6-HDC) that isolated from the noni juice. The GDY-Au nanocomposite was characterized by different spectroscopic techniques, which exhibited corrugated and folded morphology with large specific surface area. The GDY-Au nanocomposite modified electrode displayed excellent performance which is attributed to the highly conductive nanocomposite, where GDY structure with defects could immobilize more AuNPs to decrease the electron transfer resistance. In addition, the reaction mechanism of 7-6-HDC at GDY-Au surface was deduced based on the electrochemical kinetics investigations. Combined with density functional theory calculation, it was verified that the active site of 7-6-HDC and the presence of AuNPs enhanced the electrocatalytic capacity of GDY-Au nanocomposite. Under optimal conditions, the modified electrode displayed a wider linear range from 10.0 nM to 1.0 mM for 7-6-HDC analysis with a detection limit of 3.22 nM (3S0/S). This work provides a promising material to realize accurate analysis for 7-6-HDC, and the discovered sensing mechanism provides method guidance for the exploration of other novel electrochemical sensors.

A novel electrochemical sensor based on a Cu-coordinated molecularly imprinted polymer and MoS2 modified chitin-derived carbon for selective detection of dextromethorphan.

Dextromethorphan (DXM) is a widely utilized central antitussive agent, which is frequently abused by individuals seeking its recreational effect. But DXM overdose can cause some adverse effects, including brain damage, loss of consciousness, and cardiac arrhythmias, and hence its detection is significant. Herein, an electrochemical sensor based on a Cu-coordinated molecularly imprinted polymer (Cu-MIP) was fabricated for its detection. For constructing the sensor, nitrogen-doped carbon nanosheets (CCNs) were prepared through calcining chitin under an argon atmosphere, and molybdenum disulfide (MoS2) was allowed to grow on their surface. Subsequently, the obtained MoS2/CCNs composite was employed to modify a glassy carbon electrode (GCE), and the Cu-MIP was electrodeposited on the electrode in a Cu-1,10-phenanthroline (Cu-Phen) solution containing DXM, where Cu2+ played a role in facilitating electron transfer and binding DXM. Due to the large specific surface area, good electrocatalytic properties and recognition of the resulting composite, the resulting Cu-MIP/MoS2/CCNs/GCE showed high selectivity and sensitivity. Under optimized experimental conditions, the peak current of DXM and its concentration exhibited a good linear relationship over the concentration range of 0.1-100 μM, and the limit of detection (S/N = 3) was 0.02 μM. Furthermore, the electrochemical sensor presented good stability, and it was successfully used for the determination of DXM in pharmaceutical, human serum and urine samples.

Direct Affinity Ligand Immobilization onto Bare Iron Oxide Nanoparticles Enables Efficient Magnetic Separation of Antibodies.

Magnetic separation is a promising alternative to chromatography for enhancing the downstream processing (DSP) of monoclonal antibodies (mAbs). However, there is a lack of efficient magnetic particles for successful application. Aiming to fill this gap, we demonstrate the suitability of bare iron oxide nanoparticles (BION) with physical site-directed immobilization of an engineered Protein A affinity ligand (rSpA) as an innovative magnetic material. The rSpA ligand contains a short peptide tag that enables the direct and stable immobilization onto the uncoated BION surface without commonly required laborious particle activation. The resulting BION@rSpA have beneficial characteristics outperforming conventional Protein A-functionalized magnetic particles: a simple, fast, low-cost synthesis, a particle size in the nanometer range with a large effective specific surface area enabling large immunoglobulin G (IgG) binding capacity, and a high magnetophoretic velocity advantageous for fast processing. We further show rapid interactions of IgG with the easily accessible rSpA ligands. The binding of IgG to BION@rSpA is thereby highly selective and not impeded by impurity molecules in perfusion cell culture supernatant. Regarding the subsequent acidic IgG elution from BION@rSpA@IgG, we observed a hampering pH increase caused by the protonation of large iron oxide surfaces after concentrating the particles in 100 mM sodium acetate buffer. However, the pH can be stabilized by adding 50 mM glycine to the elution buffer, resulting in recoveries above 85% even at high particle concentrations. Our work shows that BION@rSpA enable efficient magnetic mAb separation and could help to overcome emerging bottlenecks in DSP.

Application of nanoparticles as novel adsorbents in blood purification strategies.

Blood purification therapy for patients overloaded with metabolic toxins or drugs still needs improvement. Blood purification therapies, such as in hemodialysis or peritoneal dialysis can profit from a combined application with nanoparticles. In this review, the published literature is analyzed with respect to nanomaterials that have been customized and functionalized as nano-adsorbents during blood purification therapy. Liposomes possess a distinct combined structure composed of a hydrophobic lipid bilayer and a hydrophilic core. The liposomes which have enzymes in their aqueous core or obtain specific surface modifications of the lipid bilayer can offer appreciated advantages. Preclinical and clinical experiments with such modified liposomes show that they are highly efficient and generally safe. They may serve as indirect and direct adsorption materials both in hemodialysis and peritoneal dialysis treatment for patients with renal or hepatic failure. Apart from dialysis, nanoparticles made of specially designed metal and activated carbon have also been utilized to enhance the removal of solutes during hemoadsorption. Results are a superior adsorption capacity and a good hemocompatibility shown during treatment of patients with toxication or end-stage renal disease. In summary, nanomaterials are promising tools for improving the treatment efficacy of organ failure or toxication. KEY MESSAGES The pH-transmembrane liposomes and enzyme-loaded liposomes are two representatives of liposomes with modified aqueous inner core which have been put into practice in dialysis. Unmodified or physiochemically modified liposomal bilayers are ideal binders for lipophilic protein-bound uremic toxins or cholestatic solutes, thus liposome-supported dialysis could become the next-generation hemodialysis treatment of artificial liver support system. Novel nano-based sorbents featuring large surface area, high adsorption capacity and decent biocompatibility have shown promise in treatment of uremia, hyperbilirubinemia, intoxication, and sepsis. A major challenge of production lies in avoiding changes in physical and chemical properties induced by manufacturing and sterilizing procedures.

One-Pot Preparation of Mixed-Mode Reversed-Phase Anion-Exchange Silica Sorbent and its Application in the Detection of Cyclopiazonic Acid in Feeds and Agricultural Products

A novel co-bonded octyl and pyridine silica (OPS) sorbent was prepared and applied for the solid phase extraction (SPE) of cyclopiazonic acid (CPA, a type of mycotoxin) in feed and agricultural products for the first time. A simple mixed-ligand one-pot reaction strategy was employed for OPS sorbent preparation. Nitrogen adsorption–desorption measurements, elemental analysis (EI), thermal gravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FT-IR) analysis demonstrated the successful immobilization of octyl and quaternary ammonium groups onto the surface of silica gel. The large specific surface area, high-density functional groups, and mixed-mode anion-exchange characteristics of these silica particles made them the ideal material for the efficient extraction of CPA. Additionally, the OPS sorbents displayed excellent batch-to-batch reproducibility, satisfactory reusability, and low cost. The SPE parameters were optimized to explore the ionic and hydrophobic interactions between CPA and the functional groups, and the ultra-high performance liquid chromatography coupled with triple-quadrupole tandem mass spectrometry (UPLC-MS/MS) parameters were optimized to obtain a desirable extraction efficiency and high sensitivity to CPA. Meanwhile, the OPS sorbent presented a satisfactory extraction selectivity and low matrix effect. Under the optimized conditions, our developed CPA detection method was used to determine CPA level in rice, wheat flour, corn flour, peanut, and feed samples, exhibiting a lower detection limit, better linearity, higher sensitivity, and satisfactory extraction recovery rate than previously reported methods. Therefore, our method can be preferentially used as a method for the detection of CPA in agricultural products and feeds.

Metal-Organic Framework for Aluminum based Energy Storage Devices: Utilizing Redox Additives for Significant Performance Enhancement.

There are various methods being tried to address the sluggish kinetics observed in Al-ion batteries (AIBs). They mostly deal with morphology tuning, but have led to limited improvement. A new approach is proposed to overcome this limitation. It focuses on the use of a redox additive modified electrolyte in combination with framework like materials, which have wider channels. The ordered microporous and interconnected framework of ZIF 67, with large surface area, effectively facilitates the diffusion of aluminum ions. Therefore, AIBs are able to exhibit a superior discharge capacity of 288 mAh g-1 at 0.2 A g-1 current density with robust cycling stability. The addition of potassium ferricyanide as a redox-active species in an aqueous solution of aluminum chloride (supporting electrolyte) leads to significant enhancement in the specific capacity with much higher cycling stability. Al-ion based BatCap devices can be assembled by using ZIF 67 as the cathode, ZIF 67 derived porous carbon as the anode, and a redox additive modified electrolyte. The BatCap device exhibits excellent energy density of 86 Wh kg-1 at a power density of 2 KW kg-1, which is higher than reported aqueous AIBs. The ex situ characterization clearly explains the unexplored mechanism of redox additives in AIBs.

Developments of photo‐/electro‐catalysis based on covalent organic frameworks: A review

AbstractPhoto‐/electro‐catalysis has the characteristics of low cost, high performance, and zero pollution, which meet the policies on environment and energy. Covalent organic frameworks (COFs), a type of crystalline organic skeleton polymers, have been widely applied and investigated in the area of photo‐/electro‐catalysis owing to their advantages of large specific surface area, regular pore size, excellent stability, flexible structural design, and massive active sites. This article reviews the structural characteristics of COFs and the strategies for strengthening the photo‐/electro‐catalytic activity of COF materials. Subsequently, deep insights were put into the photo‐/electro‐catalysis application of COF materials. In the end, the development prospects and challenges faced by COF materials in photo‐/electro‐catalysis are discussed.

Enhanced photocatalytic activity of porous TiO2 containing C/P/K derived from grapefruit peel.

Grapefruit peel possesses a porous structure and a significant specific surface area. In this study, we introduce an innovative and eco-friendly approach for synthesizing porous TiO2. This was accomplished by employing grapefruit peel as a bio-template and tetrabutyl titanate as the precursor, utilizing a two-step rotary impregnation-calcination process. The TiO2 faithfully reproduced the structural characteristics of the grapefruit peel across different scales, simultaneously incorporating C, P, K elements from the original grapefruit peel into the final samples. The fabricated samples were analyzed using XRD, XPS, SEM, TEM, BET, and UV-vis DRS. The results showed that the TiO2 displays an anatase phase, and possesses a high specific surface area. The investigation of photocatalytic performance demonstrated that the CPK-TiO2-10 sample exhibited outstanding photocatalytic activity against Rhodamine B (RhB) solution, achieving complete degradation within 60 minutes. Additionally, the total organic carbon (TOC) removal rate reached 91.34% after 60 minutes of irradiation. The sample maintained a high degradation efficiency, even after five recycling cycles. This exceptional performance can be attributed to its porous structure, enriched with pores and a larger surface area, as well as the beneficial effects of doping with C, P, K elements in TiO2.

LDH-Based Voltammetric Sensors

Layered double hydroxides (LDHs), also named hydrotalcite-like compounds, are anionic clays with a lamellar structure which have been extensively used in the last two decades as electrode modifiers for the design of electrochemical sensors. These materials can be classified into LDHs containing or not containing redox-active centers. In the former case, a transition metal cation undergoing a reversible redox reaction within a proper potential window is present in the layers, and, therefore, it can act as electron transfer mediator, and electrocatalyze the oxidation of an analyte for which the required overpotential is too high. In the latter case, a negatively charged species acting as a redox mediator can be introduced into the interlayer spaces after exchanging the anion coming from the synthesis, and, again, the material can display electrocatalytic properties. Alternatively, due to the large specific surface area of LDHs, molecules with electroactivity can be adsorbed on their surface. In this review, the most significant electroanalytical applications of LDHs as electrode modifiers for the development of voltammetric sensors are presented, grouping them based on the two types of materials.

Porous Organic Framework Materials (MOF, COF, and HOF) as the Multifunctional Separator for Rechargeable Lithium Metal Batteries.

The separator is an important component in batteries, with the primary function of separating the positive and negative electrodes and allowing the free passage of ions. Porous organic framework materials have a stable connection structure, large specific surface area, and ordered pores, which are natural places to store electrolytes. And these materials with specific functions can be designed according to the needs of researchers. The performance of porous organic framework-based separators used in rechargeable lithium metal batteries is much better than that of polyethylene/propylene separators. In this paper, thethree most classic organic framework materials (MOF, COF, and HOF) are analyzed and summarized. The applications of MOF, COF, and HOF separators in lithium-sulfur batteries, lithium metal anode, and solid electrolytes are reviewed. Meanwhile, the research progress of these three materials in different fields is discussed based on time. Finally, in the conclusion, the problems encountered by MOF, COF, and HOF in different fields as well as their future research priorities are presented. This review will provide theoretical guidance for the design of porous framework materials with specific functions and further stimulate researchers to conduct research on porous framework materials.

High carbon dioxide emissions from Australian estuaries driven by geomorphology and climate

Estuaries play an important role in connecting the global carbon cycle across the land-to-ocean continuum, but little is known about Australia’s contribution to global CO2 emissions. Here we present an Australia-wide assessment, based on CO2 concentrations for 47 estuaries upscaled to 971 assessed Australian estuaries. We estimate total mean (±SE) estuary CO2 emissions of 8.67 ± 0.54 Tg CO2-C yr−1, with tidal systems, lagoons, and small deltas contributing 94.4%, 3.1%, and 2.5%, respectively. Although higher disturbance increased water-air CO2 fluxes, its effect on total Australian estuarine CO2 emissions was small due to the large surface areas of low and moderately disturbed tidal systems. Mean water-air CO2 fluxes from Australian small deltas and tidal systems were higher than from global estuaries because of the dominance of macrotidal subtropical and tropical systems in Australia, which have higher emissions due to lateral inputs. We suggest that global estuarine CO2 emissions should be upscaled based on geomorphology, but should also consider land-use disturbance, and climate.

Multiple-component covalent organic frameworks for simultaneous extraction and determination of multitarget pollutants in sea foods

Persistent organic pollutants (POPs), such as perfluoroalkyl and polyfluoroalkyl substances (PFASs), polychlorinated biphenyls (PCBs), and bisphenols (BPs), have been raising global concerns due to their toxic effects on environment and human health. The monitoring of residues of POPs in seafood is crucial for assessing the accumulation of these contaminants in the study area and mitigating potential risks to human health. However, the diversity and complexity of POPs in seafood present significant challenges for their simultaneous detection. Here, a novel multi-component fluoro-functionalized covalent organic framework (OH-F-COF) was designed as SPE adsorbent for simultaneous extraction POPs. On this basis, the recognition and adsorption mechanisms were investigated by molecular simulation. Due to multiple interactions and large specific surface area, OH-F-COF displayed satisfactory coextraction performance for PFASs, PCBs, and BPs. Under optimized conditions, the OH-F-COF sorbent was employed in a strategy of simultaneous extraction and stepwise elution (SESE), in combination with HPLC−MS/MS and GC−MS method, to effectively determined POPs in seafood collected from coastal areas of China. The method obtained low detection limits for BPs (0.0037 −0.0089 ng/g), PFASs (0.0038 −0.0207 ng/g), and PCBs (0.2308 −0.2499 ng/g), respectively. This approach provided new research ideas for analyzing and controlling multitarget POPs in seafood. Environmental implicationsPersistent organic pollutants (POPs), such as perfluoroalkyl and polyfluoroalkyl substances (PFASs), polychlorinated biphenyls (PCBs), and bisphenols (BPs), have caused serious hazards to human health and ecosystems. Hence, there is a need to develop a quantitative method that can rapidly detect POPs in environmental and food samples. Herein, a novel multi-component fluorine-functionalized covalent organic skeletons (OH-F-COF) were prepared at room temperature, and served as adsorbent for POPs. The SESE-SPE strategy combined with chromatographic techniques was used to achieve a rapid detection of POPs in sea foods from the coastal provinces of China. This method provides a valuable tool for analyzing POPs in environmental and food samples.

Sub-nanopores enabling optimized ion storage performance of carbon cathodes for Zn-ion hybrid supercapacitors

Aqueous Zn-ion hybrid supercapacitors (ZHSs) are attracting significant attention as a promising electrochemical energy storage system. However, carbon cathodes of ZHSs exhibit unsatisfactory ion storage performance due to the large size of hydrated Zn-ions (e.g., [Zn(H2O)6]2+), which encumbers compact ion arrangement and rapid ion transport at the carbon-electrolyte interfaces. Herein, a porous carbon material (HMFC) with abundant sub-nanopores is synthesized to optimize the ion storage performance of the carbon cathode in ZHSs, in which the sub-nanopores effectively promote the dehydration of hydrated Zn-ions and thus optimize the ion storage performance of the carbon cathode in ZHSs. A novel strategy is proposed to study the dehydration behaviors of hydrated Zn-ions in carbon cathodes, including quantitatively determining the desolvation activation energy of hydrated Zn-ions and in-situ monitoring active water content at the carbon-electrolyte interface. The sub-nanopores-induced desolvation effect is verified, and its coupling with large specific surface area and hierarchically porous structure endows the HMFC cathode with improved electrochemical performance, including a 53 % capacity increase compared to the carbon cathode counterpart without sub-nanopores, fast charge/discharge ability that can output 46.0 Wh/kg energy within only 4.4 s, and 98.2 % capacity retention over 20,000 charge/discharge cycles. This work provides new insights into the rational design of porous carbon cathode materials toward high-performance ZHSs.

Incorporating ZIF-8-derived ZnSe into hollow carbon nanospheres as anodes for lithium-ion batteries

Transition metal selenides (TMSs) show great potential as anode materials for lithium-ion batteries (LIBs), boasting a high theoretical capacity. Nevertheless, their practical utility faces challenges, mainly stemming from significant volume changes that lead to rapid capacity decay during charge and discharge cycles. To overcome this challenge, we present a systematic approach involving the growth of uniformly dispersed ultrafine ZnSe nanoparticles derived from ZIF-8 on the surface of hollow carbon nanospheres (ZnSe@N-HCS/700). When utilized as an anode material for LIBs, the ZnSe@N-HCS/700 electrode demonstrates exceptional electrochemical performance. Specifically, it achieves a capacity of 1299 mAh g−1 after 100 cycles at a current density of 100 mA g−1 and maintains a capacity of 614 mAh g−1 even after 1800 cycles at 2500 mA g−1. The hollow structure of the composite alleviates the volume variation of ZnSe nanoparticles during charge and discharge processes, and provides a large reactive surface area, thereby significantly enhancing lithium storage capacity. In conclusion, our strategy presents an innovative approach to synthesize negative electrode materials with unique structures for LIBs.

Preparation of Heterogeneous Fenton Catalysts Cu-Doped MnO2 for Enhanced Degradation of Dyes in Wastewater

Herein, a series of heterogeneous Fenton catalysts, Cu doped MnO2 (CDM), with different Cu/Mn molar ratios were prepared via a hydrothermal reaction. Meanwhile, detailed characterizations were used to study the structures of CDM, and it is amazing that the morphology of CDM changed from nanowires to nanoflowers with an increasing amount of Cu doped. Apart from this, both the specific surface area and oxygen vacancy increased obviously with the increasing Cu/Mn molar ratio. Then, the degradation of different dyes was utilized to evaluate the catalytic activity of different CDM with H2O2 used as the oxidizing agent, and the 50%-CDM with the highest content of Cu doped displayed the best catalytic activity. Herein, the degradation efficiency (D%) of Congo red (CR) solution with low concentration (60 mg/L) reached 100% in 3 min, while the D% of CR solution with a high concentration (300 mg/L) reached 99.4% after 5 min with a higher dosage of H2O2. Additionally, the 50%-CDM also displayed excellent reusability, for which the D% values were still higher than 90% after the 14th cycles. Based on the structure characteristics and mechanism analysis, the excellent catalytic capacity of 50%-CDM was due to the combined influence of large specific surface area and abundant oxygen vacancy. Thus, a promising heterogeneous Fenton catalyst was developed in this study, which proved the treatment efficiency of actual dye wastewater.

MOF-on-MOF-derived Fe[sbnd]Zr bimetal oxides supported on hierarchically porous carbonized wood to promote photo-Fenton degradation of ciprofloxacin

MOF-on-MOF derivatives have served as promising heterogeneous Photo-Fenton (hetero-PF) catalysts, but its self-aggregation instability and limited photocatalytic activity inhibit the effective ciprofloxacin (CIP) removal. In this study, a novel hetero-PF catalyst, dual MOF-derived FeZr bimetal oxide embedded in a wood-converted porous carbon skeleton (ZrO2@Fe3O4/WPC), was successfully synthesized via a straightforward in-situ growth strategy combined with co-pyrolysis. The as-prepared hybrid photocatalysts, featuring a large surface area, effective porous structures, efficient light absorption and a narrow band gap demonstrated superior photo-Fenton activity, accomplishing approximately 99.1 % degradation of CIP within 120 min under neutral conditions. Furthermore, the ZrO2@Fe3O4/WPC hetero-PF system showed satisfactory performance in treating real water matrices. It can be inferred that the abundant heterojunctions, resulting from the synergistic effect of FeZr mixed oxide and the porous carbonized wood substrate, contributed to the rapid separation and migration of photogenerated electron-hole pairs. Meanwhile, the FeZr site in the graphitized carbon framework activates H2O2 to accelerate the generation of the OH and O2− radicals, leading to a heightened degradation efficiency of CIP. Besides, the photodegradation pathway of CIP is obtained by liquid chromatography-mass spectrometry (LC-MS). This study indicates that combining porous carbonized wood and heterometallic MOF derived materials provides a promising method for realizing high-efficiency photo-Fenton degradation of antibiotic water pollutions.