Rational Design and Comparison of Novel 99mTc-Labeled FAPI Dimers for Visualization of Multiple Tumor Types.

Recognizing the significance of SPECT in nuclear medicine and the pivotal role of fibroblast activation protein (FAP) in cancer diagnosis and therapy, this study focuses on the development of 99mTc-labeled dimeric HF2 with high tumor uptake and image contrast. The dimeric HF2 was synthesized and radiolabeled with 99mTc in one pot using various coligands (tricine, TPPTS, EDDA, and TPPMS) to yield [99mTc]Tc-TPPTS-HF2, [99mTc]Tc-EDDA-HF2, and [99mTc]Tc-TPPMS-HF2 dimers. SPECT imaging results indicated that [99mTc]Tc-TPPTS-HF2 exhibited higher tumor uptake and tumor-to-normal tissue (T/NT) ratio than [99mTc]Tc-EDDA-HF2 and [99mTc]Tc-TPPMS-HF2. Notably, [99mTc]Tc-TPPTS-HF2 exhibited remarkable tumor accumulation and retention in HT-1080-FAP and U87-MG tumor-bearing mice, thereby surpassing the monomeric [99mTc]Tc-TPPTS-HF. Moreover, [99mTc]Tc-TPPTS-HF2 achieved acceptable T/NT ratios in the hepatocellular carcinoma patient-derived xenograft (HCC-PDX) model, which provided identifiable contrast and imaging quality. In conclusion, this study presents proof-of-concept research on 99mTc-labeled FAP inhibitor dimers for the visualization of multiple tumor types. Among these candidate compounds, [99mTc]Tc-TPPTS-HF2 showed excellent clinical potential, thereby enriching the SPECT tracer toolbox.

Rational Design and Pharmacomodulation of 18F-Labeled Biotin/FAPI-Conjugated Heterodimers.

Due to the complex heterogeneity in different cancer types, the heterodimeric strategy has been intensively practiced to improve the effectiveness of tumor diagnostics. In this study, we developed a series of novel 18F-labeled biotin/FAPI-conjugated heterobivalent radioligands ([18F]AlF-NSFB, [18F]AlF-NSFBP2, and [18F]AlF-NSFBP4), synergistically targeting both fibroblast activation protein (FAP) and biotin receptor (BR), to enhance specific tumor uptake and retention. The in vitro and in vivo biological properties of these dual-targeting tracers were evaluated, with a particular focus on positron emission tomography imaging in A549 and HT1080-FAP tumor-bearing mice. Notably, in comparison to the corresponding FAP-targeted monomer [18F]AlF-NSF, biotin/FAPI-conjugated heterodimers exhibited a high uptake in tumor and prolong retention. In conclusion, as a proof-of-concept study, the findings validated the superiority of biotin/FAPI-conjugated heterodimers and the positive influence of biotin and linker on pharmacokinetics of radioligands. Within them, the bispecific [18F]AlF-NSFBP4 holds significant promise as a candidate for further clinical translational studies.

18F-Labeled Amidobenzimidazole Analogue for Visualizing STING Expression in Tumor.

The stimulator of interferon genes (STING) is pivotal in mediating STING-dependent type I interferon production, which is crucial for enhancing tumor rejection. Visualizing STING within the tumor microenvironment is valuable for STING-related treatments, yet the availability of suitable STING imaging probes is limited. In this study, we developed [18F]AlF-ABI, a novel 18F-labeled agent featuring an amidobenzimidazole core structure, for positron emission tomography (PET) imaging of STING in B16F10 and CT26 tumors. [18F]AlF-ABI was synthesized with a decay-corrected radiochemical yield of 38.0 ± 7.9% and radiochemical purity exceeding 97%. The probe exhibited a nanomolar STING binding affinity (KD = 35.6 nM). Upon administration, [18F]AlF-ABI rapidly accumulated at tumor sites, demonstrating significantly higher uptake in B16F10 tumors compared to CT26 tumors, consistent with STING immunofluorescence patterns. Specificity was further validated through in vitro cell experiments and in vivo blocking PET imaging. These findings suggest that [18F]AlF-ABI holds promise as an effective agent for visualizing STING in the tumor microenvironment.

Sustainable remediation of Cr(VI)-contaminated soil by soil washing and subsequent recovery of washing agents using biochar supported nanoscale zero-valent iron.

Soil contamination by Cr(VI) has attracted widespread attention globally in recent years, but it remains a significant challenge in developing an environmentally friendly and eco-sustainable technique for the disposal of Cr(VI)-contaminated soil. Herein, a sustainable cyclic soil washing system for Cr(VI)-polluted soil remediation and the recovery of washing agents using biochar supported nanoscale zero-valent iron (nZVI-BC) was established. Citric acid (CA) was initially screened to desorb Cr(VI) from contaminated soil, mobilizing Cr from the highly bioaccessible fractions. The nZVI-BC exhibited superior properties for Cr(VI) and Cr(total) removal from spent effluent, allowing effective recovery of the washing agents. The elimination mechanism of Cr(total) by nZVI-BC involved the coordinated actions of electrostatic adsorption, reduction, and co-precipitation. The contributions to Cr(VI) reduction by Fe0, surface-bound Fe(II), and soluble Fe(II) were 0.6 %, 39.8 %, and 59.6 %, respectively. Meanwhile, CA favored the activity of surface-bound Fe(II) and Fe0 in nZVI-BC, enhancing the production of soluble Fe(II) to strengthen Cr(VI) removal. Finally, the recovered washing agent was proven to be reused three times. This study showcases that the combined soil washing using biodegradable chelant CA and effluent treatment by nZVI-BC could be a sustainable and promising strategy for Cr(VI)-contaminated soil remediation.

Chalcopyrite functionalized ceramic membrane for micropollutants removal and membrane fouling control via peroxymonosulfate activation: The synergy of nanoconfinement effect and interface interaction.

This work developed a novel chalcopyrite (CuFeS2) incorporated catalytic ceramic membrane (CFSCM), and comprehensively evaluated the oxidation-filtration efficiency and mechanism of CFSCM/peroxymonosulfate (PMS) for organics removal and membrane fouling mitigation. Results showed that PMS activation was more efficient in the confined membrane pore structure. The CFSCM50/PMS filtration achieved almost complete removal of 4-Hydroxybenzoic acid (4-HBA) under the following conditions: pH = 6.0, CPMS = 0.5 mM, and C4-HBA = 10 mg/L. Meanwhile, the membrane showed good stability after multiple uses. During the reaction, SO4•- and •OH were generated in the CFSCM50/PMS system, and SO4•- was considered to be the dominant reactive species for pollutant removal. The roles of copper, iron, and sulfur species, as well as the possible catalytic mechanism were also clarified. Besides, the CFSCM50/PMS catalytic filtration exhibited excellent antifouling properties against NOM with reduced reversible and irreversible fouling resistances. The Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory analysis showed an increased in repulsive energy at the membrane-foulant interface in the CFSCM50/PMS system. Membrane fouling model analysis indicated that standard blocking was the dominant fouling pattern for CFSCM50/PMS filtration. Overall, this work demonstrates an efficient catalytic filtration process for foulants removal and outlines the synergy of catalytic oxidation and interface interaction.

Effective remediation of leachate concentrate by peroxymonosulfate in a catalytic ceramic membrane filtration process: Performance and mechanism.

Membrane concentrated landfill leachate has been characterized by complex component and degradation resistant. In this work, a new catalytic ceramic membrane (CuCM) was developed by in-situ integrating copper oxide in the membrane and used in combination with peroxymonosulfate (PMS) for leachate concentrate treatment. The performance and key factors of the CuCM/PMS system were systematically studied. Results showed that the CuCM/PMS system experienced promising efficiency in the pH range of 3 âˆ¼ 11. The highest COD, TOC, UV254 and Color removal efficiency achieved by the CuCM-3/PMS system under the conditions of pH = 7.0 and CPMS = 10 mM, which reached up to 63.4%, 50.5%, 75.1% and 90.2%, respectively. The possible mechanism of leachate remediation was proposed and non-free radicals (Cu(Ⅲ), 1O2) played an important role in the CuCM/PMS system for leachate remediation. The fluorescence spectrum and GC-MS analysis showed that the refractory organics with a high molecular weight in the leachate concentrate were mostly oxidized into small molecules, which also alleviated the membrane fouling. In addition, the slight decrease in COD (7.4%) and TOC (9.7%) after 6 cycles revealed the good catalytic stability and reusability of CuCM-3/PMS. This work provides a feasible strategy for leachate concentrate remediation via a nonradical oxidation process.

Preparation, performance and mechanism of metal oxide modified catalytic ceramic membranes for wastewater treatment.

Catalytic ceramic membranes (CMs) integrated with different metal oxides were designed and fabricated by an impregnation-sintering method. The characterization results indicated that the metal oxides (Co3O4, MnO2, Fe2O3 and CuO) were uniformly anchored around the Al2O3 particles of the membrane basal materials, which could provide a large number of active sites throughout the membrane for the activation of peroxymonosulfate (PMS). The performance of the CMs/PMS system was evaluated by filtrating a phenol solution under different operating conditions. All the four catalytic CMs showed desirable phenol removal efficiency and the performance was in order of CoCM, MnCM, FeCM and CuCM. Moreover, the low metal ion leaching and high catalytic activity even after the 6th run revealed the good stability and reusability of the catalytic CMs. Quenching experiments and electron paramagnetic resonance (EPR) measurements were conducted to discuss the mechanism of PMS activation in the CMs/PMS system. The reactive oxygen species (ROS) were supposed to be SO4˙- and 1O2 in the CoCM/PMS system, 1O2 and O2˙- in the MnCM/PMS system, SO4˙- and ·OH in the FeCM/PMS system, and SO4˙- in the CuCM/PMS system, respectively. The comparative study on the performance and mechanism of the four CMs provides a better understanding of the integrated PMS-CMs behaviors.

Efficient degradation of Congo red by persulfate activated with different particle sizes of zero-valent copper: performance and mechanism.

In this study, Congo red (CR) was degraded by different particle sizes of zero-valent copper (ZVC) activated persulfate (PS) under mild temperature. The CR removal by 50 nm, 500 nm, 15 µm of ZVC activated PS was 97%, 72%, and 16%, respectively. The co-existence of SO42- and Cl- promoted the degradation of CR, and HCO3- and H2PO4- were detrimental to the degradation. With the reduction of ZVC particle size, the effect of coexisting anions on degradation grew stronger. The high degradation efficiency of 50 nm and 500 nm ZVC was achieved at pH=7.0, while the high degradation of 15 µm ZVC was achieved at pH=3.0. It was more favorable to leach copper ions for activating PS to generate reactive oxygen species (ROS) with the smaller particle size of ZVC. The radical quenching experiment and electron paramagnetic resonance (EPR) analysis indicated that SO4-•, •OH and •O2- existed in the reaction. The mineralization of CR reached 80% and three possible paths were suggested for the degradation. Moreover, the degradation of 50 nm ZVC can still reach 96% in the 5th cycle, indicating promising application potential in dyeing wastewater treatment.

Enhancement of peroxymonosulfate activation by humic acid-modified sludge biochar: Role of singlet oxygen and electron transfer pathway.

Sludge biochar (SBC) modified by humic acid (HA) was used to activate peroxymonosulfate (PMS) for degrading naproxen (NPX). HA-modified biochar (SBC-50HA) boosted the catalytic performance of SBC for PMS activation. The SBC-50HA/PMS system had good reusability and structural stability, and was unaffected by complex water bodies. The results of Fourier transform infrared (FTIR) and X-ray diffraction spectroscopy (XPS) indicated that graphitic carbon (CC), graphitic N, and C-O on SBC-50HA played a vital part on the removal of NPX. The key role of non-radical pathways such as singlet oxygen (1O2) and electron transfer in the SBC-50HA/PMS/NPX system was verified by inhibition experiments, electron paramagnetic resonance (EPR), electrochemistry, and PMS consumption. The possible degradation pathway of NPX was proposed by density functional theory (DFT) calculations, and the toxicity of NPX and its degradation intermediates were evaluated.

Revealing the synergistic mechanism of the generation, migration and nearby utilization of reactive oxygen species in FeOCl-MOF yolk-shell reactors.

Fenton-like reactions is attractive for environmental pollutant control, but there is an urgent need to improve the utilisation of hydroxyl radicals (·OH) in practical applications. Here, for the first time, FeOCl is encapsulated within a Metal Organic Framework (MOF) (Materials of Institut Lavoisier-101 (MIL-101(Fe))) as a yolk-shell reactor (FeOCl-MOF) by in situ growth. The interaction between FeOCl and the MOF not only increases the electron density of FeOCl, but also shifts down the d-band centre. The increase of electron density could promote the efficient conversion of H2O2 to ·OH catalysed by FeOCl. And the shift of the d-band centre to the lower energy level facilitates the desorption of ·OH. Experimental and theoretical calculations showed that the high catalytic performance was attributed to the unique yolk-shell structure that concentrates the catalytic and adsorption sites in a confinement space, as well as the improved electron density and d-band centre for efficient generation, rapid desorption and utilized nearby of ·OH. Which is utilized nearby by the organic pollutants adsorbed by the surface MOF, thus greatly improving the effective conversion of H2O2 and the ·OH utilisation (from 25.5% (Fe2+/H2O2) to 77.1% (FeOCl-MOF/H2O2)). In addition, a catalytic reactor was constructed to achieve continuous efficient treatment of organic pollutants. This work provides a Fenton-like microreactor for efficient generation, rapid desorption, and nearby utilization of ·OH to improve future technologies for deep water purification in complex environments.

Ultrafast short-range catalytic pathway modified peroxymonosulfate activation over CuO with surface oxygen defects for tetracycline hydrochloride degradation.

The presence of antibiotics in water bodies seriously threatens the ecosystem and human health. Advanced oxidation processes (AOPs) based on peroxymonosulfate (PMS), an effective method to remove antibiotics, have a bottleneck problem that the low oxidant utilization is attributed to the hindered electron transfer between metal oxides and peroxides. Here, CuO with rich oxygen vacancies (OVs), MSCuO-300, was synthesized to efficiently degrade tetracycline hydrochloride (TTCH) (k = 0.095 min-1). The dominant role of direct adsorption and activation of OVs and its regulated Cu-O, rather than surface hydroxyl adsorption, mediated a short-range catalytic pathway. The shortened catalytic pathway between active sites and PMS accelerated the charge transfer at the interface, which promoted PMS activation. Compared with CuxO-500 and Commercial CuO, the activation rate of PMS was increased by 11.97, and 12.64 times, respectively. OVs contributed to the production of 1O2 and O2•-, the main active species. In addition, MSCuO-300/PMS showed excellent adaptability to real water parameters, such as pH (3-11), anions, and continuous reactor maintained for 168 h. This study provides a successful case for the purification of antibiotic-containing wastewater in the design of efficient catalysts by oxygen defect strategies.

Facilitated catalytic ozonation of atrazine over highly stabilized Zn-Al layered double oxides composites: efficacy and mechanism.

A series of Zn-Al Layered Double Oxides (ZnAl-LDO) composites were prepared by the hydrothermal and calcination method via employing the Zn-Al Layered Double Hydroxide (ZnAl-LDH) as the precursors in the present study. The structural properties and the catalytic ozonation activity of ZnrAl-T composites synthesized with different Zn/Al molar ratios and calcination temperatures were systematically investigated. Diversified characterizations were applied to analyze the phase structure and chemical composition of ZnrAl-T composites. As the calcination temperature increased, the layered ZnAl-LDH structure could be entirely destroyed and the crystallinity gradually improved. With the Zn/Al mole ratio of 4.0 and calcination temperature of 500°C, the Zn4Al-500 composite obtained the outstanding catalytic ozonation performance for atrazine (ATZ) degradation with the pseudo-first-order constant of 0.5080 min-1, which was 5 times more than that in O3 alone. Meanwhile, the ATZ degradation efficiency was gradually enhanced from 44.1% to 99.9% within 3.0 min when the solution pH ranged from 3.0 to 10.0. Besides, the Zn4Al-500 composite exhibited splendid stability over multiple reaction cycles. In addition, the radical scavenging test and electron spin resonance measurement demonstrated that superoxide radical and hydroxyl radical are the dominant reactive species in O3/Zn4Al-500 process. Moreover, nineteen and ten transformation products were detected in O3 alone and O3/Zn4Al-500 process, and possible degradation pathways of ATZ were further elucidated. Overall, the Zn4Al-500 composite would provide a potential alternative for pollutants removal due to its high catalytic ozonation efficiency, stability, and reusability.

Coagulation characteristic and mechanism of Fe(III) salts toward typical Cr(III) complexes in wastewater treatment.

Cr(III) complexes are typical pollutants in various industrial wastewater and pose a serious threat to the ecosystem and humans. The coagulation process is commonly used in water treatment plants, yet its removal characteristic and mechanism toward Cr(III) complexes have been rarely reported. In this study, the Fe(III) coagulation process was adopted for the evaluation of Cr(III) complex removal in terms of Cr residual concentration as well as floc size. The results showed that Fe(III) with a dose of 0.8 mM removed more than 80% of total Cr for Cr3+ and Cr(III)-acetate, whereas poor removal rate (~ 50%) was obtained for Cr(III)-citrate under the same conditions. Neutral and alkaline conditions facilitated Cr(III)-acetate removal by Fe(III) coagulation, while limited influence was observed for Cr(III)-citrate with various pH. The main removal mechanism of Cr(III)-acetate was precipitation. Cr(III)-citrate elimination largely relied on the adsorption property and sweeping effect of Fe floc. Moreover, Cr(III)-acetate was easier to be separated from a solution since the generated floc sizes were 270 µm. Flocs that formed in the Cr(III)-citrate treatment were only 0.3 µm, resulting in separation difficulties during the coagulation process. The presence of Cr(III)-acetate and Cr(III)-citrate caused a significant decline in membrane flux. This study provided fundamental knowledge of Fe coagulation treatment in Cr(III) complex-containing wastewater.

Ultrastable Fe-N-C Fuel Cell Electrocatalysts by Eliminating Non-Coordinating Nitrogen and Regulating Coordination Structures at High Temperatures.

Pyrolyzed Fe-N-C materials have attracted considerable interest as one of the most active noble-metal-free electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). Despite significant progress is made in improving their catalytic activity during past decades, the Fe-N-C catalysts still suffer from fairly poor electrochemical and storage stability, which greatly hurdles their practical application. Here, an effective strategy is developed to greatly improve their catalytic stability in PEMFCs and storage stability by virtue of previously unexplored high-temperature synthetic chemistry between 1100 and 1200 °C. Pyrolysis at this rarely adopted temperature range not only enables the elimination of less active nitrogen-doped carbon sites that generate detrimental peroxide byproduct but also regulates the coordination structure of Fe-N-C from less stable D1 (O-FeN4 C12 ) to a more stable D2 structure (FeN4 C10 ). The optimized Fe-N-C catalyst exhibits excellent stability in PEMFCs (>80% performance retention after 30 h under H2 /O2 condition) and no activity loss after 35 day storage while maintaining a competitive ORR activity and PEMFC performance.

The efficient adsorption of tetracycline from aqueous solutions onto polymers with different N-vinylpyrrolidone contents: equilibrium, kinetic and dynamic adsorption.

Extensive use of antibiotics in the world will cause potential risks to human health and ecosystems. The removal of these antibiotics has attracted much attention. Composite materials are growing attention for diverse pollutants separation and removal based on their specific functionality and surface area. In this study, a series of N-vinylpyrrolidone-divinylbenzene polymers (NVPD) with different N-vinylpyrrolidone (NVP) contents were facilely prepared for the adsorption of tetracycline (TC). The effect of polymer surface properties and aqueous solution chemistry (pH, ionic strength, humic acid) on TC adsorption was further studied. The dynamic adsorption and regeneration experiments were also assessed. The results showed that only 25% of NVP was involved in the reaction. When NVP dosage (%) was 75%, polymer (NVPD-g) owned the largest BET surface area (613.23 m2/g) and obtained the maximum TC adsorption capacities (258.76 mg/g). In the kinetic, the adsorption between TC and polymers with NVP was controlled by chemical adsorption and intra-particle diffusion. The TC adsorption process of NVPD-g depended on the contribution of the hydrophobic effect, electrostatic interactions, H-bonding, π-π electron donor-acceptor (EDA) interactions, and cation-π bonding. Moreover, the removal efficiency of TC by NVPD-g was enhanced in the presence of humic acid (HA) in the dynamic adsorption and 1197 BV (2394 mL) of TC simulated wastewater can be treated. These findings suggest that NVPD-g has a potential application in the purification of TC.

Fe-O-Zr in MOF for effective photo-Fenton Bisphenol A degradation: Boosting mechanism of electronic transmission.

To enhance the efficiency of photogenerated electron transport in the photo-Fenton reaction, we report a Fe-doped UiO-66 containing Fe-O-Zr bonds for the photo-Fenton reaction system. The modulation changes the energy bandgap from 3.89 eV to 2.02 eV, and its absorption edge is red-shifted from the UV region to the visible range. Simultaneously, Fe-O-Zr reduces the redox internal resistance, enhances the photocurrent and catalytic process, and suppresses the compounding of photogenerated electrons and holes. These promote the valence cycling of Fe(III)/Fe(II) in the photo-Fenton reaction. Compared with UiO-66, the hydroxyl radical generation efficiency of this reaction system was increased by 5.8 times (UiO-66: 0.0009 mM/min, FeUiO-1: 0.0053 mM/min). The degradation efficiency of BPA was increased by 100.8 times (UiO-66: 0.0012 min-1, FeUiO-1: 0.121 min-1), and the removal rate of TOC also reached 69.55%. The removal rate of BPA was maintained at more than 85% through 5 cycles. The reaction system was able to maintain a removal rate more than 97% at pH:3-9. In the presence of anions, such as Cl-, SO42-, NO32- (10 mM), the degradation rates of BPA were still above 94%. The catalytic efficiency was 2.02 times higher under natural light than relative to dark conditions. It was demonstrated by EPR and inhibition experiments that the main active species in the reaction were hydroxyl radicals and vacancies. The HOMO energy level and LUMO energy level of the intermediates were analyzed, and the possible degradation pathways of the active species were speculated. Evaluation of the biological toxicity of intermediates demonstrated that the system can effectively detoxify BPA. This investigation provides a reference method to enhance the efficiency of the photo-Fenton reaction of MOFs.

Confined Growth of Silver-Copper Janus Nanostructures with {100} Facets for Highly Selective Tandem Electrocatalytic Carbon Dioxide Reduction.

Electrocatalytic carbon dioxide reduction reaction (CO2 RR) holds significant potential to promote carbon neutrality. However, the selectivity toward multicarbon products in CO2 RR is still too low to meet practical applications. Here the authors report the delicate synthesis of three kinds of Ag-Cu Janus nanostructures with {100} facets (JNS-100) for highly selective tandem electrocatalytic reduction of CO2 to multicarbon products. By controlling the surfactant and reduction kinetics of Cu precursor, the confined growth of Cu with {100} facets on one of the six equal faces of Ag nanocubes is realized. Compared with Cu nanocubes, Ag65 -Cu35 JNS-100 demonstrates much superior selectivity for both ethylene and multicarbon products in CO2 RR at less negative potentials. Density functional theory calculations reveal that the compensating electronic structure and carbon monoxide spillover in Ag65 -Cu35 JNS-100 contribute to the enhanced CO2 RR performance. This study provides an effective strategy to design advanced tandem catalysts toward the extensive application of CO2 RR.

Catalytic ozonation oxidation of ketoprofen by peanut shell-based biochar: effects of the pyrolysis temperatures.

A series of peanut shell (HS)-based biochar were prepared at different pyrolysis temperatures and subsequently used as the effective ozonation catalysts for ketoprofen (KET) degradation in aqueous solution. The physicochemical properties and morphology of the obtained biochar were analysed by ICP, TG, XRD, FT-IR, SEM, TEM, BET and etc. characterizations. The results demonstrated that the pyrolysis temperature played an important role on the structure and morphology of HS-based biochar. As the pyrolysis temperature increased, the cellulose and hemicellulose of HS gradually decomposed, resulting in the loss of biochar mass, improvement of the surface roughness, the increase of specific surface area, and the formation of new functional groups. The HS-based biochar pyrolyzed at 600°C (HS600) achieved the fast KET degradation rate with the pseudo-first-order rate constant of 0.922 min-1 and the low adsorption rate of 1.3% in O3/HS600 process. Meanwhile, the effects of the HS600 dosage, initial KET concentration, temperature, water matrix, and solution pH on KET degradation were systematically evaluated. Besides, the HS600 displayed great stability and reusability towards KET degradation during multiple cycling experiments. Moreover, the single oxygen, superoxide radical and hydroxyl radical were involved in O3/HS600 process and the mechanisms for the improvement of KET degradation were also elucidated. It could be speculated that the enhancement of the catalytic ozonation by HS-based biochar was probably attributed to the increased active sites and the intense chemical bonds, and delocalized π electron.

Tailored d-Band Facilitating in Fe Gradient Doping CuO Boosts Peroxymonosulfate Activation for High Efficiency Generation and Release of Singlet Oxygen.

In the field of heterogeneous catalysis, limitations of the surface reaction process inevitably make improving the catalytic efficiency to remove pollutants in water a major challenge. Here, we report a unique structure of Fe surface-gradient-doped CuO that improves the overall catalytic processes of adsorption, electron transfer, and desorption. Interestingly, gradient doping leads to an imbalanced charge distribution in the crystal structure, thereby promoting the adsorption and electron transport efficiency of peroxymonosulfate (PMS). The orbital hybridization of Fe also improves the electronic activity. More importantly, the occupied d-orbital distribution is closer to the lower energy level, which improves the desorption of the reaction intermediate (1O2). As a result, the production and desorption of 1O2 have been improved, resulting in excellent BPA degradation ability (kinetic rate increased by 67.3 times). Two-dimensional infrared correlation spectroscopy is used to better understand the doping process and catalytic mechanism of Fe-CuO. Fe-O changes before Cu-O and is more active. The Fe-required active sites, active species intensity, and kinetic reaction rates show a good correlation. This research provides a scientific basis for expanding the purification of toxic organic pollutants in complex water environments by heterogeneous catalytic oxidation.

Degradation and regeneration of Fe-N x active sites for the oxygen reduction reaction: the role of surface oxidation, Fe demetallation and local carbon microporosity.

The severe degradation of Fe-N-C electrocatalysts during a long-term oxygen reduction reaction (ORR) has become a major obstacle for application in proton-exchange membrane fuel cells. Understanding the degradation mechanism and regeneration of aged Fe-N-C catalysts would be of particular interest for extending their service life. Herein, we show that the by-product hydrogen peroxide during the ORR not only results in the oxidation of the carbon surface but also causes the demetallation of Fe active sites. Quantitative analysis reveals that the Fe demetallation constitutes the main reason for catalyst degradation, while previously reported carbon surface oxidation plays a minor role. We further reveal that post thermal annealing of the aged catalysts can transform the oxygen functional groups on the carbon surface into micropores. These newly formed micropores not only help to increase the active-site density but also the intrinsic ORR activity of the neighbouring Fe-N4 sites, both contributing to complete activity recovery of aged Fe-N-C catalysts.