From nano- to macroarchitectures: designing and constructing MOF-derived porous materials for persulfate-based advanced oxidation processes.

Persulfate-based advanced oxidation processes (PS-AOPs) have gained significant attention as an effective approach for the elimination of emerging organic contaminants (EOCs) in water treatment. Metal-organic frameworks (MOFs) and their derivatives are regarded as promising catalysts for activating peroxydisulfate (PDS) and peroxymonosulfate (PMS) due to their tunable and diverse structure and composition. By the rational nanoarchitectured design of MOF-derived nanomaterials, the excellent performance and customized functions can be achieved. However, the intrinsic fine powder form and agglomeration ability of MOF-derived nanomaterials have limited their practical engineering application. Recently, a great deal of effort has been put into shaping MOFs into macroscopic objects without sacrificing the performance. This review presents recent advances in the design and synthetic strategies of MOF-derived nano- and macroarchitectures for PS-AOPs to degrade EOCs. Firstly, the strategies of preparing MOF-derived diverse nanoarchitectures including hierarchically porous, hollow, yolk-shell, and multi-shell structures are comprehensively summarized. Subsequently, the approaches of manufacturing MOF-based macroarchitectures are introduced in detail. Moreover, the PS-AOP application and mechanisms of MOF-derived nano- and macromaterials as catalysts to eliminate EOCs are discussed. Finally, the prospects and challenges of MOF-derived materials in PS-AOPs are discussed. This work will hopefully guide the design and development of MOF-derived porous materials in SR-AOPs.

Hollow CoP/carbon as an efficient catalyst for the peroxymonosulfate activation derived from phytic acid assisted metal-organic framework.

The catalyst's composition and rationally designed structure is significantly interlinked with its performance for wastewater remediation. Here, a novel hollow cobalt phosphides/carbon (HCoP/C) as an efficient catalyst for activating peroxymonosulfate (PMS) was prepared. The ZIF-67 was synthesized first, followed by phytic acid (PA) etching and then heat treatment was used to get HCoP/C. The PA was used as an etching agent and a source of phosphorus to prepare HCoP/C. To analyze catalytic performance, another solid cobalt phosphides/carbon (SCoP/C) catalyst was prepared for comparison. In contrast to SCoP/C, the HCoP/C exhibited higher catalytic efficiency when used to activate PMS to degrade Bisphenol A (BPA). The results showed that about 98 % of targeted pollutant BPA was removed from the system in 6 min with a rate constant of 0.78 min-1, which was 4 times higher than the solid structure catalyst. The higher catalytic performance of HCoP/C is attributed to its hollow structure. In the study, other parameters such as BPA concentration, temperature, pH, and different catalyst amount were also tested. Moreover, the electron paramagnetic resonance (EPR) and radical quenching analysis confirmed that sulfate radicals were dominant in the HCoP/C/PMS system.

Ultrathin nitrogen-doped carbon Ti3C2Tx-TiN heterostructure derived from ZIF-8 nanoparticles sandwiched MXene for high-performance capacitive deionization.

Rational design of high-performance electrode materials is crucial for enhancing desalination performance of capacitive deionization (CDI). Here, ultrathin nitrogen-doped carbon/Ti3C2Tx-TiN (NC/MX-TiN) heterostructure was developed by pyrolyzing zeolite imidazolate framework-8 (ZIF-8) nanoparticles sandwiched MXene (ZSM), which were formed by assembling ultrafine ZIF-8 nanoparticles with size of 20 nm on both sides of MXene nanosheets. The introduction of ultrasmall ZIF-8 particles allowed for in situ nitridation of the MXene during pyrolysis, forming consecutive TiN layers tightly connected to the internal MXene. The two-dimensional (2D) heterostructure exhibited remarkable properties, including high specific surface area and excellent conductivity. Additionally, the resulting TiN demonstrated exceptional redox capability, which significantly enhanced the performance of CDI and ensured cycling stability. Benefiting from these advantages, the NC/MX-TiN exhibited a maximum adsorption capacity of 45.6 mg g-1 and a steady cycling performance in oxygenated saline water over 50 cycles. This work explores the rational design and construction of MXene-based 2D heterostructure and broadens new horizons for the development of novel CDI electrode materials.

Ultralight and Robust Covalent Organic Framework Fiber Aerogels.

Shaping covalent organic frameworks (COFs) into macroscopic objects with robust mechanical properties and hierarchically porous structure is of great significance for practical applications but remains formidable and challenging. Herein, a general and scalable protocol is reported to prepare ultralight and robust pure COF fiber aerogels (FAGs), based on the epitaxial growth synergistic assembly (EGSA) strategy. Specifically, intertwined COF nanofibers (100-200 nm) are grown in situ on electrospinning polyacrylonitrile (PAN) microfibers (≈1.7 µm) containing urea-based linkers, followed by PAN removal via solvent extraction to obtain the hollow COF microfibers. The resultant COF FAGs possess ultralow density (14.1-15.5 mg cm-3 ) and hierarchical porosity that features both micro-, meso-, and macropores. Significantly, the unique interconnected structure composed of nanofibers and hollow microfibers endows the COF FAGs with unprecedented mechanical properties, which can fully recover at 50% strain and be compressed for 20 cycles with less than 5% stress degradation. Moreover, the aerogels exhibit excellent capacity for organic solvent absorption (e.g., chloroform uptake of >90 g g-1 ). This study opens new avenues for the design and fabrication of macroscopic COFs with excellent properties.

Iron containing sludge-derived carbon towards efficient peroxymonosulfate activation: Active site synergy, performance and alternation mechanism.

Converting industrial sludge into catalytic materials for water purification is a promising approach to simultaneously realize effective disposal of sludge and resource of water. However, manipulating the high efficiency remains a huge challenge due to the difficulty in the active sites control of the sludge. Herein, we proposed a constitutive modulation strategy by the combination of hydrothermal and pyrolysis (HTP) for the fabrication of defects-assistant Fe containing sludge-derived carbon catalysts on upgrading performance in peroxymonosulfate (PMS) activation for pollutant degradation. Adjustable defects on dyeing sludge-derived carbon catalysts (DSCC) were achieved by introducing oxygen or nitrogen functional precursors (hydroquinone or p-phenylenediamine) during hydrothermal processes and by further pyrolysis, where O was detrimental while N was beneficial to defect generation. Compared to the DSCC with less defects (DHSC-O), the defect-rich sample (DHSC-2N) exhibited superior catalytic performance of PMS activation for bisphenol A (BPA) elimination (k = 0.45 min-1, 2.52 times of DHSC-O), as well as 81.4% total organic carbon (TOC) removal. Meanwhile, the degradation capacity was verified in wide pH range (2.1-8.1) and various aqueous matrices, reflecting the excellent adaptability and anti-interference performance. Furthermore, the continuous-flow experiments on industrial wastewater showed synchronous BPA and chemical oxygen demand (COD) removal, implying great potential for practical application. Solid electron paramagnetic resonance (EPR) and 57Fe Mösssbauer spectra analysis indicated that the defects acted as secondary active sites for Fe sites, which were beneficial to accelerating the electron transfer process. The only Fe active sites preferred the radical pathway. The controllable reaction tendency provides possibilities for the on-demand design of sludge-based catalysts to meet the requirements of practical wastewater treatment under Fenton-like reaction.

Enhancing Uranium Removal with a Titanium-Incorporated Zirconium-Based Metal-Organic Framework.

The urgent need to efficiently and rapidly decontaminate uranium contamination in aquatic environments underscores its significance for ecological preservation and environmental restoration. Herein, a series of titanium-doped zirconium-based metal-organic frameworks were meticulously synthesized through a stepwise process. The resultant hybrid bimetallic materials, denoted as NU-Zr-n%Ti, exhibited remarkable efficiency in eliminating uranium (U (VI)) from aqueous solution. Batch experiments were executed to comprehensively assess the adsorption capabilities of NU-Zr-n%Ti. Notably, the hybrid materials exhibited a substantial increase in adsorption capacity for U (VI) compared to the parent NU-1000 framework. Remarkably, the optimized NU-Zr-15%Ti displayed a noteworthy adsorption capacity (∼118 mg g-1) along with exceptionally rapid kinetics at pH 4.0, surpassing that of pristine NU-1000 by a factor of 10. This heightened selectivity for U (VI) persisted even when diverse ions exist. The dominant mechanisms driving this high adsorption capacity were identified as the robust electrostatic attraction between the negatively charged surface of NU-Zr-15%Ti and positively charged U (VI) species as well as surface complexation. Consequently, NU-Zr-15%Ti emerges as a promising contender for addressing uranium-laden wastewater treatment and disposal due to its favorable sequestration performance.

Improvement of peroxymonosulfate utilization efficiency for sulfamethazine degradation by photo-electron activating peroxymonosulfate: Performance and mechanism.

Enhancing the utilization efficiency of oxidant is of great importance for advanced oxidation processes (AOPs). Herein, nitrogen-doped titania dioxide/carbon (NTC7) catalyst was fabricated via pyrolyzing NH2-MIL-125 under nitrogen atmosphere at 700 °C. Excitation of NTC7 under visible light can successfully achieve efficient activation of peroxymonosulfate (PMS) (NTC7 + PMS + Vis). Degradation performance and PMS activation mechanism were systematically investigated using sulfamethazine (SMT) as the target pollutant. It was found that the photo-generated electrons excited from NTC7 under visible light played the dominant role in enhancing the productive consumption of PMS. Its utilization increased by 66 % (Δ[PMS]/Δ[SMT] = 7.0) in NTC7 + PMS + Vis process and the degradation rate was 2.14 times higher than that of NTC7 + PMS process. The ketonic CO groups and structural defects were responsible for the generation of 1O2 in dark activation while radicals (•OH, O2•-) were more inclined to be continuously produced in NTC7 + PMS + Vis process. The involved degradation pathways, intermediates, and toxicity assessment have been studied in detail. This work provides an effective approach to enhance the utilization efficiency of oxidant for pollutant degradation by AOPs.

Rational Regulation of Co-N-C Coordination for High-Efficiency Generation of 1O2 toward Nearly 100% Selective Degradation of Organic Pollutants.

Single oxygen-based advanced oxidation processes (1O2-AOPs) exhibit great prospects in selective degradation of organic pollutants. However, efficient production of 1O2 via tailored design of catalysts to achieve selective oxidation of contaminants remains challenging. Herein, we develop a simple strategy to regulate the components and coordination of Co-N-C catalysts at the atomic level by adjusting the Zn/Co ratio of bimetallic zeolitic imidazolate frameworks (ZnxCo1-ZIFs). Zn4Co1-C demonstrates 98% selective removal of phenol in the mixed phenol/benzoic acid (phenol/BA) solutions. Density functional theory calculations and experiments reveal that more active CoN4 sites are generated in Zn4Co1-C, which are beneficial to peroxymonosulfate activation to generate 1O2. Furthermore, the correlation between the origin of selectivity and well-defined catalysts is systematically investigated by the electron paramagnetic resonance test and quenching experiments. This work may provide novel insights into selective removal of target pollutants in a complicated water matrix.

Zeolitic imidazolate framework (ZIF-8)/polyacrylonitrile derived millimeter-sized hierarchical porous carbon beads for peroxymonosulfate catalysis.

Well dispersed nanocatalysts on porous substrate with macroscopic morphology are highly desired for the application of heterogeneous catalysis. Traditional fabrication process suffers from multiple steps for controlling the structure on nanocatalysts and matrix or both. Herein, we report a facile strategy for the synthesis of millimeter-sized hierarchical porous carbon beads (HPCBs) which containing well dispersed hollow-nano carbon boxes for peroxymonosulfate catalysis. Specially, the precursors of HPCBs were prepared by phase inversion method, which involving introduction of zeolitic imidazolate framework (ZIF-8) nanocubes into polyacrylonitrile (PAN) solutions followed by solidification of the mixture. After pyrolysis, nitrogen doped and hierarchical porous HPCBs with diameter of about 1.2 mm were obtained. The merits of our synthesis strategy lie in that synchronizes the hollow microstructure evolution with the shaping of ZIF-8 nanocubes into millimeter scale beads. Attribute to its special structure feature and the appropriate chemical composition, the resultant millimeter-sized HPCBs exhibit enhanced catalytic performance by activation of peroxymonosulfate (PMS) for tetracycline degradation. The degradation efficiency of TC is up to 85.1% within 120 min, which is 18% higher than that of ZIF8-Solid/PAN carbon bead (SPCBs). In addition, the possible decomposition pathways, main reactive oxygen species, and reasonable enhanced mechanism for the HPCBs/PMS system are systematically investigated by quenching experiments, electron paramagnetic resonance (EPR) and liquid chromatography-mass spectrometry (LC-MS). This work addresses the issue of easy aggregation and recycling of carbon materials in industrial productions and extends the prospects of carbon materials in engineering applications.

Factors Associated with Gestational Diabetes Mellitus: A Meta-Analysis.

Gestational diabetes mellitus (GDM) is a major public health issue, and the aim of the present study was to identify the factors associated with GDM. Databases were searched for observational studies until August 20, 2020. Pooled odds ratios (ORs) were calculated using fixed- or random-effects models. 103 studies involving 1,826,454 pregnant women were identified. Results indicated that maternal age ≥ 25 years (OR: 2.466, 95% CI: (2.121, 2.866)), prepregnancy overweight or obese (OR: 2.637, 95% CI: (1.561, 4.453)), family history of diabetes (FHD) (OR: 2.326, 95% CI: (1.904, 2.843)), history of GDM (OR: 21.137, 95% CI: (8.785, 50.858)), macrosomia (OR: 2.539, 95% CI: (1.612, 4.000)), stillbirth (OR: 2.341, 95% CI: (1.435, 3.819)), premature delivery (OR: 3.013, 95% CI: (1.569, 5.787)), and pregestational smoking (OR: 2.322, 95% CI: (1.359, 3.967)) increased the risk of GDM with all P < 0.05, whereas history of congenital anomaly and abortion, and HIV status showed no correlation with GDM (P > 0.05). Being primigravida (OR: 0.752, 95% CI: (0.698, 0.810), P < 0.001) reduced the risk of GDM. The factors influencing GDM included maternal age ≥ 25, prepregnancy overweight or obese, FHD, history of GDM, macrosomia, stillbirth, premature delivery, pregestational smoking, and primigravida.

Aidi injection, a traditional Chinese biomedical preparation for gynecologic tumors: a systematic review and PRISMA-compliant meta-analysis.

Aidi injection (ADI), a traditional Chinese biomedical preparation, is a promising adjuvant therapy for gynecologic tumors (GTs), including cervical cancer (CC), endometrial cancer (EC), and ovarian cancer (OC). Although studies have reported positively on ADI therapy, its exact effects and safety in GT patients remain controversial. Therefore, a wide-ranging systematic search of electronic databases was performed for this meta-analysis. Data from 38 trials including 3309 GT patients were analyzed. The results indicated that the combination of conventional treatment and ADI markedly improved the patients' overall response rate (P<0.00001), disease control rate (P<0.00001), and quality of life (P<0.05) compared with conventional treatment alone. Furthermore, patient immunity was enhanced with combined treatment, as indicated by significantly increased percentages of CD3+ (P=0.005) and CD4+ (P<0.00001) and increased CD4+/CD8+ ratio (P=0.001). Most of the adverse events caused by radiochemotherapy such as gastrointestinal issues, leukopenia, thrombocytopenia, and hepatotoxicity, (P<0.05 for all) were significantly alleviated when ADI was used in the GT patients. However, other adverse events such as nephrotoxicity, diarrhea, alopecia, and neurotoxicity did not significantly differ between the two groups. Overall, these results suggest that the combination of conventional and ADI treatment is more effective than conventional treatment alone.

Efficient Removal of Organic Pollutants by Metal-organic Framework Derived Co/C Yolk-Shell Nanoreactors: Size-Exclusion and Confinement Effect.

Selective removal of organic pollutants from surface water with high efficiency is crucial in water purification. Here, yolk-shell Co/C nanoreactors (YSCCNs) are facilely synthesized via pyrolysis of controllably etched ZIF-67 by tannic acid, and their degradation performance on multiple pollutants is demonstrated. To present the structure-performance relationship between the designed nanocatalyst and the selective removal of organic pollutants, bisphenol A (BPA) was selected as the targeted pollutant with coexistence of humus acid (HA). For comparison, solid and hollow ZIF-67 derived Co/C nanoparticles denoted as SCCNs and HCCNs, were also tested. The results show that YSCCNs exhibit enhanced BPA degradation rate of 0.32 min-1, which is 23.1% and 45.4% higher than that of HCCNs and SCCNs in HA (10 ppm) system. The essential improvement can be ascribed to the synergetic effects from shell layer (size-exclusion) and core/shell (confinement effect). The degradation mechanism and pathway are further confirmed by radical quenching experiments and liquid chromatography-mass spectrograph (LC-MS), respectively. In addition, some influential factors, including reaction temperature, pH value, and peroxymonosulfate (PMS) dosage are investigated in detail. This work provides a possible way to selectively remove target contaminant from multiple pollutants in complex water system.