Structure Engineering of BiSbSx Nanocrystals Embedded within Sulfurized Polyacrylonitrile Fibers for High Performance of Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) are regarded as promising candidates in next-generation energy storage technology; however, the electrode materials in PIBs are usually restricted by the shortcomings of large volume expansion and poor cycling stability stemming from a high resistance towards diffusion and insertion of large-sized K ions. In this study, BiSbSx nanocrystals are rationally integrated with sulfurized polyacrylonitrile (SPAN) fibres through electrospinning technology with an annealing process. Such a unique structure, in which BiSbSx nanocrystals are embedded inside the SPAN fibre, affords multiple binding sites and a short diffusion length for K+ to realize fast kinetics. In addition, the molecular structure of SPAN features robust chemical interactions for stationary diffluent discharge products. Thus, the electrode demonstrates a superior potassium storage performance with an excellent reversible capacity of 790 mAh g-1 (at 0.1 A g-1 after 50 cycles) and 472 mAh g-1 (at 1 A g-1 after 2000 cycles). It's one of the best performances for metal dichalcogenides anodes for PIBs to date. The unusual performance of the BiSbSx @SPAN composite is attributed to the synergistic effects of the judicious nanostructure engineering of BiSbSx nanocrystals as well as the chemical interaction and confinement of SPAN fibers.

Pt-Chitosan-TiO2 for Efficient Photocatalytic Hydrogen Evolution via Ligand-to-Metal Charge Transfer Mechanism under Visible Light.

The Pt-chitosan-TiO2 charge transfer (CT) complex was synthesized via the sol-gel and impregnation method. The synthesized photocatalysts were thoroughly characterized, and their photocatalytic activity were evaluated toward H2 production through water reduction under visible-light irradiation. The effect of the preparation conditions of the photocatalysts (the degree of deacetylation of chitosan, addition amount of chitosan, and calcination temperature) on the photocatalytic activity was discussed. The optimal Pt-10%DD75-T200 showed a H2 generation rate of 280.4 µmol within 3 h. The remarkable visible-light photocatalytic activity of Pt-chitosan-TiO2 was due to the CT complex formation between chitosan and TiO2, which extended the visible-light absorption and induced the ligand-to-metal charge transfer (LMCT). The photocatalytic mechanism of Pt-chitosan-TiO2 was also investigated. This paper outlines a new and facile pathway for designing novel visible-light-driven photocatalysts that are based on TiO2 modified by polysaccharide biomass wastes that are widely found in nature.

N-doped CoAl oxides from hydrotalcites with enhanced oxygen vacancies for excellent low-temperature propane oxidation.

A series of nitrogen-doped CoAlO (N-CoAlO) were constructed by a hydrothermal route combined with a controllable NH3 treatment strategy. The effects of NH3 treatment on the physico-chemical properties and oxidation activities of N-CoAlO catalysts were investigated. In comparison to CoAlO, a smallest content decrease in surface Co3+ (serving as active sites) while a largest increased amount of surface Co2+ (contributing to oxygen species) are obtained over N-CoAlO/4h among the N-CoAlO catalysts. Meanwhile, a maximum N doping is found over N-CoAlO/4h. As a result, N-CoAlO/4h (under NH3 treatment at 400°C for 4 hr) with rich oxygen vacancies shows optimal catalytic activity, with a T90 (the temperature required to reach a 90% conversion of propane) at 266°C. The more oxygen vacancies are caused by the co-operative effects of N doping and suitable reduction of Co3+ for N-CoAlO/4h, leading to an enhanced oxygen mobility, which in turn promotes C3H8 total oxidation activity dominated by Langmuir-Hinshelwood mechanism. Moreover, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) analysis shows that N doping facilities the decomposition of intermediate species (propylene and formate) into CO2 over the catalyst surface of N-CoAlO/4h more easily. Our reported design in this work will provide a promising way to develop abundant oxygen vacancies of Co-based catalysts derived from hydrotalcites by a simple NH3 treatment.

Amorphous Boron Dispersed in LaCoO3 with Large Oxygen Vacancies for Efficient Catalytic Propane Oxidation.

Unsatisfactory oxygen mobility is a considerable barrier to the development of perovskites for low-temperature volatile organic compounds (VOCs) oxidation. This work introduced small amounts of dispersed non-metal boron into the LaCoO3 crystal through an easy sol-gel method to create more oxygen defects, which are conducive to the catalytic performance of propane (C3 H8 ) oxidation. It reveals that moderate addition of boron successfully induces a high distortion of the LaCoO3 crystal, decreases the perovskite particle size, and produces a large proportion of bulk Co2+ species corresponding to abundant oxygen vacancies. Additionally, surface Co3+ species, as the acid sites, which are active for cleaving the C-H bonds of C3 H8 molecules, are enriched. As a result, the LCB-7 (molar ratio of Co/B=0.93:0.07) displays the best C3 H8 oxidation activity. Simultaneously, the above catalyst exhibits superior thermal stability against CO2 and H2 O, lasting 200 h. This work provides a new strategy for modifying the catalytic VOCs oxidation performance of perovskites by the regulation of amorphous boron dispersion.

ceRNA Network and WGCNA Analyses of Differentially Expressed Genes in Cervical Cancer Tissues for Association with Survival of Patients.

The study aims to search and identify differentially expressed genes (DEGs) in cervical cancer tissues as novel biomarkers to predict cervical cancer prognosis. The Cancer Genome Atlas (TCGA) data on gene expression profiles in cervical cancer were downloaded and analyzed using R software to identify DEGs in cervical cancer tissues. miRNAs targeted by differentially expressed long non-coding RNAs (DElncRNAs) and mRNAs targeted by microRNAs (miRNAs) were identified using the online miRcode, miRTarBase, TargetScan, and miRDB tools. The ceRNA network and lncRNA expression modules in cervical cancer tissues were constructed using weighted gene co-expression network analysis (WGCNA) and analyzed bioinformatically. The Kaplan-Meier analysis was performed to confirm these DEGs as prognostic markers. Immunohistochemical (IHC) analysis was used to verify expression of the hub genes in 10 paired cervical cancer and normal tissues. A total of 1914 DEmRNAs, 210 DElncRNAs, and 67 DEmiRNAs were identified in cervical cancer samples. There were 39 lncRNAs, 19 miRNAs, and 87 mRNAs involved in the ceRNA network and 25 DElncRNAs, three DEmiRNAs, and four mRNAs involved in the ceRNA sub-network. CACNA1C-AS1 was associated with the yellow and blue modules in the ceRNA sub-network, and LIFR-AS1 was associated with the blue module. The DEmRNAs were involved in cancer-related pathways, and three hub genes (i.e., E2F1, CCNB1, and CCNE1) were highly expressed in cervical squamous cell carcinoma and adenocarcinoma tissues and associated with the prognosis of patients. The ceRNA network and WGCNA analyses are useful to identify novel DEGs that can serve as prognostic markers in cervical cancer. The DEGs will be validated in future studies.

Chitosan -NH2 derived efficient Co3O4 catalyst for styrene catalytic oxidation: Simultaneously regulating particle size and Co valence.

In this study, a Co3O4 catalyst is synthesised using the chitosan-assisted sol-gel method, which simultaneously regulates the grain size, Co valence and surface acidity of the catalyst through a chitosan functional group. The complexation of the free -NH2 complex inhibits particle agglomeration; thus, the average particle size of the catalyst decreases from 82 to 31 nm. Concurrently, Raman spectroscopy, hydrogen temperature-programmed reduction, electron paramagnetic resonance spectroscopy and X-ray photoelectron spectroscopy experiments demonstrate that doping with chitosan N sources effectively modulates Co2+ to promote the formation of oxygen vacancies. In addition, water washing after catalyst preparation can considerably improve the low-temperature (below 250 °C) activity of the catalyst and eliminate the side effects of alkali metal on catalyst activity. Moreover, the presence of Brønsted and Lewis acid sites promotes the adsorption of C8H8. Consequently, CS/Co3O4-W presents the highest catalytic oxidation activity for C8H8 at low temperatures (R250 °C = 8.33 µmol g-1 s-1, WHSV = 120,000 mL hr-1∙g-1). In situ DRIFTS and 18O2 isotope experiments demonstrate that the oxidation of the C8H8 reaction is primarily dominated by the Mars-van Krevelen mechanism. Furthermore, CS/Co3O4-W exhibits superior water resistance (1- and 2- vol% H2O), which has the potential to be implemented in industrial applications.

Identification of immunogenic cell death-related subtypes used for predicting survival and immunotherapy of endometrial carcinoma through a bioinformatics analysis.

Immunogenic cell death (ICD) is a unique phenomenon that can trigger comprehensive, adaptive immune responses through damage-associated molecular patterns, offering a promising avenue for tumor immunotherapy. However, the role of ICD-related genes and their correlation with endometrial carcinoma (EC), the most prevalent gynecologic malignancy, remains unclear. This study examined genetic, transcriptional, and clinical data of EC obtained from the Cancer Genome Atlas database. Unsupervised clustering analysis was utilized to identify distinct ICD clusters based on the expression of ICD-related genes. Regarding the different clusters, their survival analysis, assessment of the immune microenvironment, immune cell infiltration, immune checkpoint analysis, and tumor mutation burden analysis were performed. Furthermore, an ICD risk signature was established using univariate Cox regression and least absolute shrinkage and selection operator analysis. The Chi-square test was employed to investigate the relationship between the ICD score and clinical features. Multiple computational analytical tools were used to assess immune annotation, somatic mutations, tumor mutation burden, and response to immunotherapy and chemotherapy drugs in different ICD score groups. Two ICD clusters were identified, indicating that the ICD-high cluster was associated with improved prognosis, abundant immune cell infiltration, and enrichment of pathways related to immunologic activation. Moreover, the ICD risk signature showed predictive value for the immune microenvironment, immunotherapy response, chemotherapy susceptibility, and prognosis in EC. Our findings offer novel insights into personalized treatment strategies for EC patients.

Visible-Light-Driven Photocatalytic Dehydrogenation of Alcohols on TiO2 via Ligand-to-Metal Charge Transfer for Coproduction of H2 and Aldehydes.

Developing visible-light-driven photocatalysts for the catalytic dehydrogenation of organics is of great significance for sustainable solar energy utilization. Here, we first report that aromatic alcohols could be efficiently split into H2 and aldehydes over TiO2 under visible-light irradiation through a ligand-to-metal charge transfer (LMCT) mechanism. A series of TiO2 catalysts with different surface contents of the hydroxyl group (-OH) have been synthesized by controlling the hydrothermal and calcination synthesis methods. An optimal H2 production rate of 18.6 µmol h-1 is obtained on TiO2 synthesized from the hydrothermal method with a high content of surface -OH. Experimental characterizations and comparison studies reveal that the surface -OH markedly influences the formation of LMCT complexes and thus changes the visible-light-driven photocatalytic performance. This work is anticipated to inspire further research endeavors in the design and fabrication of visible-light-driven photocatalyst systems based on the LMCT mechanism to realize the simultaneous synthesis of clean fuel and fine chemicals.

Crystal Plane Effect of Co3O4 on Styrene Catalytic Oxidation: Insights into the Role of Co3+ and Oxygen Mobility at Diverse Temperatures.

In the oxidation reaction of volatile organic compounds catalyzed by metal oxides, distinguishing the role of active metal sites and oxygen mobility at specific preferentially exposed crystal planes and diverse temperatures is challenging. Herein, Co3O4 catalysts with four different preferentially exposed crystal planes [(220), (222), (311), and (422)] and oxygen vacancy formation energies were synthesized and evaluated in styrene complete oxidation. It is demonstrated that the Co3O4 sheet (Co3O4-I) presents the highest C8H8 catalytic oxidation activity (R250 °C = 8.26 µmol g-1 s-1 and WHSV = 120,000 mL h-1 g-1). Density functional theory studies reveal that it is difficult for the (311) and (222) crystal planes to form oxygen vacancies, but the (222) crystal plane is the most favorable for C8H8 adsorption regardless of the presence of oxygen vacancies. The combined analysis of temperature-programmed desorption and temperature-programmed surface reaction of C8H8 proves that Co3O4-I possesses the best C8H8 oxidation ability. It is proposed that specific surface area is vital at low temperature (below 250 °C) because it is related to the amount of surface-adsorbed oxygen species and low-temperature reducibility, while the ratio of surface Co3+/Co2+ plays a decisive role at higher temperature because of facile lattice oxygen mobility. In situ diffuse reflectance infrared Fourier spectroscopy and the 18O2 isotope experiment demonstrate that C8H8 oxidation over Co3O4-I, Co3O4-S, Co3O4-C, and Co3O4-F is mainly dominated by the Mars-van Krevelen mechanism. Furthermore, Co3O4-I shows superior thermal stability (57 h) and water resistance (1, 3, and 5 vol % H2O), which has the potential to be conducted in the actual industrial application.

3D printed cylindrical capsules as a Chlorella pyrenoidosa immobilization device for removal of lead ions contamination.

Immobilization is considered as a promising strategy toward the practical applications of powdered adsorbent. Herein, three dimensional (3D) printing cylindrical capsules with cross-linked PVA hydrogels membrane in encapsulate Chlorella pyrenoidosa (Cp) were utilized for removal of lead ions. The chemical compositions, hydrogels performance and morphologies of the membranes were determined by Fourier transformed infrared spectroscopy (FTIR), cross-linking degree, swelling degree, membrane flux and scanning electron microscopy (SEM). It is found that PVA cross-linking structure is successfully synthesized on the surface of capsule body and cap due to the presence of PVA in the filament. The lead ions adsorption capacity related to initial concentration of 50 mg/L in 48 h is reached 75.61%, revealing a good removal ability. The self-floating 3D printed capsules device also shows an excellent recovering property. After 7 runs of adsorption experiment, the lead ions adsorption ratio remains 78.56%, which will bring a broad prospect in wastewater treatment, chemical slow release along with sample preparation and separation.

Electrochemical CO2 Reduction on Cu: Synthesis-Controlled Structure Preference and Selectivity.

The electrochemical CO2 reduction reaction (ECO2 RR) on Cu catalysts affords high-value-added products and is therefore of great practical significance. The outcome and kinetics of ECO2 RR remain insufficient, requiring essentially the optimized structure design for the employed Cu catalyst, and also the fine synthesis controls. Herein, synthesis-controlled structure preferences and the modulation of intermediate's interactions are considered to provide synthesis-related insights on the design of Cu catalysts for selective ECO2 RR. First, the origin of ECO2 RR intermediate-dominated selectivity is described. Advanced structural engineering approaches, involving alloy/compound formation, doping/defect introduction, and the use of specific crystal facets/amorphization, heterostructures, single-atom catalysts, surface modification, and nano-/microstructures, are then reviewed. In particular, these structural engineering approaches are discussed in association with diversified synthesis controls, and the modulation of intermediate generation, adsorption, reaction, and additional effects. The results pertaining to synthetic methodology-controlled structural preferences and the correspondingly motivated selectivity are further summarized. Finally, the current opportunities and challenges of Cu catalyst fabrication for highly selective ECO2 RR are discussed.

Adsorption-desorption behavior of methylene blue onto aged polyethylene microplastics in aqueous environments.

In this study, polyethylene microplastics were artificially photoaged by xenon light. Experiments were then performed with methylene blue (MB) dye to compare the changes in the structure, properties, and adsorption-desorption behaviors of the aged and virgin polyethylene microplastics. The results showed that the aged polyethylene microplastics were hydrophilic with oxygen-containing functional groups, which enhanced the adsorption capacity of polyethylene for MB from 0.63 mg·g-1 to 8.12 mg·g-1. The adsorption isotherms changed from the Henry model (virgin polyethylene microplastics) to the Langmuir model (aged polyethylene microplastics), indicating that the partitioning function was gradually replaced by a single-layer covering during the adsorption process. In addition, 7% and 17.8% of the MB loaded onto the aged polyethylene microplastics was desorbed into water and a simulated intestinal fluid, respectively. These findings reveal that aged polyethylene microplastics can accumulate MB, thus posing potential risks to aqueous environments and biological tissues.

Boosting total oxidation of propane over CeO2@Co3O4 nanofiber catalysts prepared by multifluidic coaxial electrospinning with continuous grain boundary and fast lattice oxygen mobility.

A one-dimensional (1D) core-shell of Co-Ce oxide has been prepared by multifluidic coaxial electrospinning method and evaluated for the total oxidation of propane (C3H8). Activity and morphological characterizations show that the CeO2@Co3O4 nanofiber catalyst, of which the core is CeO2 and the shell is Co3O4, exhibits excellent oxidation activity. The exposed Co3O4 grown on the outside of the fibers can rapidly react with C3H8 while CeO2 with high oxygen storage capacity in the inside is conductive to the enhanced oxidation rate. Besides, the continuous grain boundary provides a fast mass transfer channel for lattice oxygen, and rich oxygen vacancies favor the mobility of active oxygen species. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) confirms that the CeO2@Co3O4 catalyst have a faster rate of C3H8 adsorption and better oxidation activity with respect to the counterpart using a single-needle electrospinning method. Moreover, the CeO2@Co3O4 catalyst displays excellent thermal stability, and strong resistance against 5 vol% H2O and 5 vol% CO2 at both 300 and 400 °C. Our strategy can give some new insights into morphological engineering to promote active oxygen mobility via the construction of one-dimensional core-shell of metal oxides for catalytic oxidation of VOCs.

Controllable P Doping of the LaCoO3 Catalyst for Efficient Propane Oxidation: Optimized Surface Co Distribution and Enhanced Oxygen Vacancies.

The properties of LaCoO3 are modified by a controllable P doping strategy via a simple sol-gel route. It is demonstrated that appropriate P doping is beneficial for forming a relatively pure perovskite phase and hinders the growth of perovskite nanoparticles. The combined results of density functional theory (DFT), extended X-ray absorption fine structure (EXAFS), X-ray absorption near-edge structure (XANES), temperature-programmed reduction of hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS), and temperature-programmed desorption of ammonia (NH3-TPD) reveal that appropriate P doping gives rise to more oxygen vacancies, optimized distribution of Co ions, and improved surface acidity, which are beneficial for the adsorption of active oxygen species and the activation of propane molecules, resulting in an excellent catalytic oxidation performance. Especially, LaCo0.97P0.03O3 exhibits more surface-active oxygen species, higher bulk Co3+ proportion, increased surface Co2+ species, and increased acidity, resulting in its superior propane oxidation performance, which is dominated by the Langmuir-Hinshelwood mechanism. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirms that the presence of P will accelerate oxygen mobility, which in turn promotes the oxidation rate. Moreover, the obtained LaCo0.97P0.03O3 catalyst displays excellent thermal stability during the 60 h durability test at 400 °C and strong resistance against 5 vol % H2O and/or 5 vol % CO2 for prolonged 150 h.

Visible light-assisted efficient degradation of dye pollutants with biomass-supported TiO2 hybrids.

The objective of this work was to develop a novel organic-inorganic hybrid nanomaterial from agricultural biomass waste for environmental applications. The sugarcane bagasse (SB) supported TiO2 hybrids were firstly synthesized via a sol-gel method. A series of characterizations were carried out to reveal the structures and components of obtained hybrids. Due to organic-inorganic hybrid (OIH) effect and element doping, the SB-TiO2 hybrid can expand its optical absorbance ranging from ultraviolet to visible light. The optimal hybrid catalyst prepared with SB doping amount of 2g in 100mL titanic gel and calcined at 200°C was able to degradate 95.0% methyl orange (MO) in 5h under visible light. This study will pave a new and facile pathway for novel visible light driven photocatalysts based on TiO2 modified by agricultural biomass waste.

Insights into the high performance of Mn-Co oxides derived from metal-organic frameworks for total toluene oxidation.

Mn-Co mixed metal oxide is considered as efficient catalyst for the total oxidation of volatile organic compounds. In this study, nanocube-like metal-organic frameworks (Mn3[Co(CN)6]2·nH2O) are adopted as the precursor to generate Mn-Co oxides with different Mn/Co molar ratios, which affect little on phase structure and textural properties. The obtained MOF-Mn1Co1 with uniform metal dispersion is rich in high valence of surface Mn4+ and Co3+ species, leading to high low-temperature catalytic activity of total toluene oxidation. The results of toluene-TPD followed by TPO and toluene-TPSR match well with the catalytic performances of MOF-Mn1Co1, MOF-Mn1Co2, and MOF-Mn2Co1, and in situ FITR proves that the benzoate route exists over MOF-Mn1Co1. It is found that a moderate ratio of Mn/Co (1:1) favors good low-temperature reducibility and high Oads/Olatt, resulting in superior oxidation performance. However, the stability in the existence of water for MOF-Mn1Co1 is not satisfied, which should be overcome in the future.

Facile fabrication of hollow tubular mixed oxides for selective catalytic reduction of NOx at low temperature: a combined experimental and theoretical study.

A new versatile method was developed for the synthesis of various transition metal oxides with uniform 1D structures via electrospinning combined with heat treatment. The 1D nanowire or hollow tubular structure can be tuned by controlling heating rates. Interestingly, NOx conversion is ca. 99% at 200 °C in hollow tubular CuCo2O4.

Preparation and characterization of electrospun La(1-x)Ce(x)CoO(δ): Application to catalytic oxidation of benzene.

An electrospinning with calcination process was employed for the synthesis of La1-xCexCoOδ (x=0, 0.2, 0.4, 0.6, 0.8, and 1.0) oxides. These catalysts were investigated in terms of total benzene oxidation, and characterized by means of XRD, BET, H2-TPR, SEM, XPS, and TEM techniques. The results show that the amount of Ce doping obviously affects the physicochemical and catalytic properties of La1-xCexCoOδ, and when x=1.0, CeCoOδ exhibits the best activity and highly thermal durability for catalytic oxidation of benzene. Additionally, it is demonstrated that the increased activity over perovskite phase dominated oxides is ascribed to a larger surface area while the activity enhancement over metal oxides mainly results from a higher valance of Co and better redox property.

Cu/Ba/bauxite: an inexpensive and efficient alternative for Pt/Ba/Al2O3 in NOx removal.

Cu/Ba/bauxite possesses superior NOx storage and reduction (NSR) performances, high thermal stability, strong resistance against SO2 poisoning and outstanding regeneration ability in comparison with Pt/Ba/Al2O3. It can serve as a cheap and promising alternative for traditional Pt/Ba/Al2O3 in NOx removal from lean-burn engines.