Synthesis of histidine, serine and folic acid-functionalized and boron and iron-doped graphene quantum dot with excellent optical behavior and peroxidase-like activity for colorimetric and fluorescence detection of H2O2 in food.

Low fluorescence under visible light excitation and catalytic activity limit many applications of graphene quantum dots in optical detection, biosensing, catalysis and biomedical. The paper reports design and synthesis of histidine, serine and folic acid-functionalized and boron and iron-doped graphene quantum dot (Fe/B-GQD-HSF). The Fe/B-GQD-HSF shows excellent fluorescence behavior and peroxidase-like activity. Excitation of 330 nm ultraviolet light produces the strongest blue fluorescence and excitation of 480 nm visible light produces the strongest yellow fluorescence. The specific activity reaches 92.67 U g-1, which is higher than that of other graphene quantum dots. The Fe/B-GQD-HSF can catalyze oxidation of 3,3',5,5'-tetramethylbenzidine with H2O2 to form blue compound. Based on this, it was used for colorimetric and fluorescence detection of H2O2. The absorbance at 652 nm linearly increases with the increase of H2O2 concentration between 0.5 and 100 µM with detection limit of 0.43 µM. The fluorescence signal linearly decreases with the increase of H2O2 concentration between 0.05 and 100 µM with detection limit of 0.035 µM. The analytical method has been satisfactorily applied in detection of H2O2 in food. The study also paves one way for design and synthesis of functional graphene quantum dots with ideal fluorescence behavior and catalytic activity.

Wenshen Xiaozheng Tang alleviates fibrosis in endometriosis by regulating differentiation and paracrine signaling of endometrium-derived mesenchymal stem cells.

ETHNOPHARMACOLOGICAL RELEVANCE: Wenshen Xiaozheng Tang (WXT), a traditional Chinese medicine (TCM) decoction, is effective for treating endometriosis. However, the effect of WXT on endometrium-derived mesenchymal stem cells (eMSCs) which play a key role in the fibrogenesis of endometriosis requires further elucidation. AIMS OF THE STUDY: The aim of this study was to clarify the potential mechanism of WXT in improving fibrosis in endometriosis by investigating the regulation of WXT on differentiation and paracrine of eMSCs. MATERIALS AND METHODS: The nude mice with endometriosis were randomly divided into model group, WXT group and mifepristone group. After 21 days of treatment, the lesion volume was calculated. Fibrosis in the lesions was evaluated by Masson staining and expression of fibrotic proteins. The differentiation of eMSCs in vivo was explored using a fate-tracking experiment. To further clarify the regulation of WXT on eMSCs, primary eMSCs from the ectopic lesions of endometriosis patients were isolated and characterized. The effect of WXT on the proliferation and differentiation of ectopic eMSCs was examined. To evaluate the role of WXT on the paracrine activity of ectopic eMSCs, the conditioned medium (CM) from ectopic eMSCs pretreated with WXT was collected and applied to treat ectopic endometrial stromal cells (ESCs), after which the expression of fibrotic proteins in ectopic ESCs was assessed. In addition, transcriptome sequencing was used to investigate the regulatory mechanism of WXT on ectopic eMSCs, and western blot and ELISA were employed to determine the key mediator. RESULTS: WXT impeded the growth of ectopic lesions in nude mice with endometriosis and reduced collagen deposition and the expression of fibrotic proteins fibronectin, collagen I, α-SMA and CTGF in the endometriotic lesions. The fate-tracking experiment showed that WXT prevented human eMSCs from differentiating into myofibroblasts in the nude mice. We successfully isolated eMSCs from the lesions of patients with endometriosis and demonstrated that WXT suppressed proliferation and myofibroblast differentiation of ectopic eMSCs. Moreover, the expression of α-SMA, collagen I, fibronectin and CTGF in ectopic ESCs was significantly down-regulated by the CM of ectopic MSCs pretreated with WXT. Combining the results of RNA sequencing, western blot and ELISA, we found that WXT not only reduced thrombospondin 4 expression in ectopic eMSCs, but also decreased thrombospondin 4 secretion from ectopic eMSCs. Thrombospondin 4 concentration-dependently upregulated the expression of collagen I, fibronectin, α-SMA and CTGF in ectopic ESCs, indicating that thrombospondin 4 was a key mediator of WXT in inhibiting the fibrotic process in endometriosis. CONCLUSION: WXT improved fibrosis in endometriosis by regulating differentiation and paracrine signaling of eMSCs. Thrombospondin 4, whose release from ectopic eMSCs is inhibited by WXT, may be a potential target for the treatment of endometriosis.

Diosmetin-7-O-ß-D-glucopyranoside from Pogostemonis Herba alleviated SARS-CoV-2-induced pneumonia by reshaping macrophage polarization and limiting viral replication.

ETHNOPHARMACOLOGICAL RELEVANCE: Viral pneumonia is the leading cause of death after SARS-CoV-2 infection. Despite effective at early stage, long-term treatment with glucocorticoids can lead to a variety of adverse effects and limited benefits. The Chinese traditional herb Pogostemonis Herba is the aerial part of Pogostemon Cablin (Blanco) Benth., which has potent antiviral, antibacterial, anti-inflammatory, and anticancer effects. It was used widely for treating various throat and respiratory diseases, including COVID-19, viral infection, cough, allergic asthma, acute lung injury and lung cancer. AIM OF THE STUDY: To investigate the antiviral and anti-inflammatory effects of chemical compounds from Pogostemonis Herba in SARS-CoV-2-infected hACE2-overexpressing mouse macrophage RAW264.7 cells and hACE2 transgenic mice. MATERIALS AND METHODS: The hACE2-overexpressing RAW264.7 cells were exposed with SARS-CoV-2. The cell viability was detected by CCK8 assay and cell apoptotic rate was by flow cytometric assay. The expressions of macrophage M1 phenotype markers (TNF-α and IL-6) and M2 markers (IL-10 and Arg-1) as well as the viral loads were detected by qPCR. The mice were inoculated intranasally with SARS-CoV-2 omicron variant to induce viral pneumonia. The levels of macrophages, neutrophils, and T cells in the lung tissues of infected mice were analyzed by full spectrum flow cytometry. The expressions of key proteins were detected by Western blot assay. RESULTS: Diosmetin-7-O-ß-D-glucopyranoside (DG) presented the strongest anti-SARS-CoV-2 activity. Intervention with DG at the concentrations of 0.625-2.5 µM not only reduced the viral replication, cell apoptosis, and the productions of inflammatory cytokines (IL-6 and TNF-α) in SARS-CoV-2-infected RAW264.7 cells, but also reversed macrophage polarity from M1 to M2 phenotype. Furthermore, treatment with DG (25-100 mg/kg) alleviated acute lung injury, and reduced macrophage infiltration in SARS-COV-2-infected mice. Mechanistically, DG inhibited SARS-COV-2 gene expression and HK3 translation via targeting YTHDF1, resulting in the inactivation of glycolysis-mediated NF-κB pathway. CONCLUSIONS: DG exerted the potent antiviral and anti-inflammatory activities. It reduced pneumonia in SARS-COV-2-infected mice via inhibiting the viral replication and accelerating M2 macrophage polarization via targeting YTHDF1, indicating its potential for COVID-19 treatment.

Enhanced VOC emission with increased temperature contributes to the shift of O3-precursors relationship and optimal control strategy.

Assessing the impact of anthropogenic volatile organic compounds (VOCs) on ozone (O3) formation is vital for the management of emission reduction and pollution control. Continuous measurement of O3 and the major precursors was conducted in a typical light industrial city in the YRD region from 1 May to 25 July in 2021. Alkanes were the most abundant VOC group, contributing to 55.0% of TVOCs concentration (56.43 ± 21.10 ppb). OVOCs, aromatics, halides, alkenes, and alkynes contributed 18.7%, 9.6%, 9.3%, 5.2% and 1.9%, respectively. The observational site shifted from a typical VOC control regime to a mixed regime from May to July, which can be explained by the significant increase of ROx production, resulting in the transition of environment from NOx saturation to radical saturation with respect to O3 production. The optimal O3 control strategy should be dynamically changed depending on the transition of control regime. Under NOx saturation condition, minimizing the proportion of NOx in reduction could lead to better achievement of O3 alleviation. Under mixed control regime, the cut percentage gets the top priority for the effectiveness of O3 control. Five VOCs sources were identified: temperature dependent source (28.1%), vehicular exhausts (19.9%), petrochemical industries (7.2%), solvent & gasoline usage (32.3%) and manufacturing industries (12.6%). The increase of temperature and radiation would enhance the evaporation related VOC emissions, resulting in the increase of VOC concentration and the change of ROx circulation. Our results highlight determination of the optimal control strategies for O3 pollution in a typical YRD industrial city.

Regulating the valence and size of the active center of Co/Al2O3 catalyst improved the performance and selectivity of NH3-SCO.

To improve the activity of Co/Al2O3 catalysts in selective catalytic oxidation of ammonia (NH3-SCO), valence state and size of active centers of Al2O3-supported Co catalysts were adjusted by conducting H2 reduction pretreatment. The NH3-SCO activity of the adjusted 2Co/Al2O3 catalyst was substantially improved, outperforming other catalysts with higher Co-loading. Fresh Co/Al2O3 catalysts exhibited multitemperature reduction processes, enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature. Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts, resulting in different reaction mechanisms for NH3-SCO. However, in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O2 activation capacity caused overoxidation of NH3 to NO and NO2. The NH3-SCO activity of the 2Co/Al2O3 catalyst with low redox capacity was successfully increased while controlling and optimizing the N2 selectivity by modulating the active centers via H2 pretreatment, which is a universal method used for enhancing the redox properties of catalysts. Thus, this method has great potential for application in the design of inexpensive and highly active catalysts.

Development and application of a nitrogen oxides analyzer based on the cavity attenuated phase shift technique.

Nitrogen oxides (NOx) are crucial in tropospheric photochemical ozone (O3) production and oxidation capacity. Currently, the widely used NOx measurement technique is chemiluminescence (CL) (CL-NOx), which tends to overestimate NO2 due to atmospheric oxidation products of NOx (i.e., NOz). We developed and characterized a NOx measurement system using the cavity attenuated phase shift (CAPS) technique (CAPS-NOx), which is free from interferences with nitrogen-containing species. The NOx measured by the CAPS-NOx and CL-NOx analyzers were compared. Results show that both analyzers showed consistent measurement results for NO, but the NO2 measured by the CAPS-NOx analyzer (NO2_CAPS) was mostly lower than that measured by the CL-NOx analyzer (NO2_CL), which led to the deviations in O3 formation sensitivity regime and Ox (= O3 + NO2) sources (i.e., regional background and photochemically produced Ox) determined by the ozone production efficiencies (OPE) calculated from NO2_CL and NO2_CAPS. Overall, OPE_CL exceeded OPE_CAPS by 18.9%, which shifted 3 out of 13 observation days from the VOCs-limited to the transition regime when judging using OPE_CL, as compared to calculations using OPE_CAPS. During the observation period, days dominated by regional background Ox accounted for 46% and 62% when determined using NO2_CL and NO2_CAPS, respectively. These findings suggest that the use of the CL-NOx analyzer tends to underestimate both the VOCs-limited regime and the regional background Ox dominated days. The newly built CAPS-NOx analyzer here can promote the accurate measurement of NO2, which is meaningful for diagnosing O3 formation regimes and Ox sources.

Synergistic photocatalysis for bacteria inactivation and organic pollutant removal by S-scheme heterojunction InVO4/Bi5O7I: Performance evaluation and mechanism investigation.

The low efficiency of charge carrier separation is a major limitation hindering the application of photocatalytic technology. Constructing S-scheme heterojunction photocatalysts not only effectively promotes the separation of charge carriers, but also maximizes the oxidative and reductive capabilities of the two monomers. In this study S-scheme heterogeneous InVO4/Bi5O7I photocatalyst was synthesized by hydrothermal method combined with calcination. The optimal sample 20 % InVO4/Bi5O7I can completely deactivate Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) in 30 min, remove 20 mg/L TC 76.0 % in 60 min and 20 mg/L BPA 93.0 % in 90 min. Intermediate products of TC and BPA degradation were detected using LC-MS, and possible degradation pathways were proposed. The photocurrent and electrochemical impedance spectroscopy (EIS) tests confirm that InVO4/Bi5O7I exhibits excellent photocurrent intensity and photocarrier migration ability, which are crucial reasons for the enhancement of the photocatalytic performance of the InVO4/Bi5O7I composite. Capture experiments indicate that OH, O2-, h+ and e-are reactive species. EPR further confirms the generation of OH and O2-. Combined with Kelvin probe force microscopy (KPFM) and band structure analysis, it is proposed that InVO4/Bi5O7I has an S-scheme charge transfer mechanism.

Construction of a hollow heterojunction interface to accelerate the photocatalytic cleavage of lignin Cß-O bonds.

Photocatalytic splitting of the Cß-O bond is regarded as a prospective strategy for transforming lignin, and it is imperative to develop novel photocatalysts with effective photogenerated charges separation and solar absorption capacity. Herein, a novel hollow ZIF-8/CdS heterostructure photocatalyst was synthesized for the catalytic splitting of lignin Cß-O bonds. The photocatalytic cleavage rate of Cß-O bond of ligin ß-O-4 reached 30.3∙mmol∙h-1∙g-1 within 20 min under visible light exposure. It is noteworthy that the utilization of intricate natural lignin molecules in this photocatalytic system has yielded successful depolymerization. The DFT and XPS results indicate a potential unidirectional electron migration from ZIF-8 to CdS in ZIF-8/CdS composites transfer. This electron transport path follows the direct Z-scheme heterostructure mechanism, resulting in the generation of an internal electric field between ZIF-8 and CdS. Impressively, the synergistic combination of the hollow structure and Z-scheme heterostructure effectively enhances the efficiency of charge carrier separation and maintains a robust redox potential, thereby facilitating Cα-radical generation. This study proposes a novel photocatalyst design strategy that integrates hollow structures and Z-scheme heterojunctions, with the aim of targeting the depolymerization of the Cß-O bond in lignin.

Oxygen vacancy-rich K-Mn3O4@CeO2 catalyst for efficient oxidation degradation of formaldehyde at near room temperature.

Synthesis of catalysts with high catalytic degradation activity for formaldehyde (HCHO) at room temperature is highly desirable for indoor air quality control. Herein, a novel K-Mn3O4@CeO2 catalyst with excellent catalytic oxidation activity toward HCHO at near room temperature was reported. In particular, the K addition in K-Mn3O4@CeO2 considerably enhanced the oxidation activity, and importantly, 99.3 % conversion of 10 mL of a 40 mg/L HCHO solution at 30 °C for 14 h was achieved, with simultaneous strong cycling stability. Moreover, the addition of K species considerably influenced the chemical valence state of Mn from +4 (ε-MnO2) to +8/3 (Mn3O4) on the surface of CeO2, which obviously changed the tunnel structure and the number of oxygen vacancies. One part of K species is uniformly dispersed on K-Mn3O4@CeO2, and the other part exists in the tunnel structure of Mn3O4@CeO2, which is mainly used to balance the negative charge of the tunnel and prevent collapse of the structure, providing enough active sites for the catalytic oxidation of HCHO. We observed a phase transition from tunneled KMnO2 to Mn3O4 to tunneled MnO2 with the decreasing K+ content, in which K-Mn3O4@CeO2 exhibited higher HCHO oxidation activity. In addition, K-Mn3O4@CeO2 exhibited lower oxygen vacancy formation and HCHO adsorption energies in aqueous solution based on density functional theory calculations. This is because the K species provide more active oxygen species and richer oxygen vacancies on the surface of K-Mn3O4@CeO2, promote the mobility of lattice oxygen and the room-temperature reduction properties of oxygen species, and enhance the ability of the catalyst to replenish the consumed oxygen species. Finally, a possible HCHO catalytic oxidation pathway on the surface of K-Mn3O4@CeO2 catalyst is proposed.

Hierarchical Bi2O3 nanosheets and ZIF-8 derived porous nitrogen-doped carbon fibers as novel assembled nanocomposites for high-performance flexible supercapacitors.

The unique design of the core-shell heterostructure is significant for obtaining electrode materials with excellent electrochemical properties. In this paper, porous carbon nanofibers (NPC@PPZ) embedded with N-doped porous carbon nanoparticles are used to construct flexible electrodes (NPC@PPZ@Bi2O3). Zeolite imidazole skeleton (ZIF)-8 and poly(methyl methacrylate) (PMMA) derived porous carbon fibers and Bi2O3 nanosheets, were utilized as the porous core and multilayer shell, respectively. The unique core and shell result in abundant pores and channels for fast ion transport and storage, high specific surface area, and additional electroactive sites. This perfect structural design enables the NPC@PPZ@Bi2O3 composite electrode to have excellent electrochemical performance. The results show that this electrode can obtain a high specific capacitance of 697 F g-1 at a current density of 1 A g-1 and a stable cycling performance at a high current density of 5 A g-1. The strategy developed in this study provides a new approach for the design and fabrication of flexible supercapacitors by electrostatic spinning combined with hierarchical porous structures.

Low blue-hazard white-light emission based on color-tunable triplet-triplet annihilation upconversion.

The commonly used artificial light sources, such as fluorescent lamps and white light-emitting diodes, often have a high ratio of blue light emission, which poses potential blue light hazards, especially one of the main culprits leading to eye diseases. Therefore, developing novel white lighting sources with low blue-hazard is highly appreciated. In this work, an air-stable and color-tunable triplet-triplet annihilation upconversion (TTA-UC) mechanism was proposed to realize the low blue-hazard white-light emission. The proposed design was composed of three primary RGB colors from the annihilator (9,10-diphenylanthracene, DPA), the laser excitation source, and the photosensitizer (palladium (II) octaetylporphyrin, PdOEP), respectively. The introduction of oil-in-water (o/w) microemulsion can effectively block the potential oxygen-induced triplet-quenching and benefit high UC efficiency. Moreover, either raising ambient temperatures or adding isobutanol can activate the UC process to yield white-light emission. Notably, the white-light emission with a Commission Internationale de l'Eclairage (CIE) coordinate of (0.33, 0.33) as well as a low ratio of blue emission (14.2 %) was achieved at an ambient temperature of 42 °C. Therefore, the proposed air-stable TTA-UC mechanism can significantly lower the blue-hazard and provide a novel solution for applications in lighting and display.

Synthesis of novel nanoflowers-like P, K co-doped graphitic carbon nitride for efficient H2O2 photoproduction.

Photocatalytic oxygen reduction is considered an economical and green way to produce H2O2. Graphitic carbon nitride is a common photocatalyst, but its activity is limited by the low specific surface area and the high recombination rate of photogenerated electron-hole pairs. Herein, nanoflowers-like phosphorus (P) and potassium (K) co-doped graphitic carbon nitride (PKCN) is synthesized by co-polymerization of ammonium dihydrogen phosphate and melamine in the mixed molten salt (KCl/LiCl) medium. Within 90 min, the synthesized PKCN-0.05 can produce 4.97 mmol L-1 of H2O2, which is 7.8 times higher than that of pure bulk g-C3N4. The enhanced photocatalytic performance of PKCN-0.05 is mainly attributed to the following: 1) KCl/LiCl molten salt induces melamine to form a three-dimensional flower-like morphology, which expands the specific surface area, exposes more active sites, and improves the light utilization efficiency; 2) high crystallinity of PKCN-0.05 and the K ions inserted between the interlayers are beneficial for accelerating electron transfer; 3) the formation of PN bonds and the existence of N vacancies promotes the separation of photoproduced carriers; 4) the negatively shifted conduction band of PKCN-0.05 favors oxygen reduction.

Solar evaporation of liquid marbles with Fe3O4/CNT hybrid nanostructures.

HYPOTHESIS: Through the rational design of nanomaterial composites, broadband light harvesting and good thermal insulation can be achieved simultaneously to improve the efficiency of water evaporation. EXPERIMENT: Solar evaporation experiments were carried out on liquid marbles (LMs) coated with Fe3O4 nanoparticles, carbon nanotubes (CNTs) and hybrid nanomaterials (Fe3O4/CNTs) with different mass ratios of 2:1, 1:1 and 1:2. FINDING: The results showed that the mixture of Fe3O4/CNTs enhances the light harvesting ability and solar interfacial evaporation performance. Fe3O4/CNT-LM at the mass ratio of 2:1 case provides the highest evaporation rate of 11.03 µg/s, which is about 1.22 and 1.34 times higher than that of Fe3O4 and CNT, respectively. This high performance is mainly due to the synergistic effect between Fe3O4 nanoparticles and CNTs, as the hybrid nanostructure significantly improves the both photothermal conversion and heat localization capability. Numerical simulation further supports that the composite can concentrate the electromagnetic field and heat at the phase-change interface. This leads to a rapid evaporation of the boundary region. This study provides a novel approach to a three-dimensional interface by assembling nanomaterials on the drop surface to enhance evaporation, which may have far-reaching implications for seawater desalination.

Enhanced photocatalytic performance of NiFe2O4/ZnIn2S4 p-n heterojunction for efficient degradation of tetracycline.

The persistent release of tetracycline into the environment significantly endangers both ecosystems and human health. Zinc indium sulfide (ZnIn2S4) capable to degrade tetracycline pollutants under visible light irradiation has attracted extensive attentions and great effort has been devoted to augment its catalytic efficacy. In this work, we synthesized a p-n heterojunction, NiFe2O4/ZnIn2S4, to enhance the carrier migration rate and explained the intrinsic mechanism by density functional theory. When the heterojunction was formed, carriers traversed from the n-type NiFe2O4 to the p-type ZnIn2S4, instigating the emergence of a built-in electric field to facilitate the separation of carriers. 2 %-NiFe2O4/ZnIn2S4 exhibited excellent photocatalytic efficiency in tetracycline (TC) degradation and total organic carbon (TOC) removal. Compared to pure ZnIn2S4 and NiFe2O4, the TC degradation rates of 2 %-NiFe2O4/ZnIn2S4 were 2.0 times and 16.9 times higher, respectively. Additionally, 2 %-NiFe2O4/ZnIn2S4 had a saturation magnetization intensity of 3.05 emu/g, allowing for rapid recovery of the catalyst under a magnetic field. Superoxide radicals (O2-) and holes (h+) were the primary active species driving the degradation process. Furthermore, potential reaction pathways of tetracycline in this photocatalytic process were determined and bioconcentration factor and developmental toxicity of the intermediate products were accessed. This work held great potentials for wastewater treatment and provided a pathway for the development of magnetic recyclable photocatalysts.

Green light all the way: Triple modification synergistic modification effect to enhance the photoelectrochemical water oxidation performance of BiVO4 photoanode.

The recombination of photogenerated electron-hole pairs of the photoanode seriously impairs the application of bismuth vanadate (BiVO4) in photoelectrochemical water splitting. To address this issue, we prepared a Yb:BiVO4/Co3O4/FeOOH composite photoanode by employing drop-casting and soaking methods to attach Co3O4/FeOOH cocatalysts to the surface of ytterbium-doped BiVO4. The prepared Yb:BiVO4/Co3O4/FeOOH photoanode demonstrates a high photocurrent density of 4.89 mA cm-2 at 1.23 V versus the reversible hydrogen electrode (RHE), which is 5.1 times that of bare BiVO4 (0.95 mA cm-2). Detailed characterization and testing demonstrated that Yb doping narrows the band gap and significantly enhances the carrier density. Furthermore, Co3O4 serves as a hole transfer layer to expedite hole migration and diminish recombination, while FeOOH offers additional active sites and minimizes surface trap states, thus boosting stability. The synergistic effects of Yb doping and Co3O4/FeOOH cocatalyst significantly improved the reaction kinetics and overall performance of PEC water oxidation. This work provides a strategy for designing efficient photoanodes for PEC water oxidation.

Regulating the zinc ion transport kinetics of Mn3O4 through copper doping towards high-capacity aqueous Zn-ion battery.

High working voltage, large theoretical capacity and cheapness render Mn3O4 promising cathode candidate for aqueous zinc ion batteries (AZIBs). Unfortunately, poor electrochemical activity and bad structural stability lead to low capacity and unsatisfactory cycling performance. Herein, Mn3O4 material was fabricated through a facile precipitation reaction and divalent copper ions were introduced into the crystal framework, and ultra-small Cu-doped Mn3O4 nanocrystalline cathode materials with mixed valence states of Mn2+, Mn3+ and Mn4+ were obtained via post-calcination. The presence of Cu acts as structural stabilizer by partial substitution of Mn, as well as enhance the conductivity and reactivity of Mn3O4. Significantly, based on electrochemical investigations and ex-situ XPS characterization, a synergistic effect between copper and manganese was revealed in the Cu-doped Mn3O4, in which divalent Cu2+ can catalyze the transformation of Mn3+ and Mn4+ to divalent Mn2+, accompanied by the translation of Cu2+ to Cu0 and Cu+. Benefitting from the above advantages, the Mn3O4 cathode doped with moderate copper (abbreviated as CMO-2) delivers large discharge capacity of 352.9 mAh g-1 at 100 mA g-1, which is significantly better than Mn3O4 (only 247.8 mAh g-1). In addition, CMO-2 holds 203.3 mAh g-1 discharge capacity after 1000 cycles at 1 A g-1 with 98.6 % retention, and after 1000 cycles at 5 A g-1, it still performs decent discharge capacity of 104.2 mAh g-1. This work provides new ideas and approaches for constructing manganese-based AZIBs with long lifespan and high capacity.

Empowering lithium-ion storage: unveiling the superior performance of niobium-based oxide/perovskite heterojunction with built-in electric field.

The increasing demand for high-performance electrode materials in lithium-ion batteries has driven significant attention towards Nb2O5 due to its high working voltage, large theoretical capacity, environmental friendliness, and cost-effectiveness. However, inherent drawbacks such as poor electrical conductivity and sluggish electrochemical reaction kinetics have hindered its lithium storage performance. In this study, we introduced KCa2Nb3O10 into Nb2O5 to form a heterojunction, creating a built-in electric field to enhance the migration and diffusion of Li+, effectively promoting electrochemical reaction kinetics. Under the regulation of the built-in electric field, the charge transfer resistance of the KCa2Nb3O10/Nb2O5 anode decreased by 3.4 times compared to pure Nb2O5, and the Li+ diffusion coefficient improved by two orders of magnitude. Specifically, the KCa2Nb3O10/Nb2O5 anode exhibited a high capacity of 276 mAh g-1 under 1 C, retaining a capacity of 128 mAh g-1 even at 100 C. After 3000 cycles at 25 C, the capacity degradation was only 0.012% per cycle. Through combined theoretical calculations and experimental validation, it was found that the built-in electric field induced by the heterojunction interface contributed to an asymmetric charge distribution, thereby improving the rates of charge and ion migration within the electrode, ultimately enhancing the electrochemical performance of the electrode material. This study provides an effective approach for the rational design of high-performance electrode materials.

Control interfacial charge transfer behavior by creating surface defects on structure unit of heterojunction to drive carrier separation for enhancing photocatalytic CO2 reduction.

Controlling interfacial charge transfer behavior of heterojunction is an arduous issue to efficiently drive separation of photogenerated carriers for improving the photocatalytic activity. Herein, the interface charge transfer behavior is effectively controlled by fabricating an unparalleled VO-NiWO4/PCN heterojunction that is prepared by encapsulating NiWO4 nanoparticles rich in surface oxygen vacancies (VO-NiWO4) in the mesoporous polymeric carbon nitride (PCN) nanosheets. Experimental and theoretical investigations show that, differing with the traditional p-n junction, the direction of built-in electric field between p-type NiWO4 and n-type PCN is reversed interestingly. The strongly codirectional built-in electric field is also produced between the surface defect region and inside of VO-NiWO4 besides in the space charge region, the dual drive effect of which forcefully propels interface charge transfer through triggering Z-Scheme mechanism, thus significantly improving the separation efficiency of photogenerated carriers. Moreover, the unique mesoporous encapsulation structure of VO-NiWO4/PCN heterostructure can not only afford the confinement effect to improve the reaction kinetics and specificity in the CO2 reduction to CO, but also significantly reduce mass transfer resistance of molecular diffusion towards the reaction sites. Therefore, the VO-NiWO4/PCN heterostructure demonstrates the preeminent activity, stability and reusability for photocatalytic CO2 reduction to CO reaction. The average evolution rate of CO over the optimal 10 %-VO-NiWO4/PCN composite reaches around 2.5 and 1.8 times higher than that of individual PCN and VO-NiWO4, respectively. This work contributes a fresh design approach of interface structure in the heterojunction to control charge transfer behaviors and thus improve the photocatalytic performance.

Synergistic regulation of d-band center photocatalytic hydrogen evolution at S-scheme heterojunction reduction sites through defect engineering and interface electric field.

The efficiency of photocatalytic hydrogen evolution can be significantly enhanced while maintaining cost-effectiveness through the synergistic effect of defect surface engineering and multi-component heterojunctions. The structure and properties of NiCo2O4 nanorods were modified by inducing oxygen vacancies at different temperatures in this study, resulting in improved optical properties and electron adsorption capacity. The presence of oxygen vacancies leads to a reduction in the band gap of NiCo2O4, thereby enhancing electron transport efficiency through band gap engineering. Simultaneously, surface properties undergo changes, and vacancy defects serve as electron trapping centers, facilitating an increased participation of electrons in the hydrogen evolution reaction process. The dodecahedron KMP with a cavity structure is additionally introduced to form an S-scheme heterojunction with NiCo2O4. This establishes a novel mechanism for electron transport, which effectively enhances the separation of electron-hole pairs and improves the redox capacity of the photocatalytic system. The adsorption of intermediates in the hydrogen production process is enhanced through synergistic regulation of d-band centers via surface defect engineering and S-scheme heterojunction. Additionally, this approach improves the separation efficiency of electron-hole pairs and accelerates electron transfer dynamics, significantly enhancing hydrogen production efficiency.

A novel Bi12O17Cl2/GO/Co3O4 Z-type heterojunction photocatalyst with ZIF-67 derivative modified for highly efficient degradation of antibiotics under visible light.

Levofloxacin (LVX) is difficult to be naturally degraded by microorganisms in water, and its residues in water will pose significant risks to human health and ecological environment. In this study, Bi12O17Cl2 was used as the main body, Bi12O17Cl2/GO/Co3O4 composite photocatalyst was prepared by pyrolysis of zeolitic imidazolate framework-67 (ZIF-67) combined with in-situ precipitation method and used to degrade LVX. A sequence of characterizations shows that addition of Co3O4 and graphene oxide (GO) increases the visible light response range, improves the separation efficiency of photogenerated electrons and holes (e--h+) of photocatalyst, and thus improves the degradation efficiency of LVX. Under the optimal reaction conditions, the LVX degradation rate of Bi12O17Cl2/1.5GO/7.5Co3O4 can reach 91.2 % at 120 min, and its reaction rate constant is the largest (0.0151 min-1), which is 2.17, 13.14 and 1.53 times that of Bi12O17Cl2, Co3O4 and Bi12O17Cl2/7.5Co3O4, respectively, showing better photocatalytic performance. Simultaneously, the recycling stability of Bi12O17Cl2/1.5GO/7.5Co3O4 was also verified. The capture experiments and electron EPR test results showed that superoxide radicals (•O2-) and photogenerated holes (h+) were the primary active substances in the reaction process. Finally, combined with HPLC-MS results, the photocatalytic degradation pathway of LVX was derived. This work will provide a theoretical basis for the design of Metal Organic Frameworks (MOFs)-derivative modified Bi12O17Cl2-based photocatalysts.