Chongqing Technology and Business University

Graphitic carbon nitride (g-C(3)N(4)), as an intriguing earth-abundant visible light photocatalyst, possesses a unique two-dimensional structure, excellent chemical stability and tunable electronic structure. Pure g-C(3)N(4) suffers from rapid recombination of photo-generated electron-hole pairs resulting in low photocatalytic activity. Because of the unique electronic structure, the g-C(3)N(4) could act as an eminent candidate for coupling with various functional materials to enhance the performance. According to the discrepancies in the photocatalytic mechanism and process, six primary systems of g-C(3)N(4)-based nanocomposites can be classified and summarized: namely, the g-C(3)N(4) based metal-free heterojunction, the g-C(3)N(4)/single metal oxide (metal sulfide) heterojunction, g-C(3)N(4)/composite oxide, the g-C(3)N(4)/halide heterojunction, g-C(3)N(4)/noble metal heterostructures, and the g-C(3)N(4) based complex system. Apart from the depiction of the fabrication methods, heterojunction structure and multifunctional application of the g-C(3)N(4)-based nanocomposites, we emphasize and elaborate on the underlying mechanisms in the photocatalytic activity enhancement of g-C(3)N(4)-based nanocomposites. The unique functions of the p-n junction (semiconductor/semiconductor heterostructures), the Schottky junction (metal/semiconductor heterostructures), the surface plasmon resonance (SPR) effect, photosensitization, superconductivity, etc. are utilized in the photocatalytic processes. Furthermore, the enhanced performance of g-C(3)N(4)-based nanocomposites has been widely employed in environmental and energetic applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation, carbon dioxide reduction, disinfection, and supercapacitors. This critical review ends with a summary and some perspectives on the challenges and new directions in exploring g-C(3)N(4)-based advanced nanomaterials.

The photocatalytic performance of the star photocatalyst g-C3N4 was restricted by the low efficiency because of the fast charge recombination. The present work developed a facile in situ method to construct g-C3N4/g-C3N4 metal-free isotype heterojunction with molecular composite precursors with the aim to greatly promote the charge separation. Considering the fact that g-C3N4 samples prepared from urea and thiourea separately have different band structure, the molecular composite precursors of urea and thiourea were treated simultaneously under the same thermal conditions, in situ creating a novel layered g-C3N4/g-C3N4 metal-free heterojunction (g-g CN heterojunction). This synthesis method is facile, economic, and environmentally benign using easily available earth-abundant green precursors. The confirmation of isotype g-g CN heterojunction was based on XRD, HRTEM, valence band XPS, ns-level PL, photocurrent, and EIS measurement. Upon visible-light irradiation, the photogenerated electrons transfer from g-C3N4 (thiourea) to g-C3N4 (urea) driven by the conduction band offset of 0.10 eV, whereas the photogenerated holes transfer from g-C3N4 (urea) to g-C3N4 (thiourea) driven by the valence band offset of 0.40 eV. The potential difference between the two g-C3N4 components in the heterojunction is the main driving force for efficient charge separation and transfer. For the removal of NO in air, the g-g CN heterojunction exhibited significantly enhanced visible light photocatalytic activity over g-C3N4 alone and physical mixture of g-C3N4 samples. The enhanced photocatalytic performance of g-g CN isotype heterojunction can be directly ascribed to efficient charge separation and transfer across the heterojunction interface as well as prolonged lifetime of charge carriers. This work demonstrated that rational design and construction of isotype heterojunction could open up a new avenue for the development of new efficient visible-light photocatalysts.

Photodynamic therapy (PDT) is a minimally invasive therapeutic modality that has gained great attention in the past years as a new therapy for cancer treatment. PDT uses photosensitizers that, after being excited by light at a specific wavelength, react with the molecular oxygen to create reactive oxygen species in the target tissue, resulting in cell death. Compared to conventional therapeutic modalities, PDT presents greater selectivity against tumor cells, due to the use of photosensitizers that are preferably localized in tumor lesions, and the precise light irradiation of these lesions. This paper presents a review of the principles, mechanisms, photosensitizers, and current applications of PDT. Moreover, the future path on the research of new photosensitizers with enhanced tumor selectivity, featuring the improvement of PDT effectiveness, has also been addressed. Finally, new applications of PDT have been covered.

Graphitic carbon nitride (g-C 3 N 4 ) has been widely investigated and applied in photocatalysis and catalysis, but its performance is still unsatisfactory. Here, we demonstrated that K-doped g-C 3 N 4 with a unique electronic structure possessed highly enhanced visible-light photocatalytic performance for NO removal, which was superior to Na-doped g-C 3 N 4 . DFT calculations revealed that K or Na doping can narrow the bandgap of g-C 3 N 4 . K atoms, intercalated into the g-C 3 N 4 interlayer via bridging the layers, could decrease the electronic localization and extend the π conjugated system, whereas Na atoms tended to be doped into the CN planes and increased the in-planar electron density. On the basis of theoretical calculation results, we synthesized K-doped g-C 3 N 4 and Na-doped g-C 3 N 4 by a facile thermal polymerization method. Consistent with the theoretical prediction, it was found that K was intercalated into the space between the g-C 3 N 4 layers. The K-intercalated g-C 3 N 4 sample showed increased visible-light absorption, efficient separation of charge carriers, and strong oxidation capability, benefiting from the narrowed band gap, extended π conjugated systems, and positive-shifted valence band position, respectively. Despite that the Na-doped g-C 3 N 4 exhibited narrowed bandgap, the high recombination rate of carriers resulted in the reduced photocatalytic performance. Our discovery provides a promising route to manipulate the photocatalytic activity simply by introducing K atoms in the interlayer and gains a deep understanding of doping chemistry with congeners. The present work could provide new insights into the mechanistic understanding and the design of electronically optimized layered photocatalysts for enhanced solar energy conversion.

Background: More than 80% of sewage generated by human activities is discharged into rivers and oceans without any treatment, which results in environmental pollution and more than 50 diseases. 80% of diseases and 50% of child deaths worldwide are related to poor water quality. Methods: This paper selected 85 relevant papers finally based on the keywords of water pollution, water quality, health, cancer, and so on. Results: The impact of water pollution on human health is significant, although there may be regional, age, gender, and other differences in degree. The most common disease caused by water pollution is diarrhea, which is mainly transmitted by enteroviruses in the aquatic environment. Discussion: Governments should strengthen water intervention management and carry out intervention measures to improve water quality and reduce water pollution’s impact on human health.

In order to develop efficient visible light driven photocatalysts for environmental applications, novel polymeric g-C3N4 layered materials with high surface areas are synthesized efficiently from an oxygen-containing precursor by directly treating urea in air between 450 and 600 °C, without the assistance of a template for the first time. The as-prepared g-C3N4 materials with strong visible light absorption have a band gap around 2.7 eV. The crystallinity and specific surface areas of g-C3N4 increases simultaneously when the heating temperatures increases. The g-C3N4 materials are demonstrated to exhibit much higher visible light photocatalytic activity than that of C-doped TiO2 and g-C3N4 prepared from dicyanamide for the degradation of aqueous RhB. The large surface areas, layered structure and band structure in all contributed to the efficient visible light photocatalytic activity. The efficient synthesis method for g-C3N4 combined with efficient photocatalytic activity is of significant interest for environmental pollutants degradation and solar energy conversion in large scale applications.

The recent progress, challenges and promising future on design, synthesis and fabrication of MnO₂for supercapacitors are reviewed and discussed.

We herein demonstrate self-doping of the CO 3 2– anionic group into a wide bandgap semiconductor Bi 2 O 2 CO 3 realized by a one-pot hydrothermal technique. The photoresponsive range of the self-doped Bi 2 O 2 CO 3 can be extended from UV to visible light and the band gap can be continuously tuned. Density functional theory (DFT) calculation results demonstrate that the foreign CO 3 2– ions are doped in the caves constructed by the four adjacent CO 3 2– ions and the CO 3 2– self-doping can effectively narrow the band gap of Bi 2 O 2 CO 3 by lowering the conduction band position and meanwhile generating impurity level. The photocatalytic performance is evaluated by monitoring NO removal from the gas phase, photodegradation of a colorless contaminant (bisphenol A, BPA) in an aqueous solution, and photocurrent generation. In comparison with the pristine Bi 2 O 2 CO 3 which is not sensitive to visible light, the self-doped Bi 2 O 2 CO 3 exhibits drastically enhanced visible-light photoreactivity, which is also superior to that of many other well-known photocatalysts such as P25, C 3 N 4, and BiOBr. The highly enhanced photocatalytic performance is attributed to combination of both efficient visible light absorption and separation of photogenerated electron–hole pairs. The self-doped Bi 2 O 2 CO 3 also shows decent photochemical stability, which is of especial importance for its practical applications. This work demonstrates that self-doping with an anionic group enables the band gap engineering and the design of high-performance photocatalysts sensitive to visible light.

To achieve efficient photocatalytic air purification, we constructed an advanced semimetal-organic Bi spheres-g-C3N4 nanohybrid through the in-situ growth of Bi nanospheres on g-C3N4 nanosheets. This Bi-g-C3N4 compound exhibited an exceptionally high and stable visible-light photocatalytic performance for NO removal due to the surface plasmon resonance (SPR) endowed by Bi metal. The SPR property of Bi could conspicuously enhance the visible-light harvesting and the charge separation. The electromagnetic field distribution of Bi spheres involving SPR effect was simulated and reaches its maximum in close proximity to the Bi particle surface. When the Bi metal content was controlled at 25%, the corresponding Bi-g-C3N4 displayed outstanding photocatalytic capability and transcended those of other visible-light photocatalysts. The Bi-g-C3N4 exhibited a high structural stability under repeated photocatalytic runs. A new visible-light-induced SPR-based photocatalysis mechanism with Bi-g-C3N4 was proposed on the basis of the DMPO-ESR spin-trapping. The photoinduced electrons could transfer from g-C3N4 to the Bi metal, as revealed with time-resolved fluorescence spectra. The function of Bi semimetal as a plasmonic cocatalyst for boosting visible light photocatalysis was similar to that of noble metals, which demonstrated a great potential of utilizing the economically feasible Bi element as a substitute for noble metals for the advancement of photocatalysis efficiency.

All-inorganic Pb-free bismuth (Bi) halogen perovskite quantum dots (PQDs) with distinct structural and photoelectric properties provide plenty of room for selective photoreduction of CO2. However, the efficient conversion of CO2-to-CO with high selectivity on Bi-based PQDs driven by solar light remains unachieved, and the precise reaction path/mechanism promoted by the surface halogen-associated active sites is still poorly understood. Herein, we screen a series of nontoxic and stable Cs3Bi2X9 (X = Cl, Br, I) PQDs for selective photocatalytic reduction of CO2-to-CO at the gas–solid interface. Among all the reported pure-phase PQDs, the as-synthesized Cs3Bi2Br9 PQDs exhibited the highest CO2-to-CO conversion efficiency generating 134.76 μmol g–1 of CO yield with 98.7% selectivity under AM 1.5G simulated solar illumination. The surface halogen-associated active sites and reaction intermediates were dynamically monitored and precisely unraveled based on in situ DRIFTS investigation. In combination with the DFT calculation, it was revealed that the surface Br sites allow for optimizing the coordination modes of surface-bound intermediate species and reducing the reaction energy of the rate-limiting step of COOH– intermediate formation from •CO2–. This work presents a mechanistic insight into the halogen-involved catalytic reaction mechanism in solar fuel production.

Novel plasmonic Bi nanoparticles deposited in situ in (BiO)2CO3 microspheres (Bi/BOC) were fabricated via a one-pot hydrothermal treatment of bismuth citrate, sodium carbonate, and thiourea. Different characterization techniques, including XRD, SEM, TEM, XPS, UV–vis DRS, PL, time-resolved fluorescence spectra, and photocurrent generation, were performed to investigate the structural and optical properties of the as-prepared samples. The results indicated that the Bi nanoparticles were generated on the surface of (BiO)2CO3 microspheres via the in situ reduction of Bi3+ by thiourea. The Bi nanoparticle deposited (BiO)2CO3 microspheres were employed for the photocatalytic removal of NO in air under visible light irradiation, and the sample exhibited a drastically enhanced photocatalytic activity and oxidation ability. The highly enhanced activity was attributed to the cooperative contribution of the surface plasmon resonance (SPR) effect, the efficient separation of electron–hole pairs, and the prolonged lifetime of charge carriers by the Bi nanoparticles. The behavior of Bi nanoparticles as a cocatalyst for enhancing photocatalytic activity is similar to that of noble metals in photocatalysis. When the amount of thiourea was controlled at 5%, the corresponding Bi/BOC sample exhibited the highest photocatalytic activity and exceeded those of other types of visible light photocatalysts, such as nonmetal-doped TiO2, C3N4, BiOBr, N-doped (BiO)2CO3, and even Ag-deposited (BiO)2CO3. The visible light photocatalytic activity of Bi/BOC was also tested at different wavelengths and with different light sources. It was found that the high activity could be well maintained even under a 5 W energy-saving light, demonstrating its great potential in practical applications. On the basis of DMPO-ESR spin trapping, the active species produced from Bi/BOC under visible light were hydroxyl radicals. Bi/BOC could produce more hydroxyl radicals in comparison to BOC due to the SPR effect of Bi, contributing to the enhanced oxidation ability. Furthermore, the Bi/BOC sample displayed a high photochemical stability under repeated irradiation. This work demonstrated the great feasibility of utilizing low-cost Bi nanoparticles as a substitute for noble metals to enhance visible light photocatalysis.

The immobilization of a photocatalyst on a proper support is pivotal for practical environmental applications. In this work, graphitic carbon nitride (g-C3N4) as a rising visible light photocatalyst was first immobilized on structured Al2O3 ceramic foam by a novel in situ approach. Immobilized g-C3N4 was applied for photocatalytic removal of 600 ppb level NO in air under real indoor illumination of an energy-saving lamp. The photocatalytic activity of immobilized g-C3N4 was gradually improved as the pyrolysis temperature was increased from 450 to 600 °C. The optimized conditions for g-C3N4 immobilization on Al2O3 supports can be achieved at 600 °C for 2 h. The NO removal ratio could reach up to 77.1%, exceeding that of other types of well-known immobilized photocatalysts. Immobilized g-C3N4 was stable in activity and can be used repeatedly without deactivation. The immobilization of g-C3N4 on Al2O3 ceramic foam was found to be firm enough to overwhelm the continuous air flowing, which can be ascribed to the special chemical interaction between g-C3N4 and Al2O3. On the basis of the 5,5'-dimethyl-1-pirroline-N-oxide electron spin resonance (DMPO ESR) spin trapping and reaction intermediate monitoring, the active species produced from g-C3N4 under illumination were confirmed and the reaction mechanism of photocatalytic NO oxidation by g-C3N4 was revealed. The present work could provide new perspectives for promoting large-scale environmental applications of supported photocatalysts.

Two-dimensional birnessite has attracted attention for electrochemical energy storage because of the presence of redox active Mn 4+ /Mn 3+ ions and spacious interlayer channels available for ions diffusion. However, current strategies are largely limited to enhancing the electrical conductivity of birnessite. One key limitation affecting the electrochemical properties of birnessite is the poor utilization of the MnO 6 unit. Here, we assemble β-MnO 2 /birnessite core–shell structure that exploits the exposed crystal face of β-MnO 2 as the core and ultrathin birnessite sheets that have the structure advantage to enhance the utilization efficiency of the Mn from the bulk. Our birnessite that has sheets parallel to each other is found to have unusual crystal structure with interlayer spacing, Mn(III)/Mn(IV) ratio and the content of the balancing cations differing from that of the common birnessite. The substrate directed growth mechanism is carefully investigated. The as-prepared core–shell nanostructures enhance the exposed surface area of birnessite and achieve high electrochemical performances (for example, 657 F g –1 in 1 M Na 2 SO 4 electrolyte based on the weight of parallel birnessite) and excellent rate capability over a potential window of up to 1.2 V. This strategy opens avenues for fundamental studies of birnessite and its properties and suggests the possibility of its use in energy storage and other applications. The potential window of an asymmetric supercapacitor that was assembled with this material can be enlarged to 2.2 V (in aqueous electrolyte) with a good cycling ability.

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Abstract Solar photocatalysis is a potential solution to satisfying energy demand and its resulting environmental impact. However, the low electron–hole separation efficiency in semiconductors has slowed the development of this technology. The effect of defects on electron–hole separation is not always clear. A model atomically thin structure of single‐unit‐cell Bi 3 O 4 Br nanosheets with surface defects is proposed to boost photocatalytic efficiency by simultaneously promoting bulk‐ and surface‐charge separation. Defect‐rich single‐unit‐cell Bi 3 O 4 Br displays 4.9 and 30.9 times enhanced photocatalytic hydrogen evolution and nitrogen fixation activity, respectively, than bulk Bi 3 O 4 Br. After the preparation of single‐unit‐cell structure, the bismuth defects are controlled to tune the oxygen defects. Benefiting from the unique single‐unit‐cell architecture and defects, the local atomic arrangement and electronic structure are tuned so as to greatly increase the charge separation efficiency and subsequently boost photocatalytic activity. This strategy provides an accessible pathway for next‐generation photocatalysts.

Cholera remains an important global cause of morbidity and mortality, capable of causing periodic epidemic disease. Beginning in August 2008, a major cholera epidemic occurred in Zimbabwe, with 98,585 reported cases and 4,287 deaths. The dynamics of such outbreaks, particularly in nonestuarine regions, are not well understood. We explored the utility of mathematical models in understanding transmission dynamics of cholera and in assessing the magnitude of interventions necessary to control epidemic disease. Weekly data on reported cholera cases were obtained from the Zimbabwe Ministry of Health and Child Welfare (MoHCW) for the period from November 13, 2008 to July 31, 2009. A mathematical model was formulated and fitted to cumulative cholera cases to estimate the basic reproductive numbers R(0) and the partial reproductive numbers from all 10 provinces for the 2008-2009 Zimbabwe cholera epidemic. Estimated basic reproductive numbers were highly heterogeneous, ranging from a low value of just above unity to 2.72. Partial reproductive numbers were also highly heterogeneous, suggesting that the transmission routes varied by province; human-to-human transmission accounted for 41-95% of all transmission. Our models suggest that the underlying patterns of cholera transmission varied widely from province to province, with a corresponding variation in the amenability of outbreaks in different provinces to control measures such as immunization. These data underscore the heterogeneity of cholera transmission dynamics, potentially linked to differences in environment, socio-economic conditions, and cultural practices. The lack of traditional estuarine reservoirs combined with these estimates of R(0) suggest that mass vaccination against cholera deployed strategically in Zimbabwe and surrounding regions could prevent future cholera epidemics and eventually eliminate cholera from the region.

Porous polymeric membranes have emerged as the core technology in the field of separation. But some challenges remain for several methods used for membrane fabrication, suggesting the need for a critical review of the literature. We present here an overview on porous polymeric membrane preparation and characterization for two commonly used polymers: polysulfone and poly (vinylidene fluoride). Five different methods for membrane fabrication are introduced: non-solvent induced phase separation, vapor-induced phase separation, electrospinning, track etching and sintering. The key factors of each method are discussed, including the solvent and non-solvent system type and composition, the polymer solution composition and concentration, the processing parameters, and the ambient conditions. To evaluate these methods, a brief description on membrane characterization is given related to morphology and performance. One objective of this review is to present the basics for selecting an appropriate method and membrane fabrication systems with appropriate processing conditions to produce membranes with the desired morphology, performance and stability, as well as to select the best methods to determine these properties.

Mesoporous C-doped TiO 2 nanomaterials with an anatase phase are prepared by a one-pot green synthetic approach using sucrose as a carbon-doping source for the first time. A facile post-thermal treatment is employed to enhance visible light photocatalytic activity of the as-prepared photocatalyst. The enhancement effect of post-thermal treatment between 100 and 300 °C is proved by the photodegradation of gas-phase toluene, and the optimum temperature is 200 °C. Physicochemical properties of the samples are characterized in detail by X-ray diffraction, Raman spectroscopy, N 2 adsorption–desorption isotherms, transmission electron microscopy, Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, UV–vis diffuse reflectance spectroscopy, and photoluminescence. The results indicate that the promotive effect of the post-thermal treatment can be attributed to the changes of the catalysts’ surface and optical properties. The results also show that the recombination of electron–hole pairs is effectively inhibited after thermal treatment due to the reduction of surface defects. The facile post-thermal treatment provides a new route for potential industrial applications of C-doped TiO 2 nanomaterials prepared by a green approach owing to its low cost and easy scale-up.

Vibration signals of gearbox are sensitive to the existence of the fault. Based on vibration signals, this paper presents an implementation of deep learning algorithm convolutional neural network (CNN) used for fault identification and classification in gearboxes. Different combinations of condition patterns based on some basic fault conditions are considered. 20 test cases with different combinations of condition patterns are used, where each test case includes 12 combinations of different basic condition patterns. Vibration signals are preprocessed using statistical measures from the time domain signal such as standard deviation, skewness, and kurtosis. In the frequency domain, the spectrum obtained with FFT is divided into multiple bands, and the root mean square (RMS) value is calculated for each one so the energy maintains its shape at the spectrum peaks. The achieved accuracy indicates that the proposed approach is highly reliable and applicable in fault diagnosis of industrial reciprocating machinery. Comparing with peer algorithms, the present method exhibits the best performance in the gearbox fault diagnosis.

Non-centrosymmetric polar Bi₂O₂(OH)(NO₃) with a rational band structure and {001} active exposing facets is developed as a robust layered photocatalyst for photooxidative diverse industrial contaminants and pharmaceuticals.