Mass-Controlled Direct Synthesis of Graphene-like Carbon Nitride Nanosheets with Exceptional High Visible Light Activity. Less is Better.

In the present work, it is very surprising to find that the precursors mass, a long overlooked factor for synthesis of 2D g-C3N4, exerts unexpected impact on g-C3N4 fabrication. The nanoarchitecture and photocatalytic capability of g-C3N4 can be well-tailored only by altering the precursors mass. As thiourea mass decreases, thin g-C3N4 nanosheets with higher surface area, elevated conduction band position and enhanced photocatalytic capability was triumphantly achieved. The optimized 2D g-C3N4 (CN-2T) exhibited exceptional high photocatalytic performance with a NO removal ratio of 48.3%, superior to that of BiOBr (21.3%), (BiO)2CO3 (18.6%) and Au/(BiO)2CO3 (33.8%). The excellent activity of CN-2T can be ascribed to the co-contribution of enlarged surface areas, strengthened electron-hole separation efficiency, enhanced electrons reduction capability and prolonged charge carriers lifetime. The DMPO ESR-spin trapping and hole trapping results demonstrate that the superoxide radicals (•O2(-)) and photogenerated holes are the main reactive species, while hydroxyl radicals (•OH) play a minor role in photocatalysis reaction. By monitoring the reaction intermediate and active species, the reaction mechanism for photocatalytic oxidation of NO by g-C3N4 was proposed. This strategy is novel and facile, which could stimulate numerous attentions in development of high-performance g-C3N4 based functional nanomaterials.

The role and synergistic effect of the light irradiation and H2O2 in photocatalytic inactivation of Escherichia coli.

Inactivation of Escherichia coli K-12 was conducted by applying a continuous supplying of commercial H2O2 to mimic the H2O2 production in a photocatalytic system, and the contribution of H2O2 in photocatalytic inactivation was investigated using a modified "partition system" and five E. coli mutants. The concentration of exogenous H2O2 required for complete inactivation of bacterial cells was much higher than that produced in-situ in common photocatalytic system, indicating that H2O2 alone plays a minor role in photocatalytic inactivation. However, the concentration of exogenously produced H2O2 required for effective inactivation of E. coli K-12 was much lower when the light irradiation was applied. To further investigate the possible physiological changes, inactivation of E. coli BW25113 (the parental strain), and its corresponding isogenic single-gene deletion mutants with light pretreatment was compared. The results indicate that light irradiation increases the bacterial intracellular Fe(2+) level and favors hydroxyl radical (OH) production via the catalytic reaction of Fe(2+), leading to increase in DNA damage. Moreover, the results indicate that the properties of light source, such as intensity and major emission wavelength, may alter the physiology of bacterial cells and affect the susceptibility to in-situ resultant H2O2 in the photocatalytic inactivation processes, leading to significant influence on the photocatalytic inactivation efficiencies of E. coli K-12.

New insights into how RGO influences the photocatalytic performance of BiOIO3/RGO nanocomposites under visible and UV irradiation.

Reduced graphene oxide (RGO) has been demonstrated to be effective in enhancing the photocatalytic activity of various semiconductors. However, an important issue that has been overlooked is the role of RGO in UV-induced photocatalysis of RGO-based nanocomposites. In the present work, novel BiOIO3/RGO nanocomposites were prepared by a simple one-pot hydrothermal method, during which BiOIO3 nanoplates were formed in situ on RGO sheets resulting from partial reduction of RGO. The two components of the composite displayed intimate interfacial contact. The as-prepared BiOIO3/RGO nanocomposites exhibited highly enhanced visible photocatalytic activity, relative to that of pure BiOIO3, toward removal of NO from air. However, the BiOIO3/RGO nanocomposites showed only slightly increased photocatalytic activity, relative to pure, under UV irradiation. The limited enhancement of UV activity can be ascribed to the fact that BiOIO3 would be expected to compete with RGO with regard to absorption and utilization of UV light. Evidence shows that RGO can act as a semiconductor rather than a photosensitizer or electron reservoir in BiOIO3/RGO nano-composites. In addition, the active species responsible for photoactivity have been investigated by a DMPO spin-trapping electron spin resonance technique. Photo-generated holes were found to be the main active species inducing the photo-oxidation of NO under visible light, whereas holes and OH radicals are considered to be responsible for photo-activity under UV light. This work points to BiOIO3/RGO nano-composites as new and efficient visible light photocatalysts for environmental remediation applications, and also as a source of new insights into the pivotal role of RGO in photocatalysis of RGO-based nanocomposites under visible as well as UV light.

Water-assisted production of honeycomb-like g-C3N4 with ultralong carrier lifetime and outstanding photocatalytic activity.

Graphitic carbon nitride (g-C3N4) is a visible light photocatalyst, limited by low activity mainly caused by rapid recombination of charge carriers. In the present work, honeycomb-like g-C3N4 was synthesized via thermal condensation of urea with addition of water at 450 °C for 1 h. Prolonging the condensation time caused the morphology of g-C3N4 to change from a porous honeycomb structure to a velvet-like nanoarchitecture. Unlike in previous studies, the photocatalytic activity of g-C3N4 decreased with increasing surface area. The honeycomb-like g-C3N4 with a relatively low surface area showed highly enhanced photocatalytic activity with an NO removal ratio of 48%. The evolution of NO2 intermediate was dramatically inhibited over the honeycomb-like g-C3N4. The short and long lifetimes of the charge carriers for honeycomb-like g-C3N4 were unprecedentedly prolonged to 22.3 and 165.4 ns, respectively. As a result, the honeycomb-like g-C3N4 was highly efficient and stable in activity and could be used repeatedly. Addition of water had the following multiple positive effects on g-C3N4: (1) formation of the honeycomb structure, (2) promotion of charge separation and migration, (3) enlargement of the band gap, (4) increase in production yield, and (5) decrease in energy cost. These advantages make the present preparation method for highly efficient g-C3N4 extremely appealing for large-scale applications. The active species produced from g-C3N4 under illumination were confirmed using DMPO-ESR spin-trapping, the reaction intermediate was monitored, and the reaction mechanism of photocatalytic NO oxidation by g-C3N4 was revealed. This work could provide an attractive alternative method for mass-production of highly active g-C3N4-based photocatalysts for environmental and energetic applications.

Enhancing the photocatalytic activity of bulk g-C3N4 by introducing mesoporous structure and hybridizing with graphene.

Bulk graphitic carbon nitride (CN) suffers from small surface area and high recombination of charge carriers, which result in low photocatalytic activity. To enhance the activity of g-C3N4, the surface area should be enlarged and charge carrier separation should be promoted. In this work, a combined strategy was employed to dramatically enhance the activity of bulk g-C3N4 by simultaneously introducing mesoporous structure and hybridizing with graphene/graphene oxide. The mesoporous g-C3N4/graphene (MCN-G) and mesoporous g-C3N4/graphene oxide (MCN-GO) nanocomposites with enhanced photocatalytic activity (NO removal ratio of 64.9% and 60.7%) were fabricated via a facile sonochemical method. The visible light-harvesting ability of MCN-G and MCN-GO hybrids was enhanced and the conduction band was negatively shifted when 1.0 wt% graphene/graphene oxide was incorporated into the matrix of MCN. As electronic conductive channels, the G/GO sheets could efficiently facilitate the separation of chare carriers. MCN-G and MCN-GO exhibited drastically enhanced visible light photocatalytic activity toward NO removal. The NO removal ratio increased from 16.8% for CN to 64.9% for MCN-G and 60.7% for MCN-GO. This enhanced photocatalytic activity could be attributed to the increased surface area and pore volume, improved visible light utilization, enhanced reduction power of electrons, and promoted separation of charge carriers. This work demonstrates that a combined strategy is extremely effective for the development of active photocatalysts in environmental and energetic applications.

Immobilization of polymeric g-C3N4 on structured ceramic foam for efficient visible light photocatalytic air purification with real indoor illumination.

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.

Growth of BiOBr nanosheets on C3N4 nanosheets to construct two-dimensional nanojunctions with enhanced photoreactivity for NO removal.

The development of approaches to effectively separate the photo-induced charge carriers is a key strategy to promote the photocatalytic activity of semiconductor photocatalysts. This work represents the construction of novel two-dimensional (2D) BiOBr/C3N4 nanojunctions by the growth of BiOBr nanosheets on the surface of C3N4 nanosheets at room temperature. The samples were characterized by XRD, FT-IR, TEM, UV-vis DRS and PL. The photocatalytic activity of the samples was evaluated by the removal of NO in air under visible light irradiation. The results indicated that electronic coupling took place between the {001} plane of BiOBr and {002} plane of C3N4. The BiOBr/C3N4 nanojunctions exhibited enhanced visible light photocatalytic activity compared with pure BiOBr and C3N4. The enhanced photoactivity can be mainly ascribed to the efficient separation and transportation of photo-induced electrons and holes due to the well-coupled crystal planes and well-matched band structures. The present work could provide new insights into the design and construction of 2D nanojunctions with well-matched crystal planes and band structures for efficient visible light photocatalysis.

In situ construction of g-C3N4/g-C3N4 metal-free heterojunction for enhanced visible-light photocatalysis.

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.

Engineering the nanoarchitecture and texture of polymeric carbon nitride semiconductor for enhanced visible light photocatalytic activity.

In order to develop g-C3N4 for better visible light photocatalysis, g-C3N4 nanoarchitectures was synthesized by direct pyrolysis of cheap urea at 550°C and engineered through the variation of pyrolysis time. By prolonging the pyrolysis time, the crystallinity of the resulted sample was enhanced, the thickness and size of the layers were reduced, the surface area and pore volume were significantly enlarged, and the band structure was modified. Especially for urea treated for 4h, the obtained g-C3N4 nanosheets possessed high surface area (288 m(2)/g) due to the reduced layer thickness and the improved porous structure. A layer exfoliation and splitting mechanism was proposed to explain the gradual reduction of layer thickness and size of g-C3N4 nanoarchitectures with increased pyrolysis time. The as-synthesized g-C3N4 samples were applied for photocatalytic removal of gaseous NO and aqueous RhB under visible light irradiation. It was found that the activity of g-C3N4 was gradually improved as the pyrolysis time was prolonged from 0 min to 240 min. The enhanced crystallinity, reduced layer thickness, high surface area, large pore volume, enlarged band gap, and reduced number of defects were responsible for the activity enhancement of g-C3N4 sample treated for a longer time. As the precursor urea is very cheap and the synthesis method is facile template-free, the as-synthesized g-C3N4 nanoscale sheets could provide an efficient visible light driven photocatalyst for large-scale applications.

Controlled synthesis, growth mechanism and highly efficient solar photocatalysis of nitrogen-doped bismuth subcarbonate hierarchical nanosheets architectures.

The synthesis and self-assembly of hierarchical architectures from nanoscale building blocks with unique morphology, orientation and dimension have opened up new opportunities to enhance their functional performances and remain a great challenge. This work represents tunable synthesis of various types of 3D monodisperse in situ N-doped (BiO)(2)CO(3) hierarchical architectures composed of 2D single-crystal nanosheets with dominant (001) facets by a one-pot template-free hydrothermal method from bismuth citrate and ammonia solution. Depending on the concentration of ammonia solution, the morphology of N-doped (BiO)(2)CO(3), including dandelion-like, hydrangea-like and peony flower-like microspheres, can be selectively constructed due to different self-assembly patterns of nanosheets. It was revealed that the ammonia played dual roles in the formation of N-doped (BiO)(2)CO(3) architectures. One is to hydrolyze bismuth citrate, and the other is to behave as a nitrogen doping source. The in situ doped nitrogen substituted for oxygen in (BiO)(2)CO(3) and subsequently narrowed the band gap, making N-doped (BiO)(2)CO(3) visible light active. Due to the special nanosheets architectures, the prepared various N-doped (BiO)(2)CO(3) materials exhibited especially efficient photocatalytic activity and high durability for the removal of NO in air under both visible and UV light irradiation. Based on the direct observation of the growth process with respect to phase structure, chemical composition and morphological structure, a novel growth mechanism is revealed, which involves a unique multistep pathway, including reaction-nucleation, aggregation, crystallization, dissolution-recrystallization, and Ostwald ripening. The facile synthesis approach and the proposed growth mechanism could provide new insights into the design and controlled synthesis of inorganic hierarchical materials with new or enhanced properties.

Novel in situ N-doped (BiO)2CO3 hierarchical microspheres self-assembled by nanosheets as efficient and durable visible light driven photocatalyst.

Novel N-doped (BiO)(2)CO(3) hierarchical microspheres (N-BOC) were fabricated by a facile one-pot template free method on the basis of hydrothermal treatment of bismuth citrate and urea in water for the first time. The N-BOC sample was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectroscopy, scanning electron microscopy, transmission electron microscopy, N(2) adsorption-desorption isotherms, and Fourier transform-infrared spectroscopy. The N-BOC was constructed by the self-assembly of single-crystalline nanosheets. The aggregation of nanosheets led to the formation of hierarchical framework with mesopores, which is favorable for efficient transport of reaction molecules and harvesting of photoenergy. Due to the in situ doped nitrogen substituting for oxygen in the lattice of (BiO)(2)CO(3), the band gap of N-BOC was reduced from 3.4 to 2.5 eV, making N-BOC visible light active. The N-BOC exhibited not only excellent visible light photocatalytic activity, but also high photochemical stability and durability during repeated and long-term photocatalytic removal of NO in air due to the special hierarchical structure. This work demonstrates that the facile fabrication method for N-BOC combined with the associated outstanding visible light photocatalytic performance could provide new insights into the morphology-controlled fabrication of nanostructured photocatalytic materials for environmental pollution control.

Rose-like monodisperse bismuth subcarbonate hierarchical hollow microspheres: one-pot template-free fabrication and excellent visible light photocatalytic activity and photochemical stability for NO removal in indoor air.

Rose-like monodisperse hierarchical (BiO)(2)CO(3) hollow microspheres are fabricated by a one-pot template-free method for the first time based on hydrothermal treatment of ammonia bismuth citrate and urea in water. The microstructure and band structure of the as-prepared (BiO)(2)CO(3) superstructure are characterized in detail by X-ray diffraction, Raman spectroscopy, Fourier transform-infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, N(2) adsorption-desorption isotherms, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The monodisperse hierarchical (BiO)(2)CO(3) microspheres are constructed by the self-assembly of single-crystalline nanosheets. The aggregation of nanosheets result in the formation of three dimensional hierarchical framework containing mesopores and macropores, which is favorable for efficient transport of reaction molecules and harvesting of photo-energy. The result reveals the existence of special two-band-gap structure (3.25 and 2.0 eV) for (BiO)(2)CO(3). The band gap of 3.25 eV is intrinsic and the formation of smaller band gap of 2.0 eV can be ascribed to the in situ doped nitrogen in lattice. The performance of hierarchical (BiO)(2)CO(3) microspheres as efficient photocatalyst are further demonstrated in the removal of NO in indoor air under both visible light and UV irradiation. It is found that the hierarchical (BiO)(2)CO(3) microspheres not only exhibit excellent photocatalytic activity but also high photochemical stability during long term photocatalytic reaction. The special microstructure, the high charge separation efficiency due to the inductive effect, and two-band-gap structure in all contribute to the outstanding photocatalytic activities. The discovery of monodisperse hierarchical nitrogen doped (BiO)(2)CO(3) hollow structure is significant because of its potential applications in environmental pollution control, solar energy conversion, catalysis and other related areas.

Growth-differentiation factor-8 (GDF-8) in the uterus: its identification and functional significance in the golden hamster.

Transforming growth factor-beta superfamily regulates many aspects of reproduction in the female. We identified a novel member of this family, growth-differentiation factor 8 (GDF-8) in the 72 h post coital uterine fluid of the golden hamster by proteomic techniques. Uterine GDF-8 mRNA decreased as pregnancy progressed while its active protein peaked at 72 h post coitus (hpc) and thereafter stayed at a lower level. At 72 hpc, the GDF-8 transcript was localized to the endometrial epithelium while its protein accumulated in the stroma. Exogenous GDF-8 slowed down proliferation of primary cultures of uterine smooth muscle cells (SMC) and endometrial epithelial cells (EEC). In addition, GDF-8 attenuated the release of LIF (leukaemia inhibiting factor) by EEC. As for the embryo in culture, GDF-8 promoted proliferation of the trophotoderm (TM) and hatching but discouraged attachment. Our study suggests that GDF-8 could regulate the behavior of preimplantation embryos and fine-tune the physiology of uterine environment during pregnancy.

Gaseous and particulate polycyclic aromatic hydrocarbons (PAHs) emissions from commercial restaurants in Hong Kong.

Commercial cooking emissions are important air pollution sources in a heavily urbanized city. Exhaust samples were collected in six representative commercial kitchens including Chinese restaurants, Western restaurants, and Western fast-food restaurants in Hong Kong during peak lunch hours. Both gaseous and particulate emissions were evaluated. Eight gaseous and twenty-two particulate polycyclic aromatic hydrocarbons (PAHs) were quantified in this study. In the gaseous phase, naphthalene (67-89%) was the most abundant PAH in all of the exhaust samples. The contribution of acenaphthylene in the gaseous phase was significantly higher in emissions from the Chinese restaurants, whereas fluorene was higher in emissions from the Western cooking style restaurants (i.e., Western restaurants and Western fast-food restaurants). Pyrene is the most abundant particulate PAH in the Chinese restaurants (14-49%) while its contribution was much lower in the Western cooking style restaurants (10-22%). Controlled cooking conditions were monitored in a staff canteen to compare the emissions from several different local cooking styles, including deep frying, steaming, and mixed cooking styles (combination of steaming and frying). Deep frying produced the highest amount of total gaseous PAHs, 6 times higher than the steaming. However, steaming produced the highest particulate emissions. The estimated annual gaseous PAH emissions for the Chinese restaurants, Western restaurants, and Western fast-food restaurants were 255, 173, and 20.2 t y(-1) whereas 252, 1.9, and 0.4 t y(-1) were estimated for particulate phase PAH emissions. The study provides useful information and estimates for PAH emissions from commercial cooking exhaust in Hong Kong.