Graphite/carbon-doped TiO2 nanocomposite synthesized by ultrasound for the degradation of diclofenac.

Graphite/C-doped TiO2 nanocomposite was synthesized at room temperature using a simple, impressive, and indirect sonication (20 kHz) by the cup horn system. Tetrabutyltitanate as the precursor of titanium and graphite (G) as the carbon source was used in the preparation of nanocomposite as a photocatalyst. The molar ratio of G/TiO2 as a key parameter was investigated in the synthesis of G/C-doped TiO2. The obtained materials were widely characterized using XRD, SEM, TEM, FTIR, XPS, and UV-Vis diffuse reflectance techniques. The UV-Vis diffuse reflectance spectroscopy results showed that the edge of light absorption of nanocomposite was distinctly red-shifted to the visible area via carbon doping. The XPS outcomes acknowledged the existence of the C, Ti, and O in the photocatalyst. The composite showed an enhancement in the dissociation efficiency of photoinduced charge carriers through the doping process. The photocatalytic activity of the synthesized nanocomposite was checked with diclofenac (DCF) as a pharmaceutical contaminant. The results displayed that G/C-doped TiO2 represented better photocatalytic performance for DCF than TiO2. This was due to the excellent crystallization, intense absorption of visible light, and the impressive separation of photoinduced charge carriers. Various active species such as •OH, •O2¯, h+, and H2O2 play a role in the degradation of DFC. Therefore, different scavengers were used and the role of each one in degradation was investigated. According to the obtained results, •O2¯ radical showed a major role in the photocatalytic process. This work not only proposes a deep insight into the photosensitization-like mechanism by using G-based materials but also develops new photocatalysts for the removal of emerging organic pollutants from waters using sunlight as available cheap energy.

Enhanced plasmonic photocatalytic performance of C doped TiN nanocrystals through ultrathin carbon layers.

Carbon-doped TiN nanoparticles on an ultrathin carbon layer, were successfully used for photocatalytic dye degradation synthesised by a simple calcination process. The resulting catalyst exhibited remarkable plasmonic photocatalytic performance under visible light irradiation. In comparison with benchmark rutile TiO2 and g-C3N4/TiO2 heterostructure catalysts, the first-order reaction rate constant of the developed catalyst improved approximately 34.2 and 6.5 times, respectively. The doping concentration of carbon and the crystal size of TiN nanoparticles, predominantly influenced by the amount of urea and calcination temperature, were identified as crucial factors governing the plasmonic photocatalytic activity. Density functional theory (DFT) calculations indicated that the introduction of carbon-sp bands into the TiN band structure promoted interband excitation of electrons and facilitated the generation of hotter holes, thereby enhancing the degradation of dyes and ultimately contributing to the superior photocatalytic activity observed.

A Novel C Doped MoS2 /CoP/MoO2 Ternary Heterostructure Nanoflower for Hydrogen Evolution Reaction at Wide pH Range and Efficient Overall Water Splitting in Alkaline Media.

The development of low-cost and high-efficiency bifunctional catalysts is still a challenge for hydrogen production through overall water splitting. This paper reports the in-situ synthesis of C-doped MoS2 /CoP/MoO2 using bacterial cellulose (BC) as the reducing agent and the source of C and using BC (MoS2 /Co1.2 MoO4.2 ⋅ 1.2H2 O/BC) as the template. Heterogeneous structure for hydrogen evolution reaction (HER) and alkaline water electrolysis in a wide pH range. Due to the large number of defect sites caused by C doping and the synergy between these three active components (MoS2 , CoP and MoO2 ), the HER and oxygen evolution reaction (OER) activities of the catalyst have been greatly improved. Therefore, during HER, a small initial overpotential (27 mV) was achieved in 1.0 M KOH. In 0.5 M H2 SO4 , 0.1 M PBS and 1.0 M KOH, the current density reached 10 mA cm-2 at overpotentials of 123.4, 150, and 139 mV, respectively. For OER, an overpotential of 268 mV was required to achieve 10 mA cm-2 . The alkaline two-electrode device composed of C doped MoS2 /CoP/MoO2 delivers 10 mA cm-2 at a low potential of 1.51 V and can be easily driven by a single AA battery. This work provides a new design strategy of C doped ternary heterostructures for electrocatalysis and related energy applications.

The Effect of Carbon Doping on the Crystal Structure and Electrical Properties of Sb2Te3.

As a new generation of non-volatile memory, phase change random access memory (PCRAM) has the potential to fill the hierarchical gap between DRAM and NAND FLASH in computer storage. Sb2Te3, one of the candidate materials for high-speed PCRAM, has high crystallization speed and poor thermal stability. In this work, we investigated the effect of carbon doping on Sb2Te3. It was found that the FCC phase of C-doped Sb2Te3 appeared at 200 °C and began to transform into the HEX phase at 25 °C, which is different from the previous reports where no FCC phase was observed in C-Sb2Te3. Based on the experimental observation and first-principles density functional theory calculation, it is found that the formation energy of FCC-Sb2Te3 structure decreases gradually with the increase in C doping concentration. Moreover, doped C atoms tend to form C molecular clusters in sp2 hybridization at the grain boundary of Sb2Te3, which is similar to the layered structure of graphite. And after doping C atoms, the thermal stability of Sb2Te3 is improved. We have fabricated the PCRAM device cell array of a C-Sb2Te3 alloy, which has an operating speed of 5 ns, a high thermal stability (10-year data retention temperature 138.1 °C), a low device power consumption (0.57 pJ), a continuously adjustable resistance value, and a very low resistance drift coefficient.

Ceftriaxone sodium degradation by carbon quantum dots (CQDs)-decorated C-doped α-Bi2O3 nanorods.

A novel carbon quantum dots decorated C-doped α-Bi2O3 photocatalyst (CBO/CQDs) was synthesized by solvothermal method. The synergistic effect of adsorption and photocatalysis highly improved contaminants removal efficiencies. The ceftriaxone sodium degradation rate constant (k) of CBO/CQDs was 11.4 and 3.2 times that of pure α-Bi2O3 and C-doped α-Bi2O3, respectively. The interstitial carbon doping generated localized states above the valence band, which enhanced the utilization of visible light and facilitated the separation of photogenerated electrons and holes; the loading of CQDs improved the charge carrier separation and extended the visible light response; the reduced particle size of CBO/CQDs accelerated the migration of photogenerated carriers. The •O2 - and h+ were identified as the dominant reactive species in ceftriaxone sodium degradation, and the key role of •O2 - was further investigated by NBT transformation experiments. The Fukui index was applied to ascertain the molecular bonds of ceftriaxone sodium susceptible to radical attack, and intermediates analysis was conducted to explore the possible degradation pathways. The toxicity evaluation revealed that some degradation intermediates possessed high toxicity, thus the contaminants require sufficient mineralization to ensure safe discharge. The present study makes new insights into synchronous carbon dopping and CQDs decoration on modification of α-Bi2O3, which provides references for future studies.

Oxygen Functionalization-Induced Charging Effect on Boron Active Sites for High-Yield Electrocatalytic NH3 Production.

Ammonia has been recognized as the future renewable energy fuel because of its wide-ranging applications in H2 storage and transportation sector. In order to avoid the environmentally hazardous Haber-Bosch process, recently, the third-generation ambient ammonia synthesis has drawn phenomenal attention and thus tremendous efforts are devoted to developing efficient electrocatalysts that would circumvent the bottlenecks of the electrochemical nitrogen reduction reaction (NRR) like competitive hydrogen evolution reaction, poor selectivity of N2 on catalyst surface. Herein, we report the synthesis of an oxygen-functionalized boron carbonitride matrix via a two-step pyrolysis technique. The conductive BNCO(1000) architecture, the compatibility of B-2pz orbital with the N-2pz orbital and the charging effect over B due to the C and O edge-atoms in a pentagon altogether facilitate N2 adsorption on the B edge-active sites. The optimum electrolyte acidity with 0.1 M HCl and the lowered anion crowding effect aid the protonation steps of NRR via an associative alternating pathway, which gives a sufficiently high yield of ammonia (211.5 µg h-1 mgcat-1) on the optimized BNCO(1000) catalyst with a Faradaic efficiency of 34.7% at - 0.1 V vs RHE. This work thus offers a cost-effective electrode material and provides a contemporary idea about reinforcing the charging effect over the secured active sites for NRR by selectively choosing the electrolyte anions and functionalizing the active edges of the BNCO(1000) catalyst.

Facile construction of high-performance 3D Co2C-doped CoAl2O4 fiber composites for capturing and decomposing tetracycline from aqueous solution.

Herein, novel 3D hollow-carved Co2C-doped CoAl2O4 fiber composites (3D-CA-FC) were successfully synthesized via a simple-green pyrolysis method and exhibited remarkably outstanding elimination performance for tetracycline (TC) by adsorption and degradation. The results indicated that the TC adsorption process of the samples could be accurately described by the pseudo-second-order and Langmuir isothermal model, and the maximum TC uptake reached up to 1889.63 mg/g under neutral conditions. Meanwhile, 3D-CA-FC showed good affinity for TC and its adsorption capacity was greatly promoted due to the presence of humic acid, CO32- ion and weakly alkaline environment. About complete degradation of TC could be completed within 60 min under suitable conditions. A significant improvement of catalyst rate was observed after the addition of CO32- ion, because of the selective degradation of CO3•- to TC. BET, XPS and FT-IR analysis indicated that the mechanisms of TC uptake can be ascribed to pore-filling, H-bonds and complexation. Radical trapping experiments showed that 1O2 should serve as predominant contributions, and SO4•- and •OH also played a role in the degradation process. This study provides some inspiration for the construction of 3D-CA-FC as a novel and promising bifunctional material for the elimination of contaminants in water treatment.

Controlled killing of human cervical cancer cells by combined action of blue light and C-doped TiO2 nanoparticles.

In this study, C-doped TiO2 nanoparticles (C-TiO2) were prepared and tested as a photosensitizer for visible-light-driven photodynamic therapy against cervical cancer cells (HeLa). X-ray diffraction and Transmission Electron Microscopy confirmed the anatase form of nanoparticles, spherical shape, and size distribution from 5 to 15 nm. Ultraviolet-visible light spectroscopy showed that C doping of TiO2 enhances the optical absorption in the visible light range caused by a bandgap narrowing. The photo-cytotoxic activity of C-TiO2 was investigated in vitro against HeLa cells. The lack of dark cytotoxicity indicates good biocompatibility of C-TiO2. In contrast, a combination with blue light significantly reduced the survival of HeLa cells: illumination only decreased cell viability by 30% (15 min of illumination, 120 µW power), and 60% when HeLa cells were preincubated with C-TiO2. We have also confirmed blue light-induced C-TiO2-catalyzed generation of reactive oxygen species in vitro and intracellularly. Oxidative stress triggered by C-TiO2/blue light was the leading cause of HeLa cell death. Fluorescent labeling of treated HeLa cells showed distinct morphological changes after the C-TiO2/blue light treatment. Unlike blue light illumination, which caused the appearance of large necrotic cells with deformed nuclei, cytoplasm swelling, and membrane blebbing, a combination of C-TiO2/blue light leads to controlled cell death, thus providing a better outcome of local anticancer therapy.

Facile one-pot synthesis of carbon self-doped graphitic carbon nitride loaded with ultra-low ceric dioxide for high-efficiency environmental photocatalysis: Organic pollutants degradation and hexavalent chromium reduction.

In the present study, an innovative carbon self-doped g-C3N4 (CCN) loaded with ultra-low CeO2 (0.067-0.74 wt%) composite photocatalyst is successfully synthesized via a facile one-pot hydrothermal and calcination method. The CeO2/CCN exhibits superior photocatalytic performance for tetracycline degradation (78.9% within 60 min), H2O2 production (151.92 µmol L-1 within 60 min), and Cr(VI) reduction (99.5% within 40 min), which much higher than that of g-C3N4, CCN, CeO2, and CeO2/g-C3N4. The enhanced photocatalytic performance is originated from the fact that the doping of C can efficaciously broaden the utilization range of solar light and improve the reduction ability of photogenerated electrons. Meanwhile, the ultra-low loading of CeO2 can effectually promote the migration of photogenerated electrons and enhance the specific surface area. Besides, the experiments of pH effect and cycle ability indicate that CeO2/CCN has excellent durability and stability. Finally, the photocatalytic mechanism of CeO2/CCN is systematically discussed. This work proves that combining element doping and semiconductor coupling is a promising strategy to design high-efficiency g-C3N4-based photocatalysts.

Metal organic framework-derived C-doped ZnO/TiO2 nanocomposite catalysts for enhanced photodegradation of Rhodamine B.

A series of C-doped ZnO/TiO2 composites with various molar ratios of ZnO to TiO2 were synthesized by one-step controllable pyrolysis of Zn/Ti bimetallic metal-organic frameworks (Zn/Ti-MOF). The Zn/Ti-MOF was prepared using a facile microwave hydrothermal method. Electron microscopic analysis proved that the composites presented regularity cubic morphology with an edge length of about 1 µm and the C atoms were successfully doped into ZnO/TiO2 composites. X-ray photoelectron spectroscopy (XPS) measurement results confirmed the C-doping in the ZnO/TiO2. Comparative experimental studies showed that 2% ZnO/TiO2 composites prepared with the calcination temperature of 600℃ displayed the best photocatalytic degradation efficiency (94%) of RhB under the simulated sunlight irradiation. Cyclical experiment indicated the high stability and reusability of 2% ZnO/TiO2 composites. Electron spin resonance (ESR) and trapping experiments illustrated that the produced O2- served as the main active species for the efficient RhB removal. This work provides an efficient way for preparing C-doped bimetal oxides composites, which would have an important application prospect in the photocatalytic degradation of organic pollutants in environmental water.

Harnessing Photocatalytic and Photothermal Effects of C-Doped Graphitic Carbon Nitride for Efficient Bacterial Disinfection.

In this work, the photocatalytic and photothermal effects of carbon-ring-doped graphitic carbon nitride materials against bacteria were systematically studied in a dispersed solution and on a membrane. C-doped graphitic carbon nitride materials C-CN 0.15, 1.5, and 7.5 were synthesized by mixing urea precursor with 0.15, 1.5, and 7.5 wt % glucose. With the increase in the doping level, the photothermal effect was clearly enhanced while the generation of reactive oxygen species (ROS) was slightly inhibited. With exposure to irradiation under a 100 mW cm-2 Xeon lamp with a cutoff filter (λ ≥ 420 nm), the ROS concentration of C-CN 1.5 increased 30% in the dispersed solution and its temperature increased about 10 °C in the dispersed solution and on the membrane compared to that of pristine carbon nitride. As a result, the bactericidal activity of C-CN 1.5 was improved by an order of magnitude in the dispersed solution and more than 2 orders of magnitude on the membrane immersed in a solution at 40 °C. To investigate the fundamental light absorption process on the membrane, an optical model using the finite-difference time-domain method was developed based on the topography of the membrane. The simulation results may explain that although C-CN produces more ROS in a solution; however, with a larger extinction coefficient, the power absorption is lower near the surface of the membrane. The ROS production is therefore inhibited and the bactericidal activity is dominated by the photothermal effect. Our experimental and simulation results provide a basis for designing high-performance photoactive disinfection materials and surfaces.

Synthesis of novel C-doped g-C3N4 nanosheets coupled with CdIn2S4 for enhanced photocatalytic hydrogen evolution.

Photocatalytic hydrogen generation from water splitting has become a favorable route for the utilization of solar energy. An effective strategy, the combination of C-doping with nanocomposite semiconductors, is presented in this work. C-doped g-C3N4 (CCN) was prepared by supramolecular self-assembly and subsequently a number of CdIn2S4/CCN composite photocatalysts were designed and fabricated though in situ decoration of CdIn2S4 crystals on the surface of CCN nanosheets via a hydrothermal method. This unique architecture was able to efficiently promote the transfer and separation of photon-generated charges, enhance light absorption, and significantly increase photocatalytic H2 production. Detailed characterization was performed to analyze the crystal structure, morphology, elementary composition, optical properties and catalytic mechanism. The CdIn2S4/CCN nanocomposites with optimal CdIn2S4 content exhibited a maximum H2 production rate of 2985 µmol h-1 g-1, almost 15 times more than that obtained using pure g-C3N4 (205 µmol h-1 g-1). In addition, the hybrid photocatalysts display good recycling stability under visible-light irradiation. This research may provide promising information for the preparation of more efficient multifunctional hybrid photocatalysts with excellent stability in fine chemical engineering.

C-doped anatase TiO2: Adsorption kinetics and photocatalytic degradation of methylene blue and phenol, and correlations with DFT estimations.

This work shows an easy and eco-friendly methodology to obtain almost pristine anatase phase of TiO2 by using furfural, a biomass-derived molecule, as a bio-template. The photocatalytic activity was studied following the degradation of methylene blue and phenol under artificial solar irradiation. Results were compared against those obtained on a commercial pristine anatase TiO2. The pseudo first-order, the second-order and the intraparticle diffusion kinetic models were verified. The textural and surface chemistry properties of the materials were correlated with the surface density of molecules adsorbed in equilibrium. The reaction-rate showed an almost perfect quadratic regression as a function of the surface density. Theoretical estimations of the density of states by DFT + U were performed showing that the total electron charge in the oxygen bonded to anatase TiO2 increased due to carbon doping in agreement with the prediction of appearance of atomic orbitals 2p from carbon atom in the hybrid material. C-doping is responsible of the red-shift from 3.14 to 2.94 eV observed for a Ti15O32C super-cell than pristine anatase Ti16O32. The increase in the activity of the C-doped TiO2 photocatalyst was due to the decrease in the energy band-gap promoting a higher absorption of photons from the visible light.

Carbon Excess C3N: A Potential Candidate as Li-Ion Battery Material.

Xu et al.'s recent experimental work ( Adv. Mater. 2017, 29, 1702007) suggested that C3N is a potential candidate as Li-ion battery with unusual electrochemical characteristics. However, the obvious capacity loss (from 787.3 to 383.3 mA h·g-1) occurs after several cycles, which restricts its high performance. To understand and further solve this issue, in the present study, we have studied the intercalation processes of Li ions into C3N via first-principle simulations. The results reveal that the Li-ion theoretical capacity in pure C3N is only 133.94 mA h·g-1, the value is obviously lower than experimental one. After examining the experimental results in detail, it is found that the chemical component of the as-generated C xN structure is actually C2.67N with N excess. In this case, the calculated theoretical capacity is 837.06 mA h·g-1, while part of Li ions are irreversibly trapped in C2.67N, resulting in the capacity loss. This phenomenon is consistent with the experimental results. Accordingly, we suggest that N excess C3N, but not pure C3N, is the proposed Li-ion battery material in Xu et al.'s experiment. To solve the capacity loss issue and maintain the excellent performance of C3N-based anode material, the C3N with slightly excess C (C3.33N), which has been successfully fabricated in the experiment, is considered in view of its relatively low chemical activity as compared with N excess C3N. Our results reveal that the C excess C3N is a potential Li-ion battery material, which exhibits the low open circle voltage (0.12 V), high reversible capacity (840.35 mA h·g-1), fast charging/discharging rate, and good electronic conductivity.

Facile microwave synthesis of pine cone derived C-doped TiO2 for the photodegradation of tetracycline hydrochloride under visible-LED light.

Pine cone derived carbon was doped into TiO2 via a facile microwave procedure at different powers, different from other conventional synthesis methods. The materials were adequately characterized and applied in the photodegradation of 5 mg/L tetracycline hydrochloride (TA) under visible-LED light. The XRD results showed that all materials exist as both anatase and rutile phase. However, both the microwave power and the carbon content of the composite material inhibited the conversion of anatase into rutile. The composite material synthesized at a microwave power of 800 W (CT800), displayed the highest band gap energy (3.14 eV) but showed the least electron-hole recombination rate. Hence, CT800 exhibited the highest apparent rate constant of 9.9 × 10-3 min-1 and a half-life of 70 min. An inverse relationship between OH• radical scavenger (isopropanol) and the percentage degradation by CT800 suggests that OH• is majorly responsible for the degradation of TA. Recyclability studies revealed that after 4 cycles of photocatalytic degradation reactions, CT800 retained approximately 83% performance confirming its stability and reusability.

High photocatalytic activity of hierarchical SiO2@C-doped TiO2 hollow spheres in UV and visible light towards degradation of rhodamine B.

Ongoing research activities are targeted to explore high photocatalytic activity of TiO2-based photocatalysts for the degradation of environmental contaminants under UV and visible light irradiation. In this work, we devise a facile, cost-effective technique to in situ synthesize hierarchical SiO2@C-doped TiO2 (SCT) hollow spheres for the first time. This strategy mainly contains the preparation of monodisperse cationic polystyrene spheres (CPS), sequential deposition of inner SiO2, the preparation of the sandwich-like CPS@SiO2@CPS particles, and formation of outer TiO2. After the one-step removal of CPS templates by calcination at 450°C, hierarchical SiO2@C-doped TiO2 hollow spheres are in situ prepared. The morphology, hierarchical structure, and properties of SCT photocatalyst were characterized by TEM. SEM, STEM Mapping, BET, XRD, UV-vis spectroscopy, and XPS. Results strongly confirm the carbon doping in the outer TiO2 lattice of SCT hollow spheres. When the as-synthesized SCT hollow spheres were employed as a photocatalyst for the degradation of Rhodamine B under visible-light and ultraviolet irradiation, the SCT photocatalyst exhibits a higher photocatalytic activity than commercial P25, effectively overcoming the limitations of poorer UV activity for many previous reported TiO2-based photocatalysts due to doping.

Regenerated cellulose membrane as bio-template for in-situ growth of visible-light driven C-modified mesoporous titania.

Visible light driven C-doped mesoporous TiO2 (C-MTiO2) nanorods have been successfully synthesized through green, low cost, and facile approach by sol-gel bio-templating method using regenerated cellulose membrane (RCM) as nanoreactor. In this study, RCM was also responsible to provide in-situ carbon sources for resultant C-MTiO2 nanorods in acidified sol at low temperatures. The composition, crystallinity, surface area, morphological structure, and optical properties of C-MTiO2 nanorods, respectively, had been characterized using FTIR, XRD, N2 adsorption/desorption, TEM, UV-vis-NIR, and XPS spectroscopy. The results suggested that the growth of C-MTiO2 nanorods was promoted by the strong interaction between the hydroxyl groups of RCMs and titanium ion. Optical and XPS analysis confirmed that carbon presence in TiO2 nanorods were responsible for band-gap narrowing, which improved the visible light absorption capability. Photocatalytic activity measurements exhibited the capability of C-MTiO2 nanorods in degradation of methyl orange in aqueous solution, with 96.6% degradation percentage under visible light irradiation.

Direct Synthesis of Carbon-Doped TiO2-Bronze Nanowires as Anode Materials for High Performance Lithium-Ion Batteries.

Carbon-doped TiO2-bronze nanowires were synthesized via a facile doping mechanism and were exploited as active material for Li-ion batteries. We demonstrate that both the wire geometry and the presence of carbon doping contribute to the high electrochemical performance of these materials. Direct carbon doping for example reduces the Li-ion diffusion length and improves the electrical conductivity of the wires, as demonstrated by cycling experiments, which evidenced remarkably higher capacities and superior rate capability over the undoped nanowires. The as-prepared carbon-doped nanowires, evaluated in lithium half-cells, exhibited lithium storage capacity of ∼306 mA h g(-1) (91% of the theoretical capacity) at the current rate of 0.1C as well as excellent discharge capacity of ∼160 mAh g(-1) even at the current rate of 10 C after 1000 charge/discharge cycles.

Biogenic C-doped titania templated by cyanobacteria for visible-light photocatalytic degradation of Rhodamine B.

Cyanobacteria, which occurred in eutrophic water harvest solar light to carry out photosynthesis with high efficiency. In this work, cyanobacteria (Microcystis sp.) were used as biotemplate to synthesize titania structure. The synthesized titania sample had similar morphology to that of the original template in spite of the fragile unicellular structures and extremely high water content of cyanobacterial cells. Incorporation of biogenic C, as well as the morphology inherited from biotemplate improved visible-light absorbance of the titania structure. The sample exhibited higher visible-light photocatalytic activity than commercial titania photocatalyst Degussa P25 for Rhodamine B (RhB) degradation. Compared with those C-doped titania photocatalysts prepared by other methods, cyanobacteria templated titania photocatalyst offer some potential for competitive advantages. The reported strategy opened up a new use for the cyanobacteria. It could also be used for titania in applications such as treatment of polluted water, dye-sensitized solar cells, or other regions.