Engineered g-C3N5-Based Nanomaterials for Photocatalytic Energy Conversion and Environmental Remediation.

Photocatalysis plays a vital role in sustainable energy conversion and environmental remediation because of its economic, eco-friendly, and effective characteristics. Nitrogen-rich graphitic carbon nitride (g-C3N5) has received worldwide interest owing to its facile accessibility, metal-free nature, and appealing electronic band structure. This review summarizes the latest progress for g-C3N5-based photocatalysts in energy and environmental applications. It begins with the synthesis of pristine g-C3N5 materials with various topologies, followed by several engineering strategies for g-C3N5, such as elemental doping, defect engineering, and heterojunction creation. In addition, the applications in energy conversion (H2 evolution, CO2 reduction, and N2 fixation) and environmental remediation (NO purification and aqueous pollutant degradation) are discussed. Finally, a summary and some inspiring perspectives on the challenges and possibilities of g-C3N5-based materials are presented. It is believed that this review will promote the development of emerging g-C3N5-based photocatalysts for more efficiency in energy conversion and environmental remediation.

Efficiently photocatalysis activation of peroxydisulfate by Fe-doped g-C3N5 for pharmaceuticals and personal care products degradation.

Peroxydisulfate (PDS) based advanced oxidation processes (AOPs) are widely used for the degradation of pharmaceutical and personal care products (PPCP) in wastewater treatment. In this study, a Fe-doped g-C3N5 (Fe@g-C3N5) was synthesized as a photocatalyst for catalyzing the PDS-based AOPs to degrade tetracycline hydrochloride (TH) at pH 3 and Naproxen (NPX) at pH 7. The photocatalytic performance of Fe@g-C3N5 was 19% and 67% higher than g-C3N5 and g-C3N4 for degradation of TH at pH 3, respectively, while it was 21% and 35% at pH 7. The Fe:N ratio in Fe@g-C3N5, was calculated as 1:3.79, indicating that the doped Fe atom formed a FeN4 structure with an adjacent two-layer graphite structure of g-C3N5, which improved the charge separation capacity of g-C3N5 and act as a new reaction center that can efficiently combine and catalyze the PDS to radicals. Although the intrinsic photo-degradation performance is weak, the photocatalytic performance of Fe@g-C3N5 has great room for the improvement and application in wastewater treatment.

Removal of As(III) and As(V) from water by chitosan and chitosan derivatives: a review.

As arsenic removal becomes a global concern, the development of removal processes for arsenic treatment is still a major challenge. With regard to environmental compatibility and cheapness, chitosan and chitosan derivatives are considered as a promising removal technology for arsenic. Chitosan and chitosan derivatives possess the properties of low cost and good sorption on the arsenic removal. The present review is concerned about the present understanding of the mechanisms involved in sorption processes. Further on, detailed discussions are given of the effects of various factors on the performance of chitosan and chitosan derivatives in arsenic treatment processes. Finally, special attention is paid to the future challenges of chitosan and chitosan derivatives utilized for industrial arsenic treatment.

The roles of polycarboxylates in Cr(VI)/sulfite reaction system: Involvement of reactive oxygen species and intramolecular electron transfer.

In this study, the effects of polycarboxylates on both Cr(VI) reduction and S(IV) consumption in Cr(VI)/S(IV) system was investigated in acidic solution. Under aerobic condition, the productions of reactive oxygen species (ROS), i.e., SO4(-) and OH, have been confirmed in S(IV) reducing Cr(VI) process by using electron spin resonance and fluorescence spectrum techniques, leading to the excess consumption of S(IV). However, when polycarboxylates (oxalic, citric, malic and tartaric acid) were present in Cr(VI)/S(IV) system, the affinity of polycarboxylates to CrSO6(2-) can greatly promote the reduction of Cr(VI) via expanding the coordination of Cr(VI) species from tetrahedron to hexahedron. Besides, as alternatives to S(IV), these polycarboxylates can also act as electron donors for Cr(VI) reduction via intramolecular electron transfer reaction, which is dependent on the energies of the highest occupied molecular orbital of these polycarboxylates. Notably, the variant electron donating capacity of these polycarboxylates resulted in different yield of ROS and therefore the oxidation efficiencies of other pollutants, e.g., rhodamine B and As(III). Generally, this study does not only shed light on the mechanism of S(IV) reducing Cr(VI) process mediated by polycarboxylates, but also provides an escalated, cost-effective and green strategy for the remediation of Cr(VI) using sulfite as a reductant.

Dual enhancement-inhibition roles of polycarboxylates in Cr(VI) reduction and organic pollutant oxidation in electrical plasma system.

In this study, the roles of polycarboxylates in synergistic Cr(VI) reduction and organic pollutant oxidation are investigated in glow discharge electrolysis (GDE). H2O2 generated in GDE plays a primary role for Cr(VI) reduction, and the presence of polycarboxylates can significantly enhance the reduction of Cr(VI) to Cr(III) with less value of [H2O2](consumption)/[Cr(VI)](reduction). Simultaneously, polycarboxylates inhibit the production of ·OH via chromium-based Fenton-like reaction, leading to the retarded oxidation of other pollutant oxidation, i.e., RhB. The formation of peroxochromate(V) is a requisite both for Cr(VI) reduction to Cr(III) and ·OH formation via Fenton-like reaction. Polycarboxylates can form complexes with peroxochromate(V), which can transform to Cr(III) spontaneously, thereby interrupting the pathway for additional ·OH production. These influences induced by polycarboxylate were found closely relative to the number and position of -OH group in polycarboxylates. Besides, 162.7 mg L(-1) Cr(VI) in actual electroplating effluent can be rapidly and almost completely reduced in GDE with introducing polycarboxylate containing nickel electroplating effluent. Generally, the present study provides a versatile strategy for Cr(VI) reduction, exhibiting a bright application future for real wastewater treatment.

Monodispersed Hollow SO3H-Functionalized Carbon/Silica as Efficient Solid Acid Catalyst for Esterification of Oleic Acid.

SO3H-functionalized monodispersed hollow carbon/silica spheres (HS/C-SO3H) with primary mesopores were prepared with polystyrene as a template and p-toluenesulfonic acid (TsOH) as a carbon precursor and -SO3H source simultaneously. The physical and chemical properties of HS/C-SO3H were characterized by N2 adsorption, TEM, SEM, XPS, XRD, Raman spectrum, NH3-TPD, element analysis and acid-base titration techniques. As a solid acid catalyst, HS/C-SO3H shows excellent performance in the esterification of oleic acid with methanol, which is a crucial reaction in biodiesel production. The well-defined hollow architecture and enhanced active sites accessibility of HS/C-SO3H guarantee the highest catalytic performance compared with the catalysts prepared by activation of TsOH deposited on the ordered mesoporous silicas SBA-15 and MCM-41. At the optimized conditions, high conversion (96.9%) was achieved and no distinct activity drop was observed after 5 recycles. This synthesis strategy will provide a highly effective solid acid catalyst for green chemical processes.

Synergetic Transformations of Multiple Pollutants Driven by Cr(VI)-Sulfite Reactions.

Reduction of Cr(VI) is often deemed necessary to detoxify chromium contaminants; however, few investigations utilized this reaction for the purpose of treating other industrial wastewaters. Here a widely used Cr(VI)-sulfite reaction system was upgraded to simultaneously transform multiple pollutants, namely, the reduction of Cr(VI) and oxidation of sulfite and other organic/inorganic pollutants in an acidic solution. As(III) was selected as a probe pollutant to examine the oxidation capacity of a Cr(VI)-sulfite system. Both (•)OH and SO4(•-) were considered as the primary oxidants for As(III) oxidation, based on the results of electron spin resonance, fluorescence spectroscopy, and specific radicals quenching. As(III)-scavenging, oxidative radicals greatly accelerated Cr(VI) reduction and simultaneously consumed less sulfite. In comparison with a Cr(VI)-H2O2 system with 50 µM Cr(VI), Cr(VI), the sulfite system had excellent performance for both As(III) oxidation and Cr(VI) reduction at pH 3.5. Moreover, in this escalated process, less sulfite was required to reduce Cr(VI) than the traditional Cr(VI) reduction by sulfite process. This effectively improves the environmental compatibility of this Cr(VI) detoxification process, alleviating the potential for SO2 release and sulfate ion production in water. Generally, this study provides an excellent example of a "waste control by waste" strategy for the detoxification of multiple industrial pollutants.

Cu-N dopants boost electron transfer and photooxidation reactions of carbon dots.

The broadband light-absorption ability of carbon dots (CDs) has inspired their application in photocatalysis, however this has been impeded by poor electron transfer inside the CDs. Herein, we report the preparation of Cu-N-doped CDs (Cu-CDs) and investigate both the doping-promoted electron transfer and the performance of the CDs in photooxidation reactions. The Cu-N doping was achieved through a one-step pyrolytic synthesis of CDs with Na2 [Cu(EDTA)] as precursor. As confirmed by ESR, FTIR, and X-ray photoelectron spectroscopies, the Cu species chelates with the carbon matrix through Cu-N complexes. As a result of the Cu-N doping, the electron-accepting and -donating abilities were enhanced 2.5 and 1.5 times, and the electric conductivity was also increased to 171.8 µs cm(-1) . As a result of these enhanced properties, the photocatalytic efficiency of CDs in the photooxidation reaction of 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate is improved 3.5-fold after CD doping.

Rapid oxidation and immobilization of arsenic by contact glow discharge plasma in acidic solution.

Arsenic is a priority pollutant in aquatic ecosystem and therefore the remediation of arsenic-bearing wastewater is an important environmental issue. This study unprecedentedly reported simultaneous oxidation of As(III) and immobilization of arsenic can be achieved using contact glow discharge process (CGDP). CGDP with thinner anodic wire and higher energy input were beneficial for higher As(V) production efficiency. Adding Fe(II) in CGDP system significantly enhanced the oxidation rate of As(III) due to the generations of additional OH and Fe(IV) species, accompanied with which arsenic can be simultaneously immobilized in one process. Arsenic immobilization can be favorably obtained at solution pH in the range of 4.0-6.0 and Fe(II) concentration from 250 to 1000 µM. The presence of organics (i.e., oxalic acid, ethanol and phenol) retarded the arsenic immobilization by scavenging OH or complexing Fe(III) in aqueous solution. On the basis of these results, a mechanism was proposed that the formed ionic As(V) rapidly coprecipitated with Fe(III) ions or was adsorbed on the ferric oxyhydroxides with the formation of amorphous ferric arsenate-bearing ferric oxyhydroxides. This CGDP-Fenton system was of great interest for engineered systems concerned with the remediation of arsenic containing wastewater.

Influence of chemical functionalization on the CO2/N2 separation performance of porous graphene membranes.

The separation of CO2 from a mixture of CO2 and N2 using a porous graphene membrane was investigated using molecular dynamics (MD) simulations. The effects of chemical functionalization of the graphene sheet and pore rim on the gas separation performance of porous graphene membranes were examined. It was found that chemical functionalization of the graphene sheet can increase the absorption ability of CO2, while chemical functionalization of the pore rim can significantly improve the selectivity of CO2 over N2. The results show that the porous graphene membrane with all-N modified pore-16 exhibits a higher CO2 selectivity over N2 (∼11) due to the enhanced electrostatic interactions compared to the unmodified graphene membrane. This demonstrates the potential use of functionalized porous graphene as single-atom-thick membrane for CO2 and N2 separation. We provide an effective way to improve the gas separation performance of porous graphene membranes, which may be useful for designing new concept membranes for other gases.

Preparation of TiO2-loaded activated carbon fiber hybrids and application in a pulsed discharge reactor for decomposition of methyl orange.

TiO(2)-loaded activated carbon fiber (TiO(2)/ACF) hybrids were prepared in a sol through a dip-coating method and added to a pulsed discharge reactor to enhance the decomposition of methyl orange. The crystalline phase transformation and the surface morphology of TiO(2)/ACF were investigated after calcination at various temperatures. X-ray diffraction results revealed the intensity of the diffraction peaks resulting from anatase increased in accordance with increasing calcination temperatures. An anatase-to-rutile phase transformation was observed for calcination at 1173 K. Morphology studies indicate that the TiO(2) film fractured into irregular flakes on the ACF surface. TiO(2)/ACF calcined at 1173 K demonstrated the highest photocatalytic activity compared with samples calcined at lower temperatures. The enhancement of chemical oxygen demand removal may be due to the adsorption of ACF and the photocatalytic ozonation of TiO(2) in the combined treatment. The surface morphology of TiO(2)/ACF showed no change after re-use. Although micropores slightly increased, mesopores significantly decreased, and some oxygen-containing surface groups increased on the ACF surface after re-use, the photocatalytic activity of TiO(2)/ACF was not affected.

Preparation, characterization and photocatalytic activities of holmium-doped titanium dioxide nanoparticles.

Holmium-doped TiO2 nanoparticles with high photocatalytic activities were prepared by sol-gel method and characterized by X-ray diffraction, transmission electron microscopy, ultraviolet-visible diffuse reflectance spectroscopy, and surface area measurement by nitrogen adsorption in this study. Experimental results indicated holmium doping could increase the surface area of TiO2 nanoparticles, and inhibit the growth of crystalline size and the anatase-to-rutile phase transformation. The results of photodegrading methyl orange showed holmium doping improved the photocatalytic activity of TiO2, and the reasons could be attributed to the synergetic effects of large surface areas, small crystallite size, lattice distortion and more charge imbalance of holmium-doped TiO2. In our experiment, the optimal doped amount was 0.3mol.% for the maximum photocatalytic degradation ratio when holmium-doped TiO2 was calcined at 500 degrees C, and the optimal calcined temperature was 600 degrees C when the doped amount was 0.5mol.%.

Design of a novel non-equilibrium plasma-based water treatment reactor.

A novel non-equilibrium plasma-based water treatment reactor consisting of high voltage multi-needle electrode submerged in aqueous phase and reticulated ground electrode suspended in gas phase above water was developed and applied to treat low concentrations of methyl orange (MO). The electrode configuration was optimized. Higher number and more uniform distribution of streamers were produced in gas phase when parallel five-needle configuration with needle spacing of 10mm for high voltage electrode, macroporous ground electrode with mesh size of 0.42mm, and electrode gap of 17mm were adopted. This case corresponds to the largest amount of hydrogen peroxide and ozone produced in aqueous phase and gas phase, respectively, and air flow rate presents an economical value. The injection of wastewater above ground electrode for pretreatment and the design of fixed mesh barriers further increase the amount of ozone dissolved in aqueous solution. The conversion of MO presents a positive correlation with input voltage and the increase of pulse repetition rate is conducive for the conversion. In addition, the effect of initial solution concentration and treating volume on the conversion, energy yield and COD removal was evaluated.

Effect of granular activated carbon on degradation of methyl orange when applied in combination with high-voltage pulse discharge.

The application of a gas-liquid series electrical discharge reactor for the degradation of methyl orange (MO) in the presence of granular activated carbon (GAC1V, GAC2V, and GAC3V) was investigated and the effect of these GACs in a combined treatment was evaluated, respectively. Under the experimental conditions used in this work, MO cannot be removed completely by GAC adsorption; the MO degradation is faster by pulse discharge, but satisfactory removal of chemical oxygen demand (COD) is never achieved. The MO degradation can be increased and COD can be removed effectively in the combined treatment through both the adsorption and the catalysis of GAC. The synergy intensity value indicates that a high correlation exists between the catalytic effect of GACs and the number of basic groups on their surface. Boehm titration and FTIR studies indicate that both acidic and basic groups on the GAC surface can be increased except that basic groups of GAC2V are slightly decreased by this process. This process can also slightly decrease their surface area and micropore and macropore volume. Furthermore, the virgin and saturated GAC samples can both be regenerated in situ after repeated use.

Catalytic ozonation of phenolic wastewater with activated carbon fiber in a fluid bed reactor.

The effect of activated carbon fiber (ACF) on the ozonation of phenol in water in a fluid bed reactor was investigated. It was observed that this combined process could increase the yield of the oxidation process significantly for phenol and COD (chemical oxygen demand) removal, especially for the phenol removal. The efficiency of ozonation increased with an increase in the dose of ACF. Higher initial phenol concentration only caused a slight decrease of phenol and COD removal. The results of repeated use found that ozonation could efficiently regenerate ACF in situ in the reactor, which was considered easy to handle without the costly ex situ regeneration of the industrial treatment process. The Boehm titrations and FTIR studies indicate that the ozonation process in water can significantly change the composition of acidic surface oxygen-containing groups of ACF, leading to the increase of carboxylic, hydroxylic, and carbonylic groups and the slight decrease of the lactonic groups. Furthermore, this process can also increase the surface area and total pore volume of ACF. Due to the new micropore formation and some pore enlargement, the micropores became smaller, and the mesopores and macropores got bigger.

Photocatalytic degradation of methylene blue by a combination of TiO2 and activated carbon fibers.

Photocatalytic degradation of methylene blue (MB) in aqueous solution was investigated using TiO2 immobilized on activated carbon fibers (ACFs). The TiO2 and ACF combination (TiO2/ACF) was prepared by using epoxy as the precursor of the link between TiO2 and ACFs, followed by calcination at 460 degrees C in a N2 atmosphere. The TiO2/ACF composite prepared was easier to handle than the original TiO2 powder in suspension. More significantly, the TiO2/ACF composite can be used repeatedly without a decline in photodegradation ability. After six cycles, the amount of MB removal for the TiO2/ACF composite was still slightly higher than that for fresh P25 TiO2 in suspension. Through measurement of chemical oxygen demand in the solution and the concentration of ammonium generated during degradation of MB, it was confirmed that MB molecules are mineralized instead of adsorbed by ACFs.

Influence of heat treatment of rayon-based activated carbon fibers on the adsorption of formaldehyde.

The influence of heat treatment of rayon-based activated carbon fibers on the adsorption behavior of formaldehyde was studied. Heat treatment in an inert atmosphere of nitrogen for rayon-based activated carbon fibers (ACFs) resulted in a significant increase in the adsorption capacities and prolongation of breakthrough time on removing of formaldehyde. The effect of different heat-treatment conditions on the adsorption characteristics was investigated. The porous structure parameters of the samples under study were investigated using nitrogen adsorption at the low temperature 77.4 K. The pore size distributions of the samples under study were calculated by density functional theory. With the aid of these analyses, the relationship between structure and adsorption properties of rayon-based ACFs for removing formaldehyde was revealed. Improvement of their performance in terms of adsorption selectivity and adsorption rate for formaldehyde were achieved by heat post-treatment in an inert atmosphere of nitrogen.

Preparation of mesoporous carbon from commercial activated carbon with steam activation in the presence of cerium oxide.

Mesoporous carbon was prepared from the commercial activated carbon by steam activation with cerium oxide as catalyst. Steam activation with a catalyst loading of 0.5-2.0 wt% at 680-870 degrees C was examined. The surface area and pore size were evaluated by nitrogen adsorption at 77 K, and the structure of cerium oxide was characterized by XRD, XPS, and TEM. The results showed that the catalyst promoted the development of a mesopore at lower temperature (680-740 degrees C), and the mesopore was concentrated around 4-10 nm. The noncatalytic activation was advantageous in mesopore development and the catalyst would restrict the formation of mesopores at high temperature (800-870 degrees C). Higher loading of cerium oxide and higher activation temperature caused the aggregation of cerium oxide and then resulted in scattered pore size distribution.

Study of Microstructure of High-Surface-Area Polyacrylonitrile Activated Carbon Fibers.

High-surface-area polyacrylonitrile (PAN) activated carbon fibers having different pore size distribution activated by KOH were investigated. Nitrogen adsorption, XRD, SEM, and TEM were used to characterize the microstructure of PAN-ACFs. The specific surface area of samples was calculated from the standard BET method, and micropore surface area and volume were obtained from the Horvath-Kawazoe equations. The average pore size and characteristic energy were calculated by the Dubinin-Radushkevich equation according to the multistage adsorption mechanism. The whole pore size distribution was calculated by employing the regularization method according to the density functional theory, which is based on a molecular model for the adsorption of nitrogen in porous solids. It was shown that the isotherms were type I, the pore size was around 0.4-0.8 nm, and the mesorpore size was around 2-4 nm. The XRD pattern showed that PAN-ACFs activated by KOH are of amorphous material composed of very small crystallites. The SEM and TEM results showed that the monograph differs with differing activation degree, and the network is uniform or disordered. That all of these methods are in good agreement with one another. Copyright 2001 Academic Press.