Optimizing filters of activated carbons obtained from biomass residues for ethylene removal in agro-food industry devices.

A series of adsorbents (activated carbons, ACs) were synthesized by physical and chemical activation of olive stones (OS) and their textural and chemical characteristics determined by complementary techniques such as N2 and CO2 physisorption, pH of the point zero of charge (pHPZC), HRSEM or XPS. Samples with a wide range of physicochemical properties were obtained by fitting the activation procedure. The performance of these adsorbents in filters working under dynamic conditions was studied by determining the corresponding breakthrough curves for the ethylene removal. The physicochemical transformations of OS during activation were related with the adsorptive performance of derivative ACs. Results were compared to those obtained using commercial carbons, in particular ACs, carbon black or carbon fibers, in order to identify the properties of these materials on influencing the adsorptive performance. In general, ACs from OS perform better than the commercial samples, being also easily regenerated and properly used during consecutive adsorption cycles. CO2-activation showed to be the best synthesis option, leading to granular ACs with a suitable microporosity and surface chemistry. These results could favour the integration of this type of inexpensive materials on devices for the preservation of climacteric fruits, in a clear example of circular economy by reusing the agricultural residues.

Recent technologies for glyphosate removal from aqueous environment: A critical review.

The growing demand for food has led to an increase in the use of herbicides and pesticides over the years. One of the most widely used herbicides is glyphosate (GLY). It has been used extensively since 1974 for weed control and is currently classified by the World Health Organization (WHO) as a Group 2A substance, probably carcinogenic to humans. The industry and academia have some disagreements regarding GLY toxicity in humans and its effects on the environment. Even though this herbicide is not mentioned in the WHO water guidelines, some countries have decided to set maximum acceptable concentrations in tap water, while others have decided to ban its use in crop production completely. Researchers around the world have employed different technologies to remove or degrade GLY, mostly at the laboratory scale. Water treatment plants combine different technologies to remove it alongside other water pollutants, in some cases achieving acceptable removal efficiencies. Certainly, there are many challenges in upscaling purification technologies due to the costs and lack of factual information about their adverse effects. This review presents different technologies that have been used to remove GLY from water since 2012 to date, its detection and removal methods, challenges, and future perspectives.

Magnetite Nanoparticles as Solar Photo-Fenton Catalysts for the Degradation of the 5-Fluorouracil Cytostatic Drug.

Heterogeneous catalysts based on magnetite nanoparticles, Fe3O4, were prepared by the chemical coprecipitation method using iron (III) chloride as a salt precursor. The physicochemical properties of the nanoparticles were determined by different techniques and the efficiency was evaluated for the degradation of the cytostatic drug, 5-fluorouracil (5-FU), in aqueous solution by photo-Fenton process under simulated solar radiation. The most influential parameters, namely pH of the solution, catalyst load, H2O2 dosage, and use of radiation, were studied and optimized in the degradation process. The optimal conditions to achieve a 100% degradation of 5-FU (10 mg L-1) and a high mineralization degree (76%) were established at the acidic pH of 3.0, 100 mg L-1 of catalyst loading, and 58 mM of H2O2 under simulated solar radiation. The contribution of iron leaching to the catalyst deactivation, the role of the dissolved iron ions on homogenous reactions, and the stability of the catalyst were assessed during consecutive reaction cycles.

One-Pot Thermal Synthesis of g-C3N4/ZnO Composites for the Degradation of 5-Fluoruracil Cytostatic Drug under UV-LED Irradiation.

Graphitic carbon nitride (g-C3N4) was used to enhance the photocatalytic activity of ZnO nanoparticles for the degradation of 5-fluorouracil (5-FU) cytostatic drug under UV-LED irradiation. CN/ZnO composites were synthetized by an easy one-pot thermal method, varying the g-C3N4 loading, i.e., from 10 to 67 wt% and a post-thermal exfoliation in air. The physicochemical and optical properties of the materials were analyzed by several techniques. CN/ZnO composites showed a coral-like structure of spherical ZnO wurtzite particles on the g-C3N4 structure. In general, the synergism and heterojunction interface between both phases allowed the enhancement of the mesoporosity, light absorption ability, and the aromaticity of the corresponding composites. Moreover, the photocatalytic activity of the CN/ZnO composites was increased with the addition of g-C3N4 in comparison with pristine ZnO. The highest activity was found for the composite containing 25 wt% of g-C3N4 (i.e., CN25/ZnO), reaching the total degradation of 5-FU and a mineralization of 48% at 180 min, as well as a good photostability during four reuse cycles. Experiments with different pH solutions and scavengers allowed for the assessment of the reactive oxygen species (ROS) involved in the 5-FU degradation pathway, with radicals and non-radical species as the main responsible active species. Furthermore, a tentative photocatalytic mechanism was proposed for CN/ZnO composites.

Specific adsorbents for the treatment of OMW phenolic compounds by activation of bio-residues from the olive oil industry.

A series of adsorbents was developed by physical (CO2) and chemical (KOH) activation of two bio-residues: olive stones (OS) and wood from olive tree pruning (OTP). The physicochemical properties of such materials were determined and correlated with their adsorptive performance in the removal of phenolic compounds of olive mill wastewater (OMW). Adsorption isotherms and kinetics of single phenolic acids, as well as the kinetics for competitive multi-compound adsorption, were fitted by applying different models, though Langmuir and pseudo-second order models fitted better the experimental results, respectively. The intraparticle diffusion model pointed out that mesoporosity reduces the influence of phenolic compounds' restrictions in the external film diffusion of the adsorbent particle-solution interphase, but adsorption capacity linearly increases with the micropore volume accessible to N2 at -196 °C (and also with BET surface area), while diffusion into ultramicropores (<0.7 nm, determined by CO2-adsorption) is slow and presents minor influence on the total adsorption capacity. After saturation, thermal regeneration of spent adsorbents allows the removal of adsorbed products, enabling the reuse of samples whilst maintaining a significant performance.

Photocatalytic Perfomance of ZnO-Graphene Oxide Composites towards the Degradation of Vanillic Acid under Solar Radiation and Visible-LED.

Graphene oxide (GO) is used to enhance the photocatalytic activity of ZnO nanoparticles for the degradation of vanillic acid (VA) under simulated solar light and visible-LED (λ > 430 nm). ZnO-GO composites are prepared by a mixing and sonication process with different GO loadings (i.e., from 1.8 to 6.5 wt.%). The materials are extensively characterized by thermogravimetric analysis (TGA), physisorption of N2, X-ray diffraction (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM), point of zero charge (pHPZC), and UV-Vis diffuse reflectance spectroscopy (DRUV). The presence of GO increases the photocatalytic activity of all the prepared composites in comparison with the pristine ZnO. The highest photocatalytic activity is found for the composite containing 5.5 wt.% of GO (i.e., ZnO-GO5.5), reaching a VA degradation of 99% and 35% under solar light and visible-LED, respectively. Higher TOC removal/VA degradation ratios are obtained from the experiments carried out under visible-LED, indicating a more effective process for the mineralization of VA than those observed under simulated solar light. The influence of hole, radical, and non-radical scavengers is studied in order to assess the occurrence of the reactive oxygen species (ROS) involved in the photocatalytic mechanism. The study of the photo-stability during three reuse experiments indicates that the presence of GO in the composites reduces the photocorrosion in comparison with pristine ZnO.

Supported Biofilms on Carbon-Oxide Composites for Nitrate Reduction in Agricultural Waste Water.

Escherichia coli colonies were grown on different supports for the removal of nitrates from water. A carbon material and different commercial metal oxides, such as SiO2, TiO2 and Al2O3, and their corresponding carbon-metal oxide composites were studied. The physicochemical properties were analyzed by different techniques and the results were correlated with their performance in the denitrification process. Developed biofilms effectively adhere to the supports and always reach the complete reduction of nitrates to gaseous products. Nevertheless, faster processes occur when the biofilm is supported on mesoporous and non-acid materials (carbon and silica).

Functionalized Graphene Derivatives and TiO2 for High Visible Light Photodegradation of Azo Dyes.

Functionalized graphene derivatives including graphene oxide (GO), reduced graphene oxide (rGO), and heteroatom (nitrogen/sulphur (N/S) or boron (B))-doped graphene were used to synthesize composites with TiO2 (T). The photocatalytic performance of composites was assessed for the degradation of Orange G dye (OG) under simulated solar light. All the prepared graphene derivatives-TiO2 composites showed better photocatalytic performance than bare TiO2. A higher photocatalytic activity was found for the composites containing GO and N/S co-doped rGO (kapp = 109.2 × 10-3 and 48.4 × 10-3 min-1, for GO-T and rGONS-T, respectively). The influence of both initial solution pH and the reactive species involved in the OG degradation pathway were studied. The photocatalytic activity of the samples decreased with the increase of the initial pH (from 3.0 to 10.0) due to the occurrence of electrostatic repulsive forces between the photocatalysts surface and the molecules of OG, both negatively charged. The use of selective scavengers showed that although the photogenerated holes dominate the degradation mechanism, radicals and singlet oxygen also participate in the OG degradation pathway. In addition, reutilization experiments indicated that the samples were stable under the reaction conditions used.

Fitting Biochars and Activated Carbons from Residues of the Olive Oil Industry as Supports of Fe- Catalysts for the Heterogeneous Fenton-Like Treatment of Simulated Olive Mill Wastewater.

A series of biochars and activated carbons (ACs) was prepared combining carbonization and physical or chemical activation of cheap and abundant residues of the olive oil industry. These materials were used as Fe-support to develop low-cost catalysts for the heterogeneous Fenton-like oxidation of simulated olive mill wastewater (OMW), the highly pollutant effluent generated by this agroindustry. Commercial ACs were also used as reference. All catalysts prepared were extensively characterized and results related with their performances in the catalytic wet peroxide oxidation (CWPO). Results showed a linear relationship of the textural properties of the catalysts with the adsorptive and catalytic performance, as well as the preferential adsorption and degradation of some phenolic compounds (caffeic and gallic acids) by specific interactions with the catalysts' surface. Despite the best performance of catalysts developed using commercial supports, those prepared from agro-industrial residues present some advantages, including a smaller catalyst deactivation by iron leaching. CWPO results show that catalysts from physically activated olive stones are the most promising materials, reaching total organic carbon and toxicity reductions of 35% and 60%, respectively, as well an efficient use of H2O2, comparable with those obtained using commercial supports. This approach showed that the optimized treatment of this type of residues will allow their integration in the circular economic process of the olive oil production.

Functionalized Cellulose for the Controlled Synthesis of Novel Carbon-Ti Nanocomposites: Physicochemical and Photocatalytic Properties.

Carbon-Ti nanocomposites were prepared by a controlled two-step method using microcrystalline cellulose as a raw material. The synthesis procedure involves the solubilization of cellulose by an acid treatment (H3PO4 or HNO3) and the impregnation with the Ti precursor followed of a carbonization step at 500 or 800 °C. The type of acid treatment leads to a different functionalization of cellulose with phosphorus- or oxygen-containing surface groups, which are able to control the load, dispersion and crystalline phase of Ti during the composite preparation. Thus, phosphorus functionalities lead to amorphous carbon-Ti composites at 500 °C, while TiP2O7 crystals are formed when prepared at 800 °C. On the contrary, oxygenated groups induce the formation of TiO2 rutile at an unusually low temperature (500 °C), while an increase of carbonization temperature promotes a progressive crystal growth. The removal of Orange G (OG) azo dye in aqueous solution, as target pollutant, was used to determine the adsorptive and photocatalytic efficiencies, with all composites being more active than the benchmark TiO2 material (Degussa P25). Carbon-Ti nanocomposites with a developed micro-mesoporosity, reduced band gap and TiO2 rutile phase were the most active in the photodegradation of OG under ultraviolet irradiation.

Element-Doped Functional Carbon-Based Materials.

Carbon materials are one of the most fascinating materials because of their unique properties and potential use in several applications. They can be obtained from agricultural waste, organic polymers, or by using advanced synthesizing technologies. The carbon family is very wide, it includes classical activated carbons to more advanced types like carbon gels, graphene, and so on. The surface chemistry of these materials is one of the most interesting aspects to be studied. The incorporation of different types of chemical functionalities and/or heteroatoms such as O, N, B, S, or P on the carbon surface enables the modification of the acidic-basic character, hydrophilicity-hydrophobicity, and the electron properties of these materials, which in turn determines the final application. This book collects original research articles focused on the synthesis, properties, and applications of heteroatom-doped functional carbon materials.

Syngas production by bi-reforming methane on an Ni-K-promoted catalyst using hydrotalcites and filamentous carbon as a support material.

Steam reforming of methane (SRM) and dry reforming of methane (DRM) are frequently used in the production of syngas; however, the bi-reforming of methane (BRM) is an interesting and alternative process. In this study, BRM was studied over MgO, a layered double hydroxide (LDH) phase that was destroyed between 600 °C and 900 °C during the reaction. It showed good sorption capacity for CO2 at relatively low temperatures (<500 °C), with CO2 adsorption being a pre-requisite for its catalytic conversion. Among the tested materials, the potassium-promoted LDH showed the highest activity, achieving a maximum CO2 conversion of 75%. The results suggest that at high temperature, the electronic structure of the used materials influences the destabilization of the feed in the order of methane, water and carbon dioxide. K promotes the catalytic activity, compensates the presence of large Ni particle sizes originating from the high metal loading, and favors the formation of Mg-Al-spinel. K is known to be an electronic promoter that releases electrons, which flow to the active metal. This electron flow induces instability on the molecule to be converted, and most probably, also induces size variations on the respective active nickel metal. The influence of the operating conditions in the range of 300 °C to 900 °C on the conversion of the reactants and product distribution was studied. Accordingly, it was concluded that it is only possible to obtain molar ratios of hydrogen-to-carbon monoxide close to two at high temperatures, a pre-requisite for the synthesis of methanol.

Correction: Syngas production by bi-reforming methane on an Ni-K-promoted catalyst using hydrotalcites and filamentous carbon as a support material.

[This corrects the article DOI: 10.1039/D0RA03264F.].

On the Interactions and Synergism between Phases of Carbon⁻Phosphorus⁻Titanium Composites Synthetized from Cellulose for the Removal of the Orange-G Dye.

Carbon⁻phosphorus⁻titanium composites (CPT) were synthesized by Ti-impregnation and carbonization of cellulose. Microcrystalline cellulose used as carbon precursor was initially dissolved by phosphoric acid (H3PO4) to favor the Ti-dispersion and the simultaneous functionalization of the cellulose chains with phosphorus-containing groups, namely phosphates and polyphosphates. These groups interacted with the Ti-precursor during impregnation and determined the interface transformations during carbonization as a function of the Ti-content and carbonization temperature. Amorphous composites with high surface area and mesoporosity were obtained at low Ti-content (Ti:cellulose ratio = 1) and carbonization temperature (500 °C), while in composites with Ti:cellulose ratio = 12 and 800 °C, Ti-particles reacted with the cellulose groups leading to different Ti-crystalline polyphosphates and a marked loss of the porosity. The efficiency of composites in the removal of the Orange G dye in solution by adsorption and photocatalysis was discussed based on their physicochemical properties. These materials were more active than the benchmark TiO2 material (Degussa P25), showing a clear synergism between phases.

An overview on exploration and environmental impact of unconventional gas sources and treatment options for produced water.

Rising global energy demands associated to unbalanced allocation of water resources highlight the importance of water management solutions for the gas industry. Advanced drilling, completion and stimulation techniques for gas extraction, allow more economical access to unconventional gas reserves. This stimulated a shale gas revolution, besides tight gas and coalbed methane, also causing escalating water handling challenges in order to avoid a major impact on the environment. Hydraulic fracturing allied to horizontal drilling is gaining higher relevance in the exploration of unconventional gas reserves, but a large amount of wastewater (known as "produced water") is generated. Its variable chemical composition and flow rates, together with more severe regulations and public concern, have promoted the development of solutions for the treatment and reuse of such produced water. This work intends to provide an overview on the exploration and subsequent environmental implications of unconventional gas sources, as well as the technologies for treatment of produced water, describing the main results and drawbacks, together with some cost estimates. In particular, the growing volumes of produced water from shale gas plays are creating an interesting market opportunity for water technology and service providers. Membrane-based technologies (membrane distillation, forward osmosis, membrane bioreactors and pervaporation) and advanced oxidation processes (ozonation, Fenton, photocatalysis) are claimed to be adequate treatment solutions.

Graphene oxide based ultrafiltration membranes for photocatalytic degradation of organic pollutants in salty water.

Flat sheet ultrafiltration (UF) membranes with photocatalytic properties were prepared with lab-made TiO2 and graphene oxide-TiO2 (GOT), and also with a reference TiO2 photocatalyst from Evonik (P25). These membranes were tested in continuous operation mode for the degradation and mineralization of a pharmaceutical compound, diphenhydramine (DP), and an organic dye, methyl orange (MO), under both near-UV/Vis and visible light irradiation. The effect of NaCl was investigated considering simulated brackish water (NaCl 0.5 g L(-1)) and simulated seawater (NaCl 35 g L(-1)). The results indicated that the membranes prepared with the GOT composite (M-GOT) exhibited the highest photocatalytic activity, outperforming those prepared with bare TiO2 (M-TiO2) and P25 (M-P25), both inactive under visible light illumination. The best performance of M-GOT may be due to the lower band-gap energy (2.9 eV) of GOT. In general, the permeate flux was also higher for M-GOT probably due to a combined effect of its highest photocatalytic activity, highest hydrophilicity (contact angles of 11°, 17° and 18° for M-GOT, M-TiO2 and M-P25, respectively) and higher porosity (71%). The presence of NaCl had a detrimental effect on the efficiency of the membranes, since chloride anions can act as hole and hydroxyl radical scavengers, but it did not affect the catalytic stability of these membranes. A hierarchically ordered membrane was also prepared by intercalating a freestanding GO membrane in the structure of the M-GOT membrane (M-GO/GOT). The results showed considerably higher pollutant removal in darkness and good photocatalytic activity under near-UV/Vis and visible light irradiation in continuous mode experiments.

Modification of the surface chemistry of single- and multi-walled carbon nanotubes by HNO3 and H2SO4 hydrothermal oxidation for application in direct contact membrane distillation.

A specific methodology based on nitric acid hydrothermal oxidation was used to control the surface chemistry of multi-walled (MWCNTs) and single-walled (SWCNTs) carbon nanotubes (CNTs) with different lengths, and this methodology was adapted to the use of sulphuric acid containing ammonium persulfate as an oxidizing agent. The amount of oxygen-containing surface groups depends on the number and length of the graphene layers of the CNTs, thicker and shorter CNTs having more reactive sites for surface functionalization. In particular, the oxidation of MWCNTs was more pronounced than that of short SWCNTs and less surface groups were introduced into long SWCNTs, regardless of the acid used at any fixed concentration. It was also possible to tailor the surface chemistry of both SWCNTs and MWCNTs by using the adopted methodologies, and the amount of both oxygen- and sulphur-containing functional groups was correlated with the concentration of each oxidizing agent used. Mathematical functions that allow precise control of the amount and type of the surface groups introduced into carbon nanotubes were obtained. Buckypapers were also prepared over a polytetrafluoroethylene commercial membrane. These membranes were tested in direct contact membrane distillation and, under salinity conditions, the membrane prepared using oxidized MWCNTs (instead of SWCNTs) was the most efficient, the permeate flux of the commercial membrane significantly increasing in the presence of these CNTs, while completely rejecting chloride ions. In addition, the permeate flux was precisely correlated with the amount of oxygenated functional surface groups (as well as with the pH of point of zero charge) of the oxidized MWCNTs.

Nanodiamond-TiO2 Composites for Heterogeneous Photocatalysis.

Invited for this month's cover are collaborators from the University of Porto in Portugal and KU Leuven in Belgium. The image shows that nanodiamond-TiO2 composites can effectively degrade organic water pollutants by photocatalysis under ambient conditions. This process will reduce human impact on freshwater systems, thereby contributing to meet worldwide targets on water footprint reduction. Read the full text of the article at 10.1002/cplu.201300094.

Nanodiamond-TiO2 Composites for Heterogeneous Photocatalysis.

This is a pioneering study on the synthesis and application of composites based on micro- and nanodiamonds for the photocatalytic degradation of environmental water pollutants. Micro- and nanodiamond powders (with particle sizes of 1-3 µm and 2-10 nm, respectively) were combined with TiO2 , by varying the carbon-phase content, and tested as composite photocatalysts for the degradation of diphenhydramine, which is a pharmaceutical water pollutant, under near-UV/Vis irradiation. These composites exhibited higher photocatalytic activity than the respective bare materials. In addition, composites prepared with pristine nanodiamonds were always more active than those prepared with microdiamonds of the same carbon content. A significant enhancement in the photocatalytic performance was observed on preparation of the composite with 15 wt % of nanodiamonds oxidised in air at 703 K; these oxidised nanodiamonds contained mainly carboxylic anhydrides, lactones, phenols and, to a lesser extent, carbonyl/quinone groups on their surface.

Design of graphene-based TiO2 photocatalysts--a review.

There is a recent increase in the interest of designing high-performance photocatalysts using graphene-based materials. This review gathers some important aspects of graphene-TiO(2), graphene oxide-TiO(2), and reduced graphene oxide-TiO(2) composites, which are of especial relevance as next generation photocatalysts. The methods used for the preparation of these materials, the associated mechanistic fundamentals, and the application of graphene-based composites on the photocatalytic degradation of pollutants are reviewed. Some structural, textural, and chemical properties of these materials and other photo-assisted applications, such as hydrogen production from water splitting and dye-sensitized solar cells, are also briefly included.