Empowering carbon materials robust gas desulfurization capability through an inclusion of active inorganic phases: A review of recent approaches.

Gas-phase desulfurization on carbon materials is an important process attracting the attention of scientists and engineers. When involving physical adsorption, reactive adsorption and catalytic oxidation combined, the process is considered as energy-efficient. Recent developments in materials science directed the attention of researchers to inorganic phases which react with H2S and participate to its oxidation to elemental sulfur. To fully utilize their capability, a developed surface area is needed and this feature is delivered by carbons. This review presents examples of recent advances in this field with focus not only on the activity of inorganic phases, dispersed on the surface or introduced as nanoparticles, but also on the important contribution of a carbon support as providing specific synergistic effects. The active phase promotes the H2S oxidation and participates in the reactions with H2S, while the carbon phase ensures its high dispersion, adds to oxygen activation and to an efficient electron transfer.

Biochemical changes in cancer cells induced by photoactive nanosystem based on carbon dots loaded with Ru-complex.

Carbon dots (CDs) and N-carbon dots (N-CDs) loaded with Ru-complex (CDs@RuCN, N-CDs@RuCN, respectively) were investigated as media imposing biochemical changes induced by UV illumination of ovarian cancer, A2780, and osteosarcoma, CAL72, cells. Synchrotron radiation-based Fourier Transform Infrared Spectroscopy was performed, and the spectra were subjected to a Principal Component Analysis. The CDs@RuCN and N-CDs@RuCN effects on cancer cells were analyzed by the theoretical modelling of the stability of the composite systems and a protein database search. Moreover, a detailed evaluation of surface and optical properties of CDs@RuCN and N-CDs@RuCN was carried out. Results demonstrated selective action of the CDs@RuCN and N-CDs@RuCN-based photodynamic therapy, with N-CDs@RuCN being the most active in inducing changes in A2780 and CDs@RuCN in CAL72 cells. We assume that different surface charges of nanoparticles led to direct interactions of N-CDs@RuCN with a Wnt signalling pathway in A2780 and those of CDs@RuCN with PI3-K/Akt in CAL72 cells and that further biochemical changes occurred upon light illumination.

Effect of 1-(3-phenoxypropyl) pyridazin-1-ium bromide on steel corrosion inhibition in acidic medium.

The effect of 1-(3-phenoxypropyl) pyridazin-1-ium bromide, a new pyridazinium derivative, on steel corrosion in a HCl (1 M) solution was analyzed using electrochemical impedance and XPS spectroscopy. Experimental results indicated that the inhibition efficiency increased with an increase in an inhibitor concentration. Electrochemical impedance spectroscopy measurements revealed that an increase in the immersion time of steel in an acidic medium from 1 to 12 h and further to 24 h decreased the charge transfer resistance (Rct) and thus decreased the inhibition efficiency. The SEM and XPS analyses linked the inhibition effect to the adsorption of the inhibitor (1-(3-phenoxypropyl) pyridazin-1-ium bromide) on the steel surface.

A New Generation of Surface Active Carbon Textiles As Reactive Adsorbents of Indoor Formaldehyde.

Highly porous carbon textiles were modified by impregnation with urea, thiourea, dicyandiamide, or penicillin G, followed by heat treatment at 800 °C. This resulted in an incorporation of nitrogen or nitrogen and sulfur heteroatoms in various configurations to the carbon surface. The volume of pores and, especially, ultramicropores was also affected to various extents. The modified textiles were then used as adsorbents of formaldehyde (1 ppmv) in dynamic conditions. The modifications applied significantly improved the adsorptive performance. For the majority of samples, formaldehyde adsorption resulted in a decrease in the volume of ultramicropores. The enhancement in the adsorption was linked not only to the physical adsorption of formaldehyde in small pores but also to its reactivity with sulfonic groups and amines present on the surface. Water on the surface and in challenge gas decreased the adsorptive performance owing to the competition with formaldehyde for polar centers. The results collected show that the S- and N-modified textiles can work as efficient media for indoor formaldehyde removal.

Mustard Gas Surrogate Interactions with Modified Porous Carbon Fabrics: Effect of Oxidative Treatment.

Removal of chemical warfare agent (CWA) surrogates by highly porous carbon textiles was investigated. The carbon cloth was modified by oxidation in a mixture of concentrated sulfuric and nitric acid. This process did not affect textile structural integrity. The surface properties of the modified textiles were investigated, and their capabilities to remove 2-chloroethyl ethyl sulfide (CEES) and diethylsulfide (EES), two mustard gas surrogates, were evaluated. The oxidized carbon textiles have a highly active surface that has the ability to form radical species. This enhances the degradation of the surrogates, and so the detoxification efficiency. The reaction products detected suggest differences in degradation mechanisms which depend on the type of fabric surface features. Thus, the oxidized surfaces eliminate CEES mainly through dehydrohalogenation, while the nonoxidized surfaces act via hydrolysis. Only the oxidized carbon has a surface active enough to react with the less reactive surrogate EES, by cleavage of the C-S bond. The surface functional groups promote not only the radical formation but also contribute to a strong adsorption of the CWA surrogates, which enhance the decomposition of these toxic species.

Moisture insensitive adsorption of ammonia on resorcinol-formaldehyde resins.

Phenolic-formaldehyde resins aged at 85, 90 and 95°C were used as ammonia adsorbents at dynamic conditions in dry and moist air. To avoid pressure drops 10% bentonite was added as a binder. The initial and hybrid materials (before and after ammonia adsorption) were extensively characterized from the point of view of their porosity and surface chemistry. The results showed that the addition of the binder had various effects on materials' properties depending on the chemistry of their surface groups. When the phenolic acidic groups were predominant, the largest increase in surface acidity upon the addition of the binder was found. It was linked to the exfoliation of bentonite by polar moieties of the resins, which made acidic groups from aluminosilicate layers available for ammonia adsorption. On this sample, a relatively high amount of ammonia was strongly adsorbed in dry conditions. Insensitivity to moisture is a significant asset of ammonia adsorbents.

Removal of hydrogen sulfide at ambient conditions on cadmium/GO-based composite adsorbents.

Cadmium-based materials with various hydroxide to carbonate ratios and their composites with graphite oxide were synthesized by a fast and simple precipitation procedure and then used as H2S adsorbents at ambient conditions in the dark or upon a visible light exposure. The structural properties and chemical features of the adsorbents were analyzed before and after hydrogen sulfide adsorption. The results showed that the high ratio of hydroxide to carbonate led to an improved H2S adsorption capacity. In moist conditions cadmium hydroxide was the best adsorbent. Moreover, it showed photoactive properties. While the incorporation of a graphene-based phase slightly decreased the extent of the improvement in the H2S adsorption capacity in moist conditions caused by photoactivity, its presence in the composites enhanced the performance in dry conditions. This was linked to photoactivity of CdS that can split H2S resulting in the formation of water in the system. The graphene-based phase enhanced the electron transfer and delayed the recombination of photoinduced charges. Carbonate-based materials showed a very good adsorption capacity in dark conditions in the presence of moisture. Upon the light exposure, CdS likely photocatalyzes the reduction of carbonate ions to formates/formaldehydes. Their deposition on the surface limits the number of sites available to H2S adsorption.

Role of surface chemistry and morphology in the reactive adsorption of H2S on iron (hydr)oxide/graphite oxide composites.

Composites of magnetite and two-line ferrihydrite with graphite oxide (GO) were synthesized and tested as hydrogen sulfide adsorbents. Exhausted and initial composites were characterized by the adsorption of nitrogen, X-ray diffraction, potentiometric titration, thermal analysis, and FTIR. The addition of GO increased the surface area of the composites due to the formation of new micropores. The extent of the increase depended on the nature of the iron (hydr)oxide and the content of GO. The addition of GO did not considerably change the crystal structure but increased the number of acidic functional groups. While for the magnetite composites an increase in the H2S adsorption capacity after GO addition was found, the opposite effect was recorded for the ferrihydrite composites. That increase in the adsorption capacity was linked to the affinity of the composites to adsorb water in mesopores of specific sizes in which the reaction with basic surface groups takes place. Elemental sulfur and ferric and ferrous sulfates were detected on the surface of the exhausted samples. A redox reactive adsorption mechanism is proposed to govern the retention of hydrogen sulfide on the surface of the composites. The incorporation of GO enhances the chemical retention of H2S due to the incorporation of OH reactive groups and an increase in surface heterogeneity.

Reactive adsorption of SO2 on activated carbons with deposited iron nanoparticles.

The effect of iron particle size anchored on the surface of commercial activated carbon on the removal of SO(2) from a gas phase was studied. Nanosize iron particles were deposited using forced hydrolysis of FeCl(3) with or without H(3)PO(4) as a capping agent. Dynamic adsorption experiments were carried out on either dry or pre-humidified materials and the adsorption capacities were calculated. The surface of the initial and exhausted materials was extensively characterized by microscopic, porosity, thermogravimetric and surface chemistry. The results indicate that the SO(2) adsorption capacity increased two and half times after the prehumidification process owing to the formation of H(2)SO(4) in the porous system. Iron species enhance the SO(2) adsorption capacity only when very small nanoparticles are deposited on the pore walls as a thin layer. Large iron nanoparticles block the ultramicropores decreasing the accessibility of the active sites and consuming oxygen that rest adsorption centers for SO(2) molecules. Iron nanoparticles of about 3-4 nm provide highly dispersed adsorption sites for SO(2) molecules and thus increase the adsorption capacity of about 80%. Fe(2)(SO(4))(3) was detected on the surface of exhausted samples.

Removal of antibiotics from water using sewage sludge- and waste oil sludge-derived adsorbents.

Sewage sludge- and waste oil sludge-derived materials were tested as adsorbents of pharmaceuticals from diluted water solutions. Simultaneous retention of eleven antibiotics plus two anticonvulsants was examined via batch adsorption experiments. Virgin and exhausted adsorbents were examined via thermal and FTIR analyses to elucidate adsorption mechanisms. Maximum adsorption capacities for the 6 materials tested ranged from 80 to 300 mg/g, comparable to the adsorption capacities of antibiotics on various activated carbons (200-400 mg/g) reported in the literature. The performance was linked to surface reactivity, polarity and porosity. A large volume of pores similar in size to the adsorbate molecules with hydrophobic carbon-based origin of pore walls was indicated as an important factor promoting the separation process. Moreover, the polar surface of an inorganic phase in the adsorbents attracted the functional groups of target molecules. The presence of reactive alkali metals promoted reaction with acidic groups, formation of salts and their precipitation in the pore system.

Reactive adsorption of NO2 at ambient conditions on iron-containing polymer-based porous carbons.

Adsorption of NO(2) and retention of NO (the product of NO(2) reduction by carbon) on iron-containing materials prepared from polystyrenesulfonic acid-co-maleic acid iron salt were studied. The surface of the materials was characterized using nitrogen adsorption, XRD, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX), and FTIR spectroscopy, and thermogravimetric analysis (TGA). The results showed the positive effects of the pore volume and well-dispersed iron species (Fe(2)O(3), FeSO(4), and FeS) on the performance of carbons as NO(2) adsorbents at room temperature. The retention of NO(2) on the carbon surface takes place either through its reduction to NO by carbon and/or by Fe(2)O(3), FeSO(4), and FeS, or through its reaction with Fe(2)O(3) and/or Fe(OH)(3), leading to the formation of Fe(NO(3))(3). The retention of NO is enhanced on carbons containing iron in the form of α-FeOOH, α-Fe(2)O(3), or γ-FeOOH. The best performance was found on the carbon with α-Fe(2)O(3). Dispersion and the particle size of iron compounds on the carbon surface affect both the adsorption/reduction process of NO(2) and the retention process of NO.

Importance of carbon surface chemistry in development of iron-carbon composite adsorbents for arsenate removal.

Micro/mesoporous activated carbon was oxidized and used either as received or after modification as a support for the deposition of iron oxyhydroxide. The prepared samples were applied as adsorbents of arsenate from water phase. The initial materials and those after adsorption were characterized using adsorption of nitrogen, - potentiometric titration, FTIR, EDX, XRD, AAS, and thermal analysis. The results obtained suggest that oxidation of the carbon support increases significantly the amount of iron oxyhydroxide species deposited on the surface and thus decreases their dispersions and the efficiency of arsenate immobilization in the carbon pore system. Iron hydroxyoxides react with arsenate forming salts. Moreover, a meso/microporous carbon surface contributes to changes in the toxicity of arsenic via reduction of As(V) to As(III). This is visible in the increased degree of carbon oxidation.

Investigation of the role of surface chemistry and accessibility of cadmium adsorption sites on open-surface carbonaceous materials.

Carbon nanotubes fabricated by the dc arc discharge method (ADCNTs) and chemical vapor deposition method (CVDCNTs) were oxidized with concentrated HNO 3 to modify their surface chemistry. The materials were characterized using SEM, TEM, FTIR, XPS, potentiometric titration, and nitrogen adsorption. The initial and oxidized materials were used as adsorbents of cadmium from aqueous solutions with different pH. Langmuir and Freundlich adsorption models were applied to fit the isotherm data, and both models fit the experimental data very well. The acid oxidation resulted in an increase in the number of oxygen-containing groups without drastic changes in the texture of the adsorbents. Although the small volume of micropores is present, the nanotube structure can be considered as nonporous. The lack of developed microporosity in carbonaceous materials eliminates the inner surface diffusion problems and makes the vast majority of surface groups available for adsorption of cadmium. The availability of these centers depends on the pH of the solution, which controls the protonation level. In spite of the fact that the pH of the solution affects the speciation of cadmium to some degree, the surface chemistry is the predominant force for adsorption at the pH range adopted in the present study, while the texture of materials also affects the nanotube's cadmium-adsorbing performance.

Tobacco waste/industrial sludge based desulfurization adsorbents: effect of phase interactions during pyrolysis on surface activity.

Industrial waste derived adsorbents were obtained by pyrolysis of tobacco waste with either metal sludge or waste oil sludge from a shipyard. The materials were used as media to remove hydrogen sulfide at room temperature in the presence of moisture. The initial and exhausted adsorbents after the breakthrough tests were characterized using sorption of nitrogen, thermal analysis, XRD, elemental analysis, and surface pH measurements. It was found that mixing tobacco and industrial sludges results in a strong synergy, enhancing the catalytic properties of adsorbents. This synergy is observed in both surface chemistry and porosity. During pyrolysis, new mineral phases are formed as a result of solid-state reactions between the components of the sludges. They are highly dispersed on the surface of mesopores. A high volume of these pores is a result of activation of the carbon phase in the composite by alkaline earth metals and also by the release of water from the decomposition of an inorganic phase that is in the predominant quantity. A high temperature of pyrolysis is beneficial for the adsorbents due to the enhanced activation of the carbonaceous phase and the chemical stabilization of the inorganic phase. Samples obtained at low temperatures are sensitive to water, which deactivates their catalytic centers.

Inorganic-organic phase arrangement as a factor affecting gas-phase desulfurization on catalytic carbonaceous adsorbents.

Dried sewage sludge was physically mixed with waste paper (paper-to-sludge ratios from 25% to 75%). To increase the catalytic activity, from 1% to 6% calcium hydroxide was added to the mixtures. Then the precursors were carbonized at 950 degrees C. The performance of materials as H2S adsorbents was tested using a home-developed dynamic breakthrough test. The samples, before and after the adsorption process, were characterized by adsorption of nitrogen, potentiometric titration, thermal analysis, XRF, and SEM. Differences in the performance were linked to the surface properties. Itwas found that mixing paper with sludge increases the amount of H2S adsorbed/oxidized in comparison with that adsorbed/oxidized by the adsorbents obtained from pure precursors (sludge or waste paper) and the capacity is comparable to those of the best activated carbons existing on the market. Although both sewage sludge and waste paper provide the catalytic centers for hydrogen sulfide oxidation, the dispersion of the catalyst and its location within accessible pores is an important factor. The presence of cellulose in the precursor mixture leads to the formation of a light macroporous char whose particles physically separate the inorganic catalytic phase of the sewage sludge origin, decreasing the density of the adsorbent and thus providing more space for storage of oxidation products. This, along with calcium, contributes to a significant increase in the capacity of the materials as hydrogen sulfide adsorbents. On their surface about 30 wt % H2S can be adsorbed, mainly as elemental sulfur or sulfates. The results demonstrate the importance of the composition and arrangement of inorganic/ organic phases for the removal of hydrogen sulfide. The interesting finding is that although some microporosity is necessary to increase the storage area for oxidation products, the carbonaceous phase does not need to be highly microporous. It is important that it provides space for deposition of sulfur, which is formed on the inorganic-phase catalyst. That space can be in meso- and macropores as shown in the case of char derived from the waste paper.

Adsorption of hydrogen sulfide on montmorillonites modified with iron.

Sodium-rich montmorillonite was modified with iron in order to introduce active centers for hydrogen sulfide adsorption. In the first modification, interlayer sodium cations were exchanged with iron. In another modification, iron oxocations were introduced to the clay surface. The most elaborated modification was based on doping of iron within the interlayer space of aluminum-pillared clay. The modified clay samples were tested as hydrogen sulfide adsorbents. Iron-doped samples showed a significant improvement in the capacity for H2S removal, despite of a noticeable decrease in microporosity compared to the initial pillared clay. The smallest capacity was obtained for the clay modified with iron oxocations. Variations in adsorption capacity are likely due to differences in the chemistry of iron species, degree of their dispersion on the surface, and accessibility of small pores for H2S molecule. The results suggest that on the surface of iron-modified clay hydrogen sulfide reacts with Fe(+3) forming sulfides or it is catalytically oxidized to SO2 on iron (hydro)oxides. Subsequent oxidation may lead to sulfate formation.

Efficient hydrogen sulfide adsorbents obtained by pyrolysis of sewage sludge derived fertilizer modified with spent mineral oil.

Terrene, sewage sludge derived granulated fertilizer, was impregnated with spent mineral oil and then pyrolyzed at 600, 800, and 950 degrees C. Materials obtained were characterized from the point of view of the pore structure and surface chemistry. Then the H2S breakthrough capacitywas measured using a lab designed test. The results showed that the new adsorbents over perform by 30% materials obtained by simple thermal treatment of Terrene and by 230% virgin coconut shell based activated carbon. The surface reaction products were evaluated using thermal analysis. On the surface of new adsorbents hydrogen sulfide is oxidized mainly to elemental sulfur which is then deposited within the pore system. The breakthrough occurs when all small pores available to promote catalytic oxidation (caused by the inorganic sludge component) are filled with sulfur. An increase in pyrolysis temperature leads to an improvement in the performance of materials as hydrogen sulfide adsorbents. This is caused likely by changes in an inorganic phase and inorganic/carbonaceous phase interactions during pyrolysis.