Adsorption of Uremic Toxins Using Ti3C2Tx MXene for Dialysate Regeneration.

The COVID-19 pandemic has become a major worldwide crisis. Although respiratory symptoms are a key feature of the disease, many people who are hospitalized with COVID-19 also suffer acute kidney injury, a condition that exacerbates patient mortality and may have to be treated through renal replacement therapy. Much of the focus on hospital capacity during the pandemic has centered on the availability of ventilators. However, supplies for dialysis treatment, including dialysate, have also run dangerously low in hospitals at the epicenter of the pandemic. Therefore, there is an urgent need to develop materials that can efficiently and rapidly regenerate dialysate, removing toxins and restoring electrolyte concentrations so that this vital resource remains readily available. In this work, Ti3C2Tx, a two-dimensional transition-metal carbide (MXene) that is known to efficiently adsorb urea, was used to remove creatinine and uric acid from an aqueous solution and dialysate, with a maximum adsorption capacity of 45.7 and 17.0 mg/g, respectively. We systematically analyzed and modeled the adsorption kinetics, isotherms, and thermodynamics, thus determining the rate-limiting step and adsorption mechanism. A fixed-bed column loaded with Ti3C2Tx was designed to further evaluate the adsorption performance under continuous fluid-flow conditions, mirroring conditions of continuous renal replacement therapy modalities. The maximum capacity and 50% breakthrough volume were calculated to further approach the practical application of Ti3C2Tx for removal of uremic toxins. Our findings suggest that Ti3C2Tx has the potential to be used as an efficient sorbent for the regeneration of dialysate, allowing for accelerated dialysate regeneration by removing filtered toxins and leading to more portable dialysis devices.

Role of acid mixtures etching on the surface chemistry and sodium ion storage in Ti3C2Tx MXene.

Two-dimensional transition metal carbides and/or nitrides (MXenes) have shown promise in developing electrochemical storage of metal ions within conductive galleries due to redox reactions with transition metal atoms. Here, effect of surface chemistry on electrochemical storage of sodium ions within MXene interlayers is investigated by etching Ti3AlC2 MAX using different etchants - HF, HF/HCl, and HF/H2SO4.

MXene Sorbents for Removal of Urea from Dialysate: A Step toward the Wearable Artificial Kidney.

The wearable artificial kidney can deliver continuous ambulatory dialysis for more than 3 million patients with end-stage renal disease. However, the efficient removal of urea is a key challenge in miniaturizing the device and making it light and small enough for practical use. Here, we show that two-dimensional titanium carbide (MXene) with the composition of Ti3C2T x, where T x represents surface termination groups such as -OH, -O-, and -F, can adsorb urea, reaching 99% removal efficiency from aqueous solution and 94% from dialysate at the initial urea concentration of 30 mg/dL, with the maximum urea adsorption capacity of 10.4 mg/g at room temperature. When tested at 37 °C, we achieved a 2-fold increase in urea removal efficiency from dialysate, with the maximum urea adsorption capacity of 21.7 mg/g. Ti3C2T x showed good hemocompatibility; it did not induce cell apoptosis or reduce the metabolizing cell fraction, indicating no impact on cell viability at concentrations of up to 200 µg/mL. The biocompatibility of Ti3C2T x and its selectivity for urea adsorption from dialysate open a new opportunity in designing a miniaturized dialysate regeneration system for a wearable artificial kidney.

Graphene-Based Materials for the Fast Removal of Cytokines from Blood Plasma.

There is a range of medical conditions, which include acute organ failure, bacterial and viral infection, and sepsis, that result in overactivation of the inflammatory response of the organism and release of proinflammatory cytokines into the bloodstream. Fast removal of these cytokines from blood circulation could offer a potentially efficient treatment of such conditions. This study aims at the development and assessment of novel biocompatible graphene-based adsorbents for blood purification from proinflammatory cytokines. These graphene-based materials were chosen on the basis of their surface accessibility for small molecules further facilitated by the interlayer porosity, which is comparable to the size of the cytokine molecules to be adsorbed. Our preliminary results show that graphene nanoplatelets (GnP) exhibit high adsorption capacity, but they cannot be used in direct contact with blood due to the risk of small carbon particle release into the bloodstream. Granulation of GnP using poly(tetrafluoroethylene) as a binder eliminated an undesirable nanoparticle release without affecting the GnP surface accessibility for the cytokine molecules. The efficiency of proinflammatory cytokine removal was shown using a specially designed flow-through system. So far, GnP proved to be among the fastest acting and most efficient sorbents for cytokine removal identified to date, outperforming porous activated carbons and porous polymers.

Photoactivity of g-C3 N4 /S-Doped Porous Carbon Composite: Synergistic Effect of Composite Formation.

A composite of g-C3 N4 with visible-light photoactive S-doped carbon was synthesized. Synergistic effects in surface chemistry and electrical conductivity, and a decrease in the band gap (Eg , estimated from optical measurements) from 2.91 eV for g-C3 N4 to 2.79 eV for the composite were found. Both the carbon and the composite showed photosensitivity but only the composite revealed a visible-light-driven reduction activity.

Metal-free Nanoporous Carbon as a Catalyst for Electrochemical Reduction of CO2 to CO and CH4.

S-doped and dual S,N-doped polymer-derived carbons were studied as electrocatalysts for the reduction of CO2. Higher Faradaic efficiencies for conversion to CO and CH4 were obtained for S,N-doped carbon than its S-doped counterpart. The former showed a maximum Faradaic efficiency of 11.3% for CO and 0.18% for CH4 formation. The S,N-nanoporous carbon was better at decreasing the overpotential of the reduction process. The pyridinic nitrogen groups were found to be actively participating in binding CO2. The quaternary nitrogen and thiophenic groups were also involved in the reduction process. It is proposed that the positively charged sites on the carbon atoms, adjacent to pyridinic nitrogen, stabilize the CO2(.-) and COOH* intermediates, promoting the formation of CO. The surface basicity of the catalysts improved the CO2 reduction selectivity when competing with H2 evolution. N2 adsorption measurements suggested that ultra-micropores enhance the reduction of CO2 to CH4.

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.

Peculiar Properties of Mesoporous Synthetic Carbon/Graphene Phase Composites and their Effect on Supercapacitive Performance.

Composites of mesoporous synthetic carbon and the graphene phase were synthesized in aqueous suspension by employing dispersive interactions of both phases. The resulting carbon-based materials were further heat treated in air at 350 °C. The composites and their components were characterized by using adsorption of nitrogen, potentiometric titration, thermal analysis-mass spectrometry, X-ray photoelectron spectroscopy, SEM, high-resolution TEM, and XRD. Then, they were tested as supercapacitors in three-electrode cells and under visible-light irradiation. The composites and the initial carbon share exactly the same pore-size distributions, but they exhibit significant differences in their surface chemistry, wettability, and conductivity. This allowed us to determine the extent of their effects on their capacitive/pseudocapacitive performance. The results showed that features other than the textural properties can increase the capacitive performance by more than 100 %. The synergistic properties of the composites and their sulfur functional group related photoactivity were linked to chemical interactions between the nanoporous carbon phase and graphite oxide during the formation of the composite.

Effect of nanoporous carbon surface chemistry on the removal of endocrine disruptors from water phase.

Wood-based activated carbon and its sulfur-doped counterpart were used as adsorbents of endocrine disruptor chemicals (EDC) from aqueous solution. Adsorption process was carried out in dynamic conditions and Thomas model was used to predict the performance of the column. The results showed a good fitting of the theoretical curve to the experimental data. S-doped carbon exhibited a higher adsorption capacity of trimethoprim (TMP) and smaller of sulfamethoxazole (SMX) and diclofenac (DCF) in comparison with the carbon with no sulfur incorporated into the matrix. The surface features of the initial carbons and those exposed to EDC were evaluated in order to derive the adsorption mechanism and elucidate the role of surface features. An increase in the amount of TMP from a low concentration solution (10 mg/L) on sulfur-doped carbon was linked to acid-base interactions and the reactive adsorption/oxidation of TMP. A decrease in SMX and DCF after sulfur doping was explained by a considerable increase in surface hydrophobicity, which does not favor the retention of polar DCF and SMX molecules. When the adsorption was measured from a high concentration solution at equilibrium conditions at the dark or under solar light irradiation different trends in the adsorption capacities were found. This was linked to the photoactivity of carbons and the degradation of EDC in the pore system promoted by visible light followed by the adsorption of the products of surface reactions.

Removal of dorzolamide from biomedical wastewaters with adsorption onto graphite oxide/poly(acrylic acid) grafted chitosan nanocomposite.

A novel graphite oxide/poly(acrylic acid) grafted chitosan nanocomposite (GO/CSA) was prepared and used as biosorbent for the removal of pharmaceutical compound (dorzolamide) from biomedical synthetic wastewaters. The performance was evaluated taking into account pH, kinetics and thermodynamics of adsorption. GO/CSA presented higher adsorption capacity in comparison with the parent materials (graphite oxide and poly(acrylic acid) grafted chitosan). All adsorbents prepared were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and potentiometric titration. The surface features were also evaluated after the dorzolamide adsorption in order to derive the adsorption mechanism. It was suggested that the reactive groups of GO and CSA can interact with the amino groups of dorzolamide and mainly the abundance of carboxyl groups of GO/CSA composite was the main reason for its enhanced adsorption capacity.

Controllable atomistic graphene oxide model and its application in hydrogen sulfide removal.

The determination of an atomistic graphene oxide (GO) model has been challenging due to the structural dependence on different synthesis methods. In this work we combine temperature-programmed molecular dynamics simulation techniques and the ReaxFF reactive force field to generate realistic atomistic GO structures. By grafting a mixture of epoxy and hydroxyl groups to the basal graphene surface and fine-tuning their initial concentrations, we produce in a controllable manner the GO structures with different functional groups and defects. The models agree with structural experimental data and with other ab initio quantum calculations. Using the generated atomistic models, we perform reactive adsorption calculations for H2S and H2O∕H2S mixtures on GO materials and compare the results with experiment. We find that H2S molecules dissociate on the carbonyl functional groups, and H2O, CO2, and CO molecules are released as reaction products from the GO surface. The calculation reveals that for the H2O∕H2S mixtures, H2O molecules are preferentially adsorbed to the carbonyl sites and block the potential active sites for H2S decomposition. The calculation agrees well with the experiments. The methodology and the procedure applied in this work open a new door to the theoretical studies of GO and can be extended to the research on other amorphous materials.

Time-resolved photoluminescence of Zn(OH)2 and its composites with graphite oxides.

Time-resolved photoluminescence is used to determine carrier recombination through radiative and nonradiative processes in zinc hydroxide Zn(OH)(2) and its porous composites with graphite oxide (GO). The decay times, measured by a streak camera, are found to be larger for zinc hydroxide (~1215±156 ps) than its composites (~976±81 ps for ZnGO-2 and 742±59 ps for ZnGO-5), but no significant changes in rise times (from 4.0 to 5.0 ps) are recorded. The dominant mechanism for the radiative process is attributed to free carrier recombination, while microporous networks present in these materials are found to be pathways for the nonradiative recombination process via multiphonon emission.

Enhanced adsorption of hydrogen sulfide on mixed zinc/cobalt hydroxides: effect of morphology and an increased number of surface hydroxyl groups.

Mixed zinc and cobalt hydroxides were synthesized using a precipitation method and tested as adsorbents of hydrogen sulfide from either dry or moist air. The adsorption capacity increased with an increase in the content of cobalt in the structure of mixed hydroxides. The synergistic effect was demonstrated by a fourfold increase in the amount of hydrogen sulfide adsorbed on the surface of the best performing mixed hydroxide in comparison with the hypothetical mixture of the two hydroxides. The initial and exhausted materials were characterized by FTIR, thermal analysis, potentiometric titration, X-ray diffraction, SEM/EDX, and adsorption of nitrogen. The results obtained suggest that an increase in the content of cobalt results in an increase in amorphicity level and in an increase in the number of hydroxyl groups. These groups, besides providing higher basicity thereby increasing the extent of H2S dissociation in the presence of water, are the main active centers reacting with hydrogen sulfide. Defects in the structure and oxygen vacancies result in the oxidation of some H2S to sulfites and sulfates.

Superior performance of copper based MOF and aminated graphite oxide composites as CO2 adsorbents at room temperature.

New composites Cu-BTC MOF and graphite oxide modified with urea (GO-U) are developed and tested as CO2 adsorbents at room temperature. The composite containing GO-U with the highest nitrogen content exhibits an excellent CO2 uptake (4.23 mmol/g) at dynamic conditions. The incorporation of GO-U into MOF changes the chemistry and microstructure of the parent MOF and results in synergistic features beneficial for CO2 retention on the surface. To identify these features the initial and exhausted materials were extensively characterized from the points of view of their porosity and chemistry. Although the adsorption forces are relatively strong, the results indicate that CO2 is mainly physisorbed on the composites at dry dynamic conditions at ambient temperature and pressure. The primary adsorption sites include small micropores specific for the composites, open Cu sites, and cage window sites.

Structural and optical characterization of Zn(OH)2 and its composites with graphite oxides.

The optical properties of zinc (hydr)oxide and its porous composites with 2% and 5% graphite oxide (GO), thus forming ZnGO-2 and ZnGO-5, are investigated using reflectance spectroscopy and two-photon fluorescence (TPF) imaging. The bandgap energies for the Zn(OH)(2), ZnGO-2, and ZnGO-5 samples are determined to be in the range between 2.88 and 3.60 eV. The size of light-emitting regions (~from 4.5 to 45 µm) and pore size (~from 20 to 255 µm) are measured using the TPF imaging technique.

Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

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.

Cobalt (hydr)oxide/graphite oxide composites: importance of surface chemical heterogeneity for reactive adsorption of hydrogen sulfide.

Composites of cobalt (hydr)oxide and graphite oxide (GO) were obtained and evaluated as adsorbents of hydrogen sulfide at ambient conditions. The surface properties of the initial and exhausted samples were studied by FTIR, TEM, SEM/EDX, XRD, adsorption of nitrogen, potentiometric titration, and thermal analysis. The results obtained show a significant improvement in their adsorption capacities compared to parent compounds. The importance of the OH groups of cobalt (hydr)oxide/GO composites and new interface chemistry for the adsorption of hydrogen sulfide on these materials is revealed. The oxygen activation by the carbonaceous component resulted in formation of sulfites. Water enhanced the removal process. This is the result of the basic environment promoting dissociation of H(2)S and acid-base reactions. Finally, the differences in the performance of the materials with different mass ratios of GO were linked to the availability of active sites on the surface of the adsorbents, dispersion of these sites, their chemical heterogeneity, and location in the pore system.

Visible-light-enhanced interactions of hydrogen sulfide with composites of zinc (oxy)hydroxide with graphite oxide and graphene.

Composites of zinc(oxy)hydroxide-graphite oxide and of zinc(oxy)hydroxide-graphene were used as adsorbents of hydrogen sulfide under ambient conditions. The initial and exhausted samples were characterized by XRD, FTIR, potentiometric titration, EDX, thermal analysis, and nitrogen adsorption. An increase in the amount of H(2)S adsorbed/oxidized on their surfaces in comparison with that of pure Zn(OH)(2) is linked to the structure of the composite, the relative number of terminal hydroxyls, and the kind of graphene-based phase used. Although terminal groups are activated by a photochemical process, the graphite oxide component owing to the chemical bonds with the zinc(oxy)hydroxide phase and conductive properties helps in electron transfer, leading to more efficient oxygen activation via the formation of superoxide ions. Elemental sulfur, zinc sulfide, sulfite, and sulfate are formed on the surface. The formation of sulfur compounds on the surface of zinc(oxy)hydroxide during the course of the breakthrough experiments and thus Zn(OH)(2)-ZnS heterojunctions can also contribute to the increased surface activity of our materials. The results show the superiority of graphite oxide in the formation of composites owing to its active surface chemistry and the possibility of interface bond formation, leading to an increase in the number of electron-transfer reactions.

Enhancement in dibenzothiophene reactive adsorption from liquid fuel via incorporation of sulfur heteroatoms into the nanoporous carbon matrix.

Adsorption of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) from simulated diesel fuel was investigated with polymer-derived carbon matrices. Sulfur was incorporated to the carbon surface via a high-temperature hydrogen sulfide reduction of oxygen-containing groups. The resultant carbons were characterized by nitrogen adsorption, thermal analysis, potentiometric titration, and elemental analysis. The selectivities for DBT and DMDBT adsorption were calculated with reference to naphthalene. The carbon matrices studied had comparable structures, hence, the effects of the sulfur functionalities were evident in an increase in dibenzothiophenes selectivity and the breakthrough capacity; this was especially visible at a breakthrough point where small pores are expected to be active in the adsorption process. Incorporation of sulfur atoms into the aromatic rings of the carbon matrix increases the ability of the surface to attract dibenzothiophenes via dispersive interactions (sulfur-sulfur bridges). Sulfur and sulfur-oxygen groups present in larger pores enhance the amount of adsorbed dibenzothiophenes via specific acid-base and polar interactions. They also contribute to the reactive adsorption of DBT and DMDBT (oxidized) and their chemisorption on the carbon surface.