Regulating the spatial arrangement of CuO and MgO within activated carbon matrix to maximize their room temperature H2S removal.

Adsorbents with dual-component active phases have attracted much attention owing to their potential application in synergistic H2S removal. The influence of spatial arrangements of two components within a support matrix on their desulfurization performance was investigated through regulating the mutual arrangements of CuO and MgO on an activated carbon surface. Their spatial locations were found to remarkably affect interfacial interactions, local pH, the conductivity of adsorbents, and electronic structure of copper oxide. A close contact of CuO with the carbon surface led to strong interactions of both components, inhibiting the reduction of CuO and decreasing its reactivity with H2S. On the other hand, a proximity of MgO to the carbon surface increased local pH, promoting the oxidation of H2S into elemental S, instead of sulfates. Cu+ in the copper oxide phase increased the desulfurization performance due to its ability to activate oxygen and to accelerate a lattice diffusion. Enhanced surface conductivity due to the interfacial interactions improved the desulfurization efficiency and favored the formation of elemental S through promoting an electron transfer in redox reactions.

Transient chemical and structural changes in graphene oxide during ripening.

Graphene oxide (GO)-the oxidized form of graphene-is actively studied in various fields, such as energy, electronic devices, separation of water, materials engineering, and medical technologies, owing to its fascinating physicochemical properties. One major drawback of GO is its instability, which leads to the difficulties in product management. A physicochemical understanding of the ever-changing nature of GO can remove the barrier for its growing applications. Here, we evidencde the presence of intrinsic, metastable and transient GO states upon ripening. The three GO states are identified using a [Formula: see text] transition peak of ultraviolet-visible absorption spectra and exhibit inherent magnetic and electrical properties. The presence of three states of GO is supported by the compositional changes of oxygen functional groups detected via X-ray photoelectron spectroscopy and structural information from X-ray diffraction analysis and transmission electron microscopy. Although intrinsic GO having a [Formula: see text] transition at 230.5 ± 0.5 nm is stable only for 5 days at 298 K, the intrinsic state can be stabilized by either storing GO dispersions below 255 K or by adding ammonium peroxydisulfate.

Converting carbon black into an efficient and multi-site ORR electrocatalyst: the importance of bottom-up construction parameters.

To boost efficient energy transitions, alternatives to expensive and unsustainable noble metal-based electrocatalysts for the oxygen reduction reaction (ORR) are needed. Having this in mind, carbon black - Black Pearls 2000 (BP) was enriched in active nitrogen-containing centers, including single-atom Fe-N sites surrounded by Fe nanoclusters, through a synthesis methodology employing only broadly available precursors. The methodical approach taken to optimize the synthesis conditions highlighted the importance of (1) a proper choice of the Fe precursor; (2) melamine as an N source to limit the formation of magnetite crystals and modulate the charge density nearby the active sites, and glucose to chelate/isolate Fe atoms and thus allow the Fe-N coordination to be established, with a limiting formation of Fe0 clusters; and (3) a careful dosing of the Fe load. The ORR on the optimized electrocatalyst (Fe0.06-N@BP) proceeds mostly through a four-electron pathway, having an onset potential (0.912 V vs. RHE) and limiting current density (4.757 mA cm-2) above those measured on Pt/C (0.882 V and 4.657 mA cm-2, respectively). Moreover, the current density yielded by Fe0.06-N@BP after 24 h at 0.4 V vs. RHE was still above that of Pt/C at t = 0 (4.44 mA cm-2), making it a promising alternative to noble metal-containing electrocatalysts in fuel cells.

Carbon Surface-Influenced Heterogeneity of Ni and Co Catalytic Sites as a Factor Affecting the Efficiency of Oxygen Reduction Reaction.

Highly porous carbon black and micro/mesoporous activated carbon were impregnated with cobalt and nickel nitrates, followed by heat treatment at 850 °C in nitrogen. Detailed information about chemistry and porosity was obtained using XPS, XRD, TEM/EDX, and nitrogen adsorption. The samples were used as ORR catalysts. Marked differences in the performance were found depending on the type of carbon. Differences in surface chemistry and porosity affected the chemistry of the deposited metal species that governed the O2 reduction efficiency along with other features of the carbon supports, including electrical conductivity and porosity. While dissociating surface acidic groups promoted the high dispersion of small metal species, carbon reactivity with oxygen and acidity limited the formation of the most catalytically active Co3O4. Formation of Co3O4 on the highly conductive carbon black resulted in an excellent performance with four electrons transferred and a current density higher than that on Pt/C. When Co3O4 was not formed in a sufficient quantity, nickel metal nanoparticles promoted ORR on the Ni/Co-containing samples. The activity was also significantly enhanced by small pores that increased the ORR efficiency by strongly adsorbing oxygen, which led to its bond splitting, followed by the acceptance of four electrons.

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.

Activated carbon versus metal-organic frameworks: A review of their PFAS adsorption performance.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are a class of fluorinated aliphatic compounds considered as emerging persistent pollutants. Owing to their adverse effects on human health and environment, efficient methods of their removal from various complex matrices need to be developed. This review focuses on recent results addressing the adsorption of PFAS on activated carbons (AC) and metal-organic frameworks (MOF). While the former are well-established adsorbents used in water treatment, the latter are relatively new and still not applied at a large scale. Nevertheless, they attract research interests owing to their developed porosity and versatile surface chemistry. While AC provide high volumes of pores and hydrophobic surfaces to strongly attract fluorinated chains, MOF supply sites for acid-base complexation and a variety of specific interactions. The modifications of AC are focused on the introduction of basicity to attract PFAS anions via electrostatic/chemical interactions, and those of MOF - on structural defects to increase the pore sizes. Based on the comparison of the performance and specifically adsorption forces provided by these two groups of materials, activated carbons were pointed out as worthy of further research efforts. This is because their surface, especially that in large pores, where dispersive forces are week and where extensive pore space might be utilized to adsorb more PFAS, can be further chemically modified and these modifications might be informed by the mechanisms of PFAS adsorption, which are specific for MOF. This review emphasizes the effects of these modifications on the adsorption mechanism and brings the critical assessment of the advantages/disadvantages of both groups as PFAS adsorbents.

Alternative view of oxygen reduction on porous carbon electrocatalysts: the substance of complex oxygen-surface interactions.

Electrochemical oxygen reduction reaction (ORR) is an important energy-related process requiring alternative catalysts to expensive platinum-based ones. Although recently some advancements in carbon catalysts have been reported, there is still a lack of understanding which surface features might enhance their efficiency for ORR. Through a detailed study of oxygen adsorption on carbon molecular sieves and using inelastic neutron scattering, we demonstrated here that the extent of oxygen adsorption/interactions with surface is an important parameter affecting ORR. It was found that both the strength of O2 physical adsorption in small pores and its specific interactions with surface ether functionalities in the proximity of pores positively influence the ORR efficiency. We have shown that ultramicropores and hydrophobic surface rich in ether-based groups and/or electrons enhance ORR on carbon electrocatalysts and the performance parameters are similar to those measured on Pt/C with the number of electron transfer equal to 4.

Exploring the Silent Aspect of Carbon Nanopores.

Recently, owing to the discovery of graphene, porous carbons experienced a revitalization in their explorations. However, nowadays, the focus is more on search for suitable energy advancing catalysts sensing, energy storage or thermal/light absorbing features than on separations. In many of these processes, adsorption, although not emphasized sufficiently, can be a significant step. It can just provide a surface accumulation of molecules used in other application-driving chemical or physical phenomena or can be even an additional mechanism adding to the efficiency of the overall performance. However, that aspect of confined molecules in pores and their involvement in the overall performance is often underrated. In many applications, nanopores might silently advance the target processes or might very directly affect or change the outcomes. Therefore, the objective of this communication is to bring awareness to the role of nanopores in carbon materials, and also in other solids, to scientists working on cutting-edge application of nonporous carbons, not necessary involving the adsorption process directly. It is not our intention to provide a clear explanation of the small pore effects, but we rather tend to indicate that such effects exist and that their full explanation is complex, as complex is the surface of nanoporous carbons.

Chemically heterogeneous carbon dots enhanced cholesterol detection by MALDI TOF mass spectrometry.

A binary system composed of carbon dots (CDs) and N-doped CDs (N-CDs) embedded in an organic matrix was used for the analysis of cholesterol by MALDI (matrix-assisted laser desorption and ionization time-of-flight) mass spectrometry, as a model for detection of small, biologically relevant molecules. The results showed that both CDs are sensitive to the cholesterol and can be used either alone or in a binary system with 2,5-dihydroxybenzoic acid (DHB) to enhance the detection process. It was found that both COOH and NH2 groups on CDs surface contributed to the enhancement in the cholesterol detection by MALDI mass spectrometry in the presence of inorganic cations. Nevertheless, in the presence of NaCl, N-CDs led to a better reproducibility of results. It was due to the coexistence of positive and negative charge on N-CDs surface that led to a homogeneous analyte/substrate distribution, which is an important detection parameter. The enhancing effect of carbon dots was linked to a negative Gibbs energy of the complex formation between CDs, Na+, cholesterol and DHB, and it was supported by theoretical calculations. Moreover, upon the addition of CDs/N-CDs, such features as a low ionization potential, vertical excitation, dipole moment and oscillator strength positively affected the cholesterol detection by MALDI in the presence of Na+.

Proposing an unbiased oxygen reduction reaction onset potential determination by using a Savitzky-Golay differentiation procedure.

For proper and fair comparison of the performance of Oxygen reduction reaction (ORR) electrocatalysts an un-biased method to determine an onset potential value is needed. Here we report an easy mathematical approach based on the second derivative of linear sweep voltammetry curves, referred to as a second order discrete differentiation method (SODDM) that allows to accurately provide the onset potential. Analysis of the published results showed that the reported values might be affected by an intrinsic human error associated with the application of the most common approaches addressed as a tangent method or those relaying on a visual estimation of the onset potential based on the shape of a linear scan voltammetry (LSV) curve. We have also demonstrated that by using SODDM, electrochemical data collected on different instruments by different researchers leads to comparable results in terms of the ORR onset potential values.

Defectous UiO-66 MOF Nanocomposites as Reactive Media of Superior Protection against Toxic Vapors.

The composites of UiO-66 with nanographite or oxidized graphitic carbon nitride nanospheres (∼10 wt %) were synthesized and used as CEES decontamination media from a vapor phase. The materials were characterized using XRD, nitrogen adsorption, SEM, potentiometric titration, FTIR, and thermal analysis. The results showed a marked improvement of the detoxification capability against the vapors of CEES compared to those of pristine UiO-66, either in terms of the amount adsorbed or surface reactivity. The maximum weight uptake for the composites reached 632 mg g-1, which was higher than that on UiO-66. The improved adsorption and catalytic activity were linked to the new interface between the modifiers and MOF units/defects, which provided additional active sites formed as a result of modifiers' surface groups acting as MOF linkers. The morphology and porosity were also altered, positively affecting the sites' accessibility and their dispersion in the MOF particles. Dehydrohalogenation and oxidation were the predominant pathways of the composites' surface reactivity. The detoxification mechanisms involving CEES vapor-UiO-66 surface interactions differ from those reported for CEES liquid/dissolved liquid-UiO-66 interactions, and dehydrohalogenation, fragmentation, and oxidation predominate.

Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity.

Composite of two MOFs, copper-based Cu-BTC (HKUST-1) and zirconium-based Zr-BDC (UiO-66), with oxidized graphitic carbon nitride nanospheres were synthesized. For comparison, pure MOFs were also obtained. The surface features were analyzed using x-ray diffraction (XRD), sorption of nitrogen, thermal analysis, and scanning electron microscopy (SEM). The incorporation of oxidized g-C3N4 to the Cu-BTC framework caused the formation of a heterogeneous material of a hierarchical pores structure, but a decreased surface area when compared to that of the parent MOF. In the case of UiO-66, functionalized nanospheres were acting as seeds around which the crystals grew. Even though the MOF phases were detected in both materials, the porosity analysis indicated that in the case of Cu-BTC, a collapsed MOF/nonporous and amorphous matter was also present and the MOF phase was more defectous than that in the case of UiO-66. The results suggested different roles of oxidized g-C3N4 during the composite synthesis, depending on the MOF geometry. While spherical units of UiO-66 grew undisturbed around oxidized and spherical g-C3N4, octahedral Cu-BTC units experienced geometrical constraints, leading to more defects, a disturbed growth of the MOF phase, and to the formation of mesopores at the contacts between the spheres and MOF units. The differences in the amounts of CO2 adsorbed between the MOFs and the composites confirm the proposed role of oxidized g-C3N4 in the composite formation.

TiO2/S-Doped Carbons Hybrids: Analysis of Their Interfacial and Surface Features.

Hybrids containing approximately equal amounts of P25 TiO2 and S-doped porous carbons were prepared using a water-based slurry mixing method. The materials were extensively characterized by adsorption of nitrogen, potentiometric titration, thermal analysis in air and in helium, XRD, XPS and SEM. The collected results showed the significant blockage of carbon micropores by TiO2 particles deposited on their outer surface. The formation of a new interface, especially for the S-rich samples, might also contribute to the porosity alteration. Analysis of surface chemistry suggested the presence of Ti-S bonds with an involvement of sulfur from thiophenic species in the carbon phase. The latter, especially when polymer-derived, was mainly deposited on the TiO2 nanoparticles. Formation of Ti-S stabilized sulfur and increased the ignition temperature of the hybrids, especially those with a high content of sulfur, in comparison with the ignition temperature of carbons. The surfaces of hybrid with S-containing carbons was also thermally very stable and of basic chemical nature. The formation of interfacial structures Ti-C was detected by XPS analysis suggesting a partial reduction of the Ti.

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.

Nitrogen-containing activated carbon of improved electrochemical performance derived from cotton stalks using indirect chemical activation.

Highly porous (specific surface area, SBET, 1400 m2/g) and rich in surface groups activated carbons (ACs) were obtained from cotton stalks using either a direct or indirect activation. They were characterized by adsorption of nitrogen, thermal analysis combined with mass spectrometry, potentiometric titration, and X-ray photoelectron spectroscopy (XPS). XPS analysis indicated that the indirect activation led to more nitrogen on the surface incorporated as pyridinic and graphitic/quaternary species. These species were beneficial for a carbon application as oxygen reduction reaction (ORR) electrocatalysts and supercapacitors. The carbons were catalytically active in ORR with a number of electron transfer from 2.15 to 3.40 and onset potential of 0.810 V vs. reference hydrogen electrode (RHE). Their capacitance was around 180 F g-1 at 1 A g-1 when measured in an alkaline medium. The dependence of the performance on the porosity and nitrogen content was found, indicating suitability of cotton stalks obtained using the indirect activation as precursors of carbons of promising electrochemically active features.

Degradation of endocrine disruptor, bisphenol-A, on an mixed oxidation state manganese oxide/modified graphite oxide composite: A role of carbonaceous phase.

Modified graphite oxide (ΝGO) was used as a support of a manganese oxide of hausmannite type (Mn3O4) nanocatalyst and applied for the degradation of an endocrine disruptor, bisphenol-A (BPA). The prepared nanocomposite/catalyst (NGO-Mn3O4), as well as pure modified graphite oxide and manganese oxide, were characterized by X-ray diffraction, Scanning Electron Microscopy, nitrogen adsorption, X-ray photoelectron spectroscopy, Fourier Transform Infrared Spectroscopy, and potentiometric titration. The maximum removal activity for all the materials was measured at pH = 3. The NGO-Mn3O4 nanocomposite showed the highest removal efficiency of BPA at an ambient temperature without light irradiation and/or the addition of chemicals, which can be attributed to the synergistic effect of the composite formation. The nanocomposite exhibited a high catalytic activity for the degradation/oxidation of BPA, which was dramatically higher than that of the pristine Mn3O4 phase. Modified graphite oxide showed also an enhanced capability for the BPA removal, which was linked to an increased physical adsorption component.

Origin and Perspectives of the Photochemical Activity of Nanoporous Carbons.

Even though, owing to the complexity of nanoporous carbons' structure and chemistry, the origin of their photoactivity is not yet fully understood, the recent works addressed here clearly show the ability of these materials to absorb light and convert the photogenerated charge carriers into chemical reactions. In many aspects, nanoporous carbons are similar to graphene; their pores are built of distorted graphene layers and defects that arise from their amorphicity and reactivity. As in graphene, the photoactivity of nanoporous carbons is linked to their semiconducting, optical, and electronic properties, defined by the composition and structural defects in the distorted graphene layers that facilitate the exciton splitting and charge separation, minimizing surface recombination. The tight confinement in the nanopores is critical to avoid surface charge recombination and to obtain high photochemical quantum yields. The results obtained so far, although the field is still in its infancy, leave no doubts on the possibilities of applying photochemistry in the confined space of carbon pores in various strategic disciplines such as degradation of pollutants, solar water splitting, or CO2 mitigation. Perhaps the future of photovoltaics and smart-self-cleaning or photocorrosion coatings is in exploring the use of nanoporous carbons.

Barium titanate perovskite nanoparticles as a photoreactive medium for chemical warfare agent detoxification.

Barium titanate nanoparticles (BTO-NPs) in the size range 8-12 nm, prepared by gel collection, are found to be a photoreactive detoxifier for Chemical Warfare Agent vapors, specifically, the sulfur mustard surrogate (2-chloroethyl ethyl sulfide). The relatively monodisperse, uniformly spherical BTO-NPs, initially dispersed in alcohol solvents, form a stable and porous aggregated structure reminiscent of a nanostructured material with voids/pores of an average diameter of 4.6 nm and a relatively narrow distribution of their sizes (2.5-8.7 nm). Due to the interparticle porosity and a polar, chemically active surface, signifcant amounts of CWA surrogate and its decomposition products were adsorbed on the BTO-NPs. The recorded weight uptake on the perovskite was the highest among a series of materials and nanocomposites known for their detoxification activity and tested at the same conditions (169 mg/g, compared to 117 mg/g for zinc oxide and <100 mg/g for other transition metal oxides). Besides adsorption, BTO nanomaterial acts simultaneously as an efficient heterogeneous catalyst by degrading the toxic vapors to alcohols, sulfides and thiols - molecules of significantly lower toxicity than the CWA surrogate. Hydrolysis and dehydrohalogenation were the predominant detoxification pathways, via the formation of the intermediate cyclic sulfonium, whether under light or in the dark. Ambient light irradiation promoted the photo-oxidation and photo-degradation by radical intermediates formed. With an unhindered oxygen rich surface, underlying highly polarizable lattice structure, and large accessible surface area, barium titanate nanoparticles are investigated as a potentially useful medium for photoreactive detoxification of chemical warfare agent vapors.