Metal organic framework anchored onto biowaste mediated carbon material (rGO) for remediation of chromium (VI) by the photocatalytic process.

Groundwater contaminated with hexavalent chromium Cr(VI) causes serious health concerns for the ecosystem. In this study, a hybrid amino functionalized MOF@rGO nanocatalyst was produced by utilization of a biowaste mediated carbon material (reduced graphene oxide; rGO) and its surface was modified by in situ synthesis of a nanocrystalline, mixed ligand octahedral MOF containing iron metal and NH2 functional groups and the prepared composite was investigated for Cr (VI) removal. The photocatalytic degradation of Cr(VI) in aqueous solutions was carried out under UV irradiation. Using a batch mode system, the effect of numerous control variables was examined, and the process design and optimization were carried out by response surface methodology (RSM). The photocatalyst, NH2-MIL(53)-Fe@rGO, was intended to be a stable and highly effective nanocatalyst throughout the recycling tests. XRD, SEM, EDS, FTIR examinations were exploited to discover more about surface carbon embedded with MOF. 2 g/L of NH2-MIL-53(Fe)/rGO was utilized in degrading 200 mg/L of Cr(VI) in just 100 min, implying the selective efficacy of such a MOF-rGO nanocatalyst. Moreover, the Eg determinations well agreed with the predicted range of 2.7 eV, confirming its possibility to be exploited underneath visible light, via the Tauc plot. Thus, MOF anchored onto biowaste derived rGO photo-catalyst was successfully implemented in chromium degradation.

Interfacial Distribution of Nafion Ionomer Thin Films on Nitrogen-Modified Carbon Surfaces.

Chemically modified carbon supports for the cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) show considerable promise for boosting the oxygen reduction reaction. This study evaluated the ionomer distribution of Nafion ionomer thin films on nitrogen (N)-modified carbon surfaces along their depth direction. Neutron reflectivity (NR) measurements performed using the double-contrast technique with H2O and D2O revealed that the introduction of N functional groups to carbon thin films promoted ionomer adsorption onto the surface under wet conditions (22 °C, 85% relative humidity). Molecular dynamics (MD) simulations conducted to verify the origin of the robust contact between the ionomer and N-modified carbon surface revealed an ionomer adsorption mechanism on the N-modified carbon surfaces, which involved Coulomb interactions between the positively charged carbon surface and the ionomer side chains with negatively charged sulfonic acid groups. The positive surface charge, which was determined using the contents of the N functional groups estimated by X-ray photoelectron spectroscopy, was found to be sufficient as an impetus for ionomer adsorption. This strategy involving NR measurements and MD simulations can provide insights into the solid-ionomer interfacial structures in a cathode catalyst layer and can therefore be extensively employed in studies on PEFCs.

Carbon Surface Chemistry: New Insight into the Old Story.

The enormous complexity of the carbon material family has provoked a phenomenological approach to develop its potential in different applications. Although the electronic, chemical, mechanical, and magnetic properties of carbon materials have been widely discussed based on defect control engineering, there is still a lack of fundamental understanding of the carbon surface chemistry, which leads to many controversial conclusions. Here, by analyzing various defects on carbon surface, some commonly neglected aspects and misunderstandings in this field are pointed out, clarifying how surface chemistry affects the chemical behaviors of carbon in some specific chemical reactions. With this full-scale consideration of the carbon surface chemistry, the behaviors of carbon materials with various functions can be well defined, which is indispensable for their scalable applications. Perspectives on future developments of carbon surface chemistry are also provided to enable practically accessible design of advanced carbon in those applications.

A study on activation mechanism in perspective of lignin structures and applicability of lignin-derived activated carbons for pollutant absorbent and supercapacitor electrode.

In this study activated carbons were produced from the biorefinery waste lignin (Asian lignin (AL) USA & Inbicon lignin (IL) Denmark) to evaluate their potential in waste water treatment and as energy storage devices. These products were studied for their surface characteristics as a function of reaction temperature, time, and catalyst loading accordingly. Under the conditions with a temperature lower than 750 °C and within a reaction time of 1 h, the catalytic reaction of alkali-carbon bonding occurred from the external surface, and a turbostratic disorder structure with a large aromatic ring system was formed. More severe reaction conditions accelerated the volatile release of de-alkylated aromatics such as benzene and naphthalene, along with structure and surface collapse. The maximum BET surface area of 2782 m2/g was obtained at 750 °C, 2 h and catalyst ratio of 4. Lignin-derived activated carbon was more efficient for the removal of organic pollutants (<50% adsorption capacity) rather than heavy metals (adsorption capacity >90%) due to interaction of π-π bonding. Furthermore, the activated carbon has a potential to be used as a supercapacitor electrode with high specific capacitance (214.0 F/g AL lignin) and an excellent cyclic stability (95% of their initial capacity). The results of this study demonstrate that lignin is an attractive precursor to produce activated carbons with diverse applications both as biosorbent and as a carbon electrode material even so with acceptable performance.

Monitoring Carbon in Electron and Ion Beam Deposition within FIB-SEM.

It is well known that carbon present in scanning electron microscopes (SEM), Focused ion beam (FIB) systems and FIB-SEMs, causes imaging artefacts and influences the quality of TEM lamellae or structures fabricated in FIB-SEMs. The severity of such effects depends not only on the quantity of carbon present but also on its bonding state. Despite this, the presence of carbon and its bonding state is not regularly monitored in FIB-SEMs. Here we demonstrated that Secondary Electron Hyperspectral Imaging (SEHI) can be implemented in different FIB-SEMs (ThermoFisher Helios G4-CXe PFIB and Helios Nanolab G3 UC) and used to observe carbon built up/removal and bonding changes resulting from electron/ion beam exposure. As well as the ability to monitor, this study also showed the capability of Plasma FIB Xe exposure to remove carbon contamination from the surface of a Ti6246 alloy without the requirement of chemical surface treatments.

Tailoring Properties of Resol Resin-Derived Spherical Carbons for Adsorption of Phenol from Aqueous Solution.

The polycondensation of resorcinol and formaldehyde in a water-ethanol mixture using the adapted Stöber method was used to obtain resol resins. An optimization of synthesis conditions and the use of an appropriate stabilizer (e.g., poly(vinyl alcohol)) resulted in spherical grains. The resins were carbonized in the temperature range of 600-1050 °C and then chemically activated in an aqueous HNO3 solution, gaseous ammonia, or by an oxidation-reduction cycle (soaking in a HNO3 solution followed by treatment with NH3). The obtained carbons were characterized by XRD, the low-temperature adsorption of nitrogen, SEM, TGA, and XPS in order to determine degree of graphitization, porosity, shape and size of particles, and surface composition, respectively. Finally, the materials were tested in phenol adsorption. The pseudo-second order model perfectly described the adsorption kinetics. A clear correlation between the micropore volume and the adsorption capacity was found. The content of graphite domains also had a positive effect on the adsorption properties. On the other hand, the presence of heteroatoms, especially oxygen groups, resulted in the clogging of the pores and a decrease in the amount of adsorbed phenol.

Controlling the Electronic Properties of a Nanoporous Carbon Surface by Modifying the Pores with Alkali Metal Atoms.

We investigate a process of controlling the electronic properties of a surface of nanoporous carbon glass-like thin films when the surface pores are filled with potassium atoms. The presence of impurities on the surface in the form of chemically adsorbed hydrogen and oxygen atoms, and also in the form of hydroxyl (OH) groups, is taken into account. It is found that even in the presence of impurities, the work function of a carbon nanoporous glass-like film can be reduced by several tenths of an electron volt when the nanopores are filled with potassium atoms. At the same time, almost all potassium atoms are ionized, losing one electron, which passes to the carbon framework of the film. This is due to the nanosizes of the pores in which the electron clouds of the potassium atom interact maximally with the electrons of the carbon framework. As a result, this leads to an improvement in the electrical conductivity and an increase in the electron density at the Fermi level. Thus, we conclude that an increase in the number of nanosized pores on the film surface makes it possible to effectively modify it, providing an effective control of the electronic structure and emission properties.

Predicting whether aromatic molecules would prefer to enter a carbon nanotube: A density functional theory study.

The interaction of a carbon nanotube (CNT) with various aromatic molecules, such as aniline, benzophenone, and diphenylamine, was studied using density functional theory able to compute intermolecular weak interactions (B3LYP-D3). CNTs of varying lengths were used, such as 4-CNT, 6-CNT, and 8-CNT (the numbers denoting relative lengths), with the lengths being chosen appropriately to save computation times. All aromatic molecules were found to exhibit strong intermolecular binding energies with the inner surface of the CNT, rather than the outer surface. Hydrogen bonding between two aromatic molecules that include N and O atoms is shown to further stabilize the intermolecular adsorption process. Therefore, when benzophenone and diphenylamine were simultaneously allowed to interact with a CNT, the aromatic molecules were expected to preferably enter the CNT. Furthermore, additional calculations of the intermolecular adsorption energy for aniline adsorbed on a graphene surface showed that the concavity of graphene-like carbon sheet is in proportion to the intermolecular binding energy between the graphene-like carbon sheet and the aromatic molecule.

Acidic surface functional groups control chemisorption of ammonium onto carbon materials in aqueous media.

Elucidation of mechanistic insight into the interaction of carbon materials' physicochemical surface properties and ammonium (NH4+) adsorption in aqueous media was made by conducting a systematic study using a wide range of carbon materials. Three types of biochars (rice husk, poultry litter, and enhanced poultry litter) and activated carbons (fresh and aged coconut shell-based and charcoal-based) were used for investigating the NH4+ adsorption mechanism. Poultry litter biochar, with lowest surface area (3 m2 g-1) and largest pore diameter (29 nm), showed the highest NH4+ adsorption capacity (0.34 mg NH4+g-1), while charcoal-based activated carbon, with the highest surface area (1133 m2 g-1) and small pore diameter (6 nm), had the least NH4+ adsorption capacity (0.09 mg NH4+g-1). The value of Freundlich isotherm constant 'n' was >1 for all tested carbon materials indicating chemisorption as the dominant sorption mechanism. Aging of the carbon surface resulted in 30% increase in NH4+ retention. Surface chemical properties that most influenced NH4+ chemisorption on to carbon materials were found to be acidic surface functional groups (ASFGs), elemental composition, ash content, and pH. The optimal conditions for NH4+ adsorption, regardless of type and source of carbon materials, were solution pH of 8, a high amount of ash content, and carboxyl, carbonyl, and phenolic functional groups. Evaluation of CEC and ASFGs indicated that CEC and ASFGs are not equivalent terms. Through this study, conducted on carbon adsorbents derived from different sources, with different surface physical and chemical properties, we established that ASFGs, and not CEC, play a critical role in ammonium chemisorption on carbon materials. The study showed that low cost and eco-friendly biochars, with optimal surface chemistry, can replace expensive activated carbons for NH4+ remediation in aqueous media.

Making Sense of Complex Carbon and Metal/Carbon Systems by Secondary Electron Hyperspectral Imaging.

Carbon and carbon/metal systems with a multitude of functionalities are ubiquitous in new technologies but understanding on the nanoscale remains elusive due to their affinity for interaction with their environment and limitations in available characterization techniques. This paper introduces a spectroscopic technique and demonstrates its capacity to reveal chemical variations of carbon. The effectiveness of this approach is validated experimentally through spatially averaging spectroscopic techniques and using Monte Carlo modeling. Characteristic spectra shapes and peak positions for varying contributions of sp2-like or sp3-like bond types and amorphous hydrogenated carbon are reported under circumstances which might be observed on highly oriented pyrolytic graphite (HOPG) surfaces as a result of air or electron beam exposure. The spectral features identified above are then used to identify the different forms of carbon present within the metallic films deposited from reactive organometallic inks. While spectra for metals is obtained in dedicated surface science instrumentation, the complex relations between carbon and metal species is only revealed by secondary electron (SE) spectroscopy and SE hyperspectral imaging obtained in a state-of-the-art scanning electron microscope (SEM). This work reveals the inhomogeneous incorporation of carbon on the nanoscale but also uncovers a link between local orientation of metallic components and carbon form.

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.

The adsorption of NO, NH3, N2 on carbon surface: a density functional theory study.

To explore the adsorption mechanism of NO, NH3, N2 on a carbon surface, and the effect of basic and acidic functional groups, density functional theory was employed to investigate the interactions between these molecules and carbon surfaces. Molecular electrostatic potential, Mulliken population analyses, reduced density gradient, and Mayer bond order analyses were used to clarify the adsorption mechanism. The results indicate that van der Waals interactions are responsible for N2 physisorption, and N2 is the least likely to adsorb on a carbon surface. Modification of carbon materials to decorate basic or acidic functional groups could enhance the NH3 physisorption because of hydrogen bonding or electrostatic interactions, however, NO physisorption on a carbon surface is poor. Zig-zag sites are more reactive than armchair sites when these gas molecules absorb on the edge sites of carbon surface. Graphical abstract NH3, N2, NO adsortion on carbon surface.