Adhesion characteristics of solution treated environmental dust.

Environmental dust is modified towards self-cleaning applications under the gravitational influence. Dust particles are collected in the local area of Dammam in Saudi Arabia and they are treated with a dilute hydrofluoric acid solution. The changes in chemical and adhesion characteristics of the dust particles prior and after the solution treatment are analyzed. Force of adhesion and work required to remove dust from hydrophobic and hydrophilic glass surfaces are assessed, separately, for solution treated and collected dust. We show that aqueous hydrofluoric acid solution treatment modifies some dust components while causing the formation of submicron cracks and nano/submicron porous/pillars like textures on the dust particles. The texture generated on dust surfaces after the solution treatment has a great influence on dust adhesion characteristics. Hence, the solution treated dust particles result in lower adhesion on hydrophobic and hydrophilic glass surfaces as compared to that of untreated dust. The gravitational force enables to remove solution treated dust from inclined glass surfaces, which becomes more apparent for hydrophobic surfaces.

Solvent Effect on Structural Elucidation of Photoluminescent Graphitic Carbon Nanodots.

Photoluminescence (PL) of carbon nanodots (CNDs) is proposed to originate from the polycyclic aromatic carbon-core and in situ synthesized molecular fluorophores. This work reports the CNDs prepared by direct pyrolysis of citric acid only at a prolonged time, 40 h, and their fluorescence emission parameters in a variety of solvents by steady-state and time-resolved emission spectroscopies. The response of fluorescence emission lifetime and emission quenching rate constants to changes in solvent parameters such as polarity and tumbling lifetime were essentially independent, unlike molecular fluorophores that display solvent-dependent emission parameters. Fluorescence emission was quenched in nitromethane additionally indicating to the polycyclic aromatic carbon-core as a predominant structural feature of the CNDs. The quenching of CND emission in the presence of benzophenone that has a strong triplet component in the excited state was observed. Quenching demonstrates the Stern-Volmer behavior and reveals the additional nonradiative decay pathways of CNDs. The main photophysical features of CNDs are discussed in terms of fluorescence emission originating from the excited state of the polycyclic aromatic carbon-core where contribution from the potential molecular fluorophores is considered minimal.

Halogen Bonding Between Anions: Association of Anion Radicals of Tetraiodo-p-benzoquinone with Iodide Anions.

Halogen bonding between two negatively charged species, tetraiodo-p-benzoquinone anion radicals (I4 Q-. ) and iodide anions, was observed and characterized for the first time. X-ray structural and EPR/UV-Vis spectral studies revealed that the anion-anion bonding led to the formation of crystals comprising 2D layers of I4 Q-. anion radicals linked by iodides and separated by Et4 N+ counter-ions. Computational analysis suggested that the seemingly antielectrostatic halogen bonds in these systems were formed via a combination of several factors. First, an attenuation of the interionic repulsion by the solvent facilitated close approach of the anions leading to their mutual polarization. This resulted in the appearance of positively charged areas (σ-holes) on the surface of the iodine substituents in I4 Q-. responsible for the attractive interaction. Finally, the solid-state associations were also stabilized by multicenter (4:4) halogen bonding between I4 Q-. and iodide.

Pore Characteristics for Efficient CO2 Storage in Hydrated Carbons.

Development of new approaches for carbon dioxide (CO2) capture is important in both scientific and technological aspects. One of the emerging methods in CO2 capture research is based on the use of gas-hydrate crystallization in confined porous media. Pore dimensions and surface functionality of the pores play important roles in the efficiency of CO2 capture. In this report, we summarize work on several porous carbons (PCs) that differ in pore dimensions that range from supermicropores to mesopores, as well as surfaces ranging from hydrophilic to hydrophobic. Water was imbibed into the PCs, and the CO2 uptake performance, in dry and hydrated forms, was determined at pressures of up to 54 bar to reveal the influence of pore characteristics on the efficiency of CO2 capture and storage. The final hydrated carbon materials had H2O-to-carbon weight ratios of 1.5:1. Upon CO2 capture, the H2O/CO2 molar ratio was found to be as low as 1.8, which indicates a far greater CO2 capture capacity in hydrated PCs than ordinarily seen in CO2-hydrate formations, wherein the H2O/CO2 ratio is 5.72. Our mechanistic proposal for attainment of such a low H2O/CO2 ratio within the PCs is based on the finding that most of the CO2 is captured in gaseous form within micropores of diameter <2 nm, wherein it is blocked by external CO2-hydrate formations generated in the larger mesopores. Therefore, to have efficient high-pressure CO2 capture by this mechanism, it is necessary to have PCs with a wide pore size distribution consisting of both micropores and mesopores. Furthermore, we found that hydrated microporous or supermicroporous PCs do not show any hysteretic CO2 uptake behavior, which indicates that CO2 hydrates cannot be formed within micropores of diameter 1-2 nm. Alternatively, mesoporous and macroporous carbons can accommodate higher yields of CO2 hydrates, which potentially limits the CO2 uptake capacity in those larger pores to a H2O/CO2 ratio of 5.72. We found that high nitrogen content prevents the formation of CO2 hydrates presumably due to their destabilization and associated increase in system entropy via stronger noncovalent interactions between the nitrogen functional groups and H2O or CO2.

Single-Crystal-to-Single-Crystal Transformation of Hydrogen-Bonded Triple-Stranded Ladder Coordination Polymer via Photodimerization Reaction.

A one-dimensional hydrogen-bonded triple-stranded ladder coordination polymer [Cd(bpe)1.5(NO3)2(H2O)] (1) (where bpe = trans-1,2-bis(4-pyridyl)ethylene) containing three parallel C═C double bonds was synthesized. This compound undergoes photochemical [2 + 2] cycloaddition and produces rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) in up to 67% yield via Single-Crystal-to-Single-Crystal (SCSC) transformation. Triple-stranded ladder-like structures have never before displayed such a kind of SCSC transformation. Furthermore, photoirradiation of ground 1 produces rctt-tpcb in up to 100% yield in the solid state. On the basis of the alignment of three C═C olefinic bonds of bpe ligands in parallel, only two out of the three aligned bpe are expected to undergo [2 + 2] photodimerization. However, the quantitative yield from the solid-state photochemical [2 + 2] cycloaddition reaction has been achieved via grinding of crystals of 1 to a powder. The effects of grinding on photoreactivity of 1 were thoroughly studied using 1H NMR spectroscopy, thermogravimetric analysis (TGA), and Raman spectroscopy. These studies indicate that the molecular movements of the hydrogen-bonded ladders are reinforced due to the loss of coordinated water molecules and the further crystal repacking via bond-breaking/forming of the hydrogen-bonded assemblies during mechanical grinding. The 100% photodimerization of ground 1 shows that the grinding accelerates internal molecular motions of ladder structures within the crystals lattice. The solid-state photoluminescence of 1, before and after UV irradiation, was investigated at room temperature, both indicative of interesting luminescent properties.

Highly Oxidized Graphene Quantum Dots from Coal as Efficient Antioxidants.

Graphene quantum dots (GQDs) have recently been employed in various fields including medicine as antioxidants, primarily because of favorable biocompatibility in comparison to common inorganic quantum dots, although the structural features that lead to the biological activities of GQDs are poorly understood. Here, we report that coal-derived GQDs and their poly(ethylene glycol)-functionalized derivatives serve as efficient antioxidants, and we evaluate their electrochemical, chemical, and in vitro biological activities.

Suppressing Li Metal Dendrites Through a Solid Li-Ion Backup Layer.

The growing demand for sustainable and off-grid energy storage is reviving the attempts to use Li metal as the anode in the next generation of batteries. However, the use of Li anodes is hampered due to the growth of Li dendrites upon charging and discharging, which compromises the life and safety of the battery. Here, it is shown that lithiated multiwall carbon nanotubes (Li-MWCNTs) act as a controlled Li diffusion interface that suppresses the growth of Li dendrites by regulating the Li+ ion flux during charge/discharge cycling at current densities between 2 and 4 mA cm-2 . A full Li-S cell is fabricated to showcase the versatility of the protected Li anode with the Li-MWCNT interface, where the full cells could support pulse discharges at high currents and over 450 cycles at different rates with coulombic efficiencies close to 99.9%. This work indicates that carbon materials in lithiated forms can be an effective and simple approach to the stabilization of Li metal anodes.

Near-White Light Emission from Lead(II) Metal-Organic Frameworks.

Reaction of bpy (bpy = 4,4'-bipyridine) with Pb(OAc)2·3H2O in DMF (DMF = dimethylformamide) afforded a metal-organic framework (MOF), [Pb2(µ-bpy)(µ-O2CCH3)2(µ-O2CCH3)2]·H2O (1). Reaction of bpy with Pb(O2CCF3)2 in a methanol and chloroform mixture furnished another MOF, [Pb(µ-bpy)(µ-O2CCF3)2]·1/2CHCl3 (2). However, the reaction of bpy with Pb(OAc)2·3H2O in the presence of trifluoroacetic acid in a similar reaction condition yielded a hydrogen-bonded zwitter-ionic complex of Pb(II), [Pb(bpy-H)2(O2CCF3)4] (3). All compounds have been characterized by single crystal X-ray crystallography, FT-IR, and 1H NMR spectroscopies. Compound 1 forms four heptacoordinated Pb(II) joined by (OCCH3)-O- linkages, resulting in a 3D noninterpenetrated MOF net with a four-connected uninodal sra (SrAl2) topology. However, in 2, tetra-connected Pb4(O2CCF3)8 cluster units are linked further through eight bpy ligands to furnish a doubly interpenetrated MOF with a new topology but having the very similar connectivity of 1, whereas 3 forms a zigzag hydrogen-bonded chain structure. The variation of carboxylate anions, pH of the reaction medium, and the ratio of the reactants profoundly affected the final topological structure of the compounds synthesized. The solid-state photoluminescence of 1-3 was investigated at room temperature. Interestingly 1, 2, and 3 achieved close to white light emission when excited at 329, 376, and 330 nm, respectively. The systematic understanding of the photophysical properties of analogous Pb-based compounds may open new perspectives for developing single-phase white-light-emitting materials using Pb(II) based MOFs.

Ultrafast Charging High Capacity Asphalt-Lithium Metal Batteries.

Li metal has been considered an outstanding candidate for anode materials in Li-ion batteries (LIBs) due to its exceedingly high specific capacity and extremely low electrochemical potential, but addressing the problem of Li dendrite formation has remained a challenge for its practical rechargeable applications. In this work, we used a porous carbon material made from asphalt (Asp), specifically untreated gilsonite, as an inexpensive host material for Li plating. The ultrahigh surface area of >3000 m2/g (by BET, N2) of the porous carbon ensures that Li was deposited on the surface of the Asp particles, as determined by scanning electron microscopy, to form Asp-Li. Graphene nanoribbons (GNRs) were added to enhance the conductivity of the host material at high current densities, to produce Asp-GNR-Li. Asp-GNR-Li has demonstrated remarkable rate performance from 5 A/gLi (1.3C) to 40 A/gLi (10.4C) with Coulombic efficiencies >96%. Stable cycling was achieved for more than 500 cycles at 5 A/gLi, and the areal capacity reached up to 9.4 mAh/cm2 at a highest discharging/charging rate of 20 mA/cm2 that was 10× faster than that of typical LIBs, suggesting use in ultrafast charging systems. Full batteries were also built combining the Asp-GNR-Li anodes with a sulfurized carbon cathode that possessed both high power density (1322 W/kg) and high energy density (943 Wh/kg).

Lightweight Hexagonal Boron Nitride Foam for CO2 Absorption.

Weak van der Waals forces between inert hexagonal boron nitride (h-BN) nanosheets make it easy for them to slide over each other, resulting in an unstable structure in macroscopic dimensions. Creating interconnections between these inert nanosheets can remarkably enhance their mechanical properties. However, controlled design of such interconnections remains a fundamental problem for many applications of h-BN foams. In this work, a scalable in situ freeze-drying synthesis of low-density, lightweight 3D macroscopic structures made of h-BN nanosheets chemically connected by poly(vinyl alcohol) (PVA) molecules via chemical cross-link is demonstrated. Unlike pristine h-BN foam which disintegrates upon handling after freeze-drying, h-BN/PVA foams exhibit stable mechanical integrity in addition to high porosity and large surface area. Fully atomistic simulations are used to understand the interactions between h-BN nanosheets and PVA molecules. In addition, the h-BN/PVA foam is investigated as a possible CO2 absorption and as laser irradiation protection material.

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters.

The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.

Perylene Diimide as a Precise Graphene-like Superoxide Dismutase Mimetic.

Here we show that the active portion of a graphitic nanoparticle can be mimicked by a perylene diimide (PDI) to explain the otherwise elusive biological and electrocatalytic activity of the nanoparticle construct. Development of molecular analogues that mimic the antioxidant properties of oxidized graphenes, in this case the poly(ethylene glycolated) hydrophilic carbon clusters (PEG-HCCs), will afford important insights into the highly efficient activity of PEG-HCCs and their graphitic analogues. PEGylated perylene diimides (PEGn-PDI) serve as well-defined molecular analogues of PEG-HCCs and oxidized graphenes in general, and their antioxidant and superoxide dismutase-like (SOD-like) properties were studied. PEGn-PDIs have two reversible reduction peaks, which are more positive than the oxidation peak of superoxide (O2•-). This is similar to the reduction peak of the HCCs. Thus, as with PEG-HCCs, PEGn-PDIs are also strong single-electron oxidants of O2•-. Furthermore, reduced PEGn-PDI, PEGn-PDI•-, in the presence of protons, was shown to reduce O2•- to H2O2 to complete the catalytic cycle in this SOD analogue. The kinetics of the conversion of O2•- to O2 and H2O2 by PEG8-PDI was measured using freeze-trap EPR experiments to provide a turnover number of 133 s-1; the similarity in kinetics further supports that PEG8-PDI is a true SOD mimetic. Finally, PDIs can be used as catalysts in the electrochemical oxygen reduction reaction in water, which proceeds by a two-electron process with the production of H2O2, mimicking graphene oxide nanoparticles that are otherwise difficult to study spectroscopically.

Mechanistic Study of the Conversion of Superoxide to Oxygen and Hydrogen Peroxide in Carbon Nanoparticles.

Hydrophilic carbon clusters (HCCs) are oxidized carbon nanoparticles with a high affinity for electrons. The electron accepting strength of HCCs, employing the efficient conversion of superoxide (O2(•-)) to molecular oxygen (O2) via single-electron oxidation, was monitored using cyclic voltammetry and electron paramagnetic resonance spectroscopy. We found that HCCs possess O2 reduction reaction (ORR) capabilities through a two-electron process with the formation of H2O2. By comparing results from aprotic solvents to those obtained from ORR activity in aqueous media, we propose a mechanism for the origin of the antioxidant and superoxide dismutase mimetic properties of poly(ethylene glycolated) hydrophilic carbon clusters (PEG-HCCs).

Helical and Dendritic Unzipping of Carbon Nanotubes: A Route to Nitrogen-Doped Graphene Nanoribbons.

Bamboo structured nitrogen-doped multiwalled carbon nanotubes (CN(x)-MWCNTs) have been successfully unzipped by a chemical oxidation route, resulting in nitrogen-doped graphene nanoribbons (CN(x)-GNRs) with a multifaceted microstructure. The oxidation of CN(x)-MWCNTs was carried out using potassium permanganate in the presence of trifluoroacetic acid or phosphoric acid. On the basis of the high resolution transmission electron microscopy studies, the bamboo compartments were unzipped via helical or dendritic mechanisms, which are different from the longitudinal unzipping of open channel MWCNTs. The product graphene oxide nanoribbons were simultaneously reduced and doped with nitrogen by thermal annealing in an ammonia atmosphere. The effects of the annealing temperature, time, and atmosphere on the doping level and types of the nitrogen functional groups have been investigated. X-ray photoelectron spectroscopy results indicate that a wide range of doping levels can be achieved (4-9 at %) simply by changing the annealing conditions. Pyridinic and pyrrolic nitrogen functional groups were the dominant species that were attached to the edges of the CN(x)-GNRs. The GNRs, with a faceted structure and pyridinic and pyrrolic groups on their edges, have abundant nitrogen sites. These active sites could play a vital role in enhancing the electrocatalytic performance of GNRs.

Electronic Interactions of Michler's Ketone with DNA Bases in Synthetic Hairpins.

The mechanism and dynamics of photoinduced electron transfer in two families of DNA hairpins possessing Michler's ketone linkers have been investigated by means of steady state and time-resolved transient absorption and emission spectroscopies. The excited state behavior of the diol linker employed in hairpin synthesis is similar to that of Michler's ketone in methanol solution. Hairpins possessing only a Michler's ketone linker undergo fast singlet state charge separation and charge recombination with an adjacent purine base, attributed to well-stacked ground state conformations, and intersystem crossing to the triplet state, attributed to poorly stacked ground state conformations. The failure of the triplet to undergo electron transfer reactions on the 7 ns time scale of our measurements is attributed to the low triplet energy and reduction potential of the twisted triplet state. Hairpins possessing both a Michler's ketone linker and a perylenediimide base surrogate separated by four base pairs undergo photoinduced hole transport from the diimide to Michler's ketone upon excitation of the diimide. The efficiency of hole transport is dependent upon the sequence of the intervening purine bases.

Asphalt-derived high surface area activated porous carbons for carbon dioxide capture.

Research activity toward the development of new sorbents for carbon dioxide (CO2) capture have been increasing quickly. Despite the variety of existing materials with high surface areas and high CO2 uptake performances, the cost of the materials remains a dominant factor in slowing their industrial applications. Here we report preparation and CO2 uptake performance of microporous carbon materials synthesized from asphalt, a very inexpensive carbon source. Carbonization of asphalt with potassium hydroxide (KOH) at high temperatures (>600 °C) yields porous carbon materials (A-PC) with high surface areas of up to 2780 m(2) g(-1) and high CO2 uptake performance of 21 mmol g(-1) or 93 wt % at 30 bar and 25 °C. Furthermore, nitrogen doping and reduction with hydrogen yields active N-doped materials (A-NPC and A-rNPC) containing up to 9.3% nitrogen, making them nucleophilic porous carbons with further increase in the Brunauer-Emmett-Teller (BET) surface areas up to 2860 m(2) g(-1) for A-NPC and CO2 uptake to 26 mmol g(-1) or 114 wt % at 30 bar and 25 °C for A-rNPC. This is the highest reported CO2 uptake among the family of the activated porous carbonaceous materials. Thus, the porous carbon materials from asphalt have excellent properties for reversibly capturing CO2 at the well-head during the extraction of natural gas, a naturally occurring high pressure source of CO2. Through a pressure swing sorption process, when the asphalt-derived material is returned to 1 bar, the CO2 is released, thereby rendering a reversible capture medium that is highly efficient yet very inexpensive.

Structure and electronic spectra of purine-methyl viologen charge transfer complexes.

The structure and properties of the electron donor-acceptor complexes formed between methyl viologen and purine nucleosides and nucleotides in water and the solid state have been investigated using a combination of experimental and theoretical methods. Solution studies were performed using UV-vis and (1)H NMR spectroscopy. Theoretical calculations were performed within the framework of density functional theory (DFT). Energy decomposition analysis indicates that dispersion and induction (charge-transfer) interactions dominate the total binding energy, whereas electrostatic interactions are largely repulsive. The appearance of charge transfer bands in the absorption spectra of the complexes are well-described by time-dependent DFT and are further explained in terms of the redox properties of purine monomers and solvation effects. Crystal structures are reported for complexes of methyl viologen with the purines 2'-deoxyguanosine 3'-monophosphate (DAD'DAD' type) and 7-deazaguanosine (DAD'ADAD' type). Comparison of the structures determined in the solid state and by theoretical methods in solution provides valuable insights into the nature of charge-transfer interactions involving purine bases as electron donors.

Oxidation products of doubly trimethylene-bridged tetrabenzyl p-phenylenediamine paracyclophane.

We report synthesis and investigation of doubly trimethylene-bridged tetrabenzyl-p-phenylenediamine 1(Bz) in its singly and doubly charged redox states. The singly oxidized monoradical cation, which is a mixed-valence (MV) system with directly interacting charge-bearing units, shows broad and solvent-sensitive intervalence bands consistent with class II compounds according to the Robin-Day classification. The doubly oxidized diradical dication of 1(Bz) exists in the spin-paired singlet state with thermally accessible triplet state. It has similar conformations as the other dimeric p-phenylenediamines, such as derivatives 1(Me) and 1(Et), in both the solid-state and solution phases. The successful isolation of the single-crystalline 1(Bz)(2+) diradical dications with two different in nature counteranions, relatively highly coordinating SbF6(-) and weakly coordinating carborane [undecamethylcarborane HCB11Me11(-) (CB(-))], reveals the distinct effect of the nature of counterions on the structural features of diradical dication. Cyclic voltammetry measurements of 1(Bz) in dichloromethane reveal separation of the first and second oxidation potential by 0.12 V (2.8 kcal/mol), indicating relatively stable mixed-valence state in the dichloromethane, whereas in the acetonitrile both the first and second oxidation potentials overlap into one unresolved redox peak with minimal separation.

Monotrimethylene-bridged bis-p-phenylenediamine radical cations and dications: spin states, conformations, and dynamics.

The properties of p-phenylenediamine- (PD-) based systems substantially depend on the molecular topology. The singly bridged PD analogues HMPD and OMPD in which the PD rings are connected by a flexible linker reveal particular electronic properties in their radical cations and dications. The EPR and UV-vis spectra of HMPD(2+••) were found to be exceptionally temperature-sensitive, following a change from the extended conformation (doublet-doublet state) predominant at room temperature to the π-stacked conformation (singlet state) prevailing at dry-ice temperature. Changing the single bridge from (CH(2))(3) to dimethylated CH(2)CMe(2)CH(2) in OMPD(2+••) causes considerably less of the π-stacked conformation to be present at low temperature as a result of the steric interactions with the methyl groups of the bridge. In contrast to HMPD(2+••) and OMPD(2+••), in which the positive charges are localized separately in each PD(+•) ring, in the extended conformation, exchange of the electron ("hole hopping") between the two PD units (fast at the time scale of EPR experiments) was observed for HMPD(+•) and OMPD(+•). This process slows in a reversible manner with decreasing temperature, thus forming the radical cation with the unpaired electron spin density predominantly on one PD core, at low temperatures. Accordingly, a subtle balance between conformational changes, electron delocalization, and spin states could be established.

Electron donor-acceptor interactions with flanking purines influence the efficiency of thymine photodimerization.

Quantum yields for thymine photodimerization (Φ(TT)) have been determined for a series of short DNA single-strand and base-paired hairpin structures possessing a single thymine-thymine step with flanking purines. Values of Φ(TT) are strongly dependent upon the oxidation potential of the flanking purine, decreasing in the order: inosine > adenine > guanine > deazaguanine. The dependence of Φ(TT) on the ionization potential of the flanking purine is more pronounced when the purine of lower oxidation potential is located at the 5'- versus 3'-position in either a single strand or a hairpin. Molecular dynamics simulations for hairpin structures indicate that the TT step is π-stacked with both the 5' and 3' purine, but that there is little π-stacking with either purine in single-strand structures. The observation of moderately intense long-wavelength UV absorption features for hairpins having 5'-Z or G flanking purines suggests that excitation of ground state donor-acceptor complexes may account for more extensive quenching of dimerization by 5'- versus 3'-purines. The "purine effect" on Φ(TT) is attributed to a combination of ground state conformation, ground state electron donor-acceptor interactions, and excited state exciplex formation.