Nitrogen-containing nanoporous carbons by a rational template carbonization method evinced in the cases of 1, 10-phenanthroline and benzimidazole

We demonstrate a rational template carbonization method to produce nitrogen-containing nanoporous carbons at 800 °C, using 1, 10-phenanthroline (or benzimidazole) as carbon/nitrogen source and magnesium citrate as template. The mass ratio of 1, 10-phenanthroline (or benzimidazole) and magnesium citrate has exerted the vital role in the determination of pore structures and the resulting electrochemical performances. It reveals that the carbon-P:Mg-1:1 (obtained by heating 1, 10-phenanthroline and magnesium citrate at 800 °C with the mass ratio of 1:1) and carbon-B:Mg-1:1 (obtained by heating benzimidazole and magnesium citrate at 800 °C with the mass ratio of 1:1) samples both are amorphous, nitrogen-containing, and highly nanoporous in nature. The carbon-P:Mg-1:1 sample has a large BET surface area of 1,657.4 m² g^?1 and high pore volume of 1.83 cm³ g^?1, and those of carbon-B:Mg-1:1 sample are of 1,105.4 m² g^?1 and 1.67 cm³ g^?1, respectively. Based on a three-electrode system using a 6-mol L^?1 KOH aqueous solution as electrolyte, the carbon-P:Mg-1:1 and carbon-B:Mg-1:1 samples can deliver large specific capacitances of 289.0 and 255.6 F g^?1 at a current density of 0.5 A g^?1. They can also exhibit high energy densities of 40.1 and 35.5 Wh kg^?1 when designated the power density as 0.25 kW kg^?1 as well as highly long-term cycling durabilities.     

Synthesis of a hybrid MIL-101(Cr)/ZTC composite for hydrogen storage applications

Metal–organic frameworks (MOFs) hybrid composites have recently attracted considerable attention in hydrogen storage applications. In this study a hybrid composite of zeolite templated carbon (ZTC) and Cr-based MOF (MIL-101) was synthesised by adding the templated carbon in situ during the synthesis of MIL-101(Cr). The obtained sample was fully characterized and hydrogen adsorption measurements performed at 77 K up to 1 bar. The results showed that the surface areas and the hydrogen uptake capacities of individual MIL-101 (2552 m² g^?1, 1.91 wt%) and zeolite templated carbon (2577 m² g^?1, 2.39 wt%) could be enhanced when a hybrid MIL-101(Cr)/ZTC composite (2957 m² g^?1, 2.55 wt%) was synthesized. The procedure presents a simple way for enhancement of hydrogen uptake capacity of the individual Cr-MOF and templated carbon samples.     

Vinylene‐Linked Covalent Organic Frameworks by Base‐Catalyzed Aldol Condensation

Two 2D covalent organic frameworks (COFs) linked by vinylene (?CH=CH?) groups (V‐COF‐1 and V‐COF‐2) are synthesized by exploiting the electron deficient nature of the aromatic s‐triazine unit of C₃‐symmetric 2,4,6‐trimethyl‐s‐triazine (TMT). The acidic terminal methyl hydrogens of TMT can easily be abstracted by a base, resulting in a stabilized carbanion, which further undergoes aldol condensation with multitopic aryl aldehydes to be reticulated into extended crystalline frameworks (V‐COFs). Both V‐COF‐1 (with terepthalaldehyde (TA)) and V‐COF‐2 (with 1,3,5‐tris(p‐formylphenyl)benzene (TFPB)) are polycrystalline and exhibit permanent porosity and BET surface areas of 1341 m² g^?1 and 627 m² g^?1, respectively. Owing to the close proximity (3.52 Å) of the pre‐organized vinylene linkages within adjacent 2D layers stacked in eclipsed fashion, [2+2] photo‐cycloadditon in V‐COF‐1 formed covalent crosslinks between the COF layers.     

2D Poly(arylene vinylene) Covalent Organic Frameworks via Aldol Condensation of Trimethyltriazine

Designing structural order in electronically active organic solids remains a great challenge in the field of materials chemistry. Now, 2D poly(arylene vinylene)s prepared as highly crystalline covalent organic frameworks (COFs) by base‐catalyzed aldol condensation of trimethyltriazine with aromatic dialdehydes are reported. The synthesized polymers are highly emissive (quantum yield of up to 50 %), as commonly observed in their 1D analogues poly(phenylene vinylene)s. The inherent well‐defined porosity (surface area ca. 1000 m² g^?1, pore diameter ca. 11 Å for the terephthaldehyde derived COF‐1) and 2D structure of these COFs also present a new set of properties and are likely responsible for the emission color, which is sensitive to the environment. COF‐1 is highly hydrophilic and reveals a dramatic macroscopic structural reorganization that has not been previously observed in framework materials.     

Survismeter Unit for Surface Tension,Viscosity, and Dipole Moment Determination for Polystyrene Interactions in Benzene

Novel instrumental set up is developed for surface tension (γ, N m^?1), viscosity (η, N s m^?2)) and dipole moment (μ/Debye) measurements. A new instrument is economic, viable and pollution free in use, the γ, η and μ from viscosities (η, N s m^?2) and surface tension (γ, N m^?1) for 0.005 to 0.125 g% polystyrene at an interval of 0.0005 g% in benzene are measured at 288.15, 293.15, and 298.15 Kelvin temperatures. The γ, η, and μ are reported stronger frictional and cohesive forces due to stronger interactions of polystyrene with benzene. The survismeter is highly accurate and mechanically operated for pulling up liquid from reservoir bulb B1 to operational bulbs B2, B3, and B4. Densities are higher than those of benzene and also infer stronger polystyrene–benzene interactions, and hydrodynamic volume (HV) calculated with intrinsic viscosity [η] is noted in 293.15 (HV) >298.15 (HV) >288.15 (HV) order with higher values at 293.15 K. Surface tension (γ) values are slightly higher than of benzene and fall in a range of 33.47 to 33.35 N m^?1.     

A Dual‐Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity

Single‐ligand‐based electronically conductive porous coordination polymers/metal–organic frameworks (EC‐PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π‐conjugated EC‐MOF containing copper units with mixed trigonal ligands was developed: Cu₃(HHTP)(THQ) (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene, THQ=tetrahydroxy‐1,4‐quinone). The modulated conductivity (σ≈2.53×10^?5 S cm^?1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m² g^?1) of the Cu₃(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor.     

Metal-free boron-doped carbon microspheres as excellent cathode catalyst for rechargeable Li–O<Subscript>2</Subscript> battery

Rechargeable Li–O₂ batteries are attracting more and more interest due to their high energy density. Meanwhile, the replacement of high-cost and scarce precious-metal catalysts has attracted more and more attention. Currently, many academic researchers have paid attention to find highly efficient metal-free catalysts as air cathode material. Herein, the boron-doped carbon microspheres (B-CMs) were prepared through a novel and facile static calcination method and showed high electrocatalytic activity as a cathode material. The battery with a B-CM cathode delivered a high initial discharge capacity of 13,757.2 mAh g^?1 and outstanding coulombic efficiency of 90.1 % at 100 mA g^?1. In addition, stable cyclability (151 cycles with stable discharge voltage of ~2.60 V with a cutoff capacity of 1000 mAh g^?1 at 200 mA g^?1) has been exhibited. These performances are due to three main points: boron carbide compound changed the surface area of the CMs and formed the mesopore architectures as well as the large surface area of 683.738 m² g^?1; the reduce of boron atom can slow down the oxidation of the CMs during the cyclings; and finally, the electron-deficient boron atom introduction greatly facilitated Li⁺ diffusion and electrolyte immersion and enhanced the oxygen reduction and evolution reaction kinetics.     

Computational design of tetrahedral silsesquioxane-based porous frameworks with diamond-like structure as hydrogen storage materials

A novel type of three-dimensional (3D) tetrahedral silsesquioxane-based porous frameworks (TSFs) with diamond-like structure was computationally designed using the density functional theory (DFT) and classical molecular mechanics (MM) calculations. The hydrogen adsorption and diffusion properties of these TSFs were evaluated by the methods of grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. The results reveal that all designed materials possess extremely high porosity (87–93 %) and large H₂ accessible surface areas (5,268–6,544 m² g^?1). Impressively, the GCMC simulation results demonstrate that at 77 K and 100 bar, TSF-2 has the highest gravimetric H₂ capacity of 29.80 wt%, while TSF-1 has the highest volumetric H₂ uptake of 65.32 g L^?1. At the same time, the gravimetric H₂ uptake of TSF-2 can reach up to 4.28 wt% at the room temperature. The extraordinary performances of these TSF materials in hydrogen storage made them enter the rank of the top hydrogen storage materials so far.     

Equilibrium isotherms and isosteric heat for CO<Subscript>2</Subscript> adsorption on nanoporous carbons from polymers

Four nanoporous carbons obtained from different polymers: polypyrrole, polyvinylidene fluoride, sulfonated styrene–divinylbenzene resin, and phenol–formaldehyde resin, were investigated as potential adsorbents for carbon dioxide. CO₂ adsorption isotherms measured at eight temperatures between 0 and 60 °C were used to study adsorption properties of these polymer-derived carbons, especially CO₂ uptakes at ambient pressure and different temperatures, working capacity, and isosteric heat of adsorption. The specific surface areas and the volumes of micropores and ultramicropores estimated for these materials by using the density functional theory-based software for pore size analysis ranged from 840 to 1990 m² g^?1, from 0.22 to 1.47 cm³ g^?1, and from 0.18 to 0.64 cm³ g^?1, respectively. The observed differences in the nanoporosity of these carbons had a pronounced effect on the CO₂ adsorption properties. The highest CO₂ uptakes, 6.92 mmol g^?1 (0 °C, 1 atm) and 1.89 mmol g^?1 (60 °C, 1 atm), were obtained for the polypyrrole-derived activated carbon prepared through a single carbonization-KOH activation step. The working capacity for this adsorbent was estimated to be 3.70 mmol g^?1. Depending on the adsorbent, the CO₂ isosteric heats of adsorption varied from 32.9 to 16.3 kJ mol^?1 in 0–2.5 mmol g^?1 range. Overall, the carbons studied showed well-developed microporosity and exceptional CO₂ adsorption, which make them viable candidates for CO₂ capture, and for other adsorption and environmental-related applications.     

Removal of uranium(VI) from aqueous solutions using nanoporous ZnO prepared with microwave-assisted combustion synthesis

The adsorption of the uranyl ions from aqueous solutions on the nanoporous ZnO powders has been investigated under different experimental conditions. The adsorption of uranyl on nanoporous ZnO powders were examined as a function of the contact times, pH of the solution, concentration of uranium(VI) and temperature. The ability of this material to remove U(VI) from aqueous solution was followed by a series of Langmuir and Freunlinch adsorption isotherms. The adsorption percent and distribution coefficient for nanoporous ZnO powders were 98.65 % ± 1.05 and 7,304 mL g^?1, respectively. The optimum conditions were found as at pH 5.0, contact time 1 h, at 1/5 Zn²⁺/urea ratio, 50 ppm U(VI) concentration and 303 K. The monomolecular adsorption capacity of nanoporous ZnO powders for U(VI) was found to be 1,111 mg g^?1 at 303 K. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, have been calculated. Thermodynamic parameters (ΔH° = 28.1 kJ mol ^?1, ΔS° = 160.30 J mol^?1 K^?1, ΔG° = ?48.54 kJ mol^?1) showed the endothermic and spontaneous of the process. The results suggested that nanoporous ZnO powders was suitable as sorbent material for recovery and adsorption of U(VI) ions from aqueous solutions.     

Reed straw derived active carbon/graphene hybrids as sustainable high-performance electrodes for advanced supercapacitors

Reed straw-derived active carbon@graphene (AC@GR) hybrids were prepared by one-step carbonization/activation process using a mixture of reed straw and graphene oxide (GO) as raw materials and ZnCl₂ as activation agent. The as-prepared hybrids exhibit high specific surface area in a range of 1971–2497 m² g^?1, abundant porosity, as well as excellent energy storage capability. The symmetric C//C supercapacitor using the hybrid obtained at 700 °C as electrodes demonstrates superior cycling durability, ca. 90 % retention after 6000 cycles at 2 A g^?1, and a high energy density of 6.12 Wh kg^?1 at a power density of up to 4660 W kg^?1 in 6 M KOH aqueous electrolyte. The excellent capacitive performance is attributed to the synergistic effect of AC and GR.     

Effects of type of nanosized carbon black on the performance of an all-solid-state potentiometric electrode for nitrate

The potentiometric properties of all-solid-state nitrate-selective electrodes based on plasticized PVC and containing different types of nanosized carbon black were investigated. The use of a carbon black interlayer is shown to significantly improve the potentiometric response. The electrodes display a close-to-Nernstian slope in the range from 10^?1 to 10^?6 M, highly stable potentials and low membrane resistance. However, different analytical features were found depending on the type of carbon black used. The best long-term potential stability was observed for the electrode with Printex XE2-B carbon black that has a relatively high BET surface area (1000 m²?·?g^?1) and an average particle size of 30 nm. Nevertheless, the electrodes with the Vulcan XC-72 (BET surface: 240 m²?·?g^?1; average size: 55 nm) showed the most repeatable and reproducible standard potential. The lowest detection limit for nitrate (2.5·10^?7 M) is observed for an electrode containing Vulcan XC-72.

Cadmium and Lead Distribution in Marine Soil Sediments,Terrestrial Soil,Terrestrial Rock,and Atmospheric Particulate Matter around Split,Croatia

The distributions of cadmium and lead in marine sediments, surrounding soil, stones, and atmospheric particulate matter were determined at different locations in Split, Croatia. The determination of cadmium and lead was performed by flame atomic absorption spectrometry whereas atmospheric particulate matter samples were analyzed by inductively coupled plasma–optical emission spectrometry. Cadmium concentrations in the stones and soil were between 0.2 to 0.6 µg g^?1 and 0.2 to 0.9 µg g^?1. The concentration in the atmospheric particulate matter were <0.2 µg m^?2 d^?1(detection limit) to 1.4 µg m^?2 d^?1. Lead concentrations in marine sediments, stones, soil, and atmospheric particulate matter ranged from 31.2 to 144.4 µg g^?1, 9.3 to 29.4 µg g^?1, 11.3 to 66.1 µg g^?1, and 0.5 to 241.4 µg m^?2 d^?1, respectively. The relationship between determined parameters was established using principal component analysis and the results are in agreement with the assumption that anthropogenic sources play important roles for lead and cadmium distribution.     

Gels dried under supercritical and ambient conditions: a comparative study and their subsequent conversion to silica–carbon composite aerogels

In present work, we have prepared gels with various compositions of methyltrimethoxysilane—3-(2,3-epoxypropoxy) propyltrimethoxysilane (MTMS-GPTMS) using a two-step acid base sol–gel process. To make a comparative study between the two common drying routes, we prepared gels under supercritical and also under ambient conditions. The density of the supercritically dried hybrid aerogels lies between 0.18 and 0.31 gcm^?3, while the density of the ambient dried ones ranges between 0.35 and 0.42 gcm^?3. The surface area of MTMS-0.25 GPTMS aerogel dried under supercritical conditions, has been found to be 464 m² g^?1 with a pore volume and average pore diameter of 1.24 cm³ g^?1 and 11 nm respectively. The same composition dried under ambient conditions is found to have similar properties i.e. a BET surface area of 439 m² g^?1, pore volume of 1.22 cm³ g^?1 and average pore diameter of 11 nm. The aerogels were later pyrolyzed yielding silica/carbon composite aerogels. The pyrolized aerogels possessed a surface area as high as 207 m² g^?1 with a total pore volume of 0.98 cm³ g^?1. The pyrolysed aerogels were also calcined to yield carbon free materials.     

Design of high-performance core-shell hollow carbon nanofiber@nickel-cobalt double hydroxide composites for supercapacitive energy storage

The supercapacitive performances of supercapacitor mainly depend on the physical nanostructure and micro-morphology of electrode materials. Here, we demonstrated the design, synthesis and electrochemical performances of core-shell hollow carbon nanofiber@nickel-cobalt-layered double hydroxide (HCNF@ Ni_0.67Co_0.33-LDH) nanocomposites with an optimized Ni/Co molar ratio of 2:1. The HCNF was used as superiorly conductive core to sustain the nanoporous silky Ni_0.67Co_0.33-LDH shell, which can efficiently provide fast transport pathways for electrons and electrolyte ions. The outstanding specific capacitance of 2486 F g^?1 at 1 A g^?1 based on galvanostatic charge-discharge curves were acquired for the highly electroactive HCNF@Ni_0.67Co_0.33-LDH. Furthermore, the HCNF@Ni_0.67Co_0.33-LDH electrode delivered a distinguished rate capability with a specific capacitance of 1890 F g^?1 even at 15 A g^?1. Notably, an asymmetric supercapacitor with HCNF@Ni_0.67Co_0.33-LDH as cathode and HCNF as anode was devised, which presented a prominent specific capacitance of 228 F g^?1, good energy density of 62.1 Wh kg^?1, and impressive cycling stability (90.6% capacitance retention after 10,000 cycles).     

Synthesis of spherical porous carbon by spray pyrolysis and its application in Li-S batteries

A spherical porous carbon (SPC) with high specific surface area is prepared by spray pyrolysis at 800 °C followed by removing silica template. The prepared SPC is employed as a conductive matrix in the sulfur cathode (S-SPC) for lithium–sulfur secondary batteries. The BET surface area of the prepared SPC sample is as high as 1,133 m² g^?1 and the total pore volume is 2.75 cm³ g^?1. The electrochemical evaluations including charge–discharge tests, cyclic voltammograms (CV), and electrochemical impedance spectrum suggest that the prepared S-SPC composite presents superior electrochemical stability when compared to the S-SP cathode. The as-prepared S-SPC composite shows improved cycle performance. The reversible discharge capacity is about 637 mAh g^?1 after 50 cycles, which is much better than that of the as-prepared sulfur–Super P carbon black composite. It may be attributed to the high porosity and excellent conductive structure of the SPC.     

Preparation of activated carbon from waste Camellia oleifera shell for supercapacitor application

The cost-effective activated carbons derived from waste Camellia oleifera shell (COS) by ZnCl₂ activation method are investigated as the active electrode material in electric double-layer capacitors (EDLCs) for the first time. The activation temperature and ZnCl₂/COS impregnation ratio are two key factors affecting the surface area and pore structure of the prepared activated carbons, which accordingly affect their capacitive performances. Electrochemical investigations indicate that the activated carbon (AC-3-600) obtained at the activation temperature of 600 °C and impregnation ratio of 3 shows the maximum specific capacitance of 374 and 266 F?g^?1 in 1 mol L^?1 H₂SO₄ and 6 mol L^?1 KOH electrolytes at 0.2 A g^?1, respectively. The high capacitance of the AC-3-600 is attributed to its high surface area (1,935 m² g^?1), high total pore volume (1.02 cm³ g^?1), and especially the large percentage of micropores (735 m² g^?1). Meanwhile, the activated carbon presents good cycle stability in both acid and alkaline electrolytes during 5,000 cycles at a fair current density of 4 A g^?1. So, we had reasons to believe that the activated carbons from waste COS by ZnCl₂ activation might be one of the innovative carbon electrode materials for EDLCs application.     

Synthesis and electrochemical properties of activated carbons and Li4Ti5O12 as electrode materials for supercapacitors

New activated nanoporous carbons, produced by carbonization of mixtures of coal tar pitch and furfural with subsequent steam activation, as well as electrochemically active oxide Li₄Ti₅O₁₂, prepared by thermal co-decomposition of oxalates, were tested and characterized as electrode materials for electrochemical supercapacitors. The phase composition, microstructure, surface morphology and porous structure of the materials were studied. Pure carbon electrodes as well as composite electrodes based on these materials obtained were fabricated. Two types of supercapacitor (SC) cells were assembled and subjected to charge–discharge cycling study at different current rates: (1) symmetric sandwich-type SC cells with identical activated carbon electrodes and different organic electrolytes, and (2) asymmetric hybrid SC cell composed by activated graphitized carbon as a negative electrode and activated carbon–Li₄Ti₅O₁₂ oxide composite as a positive electrode, and an organic electrolyte (LiPF₆–dimethyl carbonate/ethylene carbonate (DMC/EC). Four types of carbons with different specific surface area (1,000–1,600 m² g^?1) and texture parameters, as well as three types of organic electrolytes: Et₄NBF₄–propylene carbonate (PC), LiBF₄–PC and LiPF₆–DMC/EC in the symmetric SC cell, were tested and compared with each other. Capacitance value up to 70 F g^?1 for the symmetric SC, depending on the electrolyte microstructure and conductivity of the carbon material used, and capacitance of about 150 F g^?1 for the asymmetric SC cell, with good cycleability for both supercapacitor systems, were obtained.     

Differential scanning calorimetric examination of pathologic scar tissues of human skin

Keloid and hypertrophic scarring is a dermal fibroproliferative disorder characterized by increased fibroblast proliferation and excessive production of collagen. Excess scar formation occurs after dermal injury as a result of abnormal wound healing. Keloid formation has been ascribed to altered growth factor regulation, aberrant collagen turnover, genetics, immune dysfunction, sebum reaction, and altered mechanics. No single hypothesis adequately explains keloid formation. The thermal denaturations of pathologic human skin scar tissues were monitored by a SETARAM Micro DSC-II calorimeter. All the experiments were performed between 0 and 100 °C. The heating rate was 0.3 K min^?1. DSC scans clearly demonstrated significant differences between the different types and conditions of samples (intact skin: T _m = 54.8 °C and ΔH _cal = 4.5 J g^?1; normal scar: T _m = 53.8 °C and ΔH _cal = 4.2 J g^?1; hypertrophic scar: T _m = 54.2 °C and ΔH _cal = 2.4 J g^?1; keloid: T _m = 52.9 °C and ΔH _cal = 8.3 J g^?1). The heat capacity change between native and denatured states of samples increased with the degree of structural alterations indicating significant water loosing. These observations could be explained with the structural alterations caused by the biochemical processes. With our investigations, we could demonstrate that DSC is a useful and well-applicable method for the investigation of collagen tissue of the human keloid and hypertrophic scar tissues. Our results may be of clinical relevance in the future, i.e., in the diagnosis of the two different pathologic scar formations, or in the choice of the optimal therapy of the disease.     

Preparation and methane adsorption of two-dimensional carbide Ti<Subscript>2</Subscript>C

Here a novel material for methane adsorption was synthesized and studied, which is a graphene-like two-dimensional (2D) carbide (Ti₂C, a member of MXenes), formed by exfoliating Ti₂AlC powders in a solution of lithium fluoride (LiF) and hydrochloric acid (HCl) at 40 °C for 48 h. Based on first-principles calculation, theoretically perfect Ti₂C with O termination has a specific surface area (SSA) of 671 m² g^?1 and methane storage capacity is 22.9 wt%. Experimentally, 2.85 % exfoliated Ti₂C with mesopores shown methane capacity of 11.58 cm³ (STP: 0 °C, 1 bar) g^?1 (0.82 wt%) under 5 MPa and the SSA was 19.1 m² g^?1. For Ti₂C sample intercalated with NH₃·H₂O, the adsorbed amount was increased to 16.81 cm³ (STP) g^?1 at same temperature. At the temperature of 323 K, the adsorbed amount of as-prepared Ti₂C was increased to 52.76 cm³ (STP) g^?1. For fully exfoliated Ti₂C, the methane capacity was supposed to be 28.8 wt% or 1148 V (STP)v^?1. Ti₂C theoretically has much larger volume methane capacity than current methane storage materials, though its SSA is not very high.