Synthesis and characterization of small-mesopore-added silicalite-1 zeolites using single wall carbon nanohorn templating

Small-mesopore-added silicalite-1 zeolites were prepared by using single wall carbon nanohorn (SWCNH) as a template. The samples were characterized with X-ray powder diffraction, field emission scanning electron microscopy, transmission electron microscopy (TEM) and molecular probe adsorption methods. The pore size distributions determined with N₂ adsorption at 77 K showed the presence of small mesopores in 2–4 nm pore widths, in addition to their intrinsic micropores of 0.58 nm. The mesopore volume was 0.06 cm³ g^?1. The presence of small mesopores in the SWCNH-templated silicalite-1 zeolites was supported with TEM observation as well as the liquid phase adsorption of methylene blue, which was much higher than that on a bulk (purely microporous) silicalite-1.     

Mechanical deconstruction of lignocellulose cell walls and their enzymatic saccharification

Laboratory mechanical softwood pulps (MSP) and commercial bleached softwood kraft pulps (BSKP) were mechanically fibrillated by stone grinding with a SuperMassColloider^®. The extent of fibrillation was evaluated by SEM imaging, water retention value (WRV) and cellulase adsorption. Both lignin content and mechanical treatment significantly affected deconstruction and enzymatic saccharification of fibrillated MSP and BSKP. Fibrillation of MSP and BSKP cell walls occurs rapidly and then levels off; further fibrillation has only limited effect on cell wall breakdown as measured by water retention value and cellulase adsorption. Complete (100 %) saccharification can be achieved at cellulase loading of 5 FPU/g glucan for BSKP after only 15 min fibrillation with energy input of 0.69 MJ/kg. However, the presence of lignin in MSP affects the extent of fibrillation producing fibrils mainly above 1 μm. Lignin binds nonproductively to cellulases and blocks cellulose thereby reducing its accessibility. As a result, the cellulose saccharification efficiency of MSP fibrils (6 h of fibrillation, energy input of 13.33 MJ/kg) was only 55 % at same cellulase loading of 5 FPU/g glucan.     

Effects of lignin and hemicellulose contents on dissolution of wood pulp in aqueous NaOH/urea solution

Four species of delignified woodchips with about 1 % lignin content (Chlorite–Woodchips) and a series of softwood pulps with different lignin contents were prepared by sodium chlorite delignification. After mechanical defibration, some Chlorite–Woodchips were directly subjected to dissolution treatment in NaOH/urea solvent; the others were first treated with NaOH solution to remove the hemicellulose to obtain NaOH–Chlorite–Woodchips or oxidized with potassium permanganate (OPP) to remove lignin completely to obtain OPP–Chlorite–Woodchips, and then subjected to the dissolution in NaOH/urea solvent. The results showed that the dissolved proportion of the Chlorite–Woodchips ranged from 36 to 46 %, the dissolved proportion of glucan was within 12 %, and most of the hemicellulose was dissolved in NaOH/urea solvent. Compared with Chlorite–Woodchips, the dissolved proportion of NaOH–Chlorite–Woodchips was lower, but their dissolved proportion of glucan was higher. After further permanganate delignification, both the dissolved proportion of the OPP–Chlorite–Woodchips and the dissolved proportion of glucan of the OPP–Chlorite–Woodchips were higher than those of the Chlorite–Woodchips. However, the dissolved proportion of glucan was still limited to only 15–30 %. The effect of the lignin content of softwood pulps on their dissolution is complicated. With the decrease of the lignin content of softwood pulp from 6.9 to 2.8 %, the dissolved proportion of pulp increased from 14 to 26 %. However, further reduction of lignin content from 2.8 to 0.3 % led to a decrease in the dissolved proportion of pulp from 26 to 12 %. The dissolved proportion of glucan followed the same tendency. These results indicated that the dissolution of wood cellulose in NaOH/urea solvent is not simply controlled by the hemicellulose and lignin contents, but also by some other factors.     

Synthesis of TiO2/Bi2WO6 nanofibers with electrospinning technique for photocatalytic methyl blue degradation

TiO₂/Bi₂WO₆ composite nanofibers have been successfully synthesized by a simple electrospinning process. XRD, SEM, HR-TEM, nitrogen adsorption–desorption isotherms and UV–visible diffuse reflectance spectra were used to characterize the composite nanofibers. The composite fibers with diameters about 100 nm was composed of nanoparticles and possessed of high specific surface area (49.6 m² g^?1) and porous structure. Besides, the TiO₂/Bi₂WO₆ composite nanofibers exhibited excellent visible photocatalytic property in the photodegradation of methylene blue (MB), and over 97.2 % of MB was degraded within 5.5 h.     

High-temperature hydrothermal synthesis of magnetically active, ordered mesoporous resin and carbon monoliths with reusable adsorption for organic dye

Magnetically active, thermally stable, and ordered mesoporous resin (MOMR-200) and carbon (MOMC-200) monoliths were prepared by one-pot hydrothermal synthesis from resol, copolymer surfactant, and iron cations at high-temperature (200 ^°C), followed by calcination at 360 ^°C and carbonization at 600 ^°C. X-ray diffraction results show that both MOMR-200 and MOMC-200 have ordered hexagonal mesoporous symmetry, and N₂ isotherms indicate that these samples have uniform mesopores (3.71, 3.45 nm), high surface area (328, 621 m²/g) and large pore volume (0.31, 0.43 cm³/g). Transmission electron microscopy shows that iron nanoparticles, which are superparamagnetic in nature, are dispersed in the network. More importantly, the high temperature (200 ^°C) products exhibit much better stability than the samples synthesized at low temperature (100 ^°C). Interestingly, MOMC-200 has higher adsorption capacity for organic dyes when compared with commercial adsorbents (activated carbon and macroporous resin: XAD-4). Combining the advantages such as magnetically active, thermally stable networks, ordered and open mesopores, high surface area, large pore volume, adsorption of pollutants in water and desorption in ethanol solvent, MOMC-200 is potentially important for water treatments.     

Preparation,characterization and catalytic activity of biomaterial-supported copper nanoparticles

Synthesis of copper nanoparticles was carried out with nanocrystalline cellulose (NCC) as a support by reducing CuSO₄·5H₂O ions using hydrazine. Ascorbic acid and aqueous NaOH were also used as an antioxidant and pH controller, respectively. The synthesized copper nanoparticles supported on NCC (CuNPs@NCC) were characterized by UV–vis, XRD, TEM, XRF, TGA, DSC, N₂ adsorption-desorption method at 77 K and FTIR. The UV–vis confirmed the formation and stability of the CuNPs, which indicated that the maximum absorbance of CuNPs@NCC was at 590 nm due to the surface plasmon absorption of CuNPs. Morphological characterization clearly showed the formation of a spherical structure of the CuNPs with the mean diameter and standard deviation of 2.71 ± 1.12 nm. Similarly, XRD showed that the synthesized CuNPs@NCC was of high purity. The thermal analysis showed that the CuNPs@NCC exhibited better thermal behaviors than NCC. BET surface area revealed that the N₂ adsorption–desorption isotherms of CuNPs@NCC featured a type IV isotherm with an H3 hysterisis loop. This chemical method is simple, cost effective, and environmentally friendly. Compared to NCC-supported CuNPs and unsupported CuNPs, the as-prepared CuNPs@NCC exhibit a superior catalytic activity and high sustainability for the reduction of methylene blue with NaBH₄ in aqueous solution at room temperature. The CuNPs@NCC achieved complete reduction of MB with completion time, rate constant and correlation coefficient (R ²) of 12 min, 0.7421 min^?1 and 0.9922, respectively.     

Prediction of competitive adsorption on coal by a lattice DFT model

Adsorption is one of the main mechanisms involved in the ECBM process, a technology where CO₂ (or flue gas, i.e. a CO₂/N₂ mixture) is injected into a deep coal bed, with the aim of storing CO₂ by simultaneously recovering CH₄. A detailed understanding of the microscopic adsorption process is therefore needed, as the latter controls the displacement process. A lattice DFT model, previously extended to mixtures, has been applied to predict the competitive adsorption behavior of CO₂, CH₄ and N₂ and of their mixtures in slit-shaped pores of 1.2 and 8 nm width. In particular, the effect of temperature, bulk composition and density on the resulting lattice pore profiles and on the lattice excess adsorption isotherms has been investigated. Important insights could be obtained; when approaching near critical conditions in the mesopores, a characteristic peak in the excess adsorption isotherm of CO₂ appears. The same effect could be observed neither for the other gases nor in the micropores. Moreover, in the case of mixtures, a depletion of the less adsorbed species close to the adsorbent surface is observed, which eventually results in negative lattice excess adsorption at high bulk densities.     

The effect of chemical and physical characteristics of spruce SEW pulps on enzymatic hydrolysis

Conifers, which are the most abundant biomass species in Nordic countries, USA, Canada and Russia, exhibit strong resistance towards depolymerization by cellulolytic enzymes. At present, it is still not possible to isolate a single structural feature which would govern the rate and degree of enzymatic hydrolysis. On the other hand, the forest residues alone represent an important potential for biochemical production of biofuels. In this study, the effect of substrate properties on the enzymatic hydrolysis of softwood was studied. Stem wood spruce chips were fractionated by SO₂–ethanol–water (SEW) treatment to produce pulps of varying composition by applying different operating conditions. The SEW technology efficiently fractionates different types of lignocellulosic biomass by rapidly dissolving hemicelluloses and lignin. Cellulose remains fully in the solid residue which is then treated by enzymes to release glucose. The differences in enzymatic digestibility of the spruce SEW pulp fibers were interpreted in terms of their chemical and physical characteristics. A strong correlation between the residual lignin content of SEW pulp and enzymatic digestibility was observed whereas cellulose degree of polymerization and hemicellulose content of pulp were not as important. For the pulps containing about 1.5 % (w/w) lignin, 90 % enzymatic digestibility was achieved at 10 FPU enzyme charge and 24 h of hydrolysis time.     

Porous microsphere of magnesium oxide as an effective sorbent for removal of volatile iodine from off-gas stream

Porous microspheres of magnesium oxide were synthesized by calcination of precursor obtained via hydrothermal method. A sample of microsphere was characterized by transmission electron microscopy, scanning electron microscopy–energy dispersion spectroscopy, X-ray diffraction, thermogravimetric analysis, N₂ adsorption–desorption isotherms, and BET surface area. The average pore size and surface area of the microsphere were found to be 9.0 nm and 83.1 m² g^?1, respectively. The performance of sorbent was investigated in a continuous adsorption system. Iodine adsorption on sorbent was studied by varying temperature of adsorption column, sorbent calcination temperature and initial concentration of iodine. The capacity of sorbent increased by ~25 % when calcination temperature was raised from 350 to 500 °C. The maximum iodine adsorption capacity of sorbent was found to be 196 mg g^?1 using Langmuir isotherm. These results indicate the microspherical form of MgO to be effective sorbent to capture iodine vapor from off-gas stream.     

Fluorinated Porous Poly(spirobifluorene) Via Direct C‒H Arylation: Characterization,Porosity, and Gas Uptake

Considering intrinsic properties of conjugated polyfluorenes and special functions of porous polymers, synthesis of fluorinated porous poly(spirobifluorene) via direct C?H arylation polycondensation is explored. Owing to the contorted structure and cross-linking nature, the obtained polymer FPSBF shows permanent porosities with Brunauer–Emmett–Teller specific surface area up to 700 m² g^?1 and exhibits a narrow pore size distribution with the dominant pore size at about 0.63 nm, which is more suitable for adsorption of small gas molecules. Based on the measured gas physisorption isotherms with pressure up to 1.13 bar, the obtained polymer shows good uptaking capacities for hydrogen (1.30 wt% at 1.0 bar and 77 K) and methane (4.80 wt% 1.0 bar and 273 K). Moreover, FPSBF has significant adsorption selectivity for CH₄ against N₂ and the estimated ideal adsorption selectivity ratio is up to 30/1 at 1.0 bar and 273 K, which makes the material possess potential application in gas separation.     

Microstructural order in cotton fibers by relative availability of O(3)H: Never-dried fibers

Availabilities of O(3)H relative to O(2)H (that is, [O(3)H]_a/[O(2)H]_a) on accessible surfaces of microstructural units of cotton fibers were measured by chemical microstructural analysis (CMA). CMA involves a mild chemical reaction with N,N-diethylaziridinium chloride, determination of substituent distribution for this product and a corresponding product from decrystallized cellulose, and simple computations. Measurements for fibers in commercial cotton fabric, for field-dried fibers, and for never-dried fibers are reported. The [O(3)H]_a/[O(2)H]_a, an inverse measure of intact O(3)H ·· O(5′) bonds, decreased in the stated order; thus, intact O(3)H ·· O(5′) hydrogen bonding increased in this same order. Results indicate a high degree of order in intramolecular bonding in the never-dried fiber and an increasing disruption of this bonding as the never-dried fiber is dried and processed.     

Cluster-associated filling of water molecules in graphene-based mesopores

Graphene monoliths were prepared through unidirectional freeze-drying method of graphene oxide colloids-KOH mixed solution and successive reduction by heating at 573 K in Ar. The porosity- and crystallinity-controlled graphene monoliths were prepared by the KOH activation at different temperature and the post-heating in Ar. These activated graphene monoliths were characterized by N₂ adsorption at 77 K, X-ray diffraction and Raman spectroscopy. Water adsorption isotherms show a typical hydrophobicity below P/P ₀ = 0.5 and a marked hydrophilicity above P/P ₀ = 0.6, which depends on the pore width. In the water adsorption isotherms of porous graphene monoliths activated at different temperature, the higher the activation temperature, the larger the rising P/P ₀. No essential change in the shape of the water adsorption isotherm for the post-heated nanoporous graphene monoliths is observed except for the decrease in water adsorption amount with higher post-heating temperature. The linear relationship between the saturated water adsorption and pore volume whose width is smaller than 4 nm indicates clearly that water molecules are adsorbed in small mesopores by the cluster-associated filling mechanism.     

Synthesis and photocatalytic activity of nanocrystalline TiO2 co-doped with nitrogen and cobalt(II)

Nitrogen-modified cobalt-doped TiO₂ materials were successfully prepared via a modified sol–gel method. The structure and properties of the catalysts were characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM, ultraviolet–visible light diffuse reflectance spectra (UV–Vis DRS), N₂ adsorption–desorption isotherms, and energy-dispersive X-ray spectroscopy. The XRD patterns of the pure and co-doped TiO₂ samples indicate that the predominant phase was anatase. The average grain size obtained from TEM was approximately 10 nm. The Brunauer–Emmett–Teller analysis results indicate that the specific surface area was 77.7 m² g^?1. The UV–Vis DRS results for the co-doped sample reveal an absorption edge that had been red-shifted to 500 nm. The photocatalytic activities of the samples were evaluated through photodegradation of papermaking wastewater under UV and visible light irradiation. Compared with the cobalt-doped TiO₂ sample and Degussa P25, the 3 mol% N-doped mesoporous N/Co-TiO₂ photocatalyst exhibited the highest photocatalytic activity, which can be ascribed to the synergistic effect of the N and Co co-doping.     

Probing crystallinity of never-dried wood cellulose with Raman spectroscopy

The structure of wood cell wall cellulose in its native state remains poorly understood, limiting the progress of research and development in numerous areas, including plant science, biofuels, and nanocellulose based materials. It is generally believed that cellulose in cell wall microfibrils has both crystalline and amorphous regions. However, there is evidence that appears to be contrary to this assumption. Here we show, using 1064-nm FT-Raman spectroscopy, that (1) compared to the crystalline state, cellulose in the never-dried native state is laterally aggregated but in a less-than crystalline state wherein internal chains are water-accessible, (2) hydroxymethyl groups (CH₂OH) in cellulose exist not only in the tg conformation but also in the gt rotamer form, and (3) in native-state fibrils, low-frequency Raman bands due to cellulose crystal domains are absent, indicating the lack of crystallinity. Further evidence of the absence of crystallinity of the fibrils was the failure of the normal 64 % H₂SO₄ hydrolysis procedure to produce nanocellulose crystals from untreated wood. X-ray diffraction data obtained on wood, treated-wood, and wood-cellulose samples were consistent with the new finding and indicated that full-width-at-half-height of the X-ray diffractograms and lateral disorder in samples as measured by Raman were correlated (R² = 0.95).     

Amorphous and ordered organosilicas functionalized with amine groups as sorbents of platinum (II) ions

Two groups of amine-functionalized organosilicas have been synthesized: amorphous polysiloxane xerogels (APX) and ordered mesoporous organosilicas (OMO) by co-condensation of tetraethoxysilane and appropriate alkoxysilanes: aminopropyltriethoxysilane and N-[3-(trimethoxysilyl)propyl]ethylenediamine. The obtained materials were characterized by sorption measurements, X-ray diffractometry, elemental analysis, transmission electron microscopy, and scanning electron microscopy. The OMO samples have well developed porous structure—the values of specific surface area are in the range 740–840 m²/g. While the APX samples are less porous having the corresponding values in the range 280–520 m²/g. The sizes of the ordered mesopores of OMO are in the range 5.9–6.5 nm while for the APX they are 2.9–12.1 nm indicating structural differences between both groups of the samples. All samples were tested as the sorbents of Pt(II) ions. The influence of various parameters such as pH, contact time, equilibrium concentration on Pt(II) adsorption ability onto prepared adsorbents was studied in detail. Additionally, the effect of chloride concentration on Pt(II) adsorption was investigated. The values of static sorption capacities were in the range of 32–102 mg_Pt(II)/g and 20–139 mg_Pt(II)/g for OMO and APX series, respectively.     

Adsorption equilibria of CO<Subscript>2</Subscript> and CH<Subscript>4</Subscript> in cation-exchanged zeolites 13X

Ion-exchange with different cations (Na⁺, NH₄ ⁺, Li⁺, Ba²⁺ and Fe³⁺) was performed in binderless 13X zeolite pellets. Original and cation-exchanged samples were characterized by thermogravimetric analysis coupled with mass spectrometry (inert atmosphere), X-ray powder diffraction and N₂ adsorption/desorption isotherms at 77 K. Despite the presence of other cations than Na (as revealed in TG-MS), crystalline structure and textural properties were not significantly altered upon ion-exchange. Single component equilibrium adsorption isotherms of carbon dioxide (CO₂) and methane (CH₄) were measured for all samples up to 10 bar at 298 and 348 K using a magnetic suspension balance. All of these isotherms are type Ia and maximum adsorption capacities decrease in the order Li > Na > NH₄–Ba > Fe for CO₂ and NH₄–Na > Li > Ba for CH₄. In addition to that, equilibrium adsorption data were measured for CO₂/CH₄ mixtures for representative compositions of biogas (50 % each gas, in vol.) and natural gas (30 %/70 %, in vol.) in order to assess CO₂ selectivity in such scenarios. The application of the Extended Sips Model for samples BaX and NaX led to an overall better agreement with experimental data of binary gas adsorption as compared to the Extended Langmuir Model. Fresh sample LiX show promise to be a better adsorption than NaX for pressure swing separation (CO₂/CH₄), due to its higher working capacity, selectivity and lower adsorption enthalpy. Nevertheless, cation stability for both this samples and NH₄X should be further investigated.     

Carbon dioxide and nitrogen adsorption on porous copolymers of divinylbenzene and acrylic acid

Porous copolymers of divinylbenzene (DVB) and acrylic acid (AA) having DVB:AA ratios of 6:4, 8:2 and 9:1 were prepared following a distillation-precipitation method, using toluene as the porogenic agent. The materials thus obtained, which showed specific surface area in the range of 380–600 m² g^?1 and pore volume in the range of 0.14–0.18 cm³ g^?1, were investigated as possible adsorbents for CO₂ capture from the flue gas of coal-fired power stations. For that purpose, the isosteric heat of adsorption (and CO₂ adsorption capacity) was analysed from N₂ and CO₂ adsorption equilibrium isotherms obtained over a temperature range. For CO₂, q _st resulted to be in the range of 27–31 kJ mol^?1 (the highest value corresponding to the 6:4 sample), while for N₂ a value of q _st ≈ 12 kJ mol^?1 was obtained. Equilibrium adsorption capacity for CO₂ (at ambient temperature and pressure) showed the value of about 1.35 mmol g^?1. These results are discussed in the broader context of corresponding literature data for CO₂ capture using protonic zeolites.     

How does the never-dried state influence the swelling and dissolution of cellulose fibres in aqueous solvent?

The swelling and dissolution capacity of dried and never-dried hardwood and softwood pulps and cotton linters was compared in two aqueous solvents, N-methylmorpholine-N-oxide (NMMO)-water at 90 °C with water contents ranging from 16 to 22% and NaOH—water at −6 °C with NaOH contents ranging from 5 to 8%. Swelling and dissolution mechanisms were observed by optical microscopy and dissolution efficiency was evaluated by recovering insoluble fractions. The results show a contrasted picture towards the effect of the never-dried state on the swelling and the dissolution capacity depending on the origin of the fibres and the type of aqueous solvent. In the case of NMMO—water, the presence of water within and around the fibre does not seem to favour dissolution initiation but after 2 h of mixing the dissolution yield appears to be similar for either dried or never-dried state. The limiting factor for dissolution in NMMO—water is not the penetration of the solvent inside the cellulose fibres, but only the local concentration of NMMO molecules around the fibre. For NaOH—water, both optical microscopy observations on individual fibres and dissolution yield measurements show that the never-dried state is more reactive for softwood pulps and cotton linters and has no significant effect on hardwood pulps. In this case, the local decrease of solvent strength is counteracted by the opening of the structure in the never-dried state which should enable the Na⁺ hydrated ions to penetrate easier.     

Effect of synthesis duration on the morphological and structural modification of the sea urchin-nanostructured γ-MnO2 and study of its electrochemical reactivity in alkaline medium

Single-crystalline nanorods and sea urchin-like morphology of the γ-MnO₂ nanostructures were successfully synthesized by hydrothermal method at different synthesis durations. The as-synthesized products were characterized by the techniques X-ray powder diffraction (XRD), field emission gun-scanning electron microscope (FEG-SEM) coupled with energy-dispersive X-ray elemental analysis (EDX), transmission electron microscope (TEM), isotherms of N₂ adsorption/desorption and BET-BJH models. The effect of synthesis duration on the morphology, porous structure, and crystallographic form of MnO₂ powders was studied. The electrochemical reactivity of as-prepared powders was investigated in 1 mol L^?1 KOH by both cyclic voltammetry and impedance spectroscopy by using a micro-cavity electrode. The results show that the best electrochemical reactivity of the MnO₂ powder was obtained with synthesis duration of 24 h.     

Preparation,characterization and antimicrobial application of hybrid cellulose-lignin beads

In the present study, cellulose-lignin beads were prepared using pretreated dissolving grade-pulp and extracted from birch wood hydrotropic lignin as starting materials. The preparation involved dissolution of both polymers in environmentally friendly 7% NaOH/12% urea aqueous solution, shaping the solution into beads and subsequent regeneration. Lignin content in the beads varied from 0 to 40%. The beads were characterized using FTIR, scanning electron and confocal fluorescence microscopy. Porosity, swelling behavior and leaching of lignin from the beads in water were studied as well. The antibacterial properties of the beads and original hydrotropic lignin were tested using Escherichia coli (XL-1 Blue) and Staphylococcus aureus (ATCC 25923). The obtained beads in a never-dried state were highly porous spherical particles with evenly distributed lignin in them. Their shape, structure and properties were influenced by the lignin content. The beads did not show antibacterial activity against gram-negative E. coli. On the other hand, never-dried cellulose-lignin beads inhibited growth of gram-positive S. aureus, and the inhibition efficiency increased with the lignin content. The half inhibitory concentration for never-dried beads with 40% of lignin was 1.06 mg (dry weight) per 1 mL of broth determined after incubation for 24 h at 37 °C and at initial concentration of S. aureus of 6.48 log(CFU/mL). In contrast to cellulose-lignin beads, pure cellulose beads did not inhibit growth of S aureus. The results demonstrated that hydrotropic birch lignin can be used for the preparation of composite cellulose-lignin beads. Such beads show a great potential for antibacterial applications against S. aureus.