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Lignin is a phenolic polymer accumulating in the cell walls of specific plant cell types to confer unique properties such as hydrophobicity, mechanical strengthening, and resistance to degradation....

Zeolites with appropriately narrow pore apertures can kinetically enhance the selective adsorption of CO2 over N-2. Here, we showed that the exchangeable cations (e.g., Na' or K) on zeolite ZK-4 play, an important role in the CO2 selectivity. Zeolites NaK ZK-4 with Si/Al = 1.8-2.8 had very high CO2 selectivity when an intermediate number of the exchangeable cations were K+ (the rest being Na+) Zeolites NaK ZK-4 with Si/Al = 1.8 had high CO, uptake capacity and very high CO2-over-N-2 selectivity (1190). Zeolite NaK ZK-4 with Si/A1 = 2.3 and 2.8 also had enhanced CO2 selectivity with an intermediate number of K cations. The high CO, selectivity was related to the I(' cation in the 8 -rings of the alpha-cage, together with Na+ cations in the 6 -ring, obstructing the diffusion of N2 throughout the zeolite. The positions of the K+ cation in the 8 -ring moved slightly (max 0.2 angstrom) toward the center of the a-cage upon the adsorption of CO2, as revealed by in situ X-ray diffraction. The CO2-over-N-2 selectivity was somewhat reduced when the number of K+ cations approached 100%. This was possibly due to the shift in the IC' cation positions in the 8 -ring when the number of Na+ was going toward 0%, glowing N, diffusion through the 8 -ring. According to 'm situ infrared spectroscopy, the amount of chemisorbed CO2 was reduced on zeolite ZK-4s with increasing Si/Al ratio. In the context of potential applications, a kinetically enhanced selection of CO2 could be relevant for applications in carbon capture and bio- and natural gas upgrading.

Amine-modified adsorbents are being researched for their potential to capture CO2 from various gas mixtures, and we review how IR spectroscopy has been used to study the associated CO2–amine chemistry. It has been used to reveal that CO2 chemisorbs as ammonium-carbamate ion pairs especially when the amine density is high. Carbamic acid and related other moieties tend to form in parallel to the ion pairs when the amine density is low. The amines have been shown to degrade on cyclic heat treatment. To further study the formation of bicarbonates on reactive adsorption of CO2 and H2O, degradation of the organics, and the use of other supports than silica are suggested.

The biopolymer lignin is deposited in the cell walls of vascular cells and is essential for long-distance water conduction and structural support in plants. Different vascular cell types contain distinct and conserved lignin chemistries, each with specific aromatic and aliphatic substitutions. Yet, the biological role of this conserved and specific lignin chemistry in each cell type remains unclear. Here, we investigated the roles of this lignin biochemical specificity for cellular functions by producing single cell analyses for three cell morphotypes of tracheary elements, which all allow sap conduction but differ in their morphology. We determined that specific lignin chemistries accumulate in each cell type. Moreover, lignin accumulated dynamically, increasing in quantity and changing in composition, to alter the cell wall biomechanics during cell maturation. For similar aromatic substitutions, residues with alcohol aliphatic functions increased stiffness whereas aldehydes increased flexibility of the cell wall. Modifying this lignin biochemical specificity and the sequence of its formation impaired the cell wall biomechanics of each morphotype and consequently hindered sap conduction and drought recovery. Together, our results demonstrate that each sap-conducting vascular cell type distinctly controls their lignin biochemistry to adjust their biomechanics and hydraulic properties to face developmental and environmental constraints.

Zeolite |Na12|-A is a commercial adsorbent, and its CO2-over-N2(CH4) selectivity can be further enhanced kinetically by replacing Na+ in the 8-ring windows that control gas diffusion with large cations. In this study, samples of zeolite |Na12–xKx|-A with x = 0.0, 0.8, 2.0, and 3.0 were prepared, and the positions of adsorbed CO2 molecules were determined using in situ neutron powder diffraction through profile refinement. Adsorbed CO2 molecules were located at three different sites within the large α-cavities in the zeolite structure, revealing the interaction between the adsorbed CO2 and the host framework. The number of CO2 molecules at each site depends on CO2 pressure and follows site-specific CO2 isotherms described with a Langmuir model. Most of the CO2 molecules in zeolite |Na12–xKx|-A bridge two cations at neighboring 8-ring sites. These are relatively weakly physisorbed, and therefore, most of the working capacity of CO2 adsorption is related to this site. The CO2 molecules at the second most pop...

Biomethane is a renewable fuel with a small environmental footprint. In its production, the removal of CO2 from the fermentation gas is critical. Pressure and vacuum swing adsorption (PSA and VSA) processes have certain advantages over other processes for the removal. Silicoaluminophosphate-56 (SAPO-56) has promising properties as an adsorbent for PSA- or VSA-based upgrading of raw biogas. It is typically synthesized by using N,N,N’,N’-tetramethyl-1,6-hexanediamine (TMHD) as a structure directing agent (SDA). In this study, TMHD was partly replaced with three different low-cost templates: isopropylamine (IPA), dibutylamine, and tripropylamine. SAPO-56 was co-crystallized with mixtures of templating amines with up to a ratio of 30%:70% of TMHD:IPA. With using TMHD and IPA, small and defined crystals of SAPO-56 plus SAPO-47 formed instead of the large aggregates of SAPO-56 that formed when only TMHD was used. Solid-state 13C NMR spectroscopy was used to show that the IPA and TMHD had not been decomposed and that both molecules were included within the as-synthesized crystals of SAPO-56. Synthetic composition diagrams were drawn with respect to the P2O5, SiO2, and Al2O3 compositions of the reaction mixtures and the formed crystalline SAPOs. In relation to these diagrams, the domains for stability of SAPO-56 were contrasted with those of SAPO-11, -17, -20, and -47. In particular, it was observed that SAPO-47 co-crystallized with SAPO-56 when a very large fraction of IPA was used under otherwise optimized conditions. As consistent with other studies, the SAPO-56 synthesized with dual SDAs had a very high uptake of CO2 at conditions relevant for PSA- or VSA-driven upgrading of raw biogas into methane.

Inspired by the Bogolanfini dyeing technique, we report how flexible nanofibrillated cellulose (CNF) films can be functionalized and patterned by surface-bound nanoparticles of hydrolyzable tannins and multivalent metal ions with tunable colors. Molecular dynamics simulations show that gallic acid (GA) and ellagic acid (EA) rapidly adsorb and assemble on the CNF surface, and atomic force microscopy confirms that nanosized GA assemblies cover the surface of the CNF. CNF films were patterned with tannin-metal ion nanoparticles by an in-fibre reaction between the pre-impregnated tannin and the metal ions in the printing ink. Spectroscopic studies show that the Fe-III/II ions interact with GA and form surface-bound, stable GA-Fe-III/II nanoparticles. The functionalization and patterning of CNF films with metal ion-hydrolyzable tannin nanoparticles is a versatile route to functionalize films based on renewable materials and of interest for biomedical and environmental applications.

Understanding the molecular-level mechanisms of phase transformation in solids is of fundamental interest for functional materials such as zeolites. Two-dimensional (2D) zeolites, when used as shape-selective catalysts, can offer improved access to the catalytically active sites and a shortened diffusion length in comparison with their 3D analogues. However, few materials are known to maintain both their intralayer microporosity and structure during calcination for organic structure-directing agent (SDA) removal. Herein we report that PST-9, a new 2D zeolite which has been synthesized via the multiple inorganic cation approach and fulfills the requirements for true layered zeolites, can be transformed into the small-pore zeolite EU-12 under its crystallization conditions through the single-layer folding process, but not through the traditional dissolution/recrystallization route. We also show that zeolite crystal growth pathway can differ according to the type of organic SDAs employed.

Amino groups in highly dense coatings of amines on solid supports react with CO 2 of ambient air and form ammonium-carbamate ion pairs. These ion pairs change the properties of the amine-modified supports. In numerous studies, the corresponding infrared (IR) spectra have been misinterpreted. The presumption has been that such ion pairs would not form in ambient air, and therefore IR bands have been assigned to moieties of the support and the amines. Here, we discuss common misunderstandings of the IR spectra of amine-modified supports and highlight that proper sample handling is necessary before employing different characterization techniques. We exemplify by performing an IR spectroscopic study of a propylamine-modified porous silica. Such amine-modified supports are relevant to applications in gas separation, catalysis, controlled drug delivery and adsorption of pollutants from water.

Hierarchically porous carbon foams with specific surface areas exceeding 600 m2 g−1 can be derived from polystyrene foams that are synthesized via water-in-oil emulsion templating. However, most st ...

Carbonyl sulfide (COS) reacts slowly with amines in the aqueous solutions used to absorb CO

The|Na10.2KCs0.8|8[Al12Si12O48]8(Fm3[combining macron]c)-LTA zeolite adsorbs CO2-over-CH4 with a high selectivity (over 1500). The uptake of carbon dioxide is also high (3.31 mmol g(-1), 293 K, 101 kPa). This form of zeolite A is a very promising adsorbent for applications such as biogas upgrading, where keeping the adsorption of methane to a minimum is crucial.

Biobutanol produced by, e.g., acetone-butanol-ethanol (ABE) fermentation is a promising alternative to petroleum-based chemicals as, e.g., solvent and fuel. Recovery of butanol from dilute fermentation broths by hydrophobic membranes and adsorbents has been identified as a promising route. In this work, the adsorption of water and butanol vapor in a silicalite-1 film was studied using in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy to better understand the adsorption properties of silicalite-1 membranes and adsorbents. Single-component adsorption isotherms were determined in the temperature range of 35-120 °C, and the Langmuir model was successfully fitted to the experimental data. The adsorption of butanol is very favorable compared to that of water. When the silicalite-1 film was exposed to a butanol/water vapor mixture with 15 mol % butanol (which is the vapor composition of an aqueous solution containing 2 wt % butanol, a typical concentration in an ABE fermentation broth, i.e., the composition of the gas obtained from gas stripping of an ABE broth) at 35 °C, the adsorption selectivity toward butanol was as high as 107. These results confirm that silicalite-1 quite selectively adsorbs hydrocarbons from vapor mixtures. To the best of our knowledge, this is the first comprehensive study on the adsorption of water and butanol in silicalite-1 from vapor phase.

Amine-modified sorbents are relevant to the capturing of dilute carbon dioxide from gas mixtures, and micro-/mesoporous polymers are promising substrates due to their rich chemistry. Here, we prepared an aldehyde-rich polyimine with micro- and mesopores by a Schiff-base condensation of 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarboxaldehyde using an excess of aldehyde. The micropores were crucial to the physisorption of CO2, while the mesopores provided space for the post-modification with tris(2-aminoethyl)amine (tren) that induced the chemisorption of CO2. The amine modified polymer showed a high uptake of CO2 at low pressures (1.13 mmol g−1 at 0.05 bar and 273 K) and a high estimated CO2-over-N2 selectivity (1.04 × 103 at 273 K for 5 v%/95 v% CO2/N2 mixture). CO2 both physisorbed and chemisorbed on the amine-modified polyimine, which we confirmed by studying the CO2-amine chemistry using in situ FTIR spectroscopy and solid state 13C NMR spectroscopy. Carbamic acid formed during the chemisorption of CO2, as the CO2 reacted with the amine groups. Due to the formation of carbamic acid, the isosteric heat of adsorption was high, with values up to 80 kJ mol−1 at a low coverage of CO2. It appears that amine-modified porous polymers could be relevant to the removal of CO2 from gas streams with low concentrations.

A range of titanium silicates (ETS-4 and CTS-1) with interesting gas separation properties were studied as CO2 adsorbents. Some of these adsorbents, in particular NaMg-CTS-1, showed the ability to ...

Adsorbents with high capacity and selectivity for adsorption of CO2 are currently being investigated for applications in adsorption-driven separation of CO2 from flue gas. An adsorbent with a particularly high CO2-over-N2 selectivity and high capacity was tested here. Zeolite ZK-4 (Si:Al ∼ 1.3:1), which had the same structure as zeolite A (LTA), showed a high CO2 capacity of 4.85 mmol/g (273 K, 101 kPa) in its Na(+) form. When approximately 26 at. % of the extraframework cations were exchanged for K(+) (NaK-ZK-4), the material still adsorbed a large amount of CO2 (4.35 mmol/g, 273 K, 101 kPa), but the N2 uptake became negligible (0.03 mmol/g, 273 K, 101 kPa). The majority of the CO2 was physisorbed on zeolite ZK-4 as quantified by consecutive volumetric adsorption measurements. The rate of physisorption of CO2 was fast, even for the highly selective sample. The molecular details of the sorption of CO2 were revealed as well. Computer modeling (Monte Carlo, molecular dynamics simulations, and quantum chemical calculations) allowed us to partly predict the behavior of fully K(+) exchanged zeolite K-ZK-4 upon adsorption of CO2 and N2 for Si:Al ratios up to 4:1. Zeolite K-ZK-4 with Si:Al ratios below 2.5:1 restricted the diffusion of CO2 and N2 across the cages. These simulations could not probe the delicate details of the molecular sieving of CO2 over N2. Still, this study indicates that zeolites NaK-ZK-4 and K-ZK-4 could be appealing adsorbents with high CO2 uptake (∼4 mmol/g, 101 kPa, 273 K) and a kinetically enhanced CO2-over-N2 selectivity.

A modular design for a novel heterogeneous synergistic catalytic system, which simultaneously activates the electrophile and nucleophile by the combined activation modes of a separate metal and non ...

Hydrous alteration of olivine is capable of producing molecular hydrogen (H-2) under a wide variety of hydrothermal conditions. Although olivine hydrolysis (i.e., serpentinization) has commonly been assessed at elevated temperatures ( greater than 100 degrees C), the nature of these reactions in relation to H-2 production at lower temperatures has not been systematically evaluated, especially with regard to carbonate-rich fluids. Specifically, carbonate formation may kinetically infringe on geochemical routes related to serpentinization and H-2 production at lower temperatures. Here time-dependent interactions of solid, liquid, and gaseous phases with respect to olivine hydrolysis in a carbonate-rich solution (20 mM HCO3-) at 30, 50 and 70 degrees C for 315 days is investigated experimentally. Within the first two months, amorphous Si-rich (i.e., talc-like) and carbonate phases precipitated; however, no inhibition of olivine dissolution is observed at any temperature based on surface chemistry analyses. High-resolution surface analyses confirm that precipitates grew as spheroids or vertically to form topographic highs allowing further dissolution of the free olivine surfaces and exposing potential catalysts. Despite no magnetite (Fe3O4) being detected, H-2 increased with time in experiments carried out at 70 degrees C, indicating an alternative coupled route for Fe oxidation and H-2 production. Spectrophotometry analyses show that aqueous Fe(II) is largely converted to Fe(III) potentially integrating into other phases such as serpentine and talc, thus providing a viable pathway for H-2 production. No increase in H-2 production was observed in experiments carried out at 30 and 50 degrees C supporting observations that incorporation of Fe(II) into carbonates occurred faster than the intertwined processes of olivine hydrolysis and Fe(III) oxidation. Overall, carbonate formation is confirmed to be a major influence related to H-2 production in low-temperature serpentinization systems.

A new porous vanadoborate was synthesized by employing the scale chemistry theory with the vanadoborate cluster V10B28. The twofold interpenetrated lvt network was assembled with zinc-containing elliptical vanadoborate clusters and Zn polyhedra. The single lvt framework contains a three-dimensional 38×38×20 ring channel system with the pore size (24.7×12.7 Å) reaching the mesoscale, thus indicating the possibility of constructing 3D ordered mesopores with vanadoborate clusters. The porosity of the SUT-7 structure was confirmed by CO2 adsorption of the as-synthesized materials.

Carbon dioxide removal from flue gas via swing adsorption processes requires adsorbents with a high CO2 selectivity and capacity. These properties are particularly valuable to reduce the cost of ca ...

Novel organic–inorganic hybrid nanotubes containing silica and ethane (EtSNT), ethylene (ESNT) and acetylene (ASNT) units, as well as brominated ESNT (Br-ESNT) and glycine-modified Br-ESNT (Gly-ESNT) have been studied by IR and Raman spectroscopy. The results are compared with the spectral features for conventional silica nanotubes (SNT) and amorphous silica. Bands peculiar to organic moieties have been detected and assigned. Assignment of the silicate backbone vibrations was based on the results of normal coordinate calculations. Furthermore, characteristic silicate, so-called ‘nanotube’ vibrations have been identified and their band positions have been summarized to serve as a future reference for such compounds. SiOSi antisymmetric stretchings were observed in the range 1000–1110 cm−1, while the symmetric stretchings appeared between 760 and 960 cm−1 for EtSNT, ESNT and Br-ESNT. Force constants have been refined for models of the repeating structure units: O3SiOSi(OSi)3 for SNT and SiCHnCHnSi(OSi)3 for organosilica nanotubes (n = 2, EtSNT; n = 1, ESNT and n = 0, ASNT). The calculated SiO stretching force constants were increased from 4.79 to 4.88 and 5.11 N cm−1 for EtSNT, ESNT and ASNT, respectively. The force constants have been compared with those for several silicates and SiO bond length are predicted and discussed.

Pure silica zeolites are potentially hydrophobic and have therefore been considered to be interesting candidates for separating alcohols, e.g., 1-butanol, from water. Zeolites are traditionally synthesized at high pH, leading to the formation of intracrystalline defects in the form of silanol defects in the framework. These silanol groups introduce polar adsorption sites into the framework, potentially reducing the adsorption selectivity toward alcohols in alcohol/water mixtures. In contrast, zeolites prepared at neutral pH using the fluoride route contain significantly fewer defects. Such crystals should show a much higher butanol/water selectivity than crystals prepared in traditional hydroxide (OH–) media. Moreover, silanol groups are present at the external surface of the zeolite crystals; therefore, minimizing the external surface of the studied adsorbent is important. In this work, we determine adsorption isotherms of 1-butanol and water in silicalite-1 films prepared in a fluoride (F–) medium using in situ attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopy. This film was composed of well intergrown, plate-shaped b-oriented crystals, resulting in a low external area. Single-component adsorption isotherms of 1-butanol and water were determined in the temperature range of 35–80 °C. The 1-butanol isotherms were typical for an adsorbate showing a high affinity for a microporous material and a large increase in the amount adsorbed at low partial pressures of 1-butanol. The Langmuir–Freundlich model was successfully fitted to the 1-butanol isotherms, and the heat of adsorption was determined. Water showed a very low affinity for the adsorbent, and the amounts adsorbed were very similar to previous reports for large silicalite-1 crystals prepared in a fluoride medium. The sample also adsorbed much less water than did a reference silicalite-1(OH–) film containing a high density of internal defects.The results show that silicalite-1 films prepared in a F– medium with a low density of defects and external area are very promising for the selective recovery of 1-butanol from aqueous solutions.\ud \ud

In aquatic ecosystems, microplastics are a relatively new anthropogenic substrate that can readily be colonized by biofilm-forming organisms. To examine the effects of substrate type on microbial community assembly, we exposed ambient Baltic bacterioplankton to plastic substrates commonly found in marine environments (polyethylene, polypropylene and polystyrene) as well as native (cellulose) and inert (glass beads) particles for 2 weeks under controlled conditions. The source microbial communities and those of the biofilms were analyzed by Illumina sequencing of the 16S rRNA gene libraries. All biofilm communities displayed lower diversity and evenness compared with the source community, suggesting substrate-driven selection. Moreover, the plastics-associated communities were distinctly different from those on the non-plastic substrates. Whereas plastics hosted greater than twofold higher abundance of Burkholderiales, the non-plastic substrates had a significantly higher proportion of Actinobacteria and Cytophagia. Variation in the community structure, but not the cell abundance, across the treatments was strongly linked to the substrate hydrophobicity. Thus, microplastics host distinct bacterial communities, at least during early successional stages.

Detailed molecular aspects of carbon dioxide sorption on porous silica with different amounts of tethered and cross-linked n-propylamine groups were investigated. Infrared spectroscopy was applied ...

We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1-4, IFP = imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R = Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.0-1.7 Å), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and (1)H MAS and (13)C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345-400 °C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO(2) was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH(4) (at 298 K), CO(2) (at 298 K) and H(2) (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO(2) is physisorbed on IFP-1-4 under dry conditions and that both CO(2) and H(2)O are physisorbed on IFP-1 under moist conditions.

We have investigated the chemistry of the Bogolan or mud cloth dyeing process, a traditional technique of coloring cotton cloths deeply rooted in Mali. Textiles produced by the traditional Bogolan process, using tannin-rich plant extract and iron-rich clay-based mud, were compared using infrared (IR) spectroscopy, scanning electron microscopy (SEM) and X-ray absorption near-edge spectroscopy (XANES) with cotton fibers that were impregnated with tannin and iron salt solutions. IR spectroscopy in both reflective mode on the cloth and cotton and in transmission mode on single fibers, together with SEM, showed that gallic and tannic acid adsorb and precipitate onto the cotton fiber surface. IR spectroscopy and comparison with tannin and iron solution-impregnated cotton showed that the black color of the traditional Bogolan cloth is dominated by the formation of iron-tannin complexes. The presence of iron in the Bogolan cloth was confirmed using XANES data, supporting the notion that iron has been transferred from the iron-rich clay-based mud to the cloth. The chemistry of Bogolan cloth is not only historically and culturally significant and of importance in textile conservation, but may also inspire future research on sustainable dyeing and processing techniques based on natural products.

Silicoaluminophosphates (SAPO-17, SAPO-35, SAPO-56 and SAPO-RHO) synthesised via hydrothermal means are tested for their abilities to adsorb carbon dioxide. These 8-ring microporous phosphates show ...

We studied equilibrium adsorption and uptake kinetics and identified molecular species that formed during sorption of carbon dioxide on amine-modified silica. Bicontinuous silicas (AMS-6 and MCM-48) were postsynthetically modified with (3-aminopropyl)triethoxysilane or (3-aminopropyl)methyldiethoxysilane, and amine-modified AMS-6 adsorbed more CO(2) than did amine-modified MCM-48. By in situ FTIR spectroscopy, we showed that the amine groups reacted with CO(2) and formed ammonium carbamate ion pairs as well as carbamic acids under both dry and moist conditions. The carbamic acid was stabilized by hydrogen bonds, and ammonium carbamate ion pairs formed preferably on sorbents with high densities of amine groups. Under dry conditions, silylpropylcarbamate formed, slowly, by condensing carbamic acid and silanol groups. The ratio of ammonium carbamate ion pairs to silylpropylcarbamate was higher for samples with high amine contents than samples with low amine contents. Bicarbonates or carbonates did not form under dry or moist conditions. The uptake of CO(2) was enhanced in the presence of water, which was rationalized by the observed release of additional amine groups under these conditions and related formation of ammonium carbamate ion pairs. Distinct evidence for a fourth and irreversibly formed moiety was observed under sorption of CO(2) under dry conditions. Significant amounts of physisorbed, linear CO(2) were detected at relatively high partial pressures of CO(2), such that they could adsorb only after the reactive amine groups were consumed. authorCount :7

Wilkinson’s catalyst [RhCl(PPh3)3] was heterogenized on common silica by the use of a grafting/anchoring technique. The immobilized catalyst showed high activity and selectivity in transfer hydroge ...

The fine structural details of mesoporous materials possessing Pmn symmetry prepared with varying amphiphilic surfactants under acid and alkaline conditions are investigated using electron crystall ...

Adsorption-mediated CO(2) separation can reduce the cost of carbon capture and storage. The reduction in cost requires adsorbents with high capacities for CO(2) sorption and high CO(2)-over-N(2) selectivity. Amine-modified sorbents are promising candidates for carbon capture. To investigate the details of CO(2) adsorption in such materials, we studied mesocaged (cubic, Pm3n symmetry) silica adsorbents with tethered propylamines using Fourier transform infrared (FTIR) spectroscopy and volumetric uptake experiments. The degree of heterogeneity in these coatings was varied by either cosynthesizing or postsynthetically introducing the propylamine modification. In situ FTIR spectroscopy revealed the presence of both physisorbed and chemisorbed CO(2) in the materials. We present direct molecular evidence for physisorption using FTIR spectroscopy in mesoporous silica sorbents modified with propylamines. Physisorption reduced the CO(2)-over-N(2) selectivity in amine-rich sorbents. Samples with homogeneous coatings showed typical CO(2) adsorption trends and large quantities of IR-observable physisorbed CO(2). The uptake of CO(2) in mesocaged materials with heterogeneous propylamine coatings was higher at high temperatures than at low temperatures. At higher temperatures and low pressures, the postsynthetically modified materials adsorbed more CO(2) than did the extracted ones, even though the surface area after modification was clearly reduced and the coverage of primary amine groups was lower. The principal mode of CO(2) uptake in postsynthetically modified mesoporous silica was chemisorption. The chemisorbed moieties were present mainly as carbamate-ammonium ion pairs, resulting from the quantitative transformation of primary amine groups during CO(2) adsorption as established by NIR spectroscopy. The heterogeneity in the coatings promoted the formation of these ion pairs. The average propylamine-propylamine distance must be small to allow the formation of carbamate-propylammonium ion pairs.

Seven important air pollutants have been investigated by photolysis-assisted FT-IR spectroscopy. This technique renders invisible the spectra of water and carbon dioxide, which are two of the main concerns in long-path infrared spectroscopy. A cell, equipped with a UV lamp, was used to oxidise the analyte in the air sample and the spectrum recorded was used as a new background for the original sample spectrum. The optimum UV irradiation time and correctness of the concentrations were determined for this technique and compared with those from traditional methods. The signal-to-noise (S/N) ratios of the so-called "shadow spectra" were better than, or at least comparable to, the S/N ratios in the absorbance spectra obtained by using as background an air or an evacuated cell reference and subtraction of the spectra of water and carbon dioxide from a spectral library. The detection limits for the volatile organic compounds investigated have been improved by using this new method in which an appropriate background spectrum can be obtained quickly. The limitations of the method are that it cannot be applied to non-UV reactive compounds, such as methane, and the detection limits can be appreciably degraded when bands due to ozone in the shadow spectra overlap with those of the compounds under investigation.

Two phenyl rings of triphenylphosphane have been modified by electron-withdrawing trifluoromethyl groups. A methoxy group has been introduced at the para-position of the third ring. Due to the activating effect of the methoxy group, the phosphane can be monosulfonated under mild conditions and with complete selectivity. The novel ligand, sodium 5-[bis-(4-trifluoromethylphenyl)-phosphanyl]-2-methoxybenzenesulfonate, has been obtained in quantitative yield, and it has an outstanding π-acceptor capacity among the known sulfonated triarylphosphanes. It is not soluble in water but soluble in light alcohols and ionic liquids. Its solubility properties allow facile catalyst separation without water.

Fourier transform infrared (FT-IR) spectroscopy has been adapted to control the quality of light bulbs made from silica glass. Such light bulbs contain a molybdenum accessory which, if contaminated with carbon, during the melting procedure of bulb fabrication, can cause the production of carbon monoxide. This CO can be trapped in small gas cavities in the silica glass body of the bulb. A method has been developed for the detection of CO and the total pressure within these gas cavities by traditional FT-IR spectrometry using a spectral resolution of 0.5 cm(-1). The concentration of CO was determined by using a classical least-squares (CLS) method, and the accuracy of concentration determination is reported for the case with sample and reference spectra recorded at different pressures. The total pressure in the cavities was established by two different methods: either by CLS fitting of reference spectra to sample spectra or fitting a Voigt line shape function to the spectral lines within the CO fundamental stretching band. In the latter method, the width of the lines was determined and pressure-broadening coefficients are given and compared with high-resolution data from the literature. According to the measurements, 0.55-0.80 atm total pressure and 0.8-4.0% (v/v) CO was determined in the gas cavities. This method can also be applied to determine the total pressure in similar enclosed spaces in which an appropriate indicator gas component exists.

A comprehensive comparison of long‐path extractive and open‐path FTIR techniques on the bases of the available literature and on our own experience at the wastewater treatment plant of a chemical factory has been made. Two equalization basins were investigated and it was supposed that all the surface of the wastewater emits polluting compounds smoothly, since the atmospheric dispersion was found to be ideal at both sites, there were no significant chemical reactions, and the basin dimensions were rather small (7×16 m2 and 37×79 m2, respectively). Since the possibilities were different, rather different optimal spectral parameters (resolution, scan numbers, path length) were chosen for field and laboratory measurements. The S/N ratio of laboratory spectra was about 50–100 times higher than that of field spectra, which resulted in higher precision and lower detection limits of the measurements, and comparing to field measurements an additional compound (chloroform) was detected. On the other hand, ...

The basic principles and methods of FTIR spectroscopy of the atmosphere were summarized in our previous paper 1. Thanks to the continuous technical development of FTIR spectroscopy (increasing throughput, dynamic alignment, more sensitive detectors, brighter sources, increasing scanning speed, development of focal plane array detectors, flexible spectral manipulations and data handling, etc.) in the last decade, this method has offered a great number of unique applications. In this review article, attempt to summarize the results of the most significant and frequent applications of FTIR spectroscopy to the study of the atmosphere. The possibilities of techniques applied in this field, the extractive and open path measurement methods, and the in situ IR absorption measurements such as remote sensing using the sun, the sky, or natural hot objects as IR sources of radiation are discussed. We have made a special focus to FTIR emission spectroscopy, the so‐called passive technique, since there are a n...

In recent years Fourier transform infrared (FTIR) spectroscopy has been the dominant technique used for measuring the infrared (IR) absorption and emission spectra of most materials, with substantial advantages in signal‐to‐noise ratio, resolution, speed, and detection limits. The major advantage of the FTIR technique over other spectroscopic methods is that practically all compounds show characteristic absorption/emission in the IR spectral region and based on this property they can thus be analyzed both quantitatively and qualitatively. The quest for highly sensitive detection methods for atmospheric trace gas samples, either in laboratory setup or in outdoor remote sensing, has been on agenda for several decades. The fast and intensive development of FTIR spectroscopic techniques has propelled the progress of trace gas analysis of the atmosphere. Since the early 1970s the number and scope of FTIR atmospheric measurements has increased steadily. In this review article we are making an attempt t...

A modular design for a novel heterogeneous synergistic catalytic system, which simultaneously activates the electrophile and nucleophile by the combined activation modes of a separate metal and non ...

Amine-CO2 chemistry is important for a range of different chemical processes, including carbon dioxide capture. Here, we studied how aspects of this chemistry could be used to prepare calcium carbonates. Chemically crosslinked organogels were first prepared by reacting hyperbranched polyethylene imine (PEI) dissolved in DMSO with carbon dioxide. The crosslinks of the organogel consisted of ammonium-carbamate ion pairs as was shown by IR spectroscopy. These carbamate-rich organogels were subsequently subjected to aqueous solutions of calcium acetate, and amorphous calcium carbonate (ACC) precipitated. The ACC did not crystalize during the mixing for up to 20 h, as was shown by a combination of IR spectroscopy, X-ray diffraction, scanning electron microscopy, and thermal analysis. Some PEI had been included or adsorbed on the ACC particles. Traces of calcite were observed in one sample that had been subjected to water in a work-up procedure.

Amorphous order: Amorphous calcium carbonates (ACC) have an intrinsic structure relating to the crystalline polymorphs of calcite and vaterite. The proto-crystalline structures of calcite and vater ...

A method to form ordered mesoporous silica based on the use of folate supramolecular templates has been developed. Evidence based on in situ small-angle X-ray scattering (SAXS), electron microscopy, infrared spectroscopy, and in situ conductivity measurements are used to investigate the organic inorganic interactions and synthesis mechanism. The behavior of folate molecules in solution differs distinctively from that of surfactants commonly used for the preparation of ordered mesoporous silica phases, notably with the absence of a critical micellar concentration. In situ SAXS studies reveal fluctuations in X-ray scattering intensities consistent with the condensation of the silica precursor surrounding the folate template and the growth of the silica mesostructure in the initial stages. High-angle X-ray diffraction shows that the folate template is well-ordered within the pores even after a few minutes of synthesis. Direct structural data for the self-assembly of folates into chiral tetramers within the pores of mesoporous silica provide evidence for the in register stacking of folate tetramers, resulting in a chiral surface of rotated tetramers, with a rotation angle of 30 degrees. Additionally, the self-assembled folates within pores were capable of adsorbing a considerable amount of CO2 gas through the cavity space of the tetramers. The study demonstrates the validity of using a naturally occurring template to produce relevant and functional mesoporous materials., This work was supported by the Swedish Research Council (Project 2009-4716 AGB). Niklas Hedin acknowledges funding from the Swedish Energy Agency. Luis Angel Villaescusa is grateful for support from the Jose Castillejo Program of the Spanish Ministry of Sport and Education (Project JC2009-00141). The authors thank Y. Cerenius and M. Knaapila (MAX-lab Synchrotron Facitlity, Beamline 1711, Lund, Sweden) for assistance with SAXS experiments and beamline time.

The formation of hybrids of nanofibrillated cellulose and titania nanoparticles in aqueous media has been studied. Their transparency and mechanical behavior have been assessed by spectrophotometry and nanoindentation. The results show that limiting the titania nanoparticle concentration below 16 vol% yields homogeneous hybrids with a very high Young's modulus and hardness, of up to 44 GPa and 3.4 GPa, respectively, and an optical transmittance above 80%. Electron microscopy shows that higher nanoparticle contents result in agglomeration and an inhomogeneous hybrid nanostructure with a concomitant reduction of hardness and optical transmittance. Infrared spectroscopy suggests that the nanostructure of the hybrids is controlled by electrostatic adsorption of the titania nanoparticles on the negatively charged nanocellulose surfaces. AuthorCount:10

The synthesis of carbonaceous materials with a high surface density of amino functions for CO(2) sorption and sequestration is reported. The amino-rich carbonaceous materials are characterized by elemental analysis, N(2) sorption, scanning and transmission electron microscopy, zeta potential, TGA and FTIR measurements. A detailed discussion on the use of these materials in CO(2) capture is provided. The materials show significant sorption capabilities for CO(2) (4.3 mmol g(-1)at -20 degrees C and 1 bar). Furthermore, they show a high apparent selectivity for CO(2) over N(2) at both low and high temperatures.

Narrow channels with polar walls are the structural and functional features responsible for the high capacity of a zinc-organic framework based on an imidazolate-amide-imidate ligand for the uptake of H2 and CO2 (see structure: orange Zn, blue N, red O, dark gray C, light gray H). The rigid and stable chelating ligand was synthesized in situ by partial hydrolysis of a dicyanoimidazole compound.