Diffusion of ammonia in silicalite studied by QENS and PFG NMR

Ammonia diffusivities in silicalite have been studied by quasi-elastic neutron scattering (QENS) and pulsed-field gradient (PFG) NMR for temperatures between 200 and 500 K and loadings from 1.5 up to 4.3 molecules per unit cell. The diffusion coefficients obtained by both techniques increase with increasing ammonia concentration. The QENS diffusivities refer to only a certain fraction of molecules, because during the time scale of the measurement the other part of molecules is essentially immobile, in interaction with silanol groups. During the much larger time scale of the PFG NMR experiment, ammonia molecules assume both states of mobility, leading to an average diffusivity which is smaller than the diffusivity of the mobile molecules recorded by QENS. The difference between the diffusivities derived from both techniques decreases when the proportion of immobile molecules is taken into account. The residence time of ammonia in interaction with silanol groups is about two orders of magnitude longer than with oxygen atoms.     

PFG NMR and QENS diffusion study of n-alkane homologues in MFI-type zeolites

Recent methodological progress in pulsed field gradient (PFG) NMR and quasi-elastic neutron scattering (QENS) is exploited to enhance the range of diffusion measurement of the series of the n-alkane homologues in MFI-type zeolites (silicalite-1, ZSM-5) up to n-tetradecane. As observed already for the short-chain-length alkanes, the diffusivities are found to be intermediate between those for NaCaA and NaX, in agreement with the trend in the respective pore diameters. Similarly as in NaX, the diffusivities decrease monotonically with increasing chain length, in contrast to NaCaA, where recently for chain lengths above about six carbon atoms a remarkable deviation from this trend has been observed. Though agreeing in their trends, the diffusivities measured by PFG NMR are by up to one order of magnitude below the QENS data. This difference may be referred to internal diffusion barriers in the MFI-type zeolites: since PFG NMR monitors molecular displacements of typically micrometers the determined diffusivities are affected by these additional transport resistances, while these resistances are of no relevance for QENS, where much shorter displacements are recorded.     

Selective multi-component diffusion measurement in zeolites by pulsed field gradient NMR

The potential of pulsed field gradient (PFG) NMR for selective diffusion measurement in multi-component liquids is far from being fulfilled in multi-component diffusion studies with zeolites. We present two recent developments in PFG NMR instrumentation, which will significantly improve the measuring conditions for multi-component diffusion in zeolites and other nanoporous materials. They include options for an enhancement of the sensitivity with respect to smaller displacements by a novel principle of field gradient pulse matching and with respect to selectivity between different components by combining PFG NMR with magic angle spinning (MAS) NMR with a microimaging gradient system. The potentials and limitations of the two options are demonstrated by the first results of selective PFG NMR self-diffusion measurements with zeolitic adsorbate–adsorbent systems containing as much as four different species of guest molecules.     

High purity ethane/ethylene separation by gas phase simulated moving bed using ZIF-8 adsorbent

Growing population and demand for plastics and synthetic fluids in climate friendly environment sets the unprecedented industrial challenge to increase production of clean chemical precursors (e.g., ethylene) with reduced energy consumption and CO₂ foot print. The production of polymer-grade ethylene (>99.9%) from steam cracked gas or oil relies on a cascade of energy intensive distillations of gases. Therefore, in this work two simulated moving bed (SMB) cycles were employed to separate mixtures containing of about 40% of ethane and 60% of ethylene on zeolitic imidazole framework-8 granulates. The separation cycles were performed with two desorbents with different relative adsorption strength. In the experiment, with carbon dioxide as desorbent, ethylene was obtained with 99.6% purity and 94.2% recovery, while in the experiment using propane as desorbent only 77.1% of ethylene is recovered with a purity of 82.7%. Indeed, it can be concluded that when CO₂ is used as desorbent, the obtained productivity is higher. The mathematical SMB model and regions of separation were determined for each desorbent based on experimental data.     

Interaction of the perfluorinated polymer Nafion-H with water studied by proton broad-line NMR at 4 K and MAS NMR at room temperature

Broad-line¹H NMR at 4 K shows that, when Nafion-H interacts with water molecules at low concentrations, the only species formed is the hydronium ion. The chemical shift of the unsolvated hydronium ion in Nafion-H with 1 H₂O/SO ₃ ^– , determined by¹H MAS NMR at room temperature, is 10.4 ppm relative to external TMS.     

ZIF-8/乙二醇浆液连续捕集二氧化碳

有效捕获CO₂对于减少温室气体排放和控制全球变暖具有重要意义。本文采用吸收-吸附组合的方式将沸石咪唑骨架-8（ZIF-8）和乙二醇混合形成可流动浆液,分别在常压透明有机玻璃鼓泡塔（高3.7m,内径50mm）和高压不锈钢鼓泡塔（高3m,内径40mm）内连续捕集二氧化碳,浆液在解吸罐内解析后返回到吸收塔再进行二氧化碳捕集,整个分离过程可连续化进行。研究了不同环境温度、不同混合气流率、浆液再生温度和塔内不同操作压力对二氧化碳捕集能力,结果表明环境温度和混合气流率越低,浆液再生温 度和塔内压力越高,浆液吸着二氧化碳的量越大,最佳操作条件为：常压下环境温度0.5℃,气体流率 47mL/min,浆液再生温度333.13K。在此最佳操作条件下,分离因子高达395,同时在经过100h以上的分离过程后,ZIF-8结构没有发生变化并且ZIF-8/乙二醇浆液能重复利用,更进一步说明ZIF-8/乙二醇浆液具有潜在的工业应用价值。     

PFG NMR investigation of hydrocarbon diffusion in large NaX zeolite crystals: Effect of internal field gradients on diffusion data

Self-diffusion coefficients for intracrystalline diffusion of hydrocarbon molecules adsorbed in large crystals of NaX zeolite have been measured by the pulsed field gradient (PFG) NMR technique, at ambient temperature and at different diffusion times (from 6 to 12 ms). Two NMR pulse sequences, stimulated and 13-interval bipolar spin echo, were used to examine the influence of internal field gradients on diffusion data. For both sequences the effective self-diffusion coefficient of the guest molecules was found to decrease with increasing observation times. The extrapolated intracrystalline diffusion coefficient is independent of the NMR sequence. In contrast, the estimated extent of molecular diffusion depends strongly on the pulse program. For the small molecules (butane to hexane), the domain size, R, of restricted diffusion obtained with the stimulated spin-echo sequence is smaller than the crystal dimension whereas R is always comparable to it when the 13-interval pulse sequence is used. This shows the effect of internal field gradients on the diffusion data leading to wrong values of R if the stimulated pulse sequence is used. The light hydrocarbons diffuse freely inside the zeolite particles whereas the crystal boundaries act as reflecting surfaces, as previously observed. On the other hand, even with the 13-interval pulse sequence, the smaller values of R obtained for large molecules as n-heptane and octane shows that their displacement is hindered by restrictions in the NaX macro-crystals.     

NMR study of intrinsic diffusion and reaction in CsNaX type zeolites

In this contribution the catalytic behaviour of the zeolites CsNaX-60 and CsNaX-60·8CsOH (impregnated with eight CsOH per unit cell) was studied. As a model reaction, the conversion of isopropanol to acetone as the product of basic catalysis or to propene as the product of acid catalysis was chosen. The intracrystalline self-diffusivities of isopropanol, acetone and propene in these zeolites and in NaX were measured with the pulsed field gradient (PFG) NMR technique. Self-diffusivity measurements of propane and water were performed to characterize these three zeolites. ¹³C MAS NMR studies with proton decoupling were used to test the cesium containing zeolites for acid or basic catalytic activity.     

ZIF-8/乙二醇-水浆液吸收-吸附CH4/H2和CH4/N2

为了有效地捕集焦炉气及煤层气中的甲烷,提出了一种新型捕集技术:吸收-吸附组合方法,该方法通过把ZIF-8分散到乙二醇水溶液中形成悬浮浆液,实现对甲烷组分的捕集。首先测定了甲烷、氮气和氢气在浆液中的吸收-吸附容量,得出吸着量大小的顺序为CH₄> N₂> H₂,然后对CH₄/H₂和CH₄/N₂的混合气进行吸着平衡研究,发现浆液均能有选择性地吸着甲烷。对浆液中回收的ZIF-8材料进行XRD表征,分析证明在整个吸着过程中ZIF-8结构没有发生变化并且ZIF-8/乙二醇-水浆液能重复利用。     

Self-Diffusion of a Chemical Warfare Agent Simulant and Water in Nafion by Pulsed Field Gradient NMR

Pulsed field gradient (PFG) NMR at high magnetic field was used to study microscopic diffusion of dimethyl methyl phosphonate (DMMP), a common chemical warfare agent (CWA) simulant, and water in Nafion membranes. PFG NMR measurements were performed for a broad range of molecular displacements. The self-diffusivities were measured as a function of the DMMP concentration for several fixed water concentrations. The measured data suggest that DMMP and water diffuse in different regions of Nafion. While water mostly diffuses in hydrophilic regions of the membrane, viz. water channels, DMMP diffusion is mostly limited to interfacial perfluoroether regions between these water channels and the semi-crystalline matrix.     

Study on the performance of Cd2+ sorption using dimethylethylenediamine-modified zinc-based MOF (ZIF-8-mmen): optimization of the process by RSM technique

ABSTRACT

Cadmium as a highly toxic metal is released into the environment through paper production, metal processing, phosphate fertilizers, insecticides, and treatment of wastewater. Cadmium also inhibits the body activities and is very toxic for kidney and other organisms. In the current study, zinc-based metal–organic framework, zeolitic imidazolate framework (ZIF)-8, was synthesized and modified by dimethylethylenediamine (ZIF-8-mmen) for the removal of cadmium. To optimize the experiments, response surface methodology was applied with three variables including pH, adsorbent dosage, and contact time using central composite design. The optimum conditions for pH, dosage, and time were 2, 0.1 g, and 89 min, respectively, with removal efficiency of 85.38%. The Langmuir isotherm (q _m = 1000 mg/g) indicates the monolayer adsorption. The kinetic studies reveal that the Lagergren model was predominant and cadmium was not chemisorbed. Thermodynamic parameters show spontaneous, endothermic, and physisorption processes.     

CO2在ZIF-8/乙二醇-2-甲基咪唑浆液中溶解能力理论分析

有效降低CO₂排量实现碳中和是当前研究热点之一。ZIF-8/乙二醇-2-甲基咪唑浆液被发现不仅能高效地捕集CO₂,同时能利用浆液良好的流动性实现一个碳捕集-浆液流动再生-浆液再利用的连续碳捕集过程。为了有效地掌握纯CO₂气体在ZIF-8/乙二醇-2-甲基咪唑浆液中的溶解能力,本文首先测定了293.15K、303.15K和313.15K下CO₂在干ZIF-8上的吸附量和在2-甲基咪唑-乙二醇溶液中的溶解性;然后基于Langmuir方程和CO₂溶解机理进一步建立了相应吸附量和溶解度计算数学模型;最后综合考虑ZIF-8/乙二醇-2-甲基咪唑浆液中乙二醇和ZIF-8之间的共存特征和相互影响,建立了CO₂在目标浆液中溶解吸收量计算数学关联式。所得研究结果对浆液法CO₂技术的推广和后续流程模拟具有良好的指导作用和理论意义。     

Diffusion of probe polystyrenes with different molecular weights in poly(methyl methacrylate) gels and inhomogeneity of the network structure as studied by time-dependent diffusion NMR spectroscopy

Poly(methyl methacrylate) (PMMA) gels have been prepared with radical polymerization by cross-linking methyl methacrylate monomer using ethylene glycol dimethacrylate as cross-linking monomer in toluene containing polystyrenes (PSs) with M_w from 4000 to 400,000. The diffusion coefficients of the PSs in the PMMA gels swollen in deuterated chloroform have been measured by pulsed field-gradient (PFG) ¹H NMR method with the diffusing time Δ varied. From the experimental results, it is found that the network structure of PMMA gels prepared in the presence of PSs with M_w=4000 and 400,000 are relatively homogeneous and inhomogeneous, respectively, within the Δ range from 40 to 500 ms.     

Studies using Al MAS NMR of AFm and AFt phases and the formation of Friedel's salt

This paper describes the application of the magic angle spinning (MAS) NMR spectroscopy to study the chemical environment of ²⁷Al-bearing phases in Portland cement-based concrete. A specific methodology is described that allows reliable spectra to be determined for combinations of different types of cements and fillers (in this case, Portland cement, fly ash, slag, silica fume, metakaolin and limestone filler). As well as the study of ‘molecular structure’ of cement matrix, the paper reviews the mechanism of Friedel's salt formation in cement systems. Mechanisms based on ion exchange of chloride for hydroxide in hydroxy-AF_m and on chloride absorption on formation are discussed. Finally, the nature of the chloride/hydrate binding phenomena are described to provide a reasonable robust and fundamental picture of the role different cements can play in the provision of overall concrete durability to chloride ingress from a chemical perspective.     

Exploring the influence of Zn2SnO4/ZIF-8 nanocomposite photoelectrodes on boosting efficiency of dye sensitized solar cells

It is imperative to develop innovative efficient photoelectrode materials for high-performance dye-sensitized solar cells (DSSCs). In this work, cubic spinel Zn₂SnO₄ (ZTO)+(5, 10, 15, 20%) zeolite imidazole framework-8 (ZIF-8) nanoparticles were applied as photoanode materials of DSSC devices. The Zn₂SnO₄ was effectively synthesized in a simple and cost-effective manner by carefully controlling the hydrothermal conditions. The Zn₂SnO₄/ZIF-8 nanocomposite photoelectrodes were coated over the TiO₂ compact layer to decrease charge recombination at the transparent conductive oxide/mesoporous interface. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), diffuse reflectance spectroscopy (DRS), photoluminescence (PL), Brunauer–Emmett–Teller (BET) isotherms, Fourier transform infrared spectroscopy (FT-IR) and electrochemical impedance spectroscopy (EIS) analysis methods were used to study the properties of all nanostructured photoanodes. In addition, the effects of Zn₂SnO₄/ZIF-8 nanocomposites were evaluated on DSSCs performances. The results clearly showed that adding ZIF-8 to Zn₂SnO₄ improved the photovoltaic performance of the fabricated DSSCs. Furthermore, compared to pure Zn₂SnO₄ NPs, Zn₂SnO₄+15% ZIF-8 increased open circuit voltage (V_OC) from 0.64 to 0.77 V and short current density (J_SC) from 6.89 to 11.27 mA/cm². The Zn₂SnO₄+15% ZIF-8 photoanodes increased the power conversion efficiency (PCE) of DSSC by about 195% (from 2.02 to 3.94%) relative to the pure ZTO photoanode. This was due to the fact that the Zn₂SnO₄+15% ZIF-8 nanocomposite had the quickest electron transport rate, the best electron collecting efficiency, and the greatest charge recombination resistance, all of which are extremely advantageous to improve device efficiency.     

Facile synthesis of hierarchically porous carbons by controlling the initial oxygen concentration in-situ carbonization of ZIF-8 for efficient water treatment

The state-of-the-art approaches for adjusting the structural characteristics of porous carbons are the after-treatments, which are complicated and time consuming. In this work, a facile approach was developed, i.e., controlling the initial oxygen concentration in-situ during the direct carbonization of zeolitic imidazole framework-8 (ZIF-8), to adjust the pore structure and prepare hierarchically porous carbons. The introduction of oxygen can significantly affect the crystalline and pore structures of porous carbons, and promote the pore widening and the formation of mesopores. An appropriate initial oxygen concentration can notably enhance the surface area and mesopore volume of porous carbon, and then improve the adsorption capacity toward methylene blue (MB) dye from water by 3.4 times. The developed approach is more efficient at lower carbonization temperature. Moreover, the introduction of oxygen can increase the ratio of HOCO groups on the carbon surface, leading to enhanced interaction with MB molecules and higher adsorption capacity toward MB. The as-prepared porous carbons exhibit superior adsorption capacities toward MB dye as compared to the reported ZIF-8 derived carbons. These findings would aid the development of porous carbon materials with high performance.     

Study of Carbon Dioxide Transport in a Samaria Aerogel Catalyst by High Field Diffusion NMR

Pulsed field gradient (PFG) NMR employing a high magnetic field of 17.6 T was used to study self‐diffusion of carbon dioxide in alumina stabilized samaria aerogel, a promising porous catalyst for gas‐phase reactions. Such rare‐earth aerogels exhibit high porosity and surface area with active sites directly integrated into the pore framework. In the reported diffusion NMR studies, application of a high magnetic field was essential for obtaining sufficiently high signal‐to‐noise ratios under conditions of relatively low CO₂ densities in the primarily mesoporous catalyst particles. The diffusion studies were performed with the catalyst that was formed into the following two types of samples: macroscopic monoliths and beds of particles with sizes around 200 μm. The sorbate diffusivity inside the monolith was compared with the corresponding diffusivity in the bed under conditions of fast exchange of CO₂ between the particles and the interparticle voids of the bed. The two‐domain exchange model proposed by Kärger for zeolites was used to describe the latter diffusivity. The reported results are expected to be useful for elucidating an influence of possible transport limitations under reaction conditions in aerogel catalysts.     

Elongation-induced phase separation of poly(vinyl alcohol)/poly(acrylic-acid) blends as studied by C CP/MAS NMR and wide-angle X-ray diffraction

The membrane samples of poly(vinyl alcohol)/poly(acrylic-acid) (PVA/PAA) blend with different draw ratios were studied by both ¹³C CP/MAS NMR and wide-angle X-ray diffraction (WAXD) measurements. Phase separation induced by elongation of the sample was observed and the change of the phase structure with draw ratio was found to be dependent on the composition of the blend samples.     

Solid-State 13C CP/MAS NMR for Alkyl-O-Aryl Bond Determination in Lignin Preparations

Several lignin preparations (Freudenberg lignin, Björkman lignin, and Pepper lignin), technical lignins (soda, soda-AQ, Kraft, Kraft-AQ, and hydrolysis), dimeric lignin model compounds, and different polysaccharides (galactoglucomannan, arabinogalactan, xylan, and arabinan) were analyzed by means of solid-state ¹³C CP/MAS NMR. Signals assignment in solid-state NMR lignin spectra was performed on the basis of the conducted studies and earlier published data. It was established that there exists strong linear correlation (r = 0.985) between Alkyl-O-Aryl inter-unit bond content in lignin and integral signals intensity in NMR spectra in the range of chemical shifts of 96–68 ppm. The integral signals intensity was measured in correlation with the reference integral signals in the range of chemical shifts of 162–102 ppm, typical for aromatic carbon atoms. To eliminate the effect, caused by carbohydrates contained in lignin, the correction factor of 0.67% of the area of integration per 1% of carbohydrates was determined. It was shown that the solid-state ¹³C CP/MAS NMR method allowed to determine Alkyl-O-Aryl bond content in both soluble and insoluble lignin preparations, and also to determine methoxyl groups content in soluble preparations.     

Nucleotide Binding Modes in a Motor Protein Revealed by 31P- and 1H-Detected MAS Solid-State NMR Spectroscopy

Protein–nucleic acid interactions play important roles not only in energy-providing reactions, such as ATP hydrolysis, but also in reading, extending, packaging, or repairing genomes. Although they can often be analyzed in detail with X-ray crystallography, complementary methods are needed to visualize them in complexes, which are not crystalline. Here, we show how solid-state NMR spectroscopy can detect and classify protein–nucleic interactions through site-specific ¹H- and ³¹P-detected spectroscopic methods. The sensitivity of ¹H chemical-shift values on noncovalent interactions involved in these molecular recognition processes is exploited allowing us to probe directly the chemical bonding state, an information, which is not directly accessible from an X-ray structure. We show that these methods can characterize interactions in easy-to-prepare sediments of the 708 kDa dodecameric DnaB helicase in complex with ADP:AlF₄⁻:DNA, and this despite the very challenging size of the complex.