Study of the conversion of methanol to dimethyl ether on zeolite HZSM-5 using in situ flow MAS NMR

The conversion of methanol to gasoline (MTG) range hydrocarbons on zeolite catalyst HZSM-5 has been studied extensively using solid-state NMR. We have studied the reaction under batch and flow conditions using an isolated flow variable-temperature (VT) MAS NMR probe. This probe was developed to study heterogeneous catalysis reactions in situ at temperatures greater than 300 degrees C with reactant flow. In the batch studies, when 13C-labeled methanol was adsorbed on zeolite HZSM-5, sealed, and heated to 250 degrees C, dimethyl ether was formed. Two-dimensional exchange NMR shows that dimethyl ether was in equilibrium with methanol at 250 degrees C. When 13C-methanol was flowed over HZSM-5 at temperatures > or = 200 degrees C, only dimethyl ether was observed. Between 160 degrees C and 200 degrees C, both methanol and dimethyl ether were observed. The flow results are significant in that they suggest that there is no equilibrium between methanol and dimethyl ether in the catalyst at high temperatures, and that surface methoxy groups do not exist on the catalyst at high temperatures.     

High-Temperature Pulsed-Field-Gradient Multidimensional NMR of Polymers

The application of pulsed-field-gradient (PFG) techniques has been particularly important in providing the ability to detect 2D and 3D NMR cross peaks from minor structural components in synthetic organic polymers. The lack of mobility in a large percentage of polymers leads to rapid T2 relaxation which prevents the use of pulse sequences, such as the HMBC experiment, that operate based on coherence transfer via small, long-range J couplings. High-temperature NMR increases molecular motion with corresponding line narrowing (e.g., polyethylenes are typically analyzed at 120 degrees C). However, until now, the requirement for high temperature has precluded the use of PFG methods. Here we present data from a new probe which is capable of performing high-temperature PFG coherence selection experiments at temperatures typical of those used in many polymer analyses. We illustrate the performance of this probe with PFG-HMBC spectra of a copolymer from ethylene/1-hexene/1-butene at 120 degrees C.     

高温核磁共振探头

本文设计研制了一种用于动态核磁共振研究的高温探头,它适用于磁铁极间距离为30mm的核磁共振波谱仪,探头中样品处的温度从室温至1300K连续可变,探头既可用于质子(¹H)也可用于其它核(如¹¹B,³¹P,²³Na等),并给出了高温探头的结构、指标及实际应用于测量的例子。     

C NMR of polyolefins with a new high temperature 10 mm cryoprobe

Recently, a high temperature 10 mm cryoprobe was developed. This probe provides a significant sensitivity enhancement for ¹³C NMR of polyolefins at a sample temperature of 120–135 °C, as compared to conventional probes. This greatly increases the speed of NMR studies of comonomer content, sequence distribution, stereo- and regioerrors, saturated chain end, unsaturation, and diffusion of polymers. In this contribution, we first compare the ¹³C NMR sensitivity of this probe with conventional probes. Then, we demonstrate one of the advantages of this probe in its ability to perform 2D Incredible Natural Abundance Double Quantum Transfer Experiment (2D INADEQUATE) in a relatively short period of time. The 2D INADEQUATE has been rarely used for polymer studies because of its inherently very low sensitivity. It becomes even more challenging for studying infrequent polyolefin microstructures, as low probability microstructures represent a small fraction of carbons in the sample. Here, the 2D INADEQUATE experiment was used to assign the ¹³C NMR peaks of 2,1-insertion regioerrors in a poly(propylene-co-1-octene) copolymer.     

Comparative measurements on thermal plasma jet characteristics inatmospheric and low pressure plasma sprayings

The ion and electron temperatures and plasma flow velocities are measured and compared between atmospheric and low pressure plasma spraying systems. The measurements of ion temperature for two systems are carried out by an optical emission spectroscopy which uses the relative emissivities of isolated Ar I emission lines. The electron density and temperature are measured by a Langmuir probe rotating across the plasma jets. The ion saturation currents collected by a Mach probe at two orientations, perpendicular and parallel to the plasma jet, determine the flow velocity. The spatial distributions of electron density, plasma flow velocity, and the associated shock activity in thermal plasma jets are discussed in conjunction with their direct dependency upon the ambient pressures as well as the torch powers. Measurements on temperatures and velocity profiles of thermal plasma jets reveal the general features of the LPPS jet characteristics, i.e., higher velocity flow with lower temperature, longer heating zone of expanded flame, and more extended accelerating zone compared with those of the APS jets. The shock activity clearly exists in the form of standing shock waves in the plasma jet of LPPS in view of flow compression and abrupt velocity drop which are appeared in the results of measurements on the variations of electron density and flow velocity along the plasma jet. In the center of the plasma jet of APS, the electron density is high enough to reach the LTE criterion, and the difference between ion and electron temperatures becomes insignificant as the torch input power increases     

A new type of sample tube for reducing convection effects in PGSE-NMR measurements of self-diffusion coefficients of liquid samples

Pulsed gradient spin-echo (PGSE) NMR measurements of the self-diffusion coefficients of low viscosity liquids are greatly hampered by the effects of convection especially away from ambient temperature. Here we report on a new NMR tube designed to minimize the deleterious effects of convection. In this tube, which derives from a Shigemi symmetrical NMR tube, the sample is contained in an annulus formed from a concentric cylinder of susceptibility matched glass. The performance of this tube was demonstrated by conducting measurements on the electrochemically important LiN(SO3CF3)2 (LiTFSI)-diglyme (DG) system. Calibrations were first made using DG at column heights of 2, 3, and 4-mm in the temperature range between -40 and 100 degrees C. Measurements of the diffusion coefficients of the lithium, anion, and DG were then performed to probe the solvent-ion and ion-ion interactions in the DG doped with LiTFSI. Changes in the 1H, 7Li, and 19F PGSE-NMR attenuation curves at -40 degrees C provided clear evidence of interactions between the DG and lithium ion.     

Polymer relaxations determined by use of a temporally and thermally stable interferometer

We describe a phase-controlled, highly stable interferometer that is ideal for use in long-time and high-temperature studies. We recorded output intensity variations of <0.2% for over 6 h at temperatures up to 150 degrees C. The setup was used to study in situ the temperature and frequency characteristics of a thin polymer film composed of 4-dimethylamino-4?-nitrostilbene doped into poly(methyl methacrylate). The mobility of the dopant molecules, which governed the electro-optic property of the film, was used to probe the dye-doped polymer's rheology. We demonstrate one application of the interferometer in probing both the alpha and the beta relaxations of the polymer.     

Copolyacrylates with phenylalanine and anthracene entities prepared by ATRP and microwave irradiation

In this study, two amino acid copolymers containing anthracene incorporated either on the one end, poly(N-acryloyl-l-phenylalanine-co-methyl methacrylate)-1 or as pendant groups, poly-(N-acryloyl-l-phenylalanine-co-methyl methacrylate)-2 were prepared directly from N-acryloyl-l-phenylalanine (APhe) and methyl methacrylate (MMA) through atom transfer radical polymerization (ATRP) and microwave-assisted synthesis. In the first case, 9-(chloromethyl)anthracene was used as an ATRP-initiator to obtain a copolymer that contains amino acid sequences and anthracene end-capped units (0.03 molar fraction). Rapid synthesis of copolymer under microwave irradiation (250 W) in the presence of 1,1′-azobis(cyclohexanecarbonitrile) used as an initiator was followed of a functionalization of the formed copolymer with an anthracene derivative yielding copolyacrylate with pendant anthracene (0.02 molar fraction). The structure of the copolymers was verified by ¹H NMR, UV-Vis and FTIR spectroscopy, gel permeation chromatography (GPC), and fluorescence spectroscopy. The fluorescence quenching process of anthracene which exists in copolymers by FeCl₃, cobalt acetate, nitrobenzene, maleic anhydride, diethylaniline and nitromethane in DMF solutions shows that this involves an electron transfer between the excited state anthracene and the present transitional metal cations, more efficiently being FeCl₃ for poly-(APhe-co-MMA)-1 and cobalt acetate for the latter copolymer.     

Investigations of Li-containing SiCN(O) ceramics via 7Li MAS NMR

Lithium-containing silicon (oxy)carbonitride ceramics (SiCN(O):Li) were synthesized via precursor-to-ceramic-transformation of Li-containing (poly)silazanes. The precursors were obtained by lithiation of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane with n-butyllithium and by reaction of a commercial poly(organosilazane) VL20 with metallic lithium. The annealing treatment was carried out at temperatures between 200 and 1400 degrees C in argon (DeltaT=200 degrees C) and yielded Li-containing silicon (oxy)carbonitride. X-ray powder diffraction revealed that the resulting SiCN(O):Li ceramics were basically amorphous up to temperatures of 1000 degrees C and formed LiSi(2)N(3), graphite and silicon carbide as crystalline phases at higher temperatures. (7)Li MAS NMR spectroscopy was carried out to investigate the structure of the Li-containing phases and to study the reaction path of metallic Li with polysilazane. Based on the NMR spectra, there is almost no difference found in the chemical shift of the SiCN(O):Li ceramics obtained at different temperatures. Accordingly, Li is assigned to be mainly coordinated to N and O present as contaminant element. Relaxation time measurements showed that the most mobile Li(+) species seems to be present in the product obtained in the pyrolysis temperature range between 600 and 1000 degrees C.     

High-precision nuclear magnetic resonance probe suitable for in situ studies of high-temperature metallic melts

High-temperature nuclear magnetic resonance (NMR) has proven to be very useful for detecting the temperature-induced structural evolution and dynamics in melts. However, the sensitivity and precision of high-temperature NMR probes are limited. Here we report a sensitive and stable high-temperature NMR probe based on laser-heating, suitable for in situ studies of metallic melts, which can work stably at the temperature of up to 2000 K. In our design, a well-designed optical path and the use of a water-cooled copper radio-frequency (RF) coil significantly optimize the signal-to-noise ratio (S/NR) at high temperatures. Additionally, a precise temperature controlling system with an error of less than ±1 K has been designed. After temperature calibration, the temperature measurement error is controlled within ±2 K. As a performance testing, ²⁷Al NMR spectra are measured in Zr-based metallic glass-forming liquid in situ. Results show that the S/NR reaches 45 within 90 s even when the sample's temperature is up to 1500 K and that the isothermal signal drift is better than 0.001 ppm per hour. This high-temperature NMR probe can be used to clarify some highly debated issues about metallic liquids, such as glass transition and liquid-liquid transition.     

207Pb chemical shift thermometer at high temperature for magic angle spinning experiments

The temperature dependence of 207Pb chemical shift in magic angle spinning (MAS) NMR spectrum of Pb(NO3)2 provides a sensitive method to calibrate sample temperatures in MAS NMR. The temperature dependence is uniform in the temperature range between 30 degrees C and 400 degrees C. The NMR sensitivity and the line width are also favorable.     

Isochoric measurement of the equation of state of solid argon at high pressure

Isochoric P-T traces have been measured for solid argon at eight different molar volumes by using a capacitance technique which records the radial expansion of the vessel due to pressure. These measurements extend from melting curve temperatures down to 4 °K at pressures ranging up to 7 kbar.Analysis of the data indicates that, for the high temperature region (above 80 °K) the thermodynamic derivative ?P/?T_r is independent of both temperature and density to within experimental errors. Using the fact that ?P/?T_r is constant, it is possible to generate PVT and isothermal bulk modulus data at high temperatures. These data are compared with X-ray diffraction measurements and piston displacement data and are found to be in good agreement with both. The data also agree quite well with current theoretical predictions. The high-temperature bulk modulus data were found to have a simple exponential dependence on the molar volume, prividing another convenient representation of the high-temperature equation-of-state data.     

Variable temperature system using vortex tube cooling and fiber optic temperature measurement for low temperature magic angle spinning NMR

We describe the construction and operation of a variable temperature (VT) system for a high field fast magic angle spinning (MAS) probe. The probe is used in NMR investigations of biological macromolecules, where stable setting and continuous measurement of the temperature over periods of several days are required in order to prevent sample overheating and degradation. The VT system described is used at and below room temperature. A vortex tube is used to provide cooling in the temperature range of -20 to 20 degrees C, while a liquid nitrogen-cooled heat exchanger is used below -20 degrees C. Using this arrangement, the lowest temperature that is practically achievable is -140 degrees C. Measurement of the air temperature near the spinning rotor is accomplished using a fiber optic thermometer that utilizes the temperature dependence of the absorption edge of GaAs. The absorption edge of GaAs also has a magnetic field dependence that we have measured and corrected for. This dependence was calibrated at several field strengths using the well-known temperature dependence of the (1)H chemical shift difference of the protons in methanol.     

Nuclear orientation at isolde/cern

A facility for Nuclear Implantation into Cold On-Line Equipment (NICOLE) is being installed at the new on-line isotope separator ISOLDE 3 at CERN. The first on-line run was in the beginning of July 1988. The low temperature equipment has been successfully tested and first off-line experiments on various isotopes have been performed. NMR/ON has been done on vaious isotopes (Co, Xe, Pt, Au) in iron host. First experience with the top-loading dilution refrigertor (Oxford Instruments Limited) shows that it performs very well. The cooling power is 400 μW at 100 mK and 34 μW at 25 mK. The base temperature can be kept continuously well below 5 mK. NMR/ON can be performed at temperatures below 5.5 mK. The base temperature on-line is expected to be lower then 6 mK. The sample can be cooled down from room temperature to 10 mK within two hours, to 6 mK within 3 hours which is not only important for off-line but also for on-line experiments when samples have to be changed to remove long lived daughter activity. The latest results will be reported.     

NMR measurement of bitumen at different temperatures

Heavy oil (bitumen) is characterized by its high viscosity and density, which is a major obstacle to both well logging and recovery. Due to the lost information of T2 relaxation time shorter than echo spacing (TE) and interference of water signal, estimation of heavy oil properties from NMR T2 measurements is usually problematic. In this work, a new method has been developed to overcome the echo spacing restriction of NMR spectrometer during the application to heavy oil (bitumen). A FID measurement supplemented the start of CPMG. Constrained by its initial magnetization (M0) estimated from the FID and assuming log normal distribution for bitumen, the corrected T2 relaxation time of bitumen sample can be obtained from the interpretation of CPMG data. This new method successfully overcomes the TE restriction of the NMR spectrometer and is nearly independent on the TE applied in the measurement. This method was applied to the measurement at elevated temperatures (8-90 degrees C). Due to the significant signal-loss within the dead time of FID, the directly extrapolated M0 of bitumen at relatively lower temperatures (<60 degrees C) was found to be underestimated. However, resulting from the remarkably lowered viscosity, the extrapolated M0 of bitumen at over 60 degrees C can be reasonably assumed to be the real value. In this manner, based on the extrapolation at higher temperatures (> or = 60 degrees C), the M0 value of bitumen at lower temperatures (<60 degrees C) can be corrected by Curie's Law. Consequently, some important petrophysical properties of bitumen, such as hydrogen index (HI), fluid content and viscosity were evaluated by using corrected T2.     

Quantitative high-resolution on-line NMR spectroscopy in reaction and process monitoring

On-line nuclear magnetic resonance spectroscopy (on-line NMR) is a powerful technique for reaction and process monitoring. Different set-ups for direct coupling of reaction and separation equipment with on-line NMR spectroscopy are described. NMR spectroscopy can be used to obtain both qualitative and quantitative information from complex reacting multicomponent mixtures for equilibrium or reaction kinetic studies. Commercial NMR probes can be used at pressures up to 35 MPa and temperatures up to 400 K. Applications are presented for studies of equilibria and kinetics of complex formaldehyde-containing mixtures as well as homogeneously and heterogeneously catalyzed esterification kinetics. Direct coupling of a thin-film evaporator is described as an example for the benefits of on-line NMR spectroscopy in process monitoring.     

Accelerating multi-echo T2 weighted MR imaging: analysis prior group-sparse optimization

High pressure measurements in most scientific fields rely on metal vessels given the superior tensile strength of metals. We introduce high pressure magnetic resonance imaging (MRI) measurements with metallic vessels. The developed MRI compatible metallic pressure vessel concept is very general in application. Macroscopic physical systems are now amenable to spatially resolved nuclear magnetic resonance (NMR) study at variable pressure and temperature. Metallic pressure vessels not only provide inherently high tensile strengths and efficient temperature control, they also permit optimization of the MRI RF probe sensitivity. An MRI compatible pressure vessel is demonstrated with a rock core holder fabricated using non-magnetic stainless steel. Water flooding through a porous rock under pressure is shown as an example of its applications. High pressure NMR spectroscopy plays an indispensable role in several science fields. This work will open new vistas of study for high pressure material science MRI and MR.     

Magnetic hyperfine field at caesium in iron

We report temperature dependence of nuclear orientation (NO), and the first observation of NMR/ON on Cs in iron.^{132, 136}Cs were implanted at room temperature into polycrystalline and single crystal iron. NO values for the (average) magnetic hyperfine field B_hf (CsFe) are close to 34T, intermediate between the value of 40.7T found in on-line samples made at mK temperatures and the NMR/ON value of 27.8 (2)T. The latter studies. The site/field distribution is briefly discussed. ISOLDE Collaboration, CERN     

A Dynamic Nuclear Polarization spectrometer at 95 GHz/144 MHz with EPR and NMR excitation and detection capabilities

A spectrometer specifically designed for systematic studies of the spin dynamics underlying Dynamic Nuclear Polarization (DNP) in solids at low temperatures is described. The spectrometer functions as a fully operational NMR spectrometer (144 MHz) and pulse EPR spectrometer (95 GHz) with a microwave (MW) power of up to 300 mW at the sample position, generating a MW B(1) field as high as 800 KHz. The combined NMR/EPR probe comprises of an open-structure horn-reflector configuration that functions as a low Q EPR cavity and an RF coil that can accommodate a 30-50 μl sample tube. The performance of the spectrometer is demonstrated through some basic pulsed EPR experiments, such as echo-detected EPR, saturation recovery and nutation measurements, that enable quantification of the actual intensity of MW irradiation at the position of the sample. In addition, DNP enhanced NMR signals of samples containing TEMPO and trityl are followed as a function of the MW frequency. Buildup curves of the nuclear polarization are recorded as a function of the microwave irradiation time period at different temperatures and for different MW powers.