High-pressure magic angle spinning nuclear magnetic resonance

A high-pressure magic angle spinning (MAS) NMR capability, consisting of a reusable high-pressure MAS rotor, a high-pressure rotor loading/reaction chamber for in situ sealing and re-opening of the high-pressure MAS rotor, and a MAS probe with a localized RF coil for background signal suppression, is reported. The unusual technical challenges associated with development of a reusable high-pressure MAS rotor are addressed in part by modifying standard ceramics for the rotor sleeve by abrading the internal surface at both ends of the cylinder. In this way, not only is the advantage of ceramic cylinders for withstanding very high-pressure utilized, but also plastic bushings can be glued tightly in place so that other removable plastic sealing mechanisms/components and O-rings can be mounted to create the desired high-pressure seal. Using this strategy, sealed internal pressures exceeding 150 bars have been achieved and sustained under ambient external pressure with minimal loss of pressure for 72 h. As an application example, in situ¹³C MAS NMR studies of mineral carbonation reaction intermediates and final products of forsterite (Mg₂SiO₄) reacted with supercritical CO₂ and H₂O at 150 bar and 50 °C are reported, with relevance to geological sequestration of carbon dioxide.     

高温高压密闭消解-ICP-MS测定垃圾焚烧残渣中重金属及稀土元素

采用高温高压密闭消解-电感耦合等离子体质谱(ICP-MS)测定了垃圾焚烧残渣中的Cr, Co, Ni, Cu, Zn, Zr, Cd, Ba和Pb共9种重金属元素及Sc, Y, La, Ce, Pr, Nd等16项稀土元素的含量。实验确定密闭消解罐中,以HF-HNO₃-HCl(1∶2∶1)三元混酸体系于185℃烘箱中12 h可完全消解垃圾焚烧残渣样品,同时对ICP-MS测试工作条件(包括雾室温度、雾化气流速、辅助气流速、冷却气体流速、采样深度等)进行了优化。采用Rh为内标元素进行信号漂移校正和基体补偿,得到25种分析元素标准曲线的线性相关系数(r)大于0.999 9,方法检出限在0.001～1.01 ng·g^-1,样品分析测试的相对标准偏差(RSD)小于4.5%(n=3)。测试结果表明本次分析的垃圾焚烧残渣样品中Cr, Cu, Zn, Zr, Cd, Ba和Pb元素含量偏高,其中Pb含量高达(1 459±8) mg·kg^-1,稀土元素平均总量为(199±2) mg·kg^-1,整体呈下降趋势,并显示相...     

The novel YMn2D6 deuteride synthesized under high pressure of gaseous deuterium

The novel intermetallic deuteride YMn₂D₆ was synthesized under high deuterium pressure. In order to identify the structure and characterize the magnetic properties of this deuteride the powder X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Mn X-ray absorption near edge structure (XANES) and magnetization measurement (SQUID) were carried out. The crystal structure, the chemical state of Mn and the magnetic properties of this novel deuteride were examined and discussed. It should be noted that the structure of YMn₂D₆ (F-43m) differs dramatically from C15 symmetry of the parent material. Such a great rearrangement of the metal lattice due to deuterium absorption is rather exceptional for C15 Laves phase.     

固态离子晶体β-K0.294Ga1.969O3的高压与变温拉曼光谱研究

β-镓酸盐（β-gallate）型化合物是一种非常有应用前景的固态离子导体,在储能领域具有重要的应用价值。该类型化合物导电层中往往可以容纳过量的碱金属离子,使得该体系体现出复杂的晶格动力学行为,这也为进一步理解其导电机制带来了困难。压力与温度两个参量均可以通过改变原子间的间距而影响材料的结构,在研究材料的动力学过程,尤其在研究离子的扩散过程方面有很大的应用价值。迄今为止,对于温度依赖的β-镓酸盐型化合物的特性研究很少,且尚无β-镓酸盐型结构化合物的高压研究。由于激光拉曼散射技术在研究物质晶格动力学方面的独特优势,尤其压力与温度依赖的拉曼光谱可以提供重要的结构信息,是研究物质晶格动力学行为的有效实验手段。使用大腔体静高压技术成功合成了一种新型的β-镓酸盐型K_0.294Ga_1.969O₃(KGO)晶体,利用扫描电镜、能谱对晶体进行了表征,通过单晶X射线衍射对其晶体结构进行了解析,并与β-Ga₂O₃的晶体结构进行了对比分析。利用高压和变温拉曼光谱研究了KGO导电层中无序碱金属离子的晶格动力学行为。研究发现,由尖晶石层与疏松的离子导电层交替排列而成的β-镓酸盐型KGO晶体结构在压力23.3 GPa条件下仍可保持稳定;由于振动模式不同,高频拉曼模与低频拉曼模的压力系数存在着显著差异,并表现出显著的对压力诱导非谐性。在约300 ℃,KGO中K+发生热激活,表现在与碱金属K+运动相关的低频拉曼模的强度迅速增加,而与Ga-O多面体相关的高频振动模强度增加缓慢,与此同时,K+在沿着导电平面的方向上发生了无序扩散过程。研究结果将有助于深入地理解β-镓酸盐型结构化合物的导电机制,而且对于实现β-镓酸盐型化合物精确的计算控制和掺杂尤为重要。     

Exploration of synthetic strategies for the stereoselective preparation of novel tetrahydrofuran-containing biaryls: A high-pressure promoted Diels-Alder approach

Three stereoselective synthetic approaches to tetrahydrofuran-containing biaryl scaffolds are described. All approaches involve a high-pressure promoted Diels-Alder reaction of substituted diene with methyl propiolate to give, after aromatization, the corresponding biaryl. The tetrahydrofuran moiety can be created starting from aryl-Br or aryl-CO₂Me functional groups through a γ-phenylseleno ketone intermediate.     

Vibrational properties of L-cysteine hydrochloride monohydrate crystal under high-pressure

L-cysteine hydrochloride monohydrate crystals, C₃H₇NO₂S·HCl·H₂O, were studied by Raman spectroscopy as a function of pressure in a diamond anvil cell up to 6.2 GPa in the spectral range 3500−30 cm⁻¹. From the analysis of the results, we inferred that the crystal is structurally stable in this pressure range. Some changes on the Raman spectra were observed for bands related to vibrational modes of the SH, NH₃⁺, CH₂, CCN, OH and COH units. These modifications were associated with conformational changes of the molecules in the unit cell undergone at high pressures. Comparing this behavior with those of L-cysteine, DL-cysteine and L-cysteine hydrochloride crystals in the same pressure range, we note greater stability for the hydrochloride monohydrate form. In the L-cysteine hydrochloride monohydrate crystal, the chloride ion and water molecule play an essential role in increasing the number of the hydrogen bonds, improving the structural stability of the crystal.     

RIDE’n RIPT—ring down elimination in rapid imaging pulse trains

A new pulse sequence is introduced for compensation of acoustic ringing effects, which occur in rotating-frame images obtained with the rapid imaging pulse trains (RIPT). The new sequence (RIDE’n RIPT) combines features of ring down elimination (RIDE), the most common difference-spectroscopy sequence for acoustic-ringing compensation, with the advantages of RIPT for fast acquisition of magnetization profiles in B₁ field gradients. For even greater time efficiency in many experiments, the two transients of RIDE’n RIPT are combined to a single transient in which data for the difference spectroscopy are collected sequentially. RIDE’n RIPT was used to record one-dimensional profiles of the proton magnetization in supercritical fluid samples of methane in carbon dioxide. The profiles showed substantial improvements over profiles obtained from standard RIPT. To withstand the high pressures required for the supercritical carbon dioxide mixtures, a toroid cavity autoclave (TCA) was used as the NMR resonator and pressure vessel. The well-defined, strong, and nonuniform B₁ field of the TCA was used to resolve distances along the radial dimension.     

High-pressure synthesis and single-crystal structure refinement of gadolinium holmium silicate hydroxyapatite Gd4.33Ho4.33(SiO4)6(OH)2

Single crystals of gadolinium holmium silicate hydroxyapatite Gd_4.33Ho_4.33(SiO₄)₆(OH)₂ have been synthesized at 2.0 GPa and 1450 °C using a piston-cylinder-type high-pressure apparatus. The crystal symmetry by single-crystal X-ray diffraction analysis is hexagonal, space group P6₃/m (No. 176), with a=9.3142(5) Å, c=6.7010(4) Å, Z=1. Gadolinium and Ho are disordered over the two large cation positions, A(1) and A(2), and charge balance in this silicate apatite is maintained by cation vacancies in A(1). Two other apatite-structure crystals investigated have and Imma symmetry, and represent either partially ordered Gd-Ho distributions or crystal strain induced during quenching.     

Transitional properties of starch colloid with particle size reduction from micro- to nanometer

High-pressure homogenization was used to disperse starch particles in water and reduce the size from micro- to nanometer. The resultant starch colloids were characterized by particle morphology, mean size, size distribution, and zeta potential. Starch slurries were transformed from a mixture containing sediment, dispersion, and sol, to gel as a result of reduction of the particle size from 3–6 μm to 10–20 nm under a pressure of 207 MPa. Furthermore, this process led to the transition of fluid properties without affecting the crystal structure and thermal stability of starch granules. Viscosity of the colloids increased with an increased number of homogenization passes, accompanied by a decreased particle size, narrower particle size distribution (PSD), and an increased absolute zeta potential, indicating the formation of a suspension or stable gel composed of nanoparticles. Lognormal and two other mathematical functions were established to describe the PSDs and their relationship to the homogenization passes. Hence, an environmentally friendly means of producing starch-based nanoparticles or nanogels with high yields, and predictable size and viscosity properties was presented.     

Phase diagram of the La–Si binary system under high pressure and the structures of superconducting LaSi5 and LaSi10

The La–Si binary phase diagram under a high pressure of 13.5 GPa was experimentally constructed. New superconducting silicides LaSi₅ and LaSi₁₀ were found, which have peritectic decomposition temperatures at 1000 and 750 °C, respectively. The single crystal X-ray structural analysis revealed that there are two polymorphs in LaSi₅. The α-form obtained by heating a molar mixture of LaSi₂ and 3 Si at about 700 °C or by a rapid cooling from 1000 °C under pressure crystallizes with the space group C2/m and the lattice parameters a=15.11(3), b=4.032(6), c=8.26(1) Å, and β=109.11(1)°. The β-form obtained by a slow cooling from 800–950 °C to 600 °C under pressure has the same space group but with slightly different lattice parameters, a=14.922(7), b=3.906(2), c=8.807(4) Å, and β=107.19(1)°. The β-form is formed during the incomplete transformation of the α-form on cooling, and has always been obtained as a mixture with the α-form. The compound can be characterized as a Zintl phase with a polyanionic framework with large tunnels running along the b axis hosting lanthanum ions. In the β-form, three of the five Si sites are disordered. The two polymorphs contain one dimensional sila-polyacene ribbons, Si ladder polymer, running along the b axis. The α-form showed superconductivity with the transition temperature T_c of 11.5 K. LaSi₁₀ crystallizes with the space group 6₃/mmc and the lattice parameters a=9.623(4), c=4.723(3) Å. It is composed of La containing Si₁₈ polyhedra (La@Si₁₈) of hexagonal beer-barrel shape, which form straight columns by stacking along the c-axis via face sharing. One-dimensional columns of La@Si₁₈ barrels are edge-shared, and bundled with infinite Si trigonal bipyramid chains via corner sharing. The Si atoms in the straight chains have a five-fold coordination. LaSi₁₀ became a superconductor with T_c=6.7 K. The ab initio calculation of the electric band structures showed that α-LaSi₅ and LaSi₁₀ are metallic, and the conduction electrons mainly come from Si-3p orbitals.