Koji Kanehashi

Analysis of Atomic Scale Chemical Environments of Boron in Coal by 11B Solid State NMR

Atomic scale chemical environments of boron in coal has been studied by solid state NMR spectroscopy including magic angle spinning (MAS), satellite transition magic angle spinning (STMAS), and cross-polarization magic angle spinning (CPMAS). The (11)B NMR spectra can be briefly classified according to the degree of coalification. On the (11)B NMR spectra of lignite, bituminous, and sub-bituminous coals (carbon content of 70-90mass%), three sites assigned to four-coordinate boron ([4])B with small quadrupolar coupling constants (≤0.9 MHz) are observed. Two of the ([4])B sites in downfield are considered organoboron complexes with aromatic ligands, while the other in the most upper field is considered inorganic tetragonal boron (BO(4)). By contrast, on the (11)B NMR spectra of blind coal (carbon content >90mass%), the ([4])B which substitutes tetrahedral silicon of Illite is observed as a representative species. It has been considered that the organoboron is decomposed and released from the parent phase with the advance of coal maturation, and then the released boron reacts with the inorganic phase to substitute an element of inorganic minerals. Otherwise boron contained originally in inorganic minerals might remain preserved even under the high temperature condition that is generated during coalification.

Chemical state of boron in coal fly ash investigated by focused-ion-beam time-of-flight secondary ion mass spectrometry (FIB-TOF-SIMS) and satellite-transition magic angle spinning nuclear magnetic resonance (STMAS NMR).

The chemical states of boron in coal fly ash, which may control its leaching into the environment, were investigated by focused-ion-beam time-of-flight secondary ion mass spectrometry (FIB-TOF-SIMS) and satellite-transition magic angle spinning nuclear magnetic resonance (STMAS NMR) spectroscopy. The distribution of boron on the surface and in the interior of micron-sized fly ash particles was directly observed by FIB-TOF-SIMS. Coordination numbers of boron and its bonding with different atoms from particles of bulk samples were investigated by STMAS NMR. Boron in coal fly ash with relatively poor leaching characteristics appears as trigonal BO(3) and coexists with Ca and Fe at the outer layer of every particle and inside CaO-MgO particles. In contrast, boron in coal fly ash with better leaching characteristics appears as CaO- or MgO-trigonal BO(3) and tetragonal BO(4), and it is distributed only on the outer surface of each ash particle without showing any correlation with a particular element.

Practical comparison of sensitivity and resolution between STMAS and MQMAS for 27Al.

An experimental comparison of sensitivity and resolution of satellite transition (ST) MAS and multiple quantum (MQ) MAS was performed for (27)Al (I=5/2) using several pulse sequences with a z-filter and SPAM, and two inorganic samples of kaolin (Al(2)Si(2)O(5)(OH)(4)) and glass (43.1CaO-12.5Al(2)O(3)-44.4SiO(2)). Six pulse sequences of STMAS (double-quantum filter-soft pulse added mixing=DQF-SPAM, double-quantum filter=DQF, double-quantum=DQ) and MQMAS (3QMAS-z-filter=3Qz, 3QMAS-SPAM=3Q-SPAM, 5QMAS-z-filter=5Qz) are employed. All experiments have been conducted utilizing a static field of 16.4T (700MHz for (1)H) and a rotor spinning frequency of 20kHz. Dependence of S/N ratios as a function of radio frequency (r.f.) field strengths indicates that strong r.f. fields are essential to obtain a better S/N ratio in all experiments. High sensitivity is obtained in the following order: DQF-SPAM, DQF, DQ, 3QSPAM, and 3Qz, although the degree of sensitivity enhancement given by STMAS for glass is slightly smaller than that for kaolin. This might be due to the different excitation and conversion efficiencies of ST and MQ coherences as a function C(q) values because quadrupolar interaction of the glass are widely distributed, or to motional broadening caused by framework flexibility in the structure of glass. With respect to resolution, the full widths at half maximum (FWHM) of F(1) projections of DQF-STMAS and 3QMAS spectra for kaolin are found to be comparable, which agrees with a simulated result reported in a literature. For glass, the STMAS possess slightly wider line widths than 3QMAS. However, because such a difference in line widths of STMAS and 3QMAS spectra is substantially small, we have concluded that STMAS and 3QMAS have comparable resolution for crystalline and non-crystalline materials.

FIRST EVIDENCE OF MULTIPLE OCTAHEDRAL Al SITES IN Na-MONTMORILLONITE BY 27Al MULTIPLE QUANTUM MAS NMR

The configuration of hydroxyl groups around the octahedral cations of 2:1 phyllosilicate minerals has long been an important question in clay science. In the present study, 27Al multiple quantum (MQ) magic angle spinning nuclear magnetic resonance (MAS NMR) was applied to the local structural analysis of octahedral Al positions in a purified Na-montmorillonite. Three octahedral Al sites ([6]Ala, [6]Alb, and [6]Alc) are distinguished by 27Al 5QMAS NMR, whereas these sites are not differentiated by 27Al MAS and 3QMAS NMR. The isotropic chemical shift (δcs) and the quadrupolar product (PQ) were estimated to be 5.8 ppm and 2.6 MHz for [6]Ala, 6.2 ppm and 3.0 MHz for [6]Alb, and 6.7 ppm and 3.7 MHz for [6]Alc, respectively. The three Al sites originated from geometric isomers with cis and trans structures, which have mutually different configurations of the OH groups around the central Al3+ ions. From the view point of symmetry for the OH groups, [6]Ala and [6]Alb in the upfield region were assigned to cis sites, and [6]Alc in the downfield region was assigned to a trans site. The occurrence of multiple Al sites implies that Na-montmorillonite used in the present study has cis-vacant structure in the octahedral sheet. This is a reasonable insight, supported by the chemical composition and the differential thermal analysis data of the Na-montmorillonite.