27Al Magic Angle Spinning Research Articles

Structural dependence of crystallization in phosphorus‐containing sodium aluminoborosilicate glasses

AbstractThe article reports on the structural dependence of crystallization in Na2O–Al2O3–B2O3–P2O5–SiO2‐based glasses over a broad compositional space. The structure of melt‐quenched glasses has been investigated using 11B, 27Al, 29Si, and 31P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, while the crystallization behavior has been followed using X‐ray diffraction and scanning electron microscopy combined with energy dispersive spectroscopy. In general, the integration of phosphate into the sodium aluminoborosilicate network is mainly accomplished via the formation of Al–O–P and B–O–P linkages with the possibility of formation of Si–O–P linkages playing only a minor role. In terms of crystallization, at low concentrations (≤5 mol.%), P2O5 promotes the crystallization of nepheline (NaAlSiO4), while at higher concentrations (≥10 mol.%), it tends to suppress (completely or incompletely depending on the glass chemistry) the crystallization in glasses. When correlating the structure of glasses with their crystallization behavior, the MAS NMR results highlight the importance of the substitution/replacement of Si–O–Al linkages by Al–O–P, Si–O–B, and B–O–P linkages in the suppression of nepheline crystallization in glasses. The results have been discussed in the context of (1) the problem of nepheline crystallization in Hanford high‐level waste glasses and (2) designing vitreous waste forms for the immobilization of phosphate‐rich dehalogenated Echem salt waste.

Environmental assessment of metal-organic framework DUT-4 synthesis and its application for siloxane removal

In this study, the effect of different solvents in metal-organic framework (MOF) synthesis was evaluated in a technical study and an environmental study. The technical study considered the octamethylcyclotetrasiloxane (D4) adsorption on MOF DUT-4 for biogas purification, while the environmental study was implemented using the Life Cycle Assessment (LCA) methodology. In addition, the obtained DUT-4 adsorbents were characterized by X-ray diffraction, N2 adsorption-desorption isotherms, solid-state 27Al magic-angle spinning nuclear magnetic resonance, scanning electron microscopy, and Fourier transform infrared spectroscopy techniques. The results indicated that technically similar materials are obtained through solvothermal synthesis with similar D4 siloxane adsorption capacities (9.8 mg/g). Conversely, hydrothermal synthesis led to a low D4 siloxane adsorption capacity (1.8 mg/g). The environmental study demonstrated that the solvothermal synthesis had the highest contribution to the environmental damage due to the use of toxic solvents in the synthesis, cleaning, and solvent exchange stages (environmental score factor up to 244 mPt). In addition, a techno-environmental impact factor was introduced to identify the most suitable synthesis route of DUT-4. The overall results pointed out that solvothermal synthesis is the best scenario for DUT-4 production due to its low environmental impact/adsorption capacity ratio (11.44). This study is a step toward a more holistic approach integrating technical and environmental criteria in MOF synthesis for adsorption applications.

Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3

Abstract Various nuclear magnetic resonance (NMR) methods are combined to study the structure and dynamics of Li1.5Al0.5Ti1.5(PO4)3 (LATP) samples, which were obtained from sintering at various temperatures between 650 and 900 °C. 6Li, 27Al, and 31P magic angle spinning (MAS) NMR spectra show that LATP crystallites are better defined for higher calcination temperatures. Analysis of 7Li spin-lattice relaxation and line-shape changes indicates the existence of two species of lithium ions with clearly distinguishable jump dynamics, which can be attributed to crystalline and amorphous sample regions, respectively. An increase of the sintering temperature leads to higher fractions of the fast lithium species with respect to the slow one, but hardly affects the jump dynamics in either of the phases. Specifically, the fast and slow lithium ions show jumps in the nanoseconds regime near 300 and 700 K, respectively. The activation energy of the hopping motion in the LATP crystallites amounts to ca. 0.26 eV. 7Li field-gradient diffusometry reveals that the long-range ion migration is limited by the sample regions featuring slow transport. The high spatial resolution available from the high static field gradients of our setup allows the observation of the lithium ion diffusion inside the small (<100 nm) LATP crystallites, yielding a high self-diffusion coefficient of D = 2 × 10−12 m2/s at room temperature.

Electrical and Structural Properties of Li1.3Al0.3Ti1.7(PO4)3-Based Ceramics Prepared with the Addition of Li4SiO4.

The currently studied materials considered as potential candidates to be solid electrolytes for Li-ion batteries usually suffer from low total ionic conductivity. One of them, the NASICON-type ceramic of the chemical formula Li1.3Al0.3Ti1.7(PO4)3, seems to be an appropriate material for the modification of its electrical properties due to its high bulk ionic conductivity of the order of 10−3 S∙cm−1. For this purpose, we propose an approach concerning modifying the grain boundary composition towards the higher conducting one. To achieve this goal, Li4SiO4 was selected and added to the LATP base matrix to support Li+ diffusion between the grains. The properties of the Li1.3Al0.3Ti1.7(PO4)3−xLi4SiO4 (0.02 ≤ x ≤ 0.1) system were studied by means of high-temperature X-ray diffractometry (HTXRD); 6Li, 27Al, 29Si, and 31P magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR); thermogravimetry (TG); scanning electron microscopy (SEM); and impedance spectroscopy (IS) techniques. Referring to the experimental results, the Li4SiO4 additive material leads to the improvement of the electrical properties and the value of the total ionic conductivity exceeds 10−4 S∙cm−1 in most studied cases. The factors affecting the enhancement of the total ionic conductivity are discussed. The highest value of σtot = 1.4 × 10−4 S∙cm−1 has been obtained for LATP–0.1LSO material sintered at 1000 °C for 6 h.

Activator Anion Influences the Nanostructure of Alkali-Activated Slag Cements

Alkali-activated materials are promising low-carbon alternatives to Portland cement; however, there remains an absence of a fundamental understanding of the effect of different activator types on their reaction products at the atomic scale. Solid-state 27Al and 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and 1H–29Si cross-polarization MAS NMR spectroscopy are used to reveal the effect of the activator anion on the nanostructure, cross-linking, and local hydration of aged alkali-activated slag cements. The main reaction product identified is a mixed cross-linked/non-cross-linked sodium-substituted calcium aluminosilicate hydrate (C–(N)–A–S–H) gel with a structure comparable to tobermorite 11 Å. Analysis of cross-polarization kinetics revealed that a higher content of soluble silicate in the activator promoted the incorporation of Al into the aluminosilicate chains of C–(N)–A–S–H gels, charge-balanced preferentially by protons within the gel interlayer. In sodium carbonate-activated slag cements, aluminosilicate chains of C–(N)–A–S–H gels are instead charge-balanced preferentially by Ca2+ or AlV ions. Hydrotalcite was observed as a secondary reaction product independent of the activator used and in higher quantities as the content of sodium carbonate in the activator increases. The presence of soluble silicates in the activator promotes the formation of an Al-rich sodium aluminosilicate hydrate (N–A–S–H) gel which was not identified when using sodium carbonate as the activator. These results demonstrate that the anion type in the activator promotes significant differences in the nanostructure and local hydration of the main binding phases forming in alkali-activated slag cements. This explains the significant differences in properties identified when using these different activators.

Unusual cation coordination in nanostructured mullites

Abstract Nanocrystalline mullite-type bismuth-bearing complex oxides Bi2(M0.5Al0.5)4O9 (M=Fe3+, Ga3+) are prepared by high-energy ball milling of the corresponding microcrystalline counterparts. An unusual five-fold coordination of metal cations is revealed in nanostructured Bi2(M0.5Al0.5)4O9 by means of 27Al magic angle spinning nuclear magnetic resonance and 57Fe Mössbauer spectroscopies. The concentration of five-fold coordinated cations increases with decreasing crystallite size of a material at the expense of octahedrally coordinated ones. In addition to the nuclear spectroscopic methods, Rietveld analyses of the X-ray diffraction data of the as-prepared nanooxides show that the constituent tetrahedra, octahedra, and the newly formed structural units with five-fold cation coordination are strongly distorted. With decreasing crystallite size of mullites, the average volume of their octahedra increases whereas this parameter decreases for tetrahedra. The macroscopic behaviour of the non-equilibrium nanomullites is characterised by SQUID magnetometry. The Fe-containing mullites exhibit a superposition of a dominant antiferromagnetism and a weak ferromagnetism. The increase in both the remanent magnetization and the coercive field with decreasing crystallite size is attributed to the effect of spin canting. The latter is confined to the interfacial and surface regions of the nanomaterials, and arises due to both the mechanically induced deformation of constituent structural units and the formation of cation sites with the unusual five-fold coordination.

Mixed-Phase Ion-Exchangers from Waste Amber Container Glass.

This study investigated the one-pot hydrothermal synthesis of mixed-phase ion-exchangers from waste amber container glass and three different aluminium sources (Si/Al = 2) in 4.5 M NaOH(aq) at 100 °C. Reaction products were characterised by X-ray diffraction analysis, Fourier transform infrared spectroscopy, 27Al and 29Si magic angle spinning nuclear magnetic resonance spectroscopy and scanning electron microscopy at 24, 48 and 150 h. Nitrated forms of cancrinite and sodalite were the predominant products obtained with reagent grade aluminium nitrate (Al(NO3)3∙9H2O). Waste aluminium foil gave rise to sodalite, tobermorite and zeolite Na-P1 as major phases; and the principal products arising from amorphous aluminium hydroxide waste were sodalite, tobermorite and zeolite A. Minor proportions of the hydrogarnet, katoite, and calcite were also present in each sample. In each case, crystallisation was incomplete and products of 52, 65 and 49% crystallinity were obtained at 150 h for the samples prepared with aluminium nitrate (AN-150), aluminium foil (AF-150) and amorphous aluminium hydroxide waste (AH-150), respectively. Batch Pb2+-uptake (~100 mg g−1) was similar for all 150-h samples irrespective of the nature of the aluminium reagent and composition of the product. Batch Cd2+-uptakes of AF-150 (54 mg g−1) and AH-150 (48 mg g−1) were greater than that of AN-150 (36 mg g−1) indicating that the sodalite- and tobermorite-rich products exhibited a superior affinity for Cd2+ ions. The observed Pb2+- and Cd2+-uptake capacities of the mixed-product ion-exchangers compared favourably with those of other inorganic waste-derived sorbents reported in the literature.

Viscosity and structure evolution of CaO–SiO2–MgO–Al2O3–BaO slag with the CaO/SiO2 mass ratio of 0.9

Keeping a low and steady viscosity of slag is conducive to smooth operation of blast furnace. In this work, the effect of BaO on the viscosity and structure evolution of CaO–SiO2–MgO–Al2O3–BaO slag with a fixed CaO/SiO2 mass ratio of 0.9 was studied. The results revealed that the viscosity decreased firstly with BaO content rising from 0 wt% to 1.0 wt%, and then increased with further improving BaO content, which was ascribe to the contradictory effect of Ba2+ and O2− on the aluminate–silicate network structure. The structural analysis by Fourier transform infrared spectroscopy (FTIR) and Raman spectra showed that a small amount addition of BaO could promote the transformation from Q2 and Q3 units toward Q0 and Q1 units. However, the higher BaO content would induce an increasing concentration of Q2 and Q3 units, leading to an enhancement of the polymerization degree of slag. In addition, the variations of Al-related structural units were identified by the 27Al magic angle spinning nuclear magnetic resonance (27Al MAS-NMR) spectra. The relative fraction of [AlO4] units firstly decreased and then increased with the addition of BaO, and an opposite trend was observed for [AlO5] and [AlO6] units. The structural analysis supported the results of viscosity experiment well.

Structure of crystalline and amorphous materials in the NASICON system Na1+xAlxGe2-x(PO4)3.

The structure of crystalline and amorphous materials in the sodium (Na) super-ionic conductor system Na1+xAlxGe2-x(PO4)3 with x = 0, 0.4, and 0.8 was investigated by combining (i) neutron and x-ray powder diffraction and pair-distribution function analysis with (ii) 27Al and 31P magic angle spinning (MAS) and 31P/23Na double-resonance nuclear magnetic resonance (NMR) spectroscopy. A Rietveld analysis of the powder diffraction patterns shows that the x = 0 and x = 0.4 compositions crystallize into space group-type R3̄, whereas the x = 0.8 composition crystallizes into space group-type R3̄c. For the as-prepared glass, the pair-distribution functions and 27Al MAS NMR spectra show the formation of sub-octahedral Ge and Al centered units, which leads to the creation of non-bridging oxygen (NBO) atoms. The influence of these atoms on the ion mobility is discussed. When the as-prepared glass is relaxed by thermal annealing, there is an increase in the Ge and Al coordination numbers that leads to a decrease in the fraction of NBO atoms. A model is proposed for the x = 0 glass in which super-structural units containing octahedral Ge(6) and tetrahedral P(3) motifs are embedded in a matrix of tetrahedral Ge(4) units, where superscripts denote the number of bridging oxygen atoms. The super-structural units can grow in size by a reaction in which NBO atoms on the P(3) motifs are used to convert Ge(4) to Ge(6) units. The resultant P(4) motifs thereby provide the nucleation sites for crystal growth via a homogeneous nucleation mechanism.

Physico chemical and thermal resistance properties of fly ash/ground granulated blast furnace slag based geopolymer mortar

The present study investigated the physicochemical and thermal properties of fly ash and ground granulated blast furnace slag (GGBS) based geopolymer mortars exposed to elevated temperatures under different reaction conditions. The compressive strength results shows that fly ash based geopolymer mortar exhibits retention of compressive strength up to 800⁰C whereas the addition of GGBS increases the ambient temperature compressive strength, however, thereafter the retention of strength is observed as 66% at 400˚C and 30% at 800˚C. Fourier transform infra-red spectroscopy (FT- IR) and 29Si and 27Al Magic angle spinning nuclear magnetic resonance (MAS-NMR) spectrum confirmed the alumino-silicate network structure of the geopolymer. Thermogravimetry with differential thermal analysis (TGA/DTA) showed that most of the % weight loss occurred in the temperature range between 30-250ºC due to the water loss after that it was stabilized till 1000⁰C. Thermal conductivity has the direct relationship with the temperature whereas it is vice versa for the % linear thermal expansion. The Scanning electron microscopy (SEM) analysis was performed to identify the morphology changes before and after thermal exposure.

Effect of change in the silica modulus of sodium silicate solution on the microstructure of fly ash geopolymers

This study focuses on the impact of change in the silica modulus (SiO2/Na2O) (0.6–1.6) of the sodium silicate solution (SSS) on the microstructure, mechanical properties and thermal stability of fly ash geopolymer (FAGP). The variation in the compressive strength of FAGP was studied on increasing the temperature from 200 °C to 800 °C. On increasing the silica modulus (Ms) of the SSS from 0.8 to 1.6, the compressive strength of the FAGP mortars increases, but the FAGP mortar with Ms 1.2 experienced flash setting. The compressive strength does not show any uniform trend with increasing temperature. Among fabricated geopolymers, SSS with Ms 1.4 attained a strength of 28 MPa at 800 °C. The changes in Si and Al environment were studied using 29Si, 27Al magic angle spinning nuclear magnetic resonance (MAS-NMR) and Fourier transform infrared (FT-IR) frequency band of Si–O–T (T: Si/Al). The positive shift in 29Si NMR signal with higher Ms confirmed the formation of an Al-rich binding gel and the chemical shift at 56 ppm in 27Al NMR corresponds to a AlQ4(4Si) poly (sialate-siloxo)-type network... The structural changes arising from the integration of Al was further confirmed by shifting the Si–O-T asymmetric stretching vibration to lower wave number in FT-IR compared to raw fly ash. The microstructure was studied using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDAX), X-ray diffraction (XRD) and thermal properties using thermal gravimetric analysis/differential thermal analysis (TGA/DTA.

Ultrathin 2D Fe-Nanosheets Stabilized by 2D Mesoporous Silica: Synthesis and Application in Ammonia Synthesis.

Developing high-performance Fe-based ammonia catalysts through simple and cost-efficient methods has received an increased level of attention. Herein, we report for the first time, the synthesis of two-dimensional (2D) FeOOH nanoflakes encapsulated by mesoporous SiO2 (mSiO2) via a simple solution-based method for ammonia synthesis. Due to the sticking of the mSiO2 coating layers and the limited spaces in between, the Fe after reduction retains the 2D morphology, showing high resistance against the sintering in the harsh Haber–Bosch process. Compared to supported Fe particles dispersed on mSiO2 spheres, the coated catalyst shows a significantly improved catalytic activity by 50% at 425 °C. Thermal desorption spectroscopy (TDS) reveals the existence of a higher density of reactive sites for N2 activation in the 2D Fe catalyst, which is possibly coupled to a larger density of surface defect sites (kinks, steps, point defects) that are generally considered as active centers in ammonia synthesis. Besides the structural impact of the coating on the 2D Fe, the electronic one is elucidated by partially substituting Si with Al in the coating, confirmed by 29Si and 27Al magic-angle spinning nuclear magnetic resonance (MAS NMR). An increased apparent activation energy (Ea) of the Al-containing catalyst evidences an influence on the nature of the active site. The herein-developed stable 2D Fe nanostructures can serve as an example of a 2D material applied in catalysis, offering the chance of a rational catalyst design based on a stepwise introduction of various promoters, in the coating and on the metal, maintaining the spatial control of the active centers.

Structure and viscosity of CaO–Al2O3–B2O3–BaO slags with varying mass ratio of BaO to CaO

AbstractThe structure of CaO–Al2O3–B2O3–BaO glassy slags with varying mass ratio of BaO to CaO has been investigated by Raman spectroscopy, 11B and 27Al magic angle spinning nuclear magnetic resonance (MAS‐NMR) spectroscopy and atomic pair distribution function (PDF). 11B MAS‐NMR spectra reveal the dominant coordination of boron as trigonal. Both simulations on 11B MAS‐NMR spectra and Raman spectroscopy indicate the presence of orthoborate as the primary borate group with a few borate groups with one bridging oxygen and minor four‐coordinated boron sites. 27Al MAS‐NMR and PDF show the Al coordination as tetrahedral. Raman spectral study shows that the transverse vibration of AlIV–O–AlIV and AlIV–O–BIII, stretching vibration of aluminate structural units and vibration of orthoborate and pyroborate structural groups. A broader distribution of Al–O bond lengths in PDF also supports the enhanced network connectivity. Viscosity measurements show the increase in viscosity of molten slags with increasing mass ratio of BaO to CaO, which further attributes to the enhanced degree of polymerization of the aluminate network.

Adsorption Studies of Aqueous Solutions of Methyl Green for Halloysite Nanotubes: Kinetics, Isotherms, and Thermodynamic Parameters

Halloysite nanotubes (HNTs) were used to successfully remove methyl green dye from water. The HNTs were also characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), 29Si and 27Al magic angle spinning nuclear magnetic resonance with magic angle spinning (MAS-NMR) and nitrogen adsorption at 77 K. SEM and TEM micrographs showed that HNTs have lengths of 0.2 to 1.5 μm, an outer diameter of 100 nm and lumen of 20 nm wide. X-ray diffraction patterns showed that the HNTs were totally dehydrated. HNTs may be regarded as a mesoporous material with a pore size distribution in the range of 1.5-150 A and specific surface area of 34.49 m2g-1. The adsorption kinetics and equilibrium data of the dye, initial dye concentration, temperature, pH and contact time effect on removal efficiency were also investigated. Pseudo-first-order, pseudo-second-order, intraparticle diffusion and Elrich models were evaluated in order to determine the rate parameters. The adsorption rate followed pseudo-second-order kinetic model. Adsorption revealed that methyl green was adsorbed as the Langmuir isotherm model describes and the maximum adsorption capacity of the HNTs was achieved (185 mgg−1), being an efficient adsorbent for methyl green adsorption.

Combined effect of NaAlO2 and NaOH on the early age hydration of Portland cement with a high concentration of borate solution

The early age hydration of ordinary Portland cement in 5 M borate solution, with or without the addition of NaAlO2 and/or NaOH, was investigated. Hydration was measured using calorimetry, X-ray diffraction, thermogravimetric analysis, 11B and 27Al magic angle spinning NMR analysis, and scanning transmission electron microscopy. The purpose of this study was to reveal the mechanisms behind the retardation caused by a high concentration borate solution and the restoration of hydration through the combined addition of NaOH and NaAlO2. Amorphous ulexite, which formed on the surface of the cement particles and prevented the further dissolution of anhydrous phases, was identified as the retardation product. The mechanism of the combined addition of NaAlO2 and NaOH in overcoming retardation was to transform amorphous ulexite into B-AFt and gowerite (CaB6O10·5H2O). Formation of gowerite is favorable because of the much higher boron immobilization capacity in weight percentage, comparing to usual boron-containing phases reported previously.

A new quaternary Li0.19Al2.72O3.64N0.36 transparent ceramic with high hardness

A new quaternary Li0.19Al2.72O3.64N0.36 transparent ceramic with the Vickers hardness of 17.91 ± 0.2 GPa at a load of 9.8 N and the in-line transmittance of 83.4% at 3.5 µm was prepared by hot isostatic press sintering (HIP) after pressureless sintering. The 7Li and 27Al magic-angle spinning (MAS) NMR spectra combined with the XRD Rietveld refinement was adopted to analyze the crystal structure. It is revealed that all the lithium ions are located in octahedra and the cation vacancies are mainly concentrated in tetrahedra. Based on the bond valance models, the complicated relationship among composition, crystal structure and intrinsic hardness of the spinel-type transparent ceramic were disclosed. Compared with the γ-AlON, the higher hardness of Li0.19Al2.72O3.64N0.36 transparent ceramic is attributed to the coupling effect of enhanced hardness of bonds in octahedra and the slightly weakened hardness of bonds in tetrahedra.

Hydrothermal conversion of zeolite omega from magadiite with assistance of seed crystals

In this work, we report a rapid and sustainable synthetic strategy of zeolite omega with the addition of omega seeds via the transformation of magadiite with an initial chemical recipe of 0.76 NaOH: SiO2: 0.01 Al2O3: 7–14H2O, and the crystallization time was shortened to 5 h at 80 °C. The effect of experiment parameters has been discussed in details. In addition, the conversion behavior and the changes of secondary building units were characterized and studied by X-ray diffraction (XRD), scanning electron microscopy, Fourier Transform infrared (FT-IR), and Raman spectroscopy and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. During the conversion process, omega seeds would be partially destroyed and residual seeds supplied substrate for the growth of zeolite omega, most parts of five-membered rings and six-membered rings in magadiite were remained as building units to promote the formation of zeolite omega, and Al species preferred to enter T2 position which was located in six-membered rings. The toluene adsorption property of final product was also measured.

Bizeolite Pt/ZSM-5:ZSM-12/Al2O3 catalyst for hydroisomerization of C-8 fraction with various ethylbenzene content

A bizeolite catalyst based on ZSM-5 and ZSM-12 was designed to maximize the yield of valuable aromatics from ethylbenzene (EB) rich feedstocks for the first time. The catalyst Pt/ZSM-5:ZSM-12/Al2O3 was characterized by X-ray diffraction (XRD), nitrogen physisorption, temperature-programmed desorption of ammonia (TPD-NH3), transmission and scanning electron microscopy (TEM and SEM), X-ray fluorescence analysis (XRF), Fourier-transformed infrared spectroscopy (FTIR) and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The catalyst and its components were tested in isomerization of an industrial C-8 aromatic cut (C8-Ar) and feedstocks with high EB content. The catalyst demonstrated higher conversion of EB and m-xylene (MX) compared with an industrial catalyst and higher selectivity to dealkylation products.

Influence of Al/Er ratio on the optical properties and structures of Er3+/ Al3+ co-doped silica glasses

In this study, Er3+/Al3+ co-doped silica glasses with various Al/Er ratios ranging from 0 to 200 and a constant Er2O3 amount were prepared using the sol-gel method combined with high-temperature vacuum sintering. The absorption, emission spectra, and fluorescence lifetime of Er3+ ions were recorded and the absorption and emission cross sections were calculated. Using Raman, 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS-NMR), 27Al triple-quantum (TQ)-MAS-NMR, and electron paramagnetic resonance (EPR) spectroscopies, the physical and optical properties were correlated with the glass structural modifications due to the Al/Er ratio change. With the increase in the Al/Er ratio, the content of Al3+ ions around the Er3+ ions gradually increased. Meanwhile, the AlO5 and AlO6 polyhedrons increased at the expense of the AlO4 and SiO4 tetrahedrons, which resulted in an improved symmetry and better ionic Er–O bonds. These structural changes led to the site-to-site variations in the Er3+ local environment and the changes in the ligand field strength of the Er–O bonds. This, in turn, resulted in the inhomogeneous broadening of the absorption and emission spectra, with a blue shift of both absorption and emission peaks and a decrease in both absorption and emission at 1.53 μm. With the increase in Al/Er ratio, the full width at half maximum (FWHM) of the emission increased from 27.2 to 54.3 nm. The FWHM × emission cross section (σemi) parameter for evaluating broadband amplification behavior was 30.1 × 10−20 cm2 · nm. This work reveals the close relationship between the glass structure and the spectroscopic properties of Er3+ ions and provides an important reference for the design of broadband amplifier materials in the field of optical communication.

High-Field One-Dimensional and Two-Dimensional 27Al Magic-Angle Spinning Nuclear Magnetic Resonance Study of θ-, δ-, and γ-Al2O3 Dominated Aluminum Oxides: Toward Understanding the Al Sites in γ-Al2O3.

Herein, a detailed analysis was carried out using high-field (19.9 T) 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) on three specially prepared aluminum oxide samples where the γ-, δ-, and θ-Al2O3 phases are dominantly expressed through careful control of the synthesis conditions. Specifically, two-dimensional (2D) multiquantum (MQ) MAS 27Al was used to obtain high spectral resolution, which provided a guide for analyzing quantitative 1D 27Al NMR spectra. Six aluminum sites were resolved in the 2D MQ MAS NMR spectra, and seven aluminum sites were required to fit the 1D spectra. A set of octahedral and tetrahedral peaks with well-defined quadrupolar line shapes was observed in the θ-phase dominant sample and was unambiguously assigned to the θ-Al2O3 phase. The distinct line shapes related to the θ-Al2O3 phase provided an opportunity for effectively deconvoluting the more complex spectrum obtained from the δ-Al2O3 dominant sample, allowing the peaks/quadrupolar parameters related to the δ-Al2O3 phase to be extracted. The results show that the δ-Al2O3 phase contains three distinct AlO sites and three distinct AlT sites. This detailed Al site structural information offers a powerful way of analyzing the most complex γ-Al2O3 spectrum. It is found that the γ-Al2O3 phase consists of Al sites with local structures similar to those found in the δ-Al2O3 and θ-Al2O3 phases albeit with less ordering. Spin–lattice relaxation time measurement further confirms the disordering of the lattice. Collectively, this study uniquely assigns 27Al features in transition aluminas, offering a simplified method to quantify complex mixtures of aluminum sites in transition alumina samples.