Spinning Nuclear Magnetic Resonance Spectroscopy Research Articles

Monitoring the Geopolymerization Reaction of Geopolymer Foams Using 29Si and 27Al MAS NMR

This study aims to investigate the geopolymerization reaction of geopolymer foams produced with three different foaming agents: aluminum powder, zinc powder, and hydrogen peroxide. The geopolymerization reaction of geopolymer foam was monitored using the 27Al and 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy technique. 27Al MAS-NMR was used to monitor the reaction at an early stage, while 29Si and 27Al MAS-NMR analyses were employed at specific time intervals of 3, 6, 10, 15, and 28 days to examine the changes that occurred in the formed gel over time. We discussed in detail how the type of foaming agent used and the duration of the reaction both influence the quantity of gel formed and the amount of remnant fly ash. Our findings indicate that the type of foaming agent used affects the formation and structure of the gel, with aluminum powder leading to the highest gel formation. Additionally, the duration of the reaction plays a significant role in determining the quantity of remnant fly ash, with longer reaction times resulting in decreased fly ash content. This study sheds light on the relevance of understanding the role of foaming agents in the geopolymerization reactions of geopolymer foams and the influence of reaction time on the formed gel properties.

Structure and Properties of Na2S-SiS2-P2S5-NaPO3 Glassy Solid Electrolytes.

In the development of sodium all-solid-state batteries (ASSBs), research efforts have focused on synthesizing highly conducting and electrochemically stable solid-state electrolytes. Glassy solid electrolytes (GSEs) have been considered very promising due to their tunable chemistry and resistance to dendrite growth. For these reasons, we focus here on the atomic-level structures and properties of GSEs in the compositional series (0.6-0.08y)Na2S + (0.4 + 0.08y)[(1 - y)[(1 - x)SiS2 + xPS5/2] + yNaPO3] (NaPSiSO). The mechanical moduli, glass transition temperatures, and temperature-dependent conductivity were determined and related to their short-range order structures that were determined using Raman, Fourier transform infrared, and 31P and 29Si magic angle spinning nuclear magnetic resonance spectroscopies. In addition, the conductivity activation energies were modeled using the Christensen-Martin-Anderson-Stuart model. These GSEs appear to be highly crystallization-resistant in the supercooled liquid region where no measurable crystallization below 450 °C could be observed in differential scanning calorimetry studies. Additionally, these GSEs were found to be highly conducting, with conductivities on the order of 10-5 (Ω cm)-1 at room temperature, and processable in the supercooled state without crystallization. For all these reasons, these NaPSiSO GSEs are considered to be highly competitive and easily processable candidate GSEs for enabling sodium ASSBs.

Influences of alumina type and sulfate content on hydration and physicochemical changes in Portland–limestone cement

This study explored the influence of alumina type and gypsum content on the hydration, mechanical properties, and chemical changes of Portland–limestone cement (PLC) using isothermal calorimetry, inductively coupled plasma-optical emission spectroscopy (ICP-OES), ionic chromatography (IC), compressive strength testing, X-ray diffraction (XRD), 27Al magic angle spinning nuclear magnetic resonance (27Al MAS NMR) spectroscopy, and mercury intrusion porosimetry (MIP) testing. The addition of alumina shortened the induction period, accelerated the acceleration period, and increased the mechanical strength of the PLC pastes with 3 and 7 wt% gypsum. The acceleration effect and strength enhancement were not distinct in the PLC pastes with less gypsum (0.1 wt%). The addition of γ-alumina led to the greatest accelerating effect and strength improvement in the PLC pastes with 3 and 7 wt% gypsum, and the compressive strength achieved was comparable to those of pure Ordinary Portland cement (OPC) pastes without limestone. The addition of γ-alumina induced the rapid dissolution of gypsum and consumption of sulfate ions. The chemical change affected by the addition of alumina varied greatly depending on the gypsum content, and trends in AFt and AFm formation in the PLC pastes with different gypsum contents were confirmed. Finally, pore size refinement was observed through the addition of alumina to PLC pastes with 3 and 7 wt% gypsum.

Novel insights into the amorphous feature of granulated blast furnace slag-supplemented magnesium potassium phosphate cement and its effect on bulk properties

This paper reports the effects of MgO:PO4 (3, 9, and 15) ratio and granulated blast furnace slag dosage (0 wt%, 40 wt%, and 80 wt%) on the phase formation, microstructure, and bulk properties of magnesium potassium phosphate cement (MKPC). Results show that the supplementary of slag and the increment in MgO:PO4 inhibit the formation of K-struvite via X-ray diffraction. While the detections of 29Si magic-angle spinning nuclear magnetic resonance spectroscopy and scanning electron microscope-energy dispersion spectrum further unveil the dissolution of slag and the formation of Q4 amorphous structure in slag supplemented MKPCs. Although the Q4 structure increases the interplanar spacing of K-struvite even leads to its amorphization in MKPCs with high MgO:PO4 (>9), the optimum coexisting of K-struvite and Q4 structure minimizes the porosity and maximizes the compressive strength of MKPCs with MgO:PO4=3 and 40 wt% slag. These results are crucial to developing optimal mixture formulations of MKPC with superior mechanical performance and lower costs associated with their production.

An Integrated Metabolomics-Based Model, and Identification of Potential Biomarkers, of Perfluorooctane Sulfonic Acid Toxicity in Zebrafish Embryos.

Known for their high stability and surfactant properties, per- and polyfluoroalkyl substances (PFAS) have been widely used in a range of manufactured products. Despite being largely phased out due to concerns regarding their persistence, bioaccumulation, and toxicity, legacy PFAS such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid continue to persist at high levels in the environment, posing risks to aquatic organisms. We used high-resolution magic angle spinning nuclear magnetic resonance spectroscopy in intact zebrafish (Danio rerio) embryos to investigate the metabolic pathways altered by PFOS both before and after hatching (i.e., 24 and 72 h post fertilization [hpf], respectively). Assessment of embryotoxicity found embryo lethality in the parts-per-million range with no significant difference in mortality between the 24- and 72-hpf exposure groups. Metabolic profiling revealed mostly consistent changes between the two exposure groups, with altered metabolites generally associated with oxidative stress, lipid metabolism, energy production, and mitochondrial function, as well as specific targeting of the liver and central nervous system as key systems. These metabolic changes were further supported by analyses of tissue-specific production of reactive oxygen species, as well as nontargeted mass spectrometric lipid profiling. Our findings suggest that PFOS-induced metabolic changes in zebrafish embryos may be mediated through previously described interactions with regulatory and transcription factors leading to disruption of mitochondrial function and energy metabolism. The present study proposes a systems-level model of PFOS toxicity in early life stages of zebrafish, and also identifies potential biomarkers of effect and exposure for improved environmental biomonitoring. Environ Toxicol Chem 2024;43:896-914. © 2024 SETAC.

Fluorine in Complex Alumino-Boro-Silicate Glasses: Insight into Chemical Environment and Structure.

Fluorine incorporation into silicate glasses is important for technical fields as diverse as geophysics, extractive metallurgy, reconstructive dentistry, optical devices, and radioactive waste management. In this study, we explored the structural role of fluorine in alkaline alumino-borosilicate glass, with increasing amounts of fluorine up to 25 mol % F while maintaining the glass composition. Glasses were characterized by X-ray diffraction (XRD), 27Al and 19F magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and electron probe microanalysis. Results showed that essentially all F was retained; however, between 12 and 15 mol % F (∼3.6 and 4.5 wt % F), excess fluorine partitions to CaF2 and then NaF and Na-Al-F crystalline phases. Even prior to crystallization, there exist five distinct F sites, three of which evolve into crystalline phases. The two persistent glassy sites likely involve [4]Al-F-Ca/Na local structures. We propose a general understanding of the expected chemical shift of 19F NMR in systems containing Al, Ca, and Na.

The hidden depths of forest soil organic carbon chemistry in a pumice soil

Forest ecosystems can store massive amounts of organic carbon (OC) deep in their soils. Soil OC (SOC) is composed of several complex organic compounds of which groupings of these organic compounds can provide an insight into evaluating the formation and fate of SOC. However, there is little information available regarding the chemical composition of deep forest SOC and how they compare to upper soil depths. The objective of this study was to explore the SOC chemistry changes with increasing soil depth on a fine spatial scale in a planted forest soil derived from young volcanic erupted airfall deposits. Soil core samples to 1 m depth were collected from Puruki Experimental Forest (New Zealand) and examined for incremental depth changes in SOC functional groups, or chemical shift regions, using solid-state 13C cross polarisation magic angle spinning nuclear magnetic resonance (13C CPMAS-NMR) spectroscopy. The results showed that soil depth was a driver of change in soil chemical shift regions. The presence of a coarse-textured soil horizon, lapilli layer, at depth was a driver of significant (p < 0.05) differences between SOC functional groups. In the upper soil profile (0–10 cm), the chemical shift distribution was dominated by O-alkyl C (39%) followed by alkyl C (32%), aromatic C (23%), and carboxyl C (6%). In the deep soil layers, we found alkyl C increased below the lapilli layer (varying depth > 50 cm) compared to above the lapilli layer. In the deep soil layers the alkyl C was the dominant functional group (55%), followed by O-alkyl C (28%). Furthermore, there was a decrease at depth in aromatic (12%) and carboxyl C (5%). The A/O-A ratio increased with depth from soil above the lapilli layer compared to soils below the lapilli layer indicating a greater degree of organic matter decomposition and a corresponding decrease in the labile OC fractions. Within the lapilli layer the SOC functional groups and A/O-A ratio were highly variable. These results highlight that changes in SOC chemical composition occur with increasing soil depth, a property of deep soil that is frequently understudied, and are highly influenced by the multi layered nature of soil derived from volcanic airfall deposits.

Evidence for new fluoride coordination in SiO2-Al2O3-P2O5-CaO/SrO-CaF2 compositions used in ion-leachable ionomer-type cements: A 19F MAS-NMR investigation

Glass ionomer-type glasses are widely utilized in industrial and biomaterial applications due to their unique combination of biocompatibility, strong adhesive properties, and controlled ion release. The structural understanding of fluoride ions in these materials is critical for optimizing their performance and tailoring their properties to specific applications. In this study, we employ solid-state 19F magic-angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy as a powerful tool to investigate the fluoride coordination environments in glass-ionomer-type glasses. A series of strontium-substituted glasses in the system SiO2-Al2O3-P2O5-CaO/SrO-CaF2 were synthesised by the high-temperature melt-quench technique and analysed by 19F MAS-NMR spectroscopy. A previously unknown F coordination environment with Sr was discovered.

Effect of addition of LiAlSiO4 on microstructure, phase composition, and electrical properties of Li1.3Al0.3Ti1.7(PO4)3–based solid electrolyte

Li1.3Al0.3Ti1.7(PO4)3 (LATP) NASICON-type ceramic, due to its high bulk conductivity, is believed to be one of the most appropriate material for application as solid electrolyte in all-solid-state lithium-ion batteries. However, its highly resistant grain boundaries strongly limit the total ionic conductivity. Therefore, in this work, an attempt has been made to overcome this problem by introducing a Li-ion conducting additive LiAlSiO4 (LASO) to LATP base matrix in order to provide more conduction paths for lithium ions between grains. The properties of Li1.3Al0.3Ti1.7(PO4)3–xLiAlSiO4 (0.02 ≤ x ≤ 0.1) composite system were studied by means of: high-temperature X-ray powder diffractometry (HTXRD), 6Li, 27Al, and 31P magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR), scanning electron microscopy (SEM), and impedance spectroscopy (IS) methods. The obtained ceramic LATP–LASO materials exhibited high values of bulk conductivity, above 10−3 S/cm, and good total conductivity, exceeding 10−4 S/cm. The factors responsible for the enhancement, but also for the deterioration of total conductivity, i.e. microstructure and grain boundaries, are identified and discussed in this work.

Colloidal pathways of amorphous calcium carbonate formation lead to distinct water environments and conductivity.

CaCO3 is the most abundant biomineral and a major constituent of incrustations arising from water hardness. Polycarboxylates play key roles in controlling mineralization. Herein, we present an analytical and spectroscopic study of polycarboxylate-stabilized amorphous CaCO3 (ACC) and its formation via a dense liquid precursor phase (DLP). Polycarboxylates facilitate pronounced, kinetic bicarbonate entrapment in the DLP. Since bicarbonate is destabilized in the solid state, DLP dehydration towards solid ACC necessitates the formation of locally calcium deficient sites, thereby inhibiting nucleation. Magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy of poly-aspartate-stabilized ACC reveals the presence of two distinct environments. The first contains immobile calcium and carbonate ions and structural water molecules, undergoing restricted, anisotropic motion. In the second environment, water molecules undergo slow, but isotropic motion. Indeed, conductive atomic force microscopy (C-AFM) reveals that ACC conducts electrical current, strongly suggesting that the mobile environment pervades the bulk of ACC, with dissolved hydroxide ions constituting the charge carriers. We propose that the distinct environments arise from colloidally stabilized interfaces of DLP nanodroplets, consistent with the pre-nucleation cluster (PNC) pathway.

Chemical composition and thermal stability of topsoil organic carbon: Influence of cropping system and tillage practices

AbstractAgricultural management practices play a significant role in regulating the potential for soil organic carbon (SOC) sequestration. The objective of this study was to determine the effects of cropping systems and tillage practices on the chemistry and thermal stability of topsoil SOC in a long‐term field study in Ontario, Canada. The cropping system is based on rotations including corn, alfalfa, cereals, soybeans and a red clover cover crop. Tillage practices of conventional (moldboard plow, CT) and conservation (no‐till, NT) were applied to each cropping system. A 130‐day laboratory incubation was conducted to measure the potentially mineralizable SOC. The thermal stability and molecular structure of SOC were investigated using thermal analysis‐programmed pyrolysis (PP) and solid‐state 13C cross polarization/total sideband suppression magic angle spinning nuclear magnetic resonance (CP/TOSS MAS NMR) spectroscopy, respectively. The SOC stocks were larger under NT practices and the crop rotations incorporating alfalfa and cover crops. Under NT practices, an abundance of aromatic‐C components was observed, however, soil under CT showed an abundance of aliphatic‐C compounds (p &lt; 0.001), with a higher alkyl/O‐alkyl‐C ratio, indicating a higher degree of SOC decomposition. Soil under rotations that included soybeans demonstrated a significant increase in aliphatic‐C components, whereas those with cover cropping exhibited an enrichment in O‐alkyl‐C groups (p &lt; 0.05), representing the presence of more resistant and easily decomposable SOC constituents, respectively. The results demonstrated that the thermal stability of SOC in CT systems was higher than that of NT practices (p &lt; 0.05), while NT practices and crop rotations including cover crops are better capable of conserving the labile pool of SOC. Our findings confirmed the correlations among the parameters that characterize both the labile and stable pools of SOC as determined by the methods employed in this study. These results demonstrated that agricultural management practices significantly influence the chemical composition and thermal stability of soil organic matter (SOM), which can have significant impacts on soil health and C sequestration potential.

Molecular Profiling of Peanut under Raw, Roasting, and Autoclaving Conditions Using High-Resolution Magic Angle Spinning and Solution 1H NMR Spectroscopy.

Higher rates of peanut allergy have been observed in countries that commonly roast peanuts prior to consumption. Despite the importance of understanding the role of thermal processing in allergy and on peanut composition, studies toward generating signatures that identify molecular contents following processing are scant. Here, we identified spectral signatures to track changes and differences in the molecular composition of peanuts under raw, roasted, and high-pressure and high-temperature autoclaved conditions. We analyzed both the solid flesh of the seed and solutions derived from soaking peanuts using High-Resolution Magic Angle Spinning (HR-MAS) and solution 1H Nuclear Magnetic Resonance (NMR) spectroscopy, respectively. The NMR spectra of intact peanuts revealed triglycerides as the dominant species, assigned on the basis of multiplets at 4.1 and 4.3 ppm, and corresponding defatted flours revealed the presence of sugars. Sucrose assigned based on a doublet at 5.4 ppm (anomeric proton), and triglycerides were the most abundant small molecules observed, with little variation between conditions. Soaked peanut solutions were devoid of lipids, and their resulting spectra matched the profiles of defatted peanuts. Spectral signatures resulting from autoclaving differed strikingly between those from raw and roasted peanuts, with considerable line-broadening in regions corresponding to proteins and amino-acid side chains, from 0.5 to 2.0 ppm and 6.5 to 8.5 ppm. Taken together, by using complementary NMR methods to obtain a fingerprint of the molecular components in peanuts, we demonstrated that autoclaving led to a distinct composition, likely resulting from the hydrolytic cleavage of proteins, the most important molecule of the allergic reaction.

Infrared transparent CaO–Ta2O5–Al2O3 glass-ceramics with high microhardness: Crystallization behavior and microstructure development

Infrared (IR) transparent materials with longer optical window and higher mechanical properties are highly demanded in optical communication, IR imaging, sensing and laser optics. Although transparent ceramics have higher mechanical strength, their production is still difficult using conventional sintering techniques. Herein, new IR transparent CaO–Ta2O5–Al2O3 glass-ceramics (TGCs) containing cubic ɑ-CaTa2O6 nanocrystals are reported. They exhibit a broadband transmitting window (0.5–5.5 μm) with high IR transmittance (∼80 %) and high refractive indices (nd = 1.96, n1530 = 1.93). The effects of heat treatment holding time on the structure and properties of TGCs are investigated. A slightly increased proportion of crystalline phase is determined by Rietveld refinement. 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy reveals that partial Al[4] and almost all Al[5] in the precursor glass are converted to Al[6] in the residual glass after crystallization. CaTa2O6 nanocrystals with amorphous shells are present within the nanodroplet domains, and a significant Ta enrichment is clearly observed. A confined crystallization process is proposed to understand the heat treatment time dependent structural characteristics and mechanical properties of the obtained TGCs. Vickers hardness (HV) of 12.01 GPa and Young's modulus (E) of 248.8 GPa are achieved in TGCs, making them promising candidates as high-performance IR materials for optical applications.

Game meat and high-resolution magic angle spinning nuclear magnetic resonance spectroscopy: a traditional foodstuff versus a novel analysis technology

Game meat and high-resolution magic angle spinning nuclear magnetic resonance spectroscopy: a traditional foodstuff versus a novel analysis technology

Conversion of methanol and ethanol into hydrocarbons over zeolites with different pore structure and acid properties

Methanol and ethanol are converted into hydrocarbons over zeolites with different pore structures and acid properties. It is an alternative technology for generating petrochemical feedstocks, particularly ethene and propene. Thus, the search for catalysts with physicochemical properties that maximize activity and selectivity to products of interest in the reaction has increased. In this study, ZSM-5 and MCM-22 zeolites in their acid form (HZSM-5 and HMCM-22), as well as ITQ-2, the delaminated form of MCM-22, were investigated as catalysts for methanol (MeOH) and ethanol (EtOH) conversion. All samples were characterized by X-ray diffractometry (XRD), X-ray fluorescence spectrometry (XRF), 27Al magic angle spinning nuclear magnetic resonance spectrometry (27Al MAS/NMR), N2 physisorption and temperature programmed desorption of ammonia (TPD of NH3). A comparison of the catalytic performance at 500 °C and atmospheric pressure showed that the product distribution and catalyst stability were significantly influenced by the studied alcohol, suggesting that these results reflected the differences in the mechanism for the formation of hydrocarbons.

Unveiling the structure of calcium borate glass by neutron diffraction, MAS-NMR, Raman and first-principles calculations

Calcium borate glass is a challenging system, due to the rich variety of borate units and alterable boron coordination number, and hence they are also of particular interest for academic study. In this study, neutron diffraction, solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR) and Raman spectroscopy were combined with first-principles calculations, experience potential structure refinement (EPSR) simulations to investigate the structure of xCaO·(1-x)11B2O3 glass. Property data such as density and glass transition temperature were also measured to study the impact of structural changes on the properties of glasses. The structure of calcium borate glass was analyzed using various methods including structural unit, atomic pair bond length, coordination number, ring structure, chain structure and cavity distribution. Most notably, the atomic labeling method plays a key role in the structural analysis process. Through this method some new conclusions were obtained. For example, the increase of CaO content mainly leads to the conversion of BO to NBO in the glass structure, and has little effect on the content of BO3 and BØ4-. This result further leads to an increase in Ca-NBO interactions. Interestingly, the bond length distribution of Ca-NBO and B-NBO is shorter than that of Ca-BO and B-BO, so the glass structure becomes denser. The structural reason why the density of calcium borate glass is less than the crystal density was also revealed. This study contributes to unveiling the structure of calcium borate glass and exploring the correlation between the structure and properties of calcium borate glass, which provides a valuable reference for developing more valuable amorphous materials.

Evidence for Mixed Mg Coordination Environments in Silicate Glasses: Results from 25Mg NMR Spectroscopy at 35.2 T.

The Mg-O coordination environment of silicate glasses of composition CaMgSi2O6, Na2MgSi3O8, and K2MgSi5O12 is probed using ultrahigh-field (35.2 T) 25Mg magic angle spinning nuclear magnetic resonance (MAS NMR) and triple-quantum MAS NMR spectroscopy. These spectra clearly reveal the coexistence of 4-fold- (MgIV) and 6-fold- (MgVI) coordinated Mg in all glasses. The MgIV/MgVI ratio implies an average Mg-O coordination number of ∼5 for CaMgSi2O6 glass, bringing NMR results for the first time in good agreement with those reported in previous studies based on diffraction and X-ray absorption spectroscopy, thus resolving a decade-long controversy regarding Mg coordination in alkaline-earth silicate glasses. The Mg-O coordination number decreases to ∼4.5 in the alkali-Mg silicate glasses, indicating that Mg competes effectively with the low field strength alkali cations for the nonbridging oxygen in the structure to attain tetrahedral coordination. This work illustrates the promise of ultrahigh-field NMR spectroscopy in structural studies involving nuclides with low gyromagnetic ratio.

Precise Confinement and Position Distribution of Atomic Cu and Zn in ZSM-5 for CO2 Hydrogenation to Methanol

CuZn-based catalysts are widely used in CO2 hydrogenation, which may effectively convert CO2 to methanol and alleviate CO2 emission issues. The precise design of a model catalyst with a clear atomic structure is crucial in studying the relationship between structure and catalytic activity. In this work, a one-pot strategy was used to synthesize CuZn@ZSM-5 catalysts with approximately two Cu atoms and one Zn atom per unit cell. Atomic Cu and Zn species are confirmed to be located in the [54.6.102] and [62.104] tilings, respectively, by using magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR), synchrotron X-ray powder diffraction (SXRD) and high-signal-to-noise-ratio annular dark field scanning transmission electron microscopy (High SNR ADF-STEM). Catalytic hydrogenation of CO2 to methanol was used as a model reaction to investigate the activity of the catalyst with confined active species. Compared to the Cu@ZSM-5, Zn@ZSM-5 and their mixture, the CuZn@ZSM-5 catalyst with a close Cu–Zn distance of 4.5 Å achieves a comparable methanol space–time yield (STY) of 92.0 mgmethanol·gcatal−1·h−1 at 533 K and 4 MPa with high stability. This method is able to confine one to three metal atoms in the zeolite channel and avoid migration and agglomeration of the atoms during the reaction, which maintains the stability of the catalyst and provides an efficient way for adjustment of the type and number of metal atoms along with the distances between them in zeolites.

Conversion of N-Acetylglucosamine to 3-Acetamido-5-Acetylfuran over Al-Exchanged Montmorillonite.

3-Acetamido-5-acetylfuran (3A5AF) is a potential platform compound for the production of nitrogen-containing pharmaceuticals and chemicals. 3A5AF can be obtained by dehydration of chitin or its monomer, N-acetylglucosamine (NAG). Here, we examined the use of solid catalysts for the dehydration of NAG to 3A5AF to achieve a more economical process that uses a recyclable catalyst. NAG was dehydrated using various solid catalysts in the presence of NaCl and N,N-dimethyl acetamide as solvent at 433 K. The yield of 3A5AF with the solid catalysts decreased in the following order: Al-exchanged montmorillonite>H-ZSM-5 (SiO2 /Al2 O3 =40)>H-montmorillonite (K-10)>Amberlyst15>H-ZSM-5 (SiO2 /Al2 O3 =300)>TiO2 >γ-Al2 O3 >ZrO2 >SiO2 ⋅ MgO>Na-montmorillonite. The highest yield of 3A5AF (14 %) was obtained with the Al-exchanged montmorillonite. The montmorillonite catalysts were characterized by using inductively coupled plasma optical emission spectroscopy, energy-dispersive X-ray spectroscopy, N2 adsorption, Fourier-transformed infrared spectroscopy, X-ray diffraction, and 27 Al magic-angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR). In addition, a combined catalyst of Al-exchanged montmorillonite and Cl- from synthetic hydrotalcite was found to be an active and recyclable solid catalyst for NAG dehydration to 3A5AF.

Ether Bond Formation in Waste Biomass–Derived, Value-Added Technical Hardwood Kraft Lignin Using Glycolic Acid

Ether bond formation in technical hardwood kraft lignin (THKL) by crosslinking using glycolic acid was investigated for bio-adhesive applications. Industrial hardwood kraft black liquor was used to extract the THKL utilized by acidification. Chemical and thermal properties of the THKL with and without crosslinking were analyzed by Fourier transform infrared (FTIR) spectroscopy, solid-state 13C cross-polarization/magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). FTIR results revealed a new peak corresponding to the ether bond and hemiacetal formation due to crosslinking at 1075 cm-1 and 1324 cm-1. 13C CP/MAS NMR spectra revealed the presence of a higher number of ether bonds due to the reduced aromatic and aliphatic hydroxyl groups in THKL and new bonds formed at 62-64 ppm and 168-191 ppm due to crosslinking. XPS results revealed that new bonds were formed between glycolic acid and THKL, leading to increased atomic oxygen percentage and carbon–oxygen bonds in crosslinked THKL detected by peak intensity changes at 287.7 and 288.8 related to O–C–O and O–C=O. Also, the oxygen content increased from 14.88% to 31.76% due to bond formation. GPC confirmed a higher molecular weight and broader molecular-weight distribution of THKL. DSC and TGA curves of crosslinked THKL revealed exothermic behavior, high thermal stability, and low thermal degradation rate. Owing to a significant amount of kraft black liquor being generated by wood pulp industries and attractive chemical properties of THKL, THKL demonstrates promise as a raw material to produce green, sustainable bio-adhesives via the crosslinking of its different hydroxyl groups using glycolic acid.