Solid-state 31P Nuclear Magnetic Resonance Research Articles

Phosphorus release and realignment in anaerobic digestion of thermal hydrolysis pretreatment sludge – Masking effects from high ammonium

Waste activated sludge (WAS) is a significant phosphorus (P) repository, and there is a growing interest in P recovery from WAS. Typically, the commercial technology for treating WAS involves thermal hydrolysis pretreatment (THP) coupled with anaerobic digestion (AD). However, there is ongoing debate regarding the transformation and distribution of P throughout this process. To address this, a long-term THP-AD process was operated in this study to comprehensively investigate P transformation and distribution. The results revealed that a substantial biodegradation of dissolved organic nitrogen (DON) raised the pH of the digestate to 8.3 during the AD process. This increased pH facilitated the dissolution of Al, leading to a reduction of 6.92 mg/L of NaOH-P. Simultaneously, sulfate reduction contributed to a decrease of 11.04 mg/L of Bipy-P in the solid. However, the reduction of Bipy-P and NaOH-P in the solid did not result in an improved P release to the supernatant. Conversely, a decrease of 23.60 mg/L P in the aqueous phase was observed after anaerobic digestion. The disappeared P was primarily precipitated with Mg and Ca, driven by the increased pH, and it contributed to the increase of HCl-P in the solid from 107.80 to 144.52 mg/L. These findings were further confirmed by results obtained from scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and solid-state 31P nuclear magnetic resonance (NMR) spectroscopy. This study provides valuable insights into the mechanisms of P transformation during THP-AD process that is nearly opposite from conventional AD system.

Arrangement of lipid vesicles and bicelle-like structures formed in the presence of Aβ(25–35) peptide

Our complementary experimental data and molecular dynamics (MD) simulations results reveal the structure of previously observed lipid bicelle-like structures (BLSs) formed in the presence of amyloid-beta peptide Aβ(25–35) below the main phase transition temperature (Tm) of saturated phosphatidylcholine lipids and small unilamellar vesicles (SUVs) above this temperature. First, we show by using solid-state 31P nuclear magnetic resonance (NMR) spectroscopy that our BLSs being in the lipid gel phase demonstrate magnetic alignment along the magnetic field of NMR spectrometer and undergo a transition to SUVs in the lipid fluid phase when heated through the Tm. Secondly, thanks to the BLS alignment we present their lipid structure. Lipids are found located not only in the flat bilayered part but also around its perimeter, which is corroborated by the results of coarse-grained (CG) MD simulations. Finally, peptides appear to mix randomly with lipids in SUVs while assuming predominantly unordered secondary structures revealed by circular dichroism (CD), Raman spectroscopy, and all-atom MD simulations. Importantly, the former is changing little when the system undergoes morphological transitions between BLSs and SUVs. Our structural results then offer a platform for studying and understanding mechanisms of morphological transformations caused by the disruptive effect of amyloid-beta peptides on the lipid bilayer.

31P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium-Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal-Phosphorus Bond Order.

We report the use of solution and solid-state 31P Nuclear Magnetic Resonance (NMR) spectroscopy combined with Density Functional Theory calculations to benchmark the covalency of actinide-phosphorus bonds, thus introducing 31P NMR spectroscopy to the investigation of molecular f-element chemical bond covalency. The 31P NMR data for [Th(PH2)(TrenTIPS)] (1, TrenTIPS = {N(CH2CH2NSiPri3)3}3-), [Th(PH)(TrenTIPS)][Na(12C4)2] (2, 12C4 = 12-crown-4 ether), [{Th(TrenTIPS)}2(μ-PH)] (3), and [{Th(TrenTIPS)}2(μ-P)][Na(12C4)2] (4) demonstrate a chemical shift anisotropy (CSA) ordering of (μ-P)3- > (═PH)2- > (μ-PH)2- > (-PH2)1- and for 4 the largest CSA for any bridging phosphido unit. The B3LYP functional with 50% Hartree-Fock mixing produced spin-orbit δiso values that closely match the experimental data, providing experimentally benchmarked quantification of the nature and extent of covalency in the Th-P linkages in 1-4 via Natural Bond Orbital and Natural Localized Molecular Orbital analyses. Shielding analysis revealed that the 31P δiso values are essentially only due to the nature of the Th-P bonds in 1-4, with largely invariant diamagnetic but variable paramagnetic and spin-orbit shieldings that reflect the Th-P bond multiplicities and s-orbital mediated transmission of spin-orbit effects from Th to P. This study has permitted correlation of Th-P δiso values to Mayer bond orders, revealing qualitative correlations generally, but which should be examined with respect to specific ancillary ligand families rather than generally to be quantitative, reflecting that 31P δiso values are a very sensitive reporter due to phosphorus being a soft donor that responds to the rest of the ligand field much more than stronger, harder donors like nitrogen.

Phosphorus/Sulfur-Enriched Reduced Graphene Oxide Papers Obtained from Recycled Graphite: Solid-State NMR Characterization and Electrochemical Performance for Energy Storage

The reduction of graphene oxide (GO) by means of thermal and/or chemical treatments leads to the production of reduced graphene oxide (rGO)—a material with improved electrical conductivity and considered a viable and low-cost alternative to pure graphene in several applications, including the production of supercapacitor electrodes. In the present work, GO was prepared by the oxidation of graphite recycled from spent Li-ion batteries using mixtures of sulfuric and phosphoric acids (with different H2SO4/H3PO4 ratios), leading to the production of materials with significant S and P contents. These materials were then thermally reduced, resulting in rGO papers that were investigated by solid-state 13C and 31P nuclear magnetic resonance, along with other methods. The electrochemical properties of the produced rGO papers were evaluated, including the recording of cyclic voltammetry and galvanostatic charge–discharge curves, besides electrochemical impedance spectroscopy analyses. The samples obtained by thermal reduction at 150 °C exhibited good rate capability at high current density and high capacitance retention after a large number of charge–discharge cycles. The results evidenced a strong relationship between the electrochemical properties of the produced materials and their chemical and structural features, especially for the samples containing both S and P elements. The methods described in this work represent, then, a facile and low-cost alternative for the production of rGO papers using graphite recycled from spent batteries, with promising applications as supercapacitor electrodes.

Effects of different chemical agents on changes in sediment phosphorus composition and the response of sediment microbial community

Controlling the release of sediment phosphorus (P) using chemical agents is a promising method for controlling internal P in eutrophic lakes. However, mineral P formation and changes in the organic P composition after sediment amendment with P-inactivation agents remain poorly understood. Furthermore, little is known about the changes in the sediment microbial community composition after remediation. Here, various ratios of poly aluminum chloride (PAC) and lanthanum-modified bentonite (LMB) were added to nutrient-rich sediments and incubated. Sequential P extraction, solution/solid-state 31P nuclear magnetic resonance (NMR), and microbial analyses were periodically performed on the inactivated sediments. The results indicate that PAC and LMB effectively reduced sediment iron-bound P and organic P, respectively, markedly increasing the content of aluminum- and calcium-bound P in the sediment, respectively. Solid-state 31P NMR results confirmed the formation of rhabdophane (LaPO4. nH2O) in the LMB-amended sediment. Solution 31P NMR results showed that PAC preferentially reduced the organic P fractions of pyrophosphate, whereas LMB efficiently reduced the organic P fractions of orthophosphate, monoesters, and diesters in the sediment. Compared with the control sediment, PAC addition can cause short-term negative effects on sediment microbes at high doses, whereas LMB addition can increase bacterial diversity or richness in the sediment. These results provide a deeper understanding of the differences between PAC and LMB in internal sediment P control.

Improvement of fungal extraction of phosphorus from sewage sludge ash by Aspergillus niger using sludge filtrate as nutrient substrate

Fungal extraction is a promising approach for reclaiming phosphorus (P) from sewage sludge ash (SSA). However, this approach faces notable technical and economic challenges, including an unknown P speciation evolution and the addition of expensive chemical organic carbon. In this study, the use of an organic-rich effluent produced in sludge dewatering as nutrient source is proposed to initiate the fungal extraction of SSA-borne P with Aspergillus niger. The changes in P speciation in the ash during fungal treatment was analyzed by combined sequential extraction, solid-state 31P nuclear magnetic resonance, and P X-ray absorption near edge spectroscopy. Results showed that after 5 days of fungal treatment using sludge-derived organics, 85 % of P was leached from SSA. Dominantly, this considerable release of P resulted from the dissolution of Ca3(PO4)2, AlPO4, FePO4, and Mg3(PO4)2 in the ash, and their individual contribution rates to P released accounted for 28.0 %, 24.3 %, 20.6 %, and 18.8 %, respectively. After removal of metal cations (e.g., Mg2+, Al3+, Fe3+, and heavy metals) by cation exchange resin (CER), a hydroxyapatite (HAP) product with a purity of > 85 % was harvested from the extract by precipitation with CaCl2. By contrast, without CER purification, a crude product of Ca/Mg-carbonates and phosphates mixture were obtained from this extract. A total of 73.2 wt% of P was ultimately recovered from SSA through integrated fungal extraction, CER purification, and HAP crystallization. These findings provide a mechanistic basis for the development of waste management strategies for improved P reclamation with minimal chemical organics consumption.

Surface reactivity of anatase particles towards phosphated species

This multi-scale and multi-technique work investigates the adsorption of phosphated species on the TiO2 anatase surface. Our original approach declines for the first time the progressive ethyl substitution of phosphates to identify the structure of complexes formed upon adsorption of these molecules on anatase in aqueous dispersions, under various pH conditions. To quantify the adsorbed amount of these molecules on TiO2, adsorption isotherms were recorded as a function of pH. In parallel, zeta potential measurements were performed to screen the evolution of the TiO2 surface charge in the presence of the phosphated compounds. Lastly, surface complexes structure was characterized using spectroscopic methods: solid-state 31P Nuclear Magnetic Resonance, Attenuated Total Reflectance Fourier Transform Infrared, and Diffuse Reflectance Infrared Fourier Transform Spectroscopy in the near infrared spectral range. Upon decreasing pH, the amount of adsorbed species increases, reaching a maximum of 1.5 phosphorus atom per nm2 at pH 2. Monoethyl-phosphate remains adsorbed in similar amounts to orthophosphate, but di- and tri-ethyl substitutions lead to a sharp decrease of adsorption. Spectroscopic analyses reveal the affinity of othophosphate and monoethyl-phosphate for the anatase surface, with formation of bridging or chelating bidentate complexes, more or less protonated according to pH values.

Isosorbide-based cyclomatrix polyphosphazene for high-efficient and selective adsorption of cationic dyes: Experimental and computational studies

A novel bio-based cyclomatrix polyphosphazene microsphere, namely poly(cyclotriphosphazene-co-isosorbide) (HISP), for efficient cationic-dyes adsorption was prepared by solvothermal method using hexachlorocyclotriphosphazene (HCCP) and isosorbide (IS). The chemical structure and morphology of HISP microsphere were characterized by Fourier transform infrared (FTIR), solid-state 31P nuclear magnetic resonance (NMR) spectroscopy, X-Ray photoelectron spectroscopy (XPS), andscanning electron microscope (SEM). The adsorption study towards different organic dyes and their mixtures showed that HISP exhibits an over 850 mg/g adsorption capacity for cationic dyes (e.g., rhodamine B (RhB), methylene blue (MB), and bismarck brown Y (BY)), respectively, and highly selective adsorption ability for MB. Using the adsorption of MB as a model system, the results show that alkaline condition is able to promote the adsorption performance. A high adsorption capacity of 1143.6 mg/g can be obtained towards 200 mg/L MB solution at 25 °C and pH = 10 using 6 mg of HISP. Adsorption kinetics and isotherm studies indicate that the adsorption behavior of HISP can be well described by pseudo-second-order kinetic model and Langmuir isotherm model. Importantly, the adsorption mechanism of HISP was demonstratedto be the electrostatic attractions derived from the numerous electron-rich O atoms in isosorbide, which was clarified by the electrostatic screening experiment and density functional theory (DFT) calculation. This systematic work paves a path to the preparation of highly selective dye adsorbents.

Flame Retardancy of Lightweight Sandwich Composites

This study proposes an innovative solution to flame-retard a sandwich composite made of unsaturated polyester resin, glass fibre skins and polyester nonwoven core material. The strategy uses the core material as flame-retardant carrier, while the resin is also flame-retarded with aluminum trihydroxide (ATH). A screening of the fire-retardant performances of the core materials, covered with different types of phosphorous flame-retardant additives (phosphate, phosphinate, phosphonate), was performed using cone calorimetry. The best candidate was selected and evaluated in the sandwich panel. Great performances were obtained with ammonium polyphosphate (AP422) at 262 g/m2. The core material, when tested alone, did not ignite, and when used in the laminate, improved the fire behaviour by decreasing the peak of heat release rate (pHRR) and the total heat release (THR): the second peak in HRR observed for the references (full glass monolith and sandwich with the untreated core) was suppressed in this case. This improvement is attributed to the interaction occurring between the two FR additives, which leads to the formation of aluminophosphates, as shown using Electron Probe Micro-Analysis (EPMA), X-ray Diffraction (XRD) and solid-state 31P Nuclear Magnetic Resonance (NMR). The influence of the FR add-on on the core, as well as the ATH loading in the matrix, was studied separately to optimize the material performances in terms of smoke and heat release. The best compromise was obtained using AP422 at 182 g/m2 and 160 phr of ATH.

Calcium Affects Polyphosphate and Lipid Accumulation in Mucoromycota Fungi.

Calcium controls important processes in fungal metabolism, such as hyphae growth, cell wall synthesis, and stress tolerance. Recently, it was reported that calcium affects polyphosphate and lipid accumulation in fungi. The purpose of this study was to assess the effect of calcium on the accumulation of lipids and polyphosphate for six oleaginous Mucoromycota fungi grown under different phosphorus/pH conditions. A Duetz microtiter plate system (Duetz MTPS) was used for the cultivation. The compositional profile of the microbial biomass was recorded using Fourier-transform infrared spectroscopy, the high throughput screening extension (FTIR-HTS). Lipid content and fatty acid profiles were determined using gas chromatography (GC). Cellular phosphorus was determined using assay-based UV-Vis spectroscopy, and accumulated phosphates were characterized using solid-state 31P nuclear magnetic resonance spectroscopy. Glucose consumption was estimated by FTIR-attenuated total reflection (FTIR-ATR). Overall, the data indicated that calcium availability enhances polyphosphate accumulation in Mucoromycota fungi, while calcium deficiency increases lipid production, especially under acidic conditions (pH 2–3) caused by the phosphorus limitation. In addition, it was observed that under acidic conditions, calcium deficiency leads to increase in carotenoid production. It can be concluded that calcium availability can be used as an optimization parameter in fungal fermentation processes to enhance the production of lipids or polyphosphates.

An Efficient and Recyclable Sn-Based Phosphotungstic Acid with Tunable Brønsted/Lewis Acidity for Selective Oxidation of Benzyl Alcohol

A series of metal ion (M = Sn2+, Fe3+, Ni2+, Co2+, Ag+, Cu2+) exchanged tungstophosphoric acid (H3PW12O40; TPA) catalysts with tunable Bronsted/Lewis acidity were synthesized and exploited for the oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) using hydrogen peroxide (H2O2) as oxidant. The structure of these M-TPA composite salts was also characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analyses (TGA) and solid-state 31P nuclear magnetic resonance (NMR) probe molecule method. Among these M-TPAs, the Sn1/2H2PW12O40 catalyst, which presented strong Bronsted acidity, the synergistic effect of Bronsted/Lewis and pseudo-liquid characteristic property, exhibited excellent catalytic activity and durability with 98.2% of BzH selectivity and 95.1% of BzH yield. The optimal conditions for the oxidation of BzOH optimized by response surface methodology (RSM) were as follows: n(BzOH)/n(H2O2) = 1:1.25, catalyst amount of 5.5 wt.% to BzOH, water amount of 17 mL, 3.3 h of reaction time, and temperature 393 K. Moreover, further kinetic study confirmed that the reaction order was 2.64 and the activation energy was 21.75 kJ mol-1.

Structure and ionic conductivity of Na3+xSc2SixP3-xO12 (x=0.0, 0.2, 0.4, 0.8) NASICON materials: A combined neutron diffraction, MAS NMR and impedance study

A knowledge of structural parameters that play a role in influencing ionic conduction is the key to the design of improved NASICON materials which have attracted significant attention in recent years as potential solid electrolytes for sodium ion batteries. In this article, we report the results of our study on a series of scandium-based NASICON compounds, namely Na3+xSc2SixP3-xO12 (x= 0.0, 0.2, 0.4, 0.8) that have been prepared by the ceramic route. These materials have been characterized by powder X-ray and neutron diffraction, as well as solid-state 23Na, 45Sc, 31P, and 29Si nuclear magnetic resonance (NMR) spectroscopy at room temperature (RT). The electrical conductivity of the compounds in the temperature range of RT ̶400 °C has been determined by impedance spectroscopy. Rietveld refinement of the diffraction patterns confirms monoclinic C2/c unit cell for the Na3Sc2P3O12 but indicates a rhombohedral R3‾c unit cell for Na3+xSc2SixP3-xO12 compounds. The local environments surrounding sodium, scandium, phosphorus and silicon atoms have been deduced from solid-state NMR. 23Na NMR results gave evidence of Na-ion mobility at RT. AC impedance measurements show that the total conductivity of the sample increases with increasing substitution of P with Si. However, it is much reduced for x = 0.8 composition. Na-ion conductivity of 2.4×10-3 S cm−1 at 30 °C has been measured in Na3.4Sc2Si0·4P2·6O12 compound, which is comparable to the best-performing polycrystalline NASICONs. Parameters such as the area of the bottleneck region, Na–Na hopping distances, and the activation energy for Na-ion conduction have been determined from the structural data. A correlation has been found between the conductivity and the ratio of Na site vacancy to Na site occupancy. Possible reasons for the significant variation of the Na-ion conductivity with x are also discussed in the context of the structure and Na site occupancy.

Polyphosphate Adsorption and Hydrolysis on Aluminum Oxides.

The geochemical behaviors of phosphate-containing species at mineral-water interfaces are of fundamental importance for controlling phosphorus mobility, fate, and bioavailability. This study investigates the sorption and hydrolysis of polyphosphate (a group of important long-chained phosphate molecules) on aluminum oxides in the presence of divalent metal cations (Ca2+, Cu2+, Mg2+, Mn2+, and Zn2+) at pH 6-8. γ-Al2O3 with three particle sizes (5, 35, and 70 nm) was used as an analogue of natural aluminum oxides to investigate the particle size effect. All metal cations enhanced polyphosphate hydrolysis at different levels, with Ca2+ showing the most significant enhancement, and the difference in the enhancement might be due to the intrinsic affinity of metal cations to polyphosphate. In the presence of Ca2+, the hydrolysis rate decreased with increasing mineral particle size. Solid-state 31P nuclear magnetic resonance spectroscopy (NMR)revealed the main surface P species to be amorphous calcium phosphate precipitates, phosphate groups in polyphosphate that formed direct bonds with the mineral surface as inner-sphere complexes, and phosphate groups in polyphosphate that were not directly bonded to the mineral surfaces. Our results reveal the critical roles of mineral-water interface processes and divalent metal cations on controlling polyphosphate speciation and transformationand phosphorus cycling.

Phosphonated mesoporous silica based composite membranes for high temperature proton exchange membrane fuel cells

Mesoporous Santa Barbara Amorphous (SBA-15) was synthesized, and it was grafted with phosphonate functionality using a simple two-step process involving chloromethylation and subsequent phosphonation. The phosphonated SBA-15 (PSBA-15) was characterized using Fourier transform infra-red (FTIR) spectroscopy, solid-state 13C nuclear magnetic resonance (NMR), 29Si NMR, and 31P NMR for confirming successful modification. Morphology features were verified by small angle X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy TEM analyses. Poly(styrene-ethylene-butylene-styrene) (PSEBS) was chosen as the base polymer and phosphonic acid functional groups were grafted onto the polymer using the aforementioned approach, where chloromethyl (-CH2Cl) groups were attached to the main chain using Friedel Craft’s alkylation, followed by the phosphonation of the chloromethylated polymer by the Michaels-Arbuzov reaction resulting in phosphonated PSEBS (PPSEBS). The functionalization was confirmed using NMR and FTIR spectroscopy studies. Composite PPSEBS/PSBA-15 membranes were fabricated with different filler concentrations (2, 4, 6, and 8%) of PSBA-15. Various studies such as water uptake, ion exchange capacity, and the proton conductivity of the composite membranes were undertaken with respect to fuel cell applications. From the studies, it was found that the PPSEBS/PSBA-15 membrane with 6 wt% of filler exhibited maximum proton conductivity of 8.62 mS/cm at 140 °C. Finally, membrane electrode assembly (MEA) was fabricated using PPSEBS/6% PSBA composite membrane, platinium (Pt) anode, and Pt cathode, and was tested in an in-house built fuel cell setup. A maximum power density of 226 mW/cm2 and an open circuit voltage of 0.89 V were achieved at 140 °C under un-humidified condition.

Characterization of phosphorus forms in a Eutrophic Lake, China

In this study, molecular compositions of cyanobacteria, suspended matter, and surface sediments in the Dianchi Lake, a highly eutrophic lake, were investigated by solution and solid-state 31P nuclear magnetic resonance (NMR) spectroscopy. A solution-state 31P NMR spectral analysis of NaOH-EDTA-extracted samples revealed the presence of orthophosphate (ortho-P, 48.5%–91.2% of the total extracted phosphate), orthophosphate monoester (mono-P, 7.3%–43.9%), orthophosphate diester (diester-P, 0.9%–3.9%), and pyrophosphate (pyro-P, 0.7%–5.5%). The organic phosphorus (Po) distribution in suspended matters and cyanobacteria was relatively similar but different from surface sediments. The inorganic phosphorus (Pi) distribution in suspended matters and surface sediments was slightly similar. Results of the solid-state 31P NMR spectral analysis of non-extractable residue showed that cyanobacteria and suspended matter contain a large proportion of Po and poly-P. For surface sediment, only metal-bonded pyro-P and a high proportion of ortho-P were detected. The solid-state 31P NMR spectra results of extracted residual indicated that several of the pyro-P bound to metals and other Pi or Po compounds associated with mineral phases in suspended matter and surface sediment are non-extractable. This result revealed that a high proportion of biogenic phosphorus is bioavailable. These results verify the process of biogenic poly-P regeneration in the Dianchi Lake given that Po, poly-P, and pyro-P are predominant in cyanobacteria and can be released into lake water through chemical and biological degradation, thus further worsening eutrophication.

Quantitative composition–bioactivity relationships of phosphosilicate glasses: Bearings from the phosphorus content and network polymerization

Bioactive phosphosilicate glasses integrate with bone/tooth tissues by forming a bone-mineral mimicking surface layer of calcium hydroxyapatite (HA). The HA formation (“in vitro bioactivity”) in a simulated body fluid (SBF) solution is known to depend both on the P content (nP) and silicate network connectivity (N¯BOSi) of the glass, but the precise bioactivity–composition relationships remain poorly understood. We present a comprehensive study that clarifies the dependence of the in vitro bioactivity on the {nP, N¯BOSi} parameters for Na2O–CaO–SiO2–P2O5 glass powders (2.6–6.0 mol% P2O5) exposed to SBF for 24 h, using infrared (IR) and solid-state 31P nuclear magnetic resonance (NMR) spectroscopy in conjunction with measured Ca and P concentrations in the solution. IR-derived relative apatite amounts reveal that an increase in the P content of the pristine glass promotes apatite formation by gradually reducing its dependence on the silicate network polymerization: increasing nP widens the N¯BOSi range that provides a high and nearly constant amount of HA, which scales roughly linearly with nP; these properties assist future design of P-rich bioactive glasses. All glasses provide significant HA formation for increasing N¯BOSi values up to ≈2.6, above which the in vitro bioactivity is lost due to insufficient glass dissolution. We also discuss the complex dependence of the SBF-testing outcome on the mass concentration and composition of the glass powder, as well as on its particle sizes, highlighting critical concerns that may guide developments of improved in vitro bioactivity-testing protocols. A strong dependence of the HA formation on the particle sizes is observed for glass powders with low P2O5 content (2.6 mol%), as opposed to their P-richer counterparts that reveal no pronounced particle-size effects.

Solid-State 31P Nuclear Magnetic Resonance Study of Interlayer Hydroxide Surfaces of Kaolinite Probed with an Interlayer Triethylphosphine Oxide Monolayer.

The solid acidity of the interlayer aluminolsurfaces of kaolinite was explored by solid-state31P nuclear magnetic resonance with magic angle spinning (MAS) using triethylphosphine oxide (TEPO), which formed a monolayer with a uniform orientation between the layers of kaolinite as a probe molecule. Intercalation of TEPO between the layers of kaolinite was achieved using methoxy-modified kaolinite as an intermediate. The presence of TEPO in the reaction products was revealed by the two signals at 21 and 7 ppm, which were assignable to ethyl groups in TEPO, in the solid-state 13C nuclear magnetic resonance with cross polarization and magic angle spinning techniques (13C CP/MAS NMR). The presence of TEPO between the layers of kaolinite was demonstrated by the expansion of basal spacing from 0.86 nm, the interlayer distance of methoxy-modified kaolinite to 1.16 nm, as shown by the X-ray diffraction patterns, suggesting the formation of a TEPO monolayer between the layers of kaolinite. The formation of hydrogen bonds between the P═O groups of TEPO and the aluminol groups on the interlayer surfaces of kaolinite was also revealed by the appearance of an additional OH stretching band at 3598 cm-1 in the Fourier-transform infrared spectrum and narrow solid-state 31P MAS NMR signals observed at 55-53 ppm which were shifted from the position of the physisorbed TEPO (50 ppm). These results clearly indicate that the solid acidity of interlayer aluminol groups of methoxy-modified kaolinite was probed using an interacted TEPO monolayer.

Transformation of Phosphorus in Speciation and Bioavailability During Converting Poultry Litter to Biochar

Converting poultry litter (PL) to biochar and applying the biochar to cropland as a soil amendment may be a best approach for recovering nutrients from solid biowastes while minimizing the nutrient runoff losses from the treated field. To evaluate the potential of PL-derived biochar as a slow-release phosphorus (P) fertilizer, the speciation, mobilitylability, and bioavailability of P in PL and the derived biochars were examined and compared. Raw PL and its derived biochars through 300–600°C slow pyrolysis were analyzed for total P (TP), inorganic P (IP), and organic P (OP) contents. The TP was fractionated into readily, generally, moderately, low, and non-labile pools by sequential extraction with different solutions. The TP was further assessed for bioavailability using batch extraction by water, Olsen, Bray-1, Mehlich-3, and 1 M HCl extractants. The P species in biochars were characterized using solid-state 31P nuclear magnetic resonance (NMR) techniques. The results indicate that during pyrolysis OP in PL was transformed to IP and water-soluble P to low labile forms such as hydroxyapatite and oxyapatite especially during pyrolysis, initially to polyphosphate-P and subsequently to orthophosphate-P at higher temperature. Orthophosphate-P was the predominant form in biochar, with products from higher pyrolysis temperature demonstrating reduced labile P pools yet enlarged low to non-labile fractions. Bray-1 and Mehlich-3 were appropriate extractants for evaluating the immediate to medium-term available and the long-term available P in biochar, respectively. Converting PL to biochar through 450°C pyrolysis significantly reduced the water-soluble proportion and the lability of P but did not compromise the long-term P bioavailability, resulting in a P-enriched, slow release soil amendment that would minimize the P runoff risks following field application. The promising results need to be further validated in soil-biochar-plant systems.

Phosphorus speciation in sewage sludge and the sludge-derived biochar by a combination of experimental methods and theoretical simulation

Sewage sludge is an inevitable byproduct from municipal wastewater treatment processes and conversion of sewage sludge into high value-added biochar is an effective strategy for resource utilization of sewage sludge. The characterization on P speciation is important to control the practical applications and environmental behavior of the sewage sludge and its derived biochar. The mobility and bioavailability of P is closely related to its speciation, but knowledge gap in P speciation is still existed which needs to be narrowed by a systematic study including existing experimental methods and techniques as well as theoretical prediction. To achieve a comprehensive understanding of P speciation, this study conducted a series of research combining conventional fractionation of P with consideration of major concomitant elements (Al, Ca, Fe), advanced analytical techniques (solution and solid-state 31P nuclear magnetic resonance (NMR), X-ray diffraction (XRD)), and theoretical simulation with respect to solubility of major elements in different acid-base extractants. Results showed that Ca and Fe were dominantly extracted by HCl whereas P and Al were both NaOH- and HCl-soluble. Inorganic orthophosphates were detected as predominant molecular configurations of P from solution 31P NMR spectra, while the existence of calcium and aluminum orthophosphates was revealed by solid-state 31P NMR. Moreover, the poor-crystalline AlPO4 mineral was further evidenced by XRD patterns of the sewage sludge and biochar. Finally, a theoretical simulation of P-containing minerals was performed on the basis of results above, which suggested the existence of variscite/berlinite and amorphous Ca3(PO4)2 in the sludge and biochar. This study does not only explore the P speciation in the sewage sludge and its derived biochar, but also provides a methodology for further research on P speciation. Through the intensive study on the environmental behavior of P, this work might further contribute to the fundamental knowledge basis for the recycle of P during integrate waste management.

Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes

The importance of exploring new solid electrolytes for all-solid-state batteries has led to significant interest in NASICON-type materials. Here, the Sc3+-substituted NASICON compositions Na3ScxZr2–x(SiO4)2–x(PO4)1+x (termed N3) and Na2ScyZr2–y(SiO4)1–y(PO4)2+y (termed N2) (x, y = 0–1) are studied as model Na+-ion conducting electrolytes for solid-state batteries. The influence of Sc3+ substitution on the crystal structures and local atomic environments has been characterized by powder X-ray diffraction (XRD) and neutron powder diffraction (NPD), as well as solid-state 23Na, 31P, and 29Si nuclear magnetic resonance (NMR) spectroscopy. A phase transition between 295 and 473 K from monoclinic C2/c to rhombohedral R3̅c is observed for the N3 compositions, while N2 compositions crystallize in a rhombohedral R3̅c unit cell in this temperature range. Alternating current (AC) impedance spectroscopy, molecular dynamics (MD), and high temperature 23Na NMR studies are in good agreement, showing that, with a higher Sc3+ concentration, the ionic conductivity (of about 10–4 S/cm at 473 K) decreases and the activation energy for ion diffusion increases. 23Na NMR experiments indicate that the nature of the Na+-ion motion is two-dimensional on the local atomic scale of NMR although the long-range diffusion pathways are three-dimensional. In addition, a combination of MD, bond valence, maximum entropy/Rietveld, and van Hove correlation methods has been used to reveal that the Na+-ion diffusion in these NASICON materials is three-dimensional and that there is a continuous exchange of sodium ions between Na(1) and Na(2) sites.