Bulk Crystallinity Research Articles

Suppressed Defects by Functional Thermally Cross-Linked Fullerene for High-Efficiency Tin-Lead Perovskite Solar Cells.

Mixed tin-lead (Sn-Pb) perovskites have attracted the attention of the community due to their narrow bandgap, ideal for photovoltaic applications, especially tandem solar cells. However, the oxidation and rapid crystallization of Sn2+ and the interfacial traps hinder their development. Here, cross-linkable [6,6]-phenyl-C61-butyric styryl dendron ester (C-PCBSD) is introduced during the quenching step of perovskite thin film processing to suppress the generation of surface defects at the electron transport layer interface and improve the bulk crystallinity. The C-PCBSD has strong coordination ability with Sn2+ and Pb2+ perovskite precursors, which retards the crystallization process, suppresses the oxidation of Sn2+, and improves the perovskite bulk and surface crystallinity, yielding films with reduced nonradiative recombination and enhanced interface charge extraction. Besides, the C-PCBSD network deposited on the perovskite surface displays superior hydrophobicity and oxygen resistance. Consequently, the devices with C-PCBSD obtain PCEs of up to 23.4% and retained 97% of initial efficiency after 2000h of storage in a N2 atmosphere.

Ternary polymer solar cells using two nonfullerene acceptors with cascading energy level and complementary absorptions

In this paper, we have fabricated ternary PSC with BTP-eC9 as the host acceptor, IT-M as the guest acceptor, and PM6 as donor. The optimized ternary PSC (PM6:BTP-eC9:IT-M ratio is 1:1.2:0.2) has the highest power conversion efficiency (PCE) of 17.06 % compared to the PM6:BTP-eC9 binary PSC (16.46 %) and PM6:L8-BO reference binary PSC (16.92 %). We systematically investigated the effect of blend acceptors on morphology, photovoltaic performance and charge carrier dynamics. After the addition of IT-M to PM6:BTP-eC9 binary film, the highest JSC (from 26.39 to 26.82 mA cm−2) was achieved for optimized ternary PSCs compared to PM6:BTP-eC9 binary PSC, which was attributed to the high efficiency of light absorption in the medium to long-wavelength region of IT-M. Shallower lowest unoccupied molecular orbitals (LUMO) level of IT-M enlarged the optical bandgap, which leads to an increase in the open-circuit voltage (VOC, from 0.86 V to 0.875 V). In addition, a small amount of IT-M improves the surface and bulk morphology and crystallinity of the ternary film. The ternary films shown high charge mobility ability. This work demonstrates that supplementing the light absorption and broadening the optical bandgap of PM6:BTP-eC9 binary films by IT-M as third component can effectively improve the PCE and obtain higher photovoltaic performance than that of PM6:BTP-eC9 binary PSCs and PM6:L8-BO reference binary PSCs.

Effects of gamma(γ)-irradiation on the physicochemical properties and bioavailability of iron oxyhydroxides coprecipitated with varying concentrations of Na-alginate

This study investigated the impacts of γ-radiation at a final dose of 25 kGy on the physicochemical properties of a range of wet iron oxyhydroxides (2-line ferrihydrite, lepidocrocite, and goethite) synthesized in the presence of varying concentrations of the polysaccharide Na-alginate (starting solutions containing C/Fe ratios of 0, 0.5, 1.0, and 1.5). The degree of impact to the minerals was examined by chemical extractions, and various analytical techniques including XRD, FTIR-ATR, Mössbauer spectroscopy, and N2 adsorption-desorption isotherms, as well as by assessing their bioavailability towards the model Fe(III) reducing bacteria Shewanella putrefaciens CN32. Across all the coprecipitates studied, it was found that γ-irradiation led to a substantial dissolution of Fe and the concomitant release of Fe(II) and alginate into solution. Despite this observation, the bulk mineralogy and crystallinity of the studied iron oxyhydroxides, as determined by XRD and FTIR-ATR, did not appear to change. However, analyses via Mössbauer spectroscopy (77 and 5 K) revealed that the crystallinity of the 2-line ferrihydrites increased post-irradiation. Moreover, among the minerals studied, the specific surface area and porosity decreased for only the post-irradiated 2-line ferrihydrite coprecipitates with a C/Fe ratio of 0.5 or 1.0. The bioreduction rates of the studied minerals and their irradiated counterparts did not significantly differ, whereas the extent of bioreduction of post-irradiated 2-line ferrihydrite coprecipitates (C/Fe 0.5, 1.0, and 1.5) exhibited a significant increase of up to 28%. In contrast, the extent of Fe reduction for select post-irradiated lepidocrocite (C/Fe 0.5) and goethite (C/Fe 1.5) coprecipitates was slightly higher than determined for their corresponding native controls. The observed differences in bioavailability between the native and irradiated coprecipitates were attributed to irradiation induced alteration of particle aggregation and coagulation as determined by particle size analyses and visual observations. In summary, the findings suggest that even a low total dose of 25 kGy, γ-radiation can lead to significant physicochemical changes in coprecipitates with relatively low organic matter content. Therefore, future research designed to investigate organic matter-Fe composite systems in natural samples should be cognizant of the potential effects of sterilization through γ-irradiation. These effects could potentially result in inaccurate over- or under- estimations of the bioavailability of Fe or organic matter, as well as the possible adsorption capacity of organic matter-Fe coprecipitates for contaminants.

Unraveling the relationship between the mineralogical characteristics and lithium storage performance of natural graphite anode materials

Anode materials play critical role in cycling life of lithium-ion batteries in practical applications such as electric vehicles (EVs), portable electronic devices, and large-scale power grids. Natural graphite is one of the most successful anodes for commercial lithium-ion batteries due to its high theoretical capacity and low cost and low operating voltage. The mineralogical properties of graphite minerals have an important effect on the electrochemical performance of graphite anode, while their relationship remains ambiguous. In this work, natural graphite samples from four main graphite mining areas in China were selected as the research object, and their mineralogical characteristics were characterized by XRD, SEM, Raman, ICP, SEM, FIB, BET and other test methods. The properties of crystallinity, morphology, surface/phase defects, impurities, and specific surface area of graphite were studied. The results show that the cyclic stability of graphite is mainly affected by bulk defects and crystallinity, and the initial coulombic efficiency is mainly affected by surface defects and specific surface area. Graphite samples with appropriate surface defects, fewer volume defects, appropriate crystallinity, and small specific surface area have better electrochemical performance. It is hoped that this work should guide the manufacture and modification of the natural graphite anodes and promote its wider application in lithium-ion batteries.

Expedient Bayesian prediction of subfossil bone protein content using portable ATR-FTIR data

Rapid and minimally destructive methods for estimating the endogenous organic content of subfossil bone save time, lab consumables, and valuable ancient materials. Fourier transform infrared (FTIR) spectroscopy is an established method to estimate bone protein content, and portable spectroscopes enable field applications. We review the ability of benchtop and portable FTIR indices to predict %N and %collagen from 137 bone specimens drawn from eight taxa. We also explore associations of these indices with the endogenous DNA content estimated for 105 specimens. Bulk bone elemental abundance and crystallinity index data reflect diagenetic alteration of these specimens, which come from a variety of depositional environments in four countries (Madagascar, Greece, Monaco, and Germany). Infrared (IR) indices from benchtop and portable units perform similarly well in predicting observed sample N content and collagen yields. Samples that include little collagen (0–5 wt%) tend to have similar IR index values, and we present a Bayesian approach for the prediction of collagen yields. Bone type best explains variation in target species DNA content (endogenous DNA being particularly abundant in petrosals), but low IR index values were consistently associated with minimal DNA content. We conclude that, although portable FTIR fails to distinguish collagen preservation among poorly preserved samples, a simple approach with minimal sample preparation can effectively screen bone from a variety of taxa, elements, and environments for the extraction of organics.

Grazing-incidence synchrotron radiation diffraction studies on irradiated Ce-doped and pristine Y-stabilized ZrO2 at the Rossendorf beamline.

In this work, Ce-doped yttria-stabilized zirconia (YSZ) and pure YSZ phases were subjected to irradiation with 14 MeV Au ions. Irradiation studies were performed to simulate long-term structural and microstructural damage due to self-irradiation in YSZ phases hosting alpha-active radioactive species. It was found that both the Ce-doped YSZ and the YSZ phases had a reasonable tolerance to irradiation at high ion fluences and the bulk crystallinity was well preserved. Nevertheless, local microstrain increased in all compounds under study after irradiation, with the Ce-doped phases being less affected than pure YSZ. Doping with cerium ions increased the microstructural stability of YSZ phases through a possible reduction in the mobility of oxygen atoms, which limits the formation of structural defects. Doping of YSZ with tetravalent actinide elements is expected to have a similar effect. Thus, YSZ phases are promising for the safe long-term storage of radioactive elements. Using synchrotron radiation diffraction, measurements of the thin irradiated layers of the Ce-YSZ and YSZ samples were performed in grazing incidence (GI) mode. A corresponding module for measurements in GI mode was developed at the Rossendorf Beamline and relevant technical details for sample alignment and data collection are also presented.

Evaluation of microscale crystallinity modification induced by laser writing on Mn3O4 thin films

Defining microstructures and managing local crystallinity allow the implementation of several functionalities in thin film technology. The use of ultrashort Bessel beams for bulk crystallinity modification has garnered considerable attention as a versatile technique for semiconductor materials, dielectrics, or metal oxide substrates. The aim of this work is the quantitative evaluation of the crystalline changes induced by ultrafast laser micromachining on manganese oxide thin films using micro-Raman spectroscopy. Pulsed Bessel beams featured by a 1 μm-sized central core are used to define structures with high spatial precision. The dispersion relation of Mn3O4 optical phonons is determined by considering the conjunction between X-ray diffraction characterization and the phonon localization model. The asymmetries in Raman spectra indicate phonon localization and enable a quantitative tool to determine the crystallite size at micrometer resolution. The results indicate that laser-writing is effective in modifying the low-crystallinity films locally, increasing crystallite sizes from ∼8 nm up to 12 nm, and thus highlighting an interesting approach to evaluate laser-induced structural modifications on metal oxide thin films.

Modification of Bulk Density, Flow Property and Crystallinity of Microcrystalline Cellulose Prepared from Waste Cotton.

The most affordable type of tablet is the immediately compressible tablet, which uses microcrystalline cellulose (MCC), a popular pharmaceutical excipient, as a filler or binder. To make it compatible with different active drugs and excipients, we tried to change some physical properties of the MCC. In the current study, we used a chelating agent to pretreat the waste cotton before pulping, bleaching, and finally, hydrochloric acid degradation with a concentration of 2N at 100 °C temperature for 20 min to prepare MCC. The prepared MCC was treated with different concentrations of sodium hydroxide at room temperature or at -20 °C followed by precipitation with hydrochloric acid or ethanol with complete washing with distilled water till neutralization. Evaluation of the degree of polymerization (DP) and FT-IR spectrum confirm the identity of the microcrystalline cellulose. The DP was found to be 216. The bulk density of the unmodified MCC was 0.21 while that of modified MCC varied from 0.253 to 0.594. The modified MCC powder showed good flow properties compared to the unmodified MCC as evaluated by the Hausner index, Carr's index and the angle of repose. The scanning electron microscopy (SEM) of the MCC revealed that the rod shape has been changed to an oval shape due to treatment with sodium hydroxide at -20 °C. The X-ray crystallographic (XRD) analysis indicated that the unmodified MCC and standard MCC showed the crystallinity index (CrI) value of 86.82% and 87.63%, respectively, while the value ranges from 80.18% to 60.7% among the modified MCC powder. The differences in properties of the MCC might be due to the variation of rearrangement of the cellulose chain among the MCC particles due to treatment with different concentrations of a base at different temperatures and precipitation environments. This has enabled us to prepare MCC with different properties which might be compatible with different drugs.

Characterizing basalt-atmosphere interactions on Venus: A review of thermodynamic and experimental results

Abstract The surface of Venus is in contact with a hot (~470 °C), high pressure (92 bars), and caustic (CO2 with S, but little H2O) atmosphere, which should cause progressive alteration of the crust in the form of sulfate and iron-oxide coatings; however, the exact rate of alteration and mineral species are not well constrained. Different experimental approaches, each with its own limitations, are currently being used to constrain mineralogy and alteration rates. One note is that no experimental approach has been able to fully replicate the necessary conditions and sustain them for a significant length of time. Furthermore, geochemical modeling studies can also constrain surface alteration mineralogy, again with different assumptions and limitations. Here, we review recent geochemical modeling and experimental studies to constrain the state of the art for alteration mineralogy, rate of alteration, open questions about the surface mineralogy of Venus, and what can be constrained before the fleet of missions arrives later this decade. Combining the new results confirms that basalt on the surface of Venus should react quickly and form coatings of sulfates and iron-oxides; however, the mineralogy and rate of alteration are dependent on physical properties of the protolith (including bulk composition, mineralogy, and crystallinity), as well as atmospheric composition, and surface temperature. Importantly, the geochemical modeling results show that the mineralogy is largely controlled by atmospheric oxygen fugacity, which is not well constrained for the near-surface environment on Venus. Therefore, alteration experiments run over a range of oxygen and sulfur fugacities are needed across a wide range of Venus analog materials with varying mineralogy and crystallinity.

Quantification of Polymer Surface Degradation Using Fluorescence Spectroscopy.

One solution to minimizing plastic pollution is to improve reuse and recycling strategies. Recycling, however, is limited by the overall degradation of plastics being used, and current techniques for monitoring this plastic degradation fail to observe this in its early stages, which is key for optimizing reusability. This research seeks to develop an inexpensive, reproducible, and nondestructive technique for monitoring degradation of polyethylene (PE) and polypropylene (PP) materials using Nile red as a fluorescent probe. Changes in Nile red's fluorescence spectra were observed upon exposure to stained, aged PE and PP samples. As the surface hydrophobicity of the plastic decreases, Nile red's fluorescence signal undergoes a corresponding signal shift to longer wavelengths (lower energy). The trends seen in the fluorescent profile were related to more commonly used measurements of plastic degradation, namely, the carbonyl index from infrared spectroscopy and bulk crystallinity from calorimetry. Results demonstrate clear trends in fluorescence spectra shifts as related to the chemical and physical changes to the plastics, with trends dependent on the polymer type but independent of polymer film thickness. The strength of this technique is divided into two defined fits of the fluorescence signal; one fit characterizes the degradation throughout the whole range of degradative oxidation and the other is tailored to provide insight into the early stages of degradation. Overall, this work establishes a characterization tool that assesses the extent of plastics' degradation, which may ultimately impact our ability to recover plastics and minimize plastic waste.

Improving graphenic quality by oxidative liberation of crosslinks in non-graphitizable carbons

This work assesses the potential for improving the crystallinity of non-graphitizable carbon materials by oxidative liberation of crosslinks. A model non-graphitizable carbon – sucrose char and two commercial carbon blacks of varied nanostructure have been used to study crystallinity improvements at two oxidative burnout levels. The virgin materials have been compared to their partially oxidized counterparts at a series of heat treatment temperatures using X-ray diffraction for bulk crystallinity analysis and high-resolution transmission electron microscopy for nanostructural characterization. Remarkable improvements were observed in the case of sucrose char where non-graphitizable sponge-like particles transformed into highly ordered graphenic flakes by the mechanism of oxidative liberation of crosslinks. The in-plane crystallite size and stacking height tripled after the liberation of the restrictive crosslinks. Molecular level changes after partial oxidation have been assessed using Raman spectroscopy while X-ray photoelectron spectroscopy is used to assess changes in elemental composition. Notable improvements were also observed in carbon blacks with the development of longer and lower tortuosity lamellae accompanied by expanded particle sizes. Fringe analysis algorithms have been applied to obtain lamellae statistics and highlight nuances in the nanostructure changes after partial oxidation and heat treatment.

Influence of Hydrogen on Vintage Polyethylene Pipes: Slow Crack Growth Performance and Material Properties

The distribution of hydrogen and how this can be widely achieved plays a significant role in the transition from fossil fuels to clean fuel. Using the existing natural gas pipeline network can be a suitable option for countries with extensive pipeline infrastructure. This study is aimed at investigating the compatibility of the existing polyethylene (PE) distribution pipe network with hydrogen. This paper utilises the cyclic pennsylvania edge notch test (CPENT) method together with material property measurements including melting point, crystallinity, and oxidative induction time (OIT) to understand the impact of exposing two different PE pipe resins to hydrogen at different exposure times. It was found that exposure to hydrogen has a noticeable impact time to failure, while the bulk crystallinity, OIT, and melting point showed little change. A change in crystal orientation was observed, and this likely accounts for the difference in time to failure when exposed to hydrogen.

Effect of Polydopamine Coating of Cellulose Nanocrystals on Performance of PCL/PLA Bio-Nanocomposites.

In bio-nanocomposites with a poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) matrix with neat and polydopamine (PDA)-coated cellulose nanocrystals (CNCd), the use of different mixing protocols with masterbatches prepared by solution casting led to marked variation of localization, as well as reinforcing and structure-directing effects, of cellulose nanocrystals (CNC). The most balanced mechanical properties were found with an 80/20 PLA/PCL ratio, and complex PCL/CNC structures were formed. In the nanocomposites with a bicontinuous structure (60/40 and 40/60 PLA/PCL ratios), pre-blending the CNC and CNCd/PLA caused a marked increase in the continuity of mechanically stronger PLA and an improvement in related parameters of the system. On the other hand, improved continuity of the PCL phase when using a PCL masterbatch may lead to the reduction in or elimination of reinforcing effects. The PDA coating of CNC significantly changed its behavior. In particular, a higher affinity to PCL and ordering of PLA led to dissimilar structures and interface transformations, while also having antagonistic effects on mechanical properties. The negligible differences in bulk crystallinity indicate that alteration of mechanical properties may have originated from differences in crystallinity at the interface, also influenced by presence of CNC in this area. The complex effect of CNC on bio-nanocomposites, including the potential of PDA coating to increase thermal stability, is worthy of further study.

Probing shock-induced structural changes in GaSb.

Laser-driven hypervelocity impact experiments were used to study pressure-induced long-term effects on the crystal structure of undoped GaSb. X-ray diffraction and confocal micro-Raman spectra were collected on unshocked and shock-compressed samples, with corresponding pressures ranging between 8 and 23 GPa. GaSb retained bulk crystallinity at 8 GPa but showed localized site disordering, transformed into an amorphous state at 13 GPa, and stayed in that phase until 23 GPa.

Influencing the Crystalline Domains of Poly(vinylidenedifluoride) Composites Using Fluorinated Silica Nanoparticles as Drop-In Modifiers

Improvements to fluoropolymer processing techniques by way of utilizing nanoparticles as drop-in processing aids have pronounced effects on bulk composite properties. In this work, we prepared fluoroalkyl-silanized silica nanoparticles (F-SiNPs, ca. 200 nm) that were solvent-blended with polyvinylenedifluoride (PVDF) in order to prepare composites with varying weight fractions. We demonstrated that the ability to functionalize SiNPs with long fluoroalkylchains that induced co-crystallization with the PVDF matrix, resulting in uniform particle dispersion and improved interlaminate adhesion. This was quantitatively investigated using calorimetry and thermogravimetric analysis, which showed a decrease in the bulk crystallinity of the virgin PVDF from 37% to 10% with minimal 10 wt % F-SiNP loading, rendering a nearly amorphous PVDF. Additional discussions in this work include the effects of various bare and fluoroalkyl-functionalized SiNP loadings on the amorphous and crystalline domains of the PVDF matrix, as well as thermal decomposition.

Catalytic hydrogenation of CO2 to light olefins by using K-doped FeCx catalysts derived from the Fe-chitosan complex

K-doped FeCx catalysts derived from the carbothermal reduction of the Fe-chitosan complex were investigated and tested in the hydrogenation of CO2 to light olefins (C2-6=). Catalyst characterization, including bulk composition, porosity, crystallinity, Fe coordination, morphology, surface property, and basicity, was conducted. The physicochemical properties of tested catalysts were correlated with their performances. The mechanistic study discovered that bidentate carbonates, monodentate carbonate, bicarbonate, and formate species were intermediates involved in C2-6= synthesis. The yield of C2-6= was found to be dependent on the composition of the carbide phases of K-doped FeCx catalysts. The most active catalyst, i.e., FeK@CS-(0.5)-py, showed the most promising space-time yield of C2-6= (13.7 μmolC2-6=/gFe/s).

Photo-Oxidative Degradation and Hydrolytic Degradation of Micro-Graphite Filled Poly(lactic acid) Composites

In a specific range of electrical conductivity, poly(lactic acid)/PLA has the potential to be developed into environmentally friendly antistatic packaging after a modification process. PLA was blended in a mini single screw extruder at 180oC with different compositions of micro-graphite (0, 0.5, 1, and 1.5 %wt.). This report discusses the degradability of PLA composite, i.e., photo-oxidative degradation and hydrolytic degradation. The weight loss, thermal properties, and cross-section morphology of the tested specimens were monitored periodically. During the degradation test, micro-graphite could be released from the composite, leaving a rough surface and reducing the weight of the composite. Differential scanning calorimetry (DSC) test exhibited that the presence of micro-graphite did not influence the melting temperature of the composition studied. However, the onset temperature of the melting point showed a slight shift of about 2-4oC. Bulk crystallinity demonstrated a considerable dependence on the micro-graphite loading (0-1.5%wt). However, there were two contradictory phenomena after both degradation tests. UV exposure could stimulate the fragmentation of PLA chains, break the crystal structure and increase the embrittlement. Thus, crystallinity tended to decrease during photo-oxidative degradation. In hydrolytic degradation, degradation firstly occurred in the amorphous regions and was ongoing within the studied range of time (0-20 weeks). Thus, the bulk crystallinity of composite tended to increase.

Machine Learning Guided Synthesis of Flash Graphene.

Advances in nanoscience have enabled the synthesis of nanomaterials, such as graphene, from low-value or waste materials through flash Joule heating. Though this capability is promising, the complex and entangled variables that govern nanocrystal formation in the Joule heating process remain poorly understood. In this work, machine learning (ML) models are constructed to explore the factors that drive the transformation of amorphous carbon into graphene nanocrystals during flash Joule heating. An XGBoost regression model of crystallinity achieves an r2 score of 0.8051 ± 0.054. Feature importance assays and decision trees extracted from these models reveal key considerations in the selection of starting materials and the role of stochastic current fluctuations in flash Joule heating synthesis. Furthermore, partial dependence analyses demonstrate the importance of charge and current density as predictors of crystallinity, implying a progression from reaction-limited to diffusion-limited kinetics as flash Joule heating parameters change. Finally, a practical application of the ML models is shown by using Bayesian meta-learning algorithms to automatically improve bulk crystallinity over many Joule heating reactions. These results illustrate the power of ML as a tool to analyze complex nanomanufacturing processes and enable the synthesis of 2D crystals with desirable properties by flash Joule heating.

Epoxidation catalysts prepared by encapsulation of molybdenum hexacarbonyl in UiO-66(Zr/Hf)-type metal-organic frameworks

The confinement and catalytic behavior of Mo(CO)6 species inside UiO-66 (zirconium and hafnium) metal-organic frameworks (MOFs) have been investigated by means of multitechnique characterization and catalytic olefin epoxidation. Mo(CO)6 was encapsulated in nanocrystalline MOFs by solvothermal and vapor phase impregnation methods (STI and VPI, respectively), resulting in Mo loadings of 2.0–8.8 wt% (STI) or 15 wt% (VPI). Powder X-ray diffraction, SEM-EDS, N2 adsorption, FT-IR and 13C{1H} CP MAS NMR collectively confirmed immobilization within the pore spaces of the hosts, which maintained their bulk crystallinity and crystal morphologies. CO resonances in the 13C{1H} CP MAS NMR spectra were assigned to hexacarbonyl guest molecules located in the larger pore spaces, such as the octahedral cavities (for STI and VPI samples), and in more restricted environments such as the tetrahedral cavities (for the VPI sample). FT-IR spectra displayed the characteristic pattern of νCO stretching modes for an octahedral symmetry molecule slightly perturbed by interaction of one of the carbonyl groups with the MOF support. The spectra evidenced the formation of a weak hydrogen bonding interaction of the type μ3-OH···OCMo(CO)5 involving the μ3-OH groups that are exclusively present in the tetrahedral cavities of the UiO-66 structure. The Mo(CO)6 loaded MOFs are active and reusable pre-catalysts for cis-cyclooctene epoxidation, exhibiting excellent epoxide selectivity (up to quantitative epoxide yield within 1 h reaction) and tert-butyl hydroperoxide efficiency. Catalyst recycling and retention of structural integrity were demonstrated for UiO-66(Hf) loaded with 8.8 wt% Mo by the STI method. The UiO-66(Hf) host may be a better catalyst support than its Zr counterpart due its smaller crystallite size (≈100 nm) and higher defectivity. The substrate scope was broadened for Mo(8.8-STI)/Hf-MOF which promoted the epoxidation of biobased olefins (methyl oleate and dl-limonene) and oxidative dehydrogenation of cyclooctanol to cyclooctanone.

Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite

AbstractFaujasite (FAU) zeolites (with Si/Al ratio of ca. 1.7) undergo mild dealumination at moderate ion exchange conditions (0.01 to 0.6 M of NH4NO3 solutions) resulting in protons circumscribed by sodalite cages becoming accessible for reaction without conspicuous changes to bulk crystallinity. The ratio of protons in sodalite cages (HSOD) to supercages (HSUP) can be systematically manipulated from 0 to ca. 1 by adjusting ammonium concentrations used in ion exchange. The fraction of accessible protons in the sodalite cages is assessed by virtue of infrared spectra for H‐D exchange of deuterated propane based on the band area ratio of OD2620/OD2680 (ODSOD/ODSUP). Protons in sodalite cages (HSOD) show higher rate constants of propane dehydrogenation (kD) and cracking (kC) than protons in supercages (HSUP) plausibly due to confinement effects being more prominent in smaller voids. Rate constants of dehydrogenation and cracking including kD/kC ratios are also augmented as the fraction of accessible protons in the sodalite cages is enhanced. These effects of accessibility and reactivity of protons in sodalite cages hitherto inconspicuous are revealed herein via methods that systematically increase accessibility of cations located in sodalite cages.