Phosphorus modification of a HZSM-5 (MFI) zeolite by wet impregnation has long been known to decrease aromatic formation in methanol conversion chemistry. We prepared and studied a catalyst modified by introducing trimethylphosphine under reaction conditions followed by oxidation. Magic-angle spinning (MAS) NMR shows that extensive dealumination occurs, resulting in a catalyst with a much higher framework SiO2/Al2O3 ratio, as well as extraframework aluminum and approximately 1.4 equiv of entrained phosphoric acid (under working conditions) per aluminum. Upon dehydration or regeneration, the phosphoric acid is converted, reversibly, to entrained P4O10. The aromatic selectivity of the modified catalyst is significantly lower than that of an unmodified zeolite with a similar, increased framework SiO2/Al2O3 ratio. By comparing the rates of H/D exchange in propene under conditions similar to those in methanol conversion chemistry, we determined that the acid site strength is indistinguishable on modified and unmodified zeolites, and this is consistent with theoretical modeling. On the phosphorus-modified zeolite, the rate of propene oligomerization is greatly suppressed, suggesting that entrained phosphate is an impediment to sterically demanding reactions.

Framework-bound alkoxy groups are well-studied intermediates in zeolite chemistry, but their low stability complicates their spectroscopic study in high-temperature reactions such as alkylation or dealkylation. Taking advantage of the much higher bond strength of Si-O versus C-O, we synthesized trimethylsilylated zeolites by reacting them with phenyltrimethylsilane in a catalytic flow reactor at 648 K. In favorable cases, the reaction accurately titrated the acid sites, and 29Si and 13C MAS NMR spectra of the derivatized catalysts measured at room temperature confirmed the proposed reaction.

Carbon capture and storage [CCS] is crucial for mitigating CO2 emissions. One of the potential CCS concepts is to compress and store the captured CO2 into deep oceanic sediments as gas hydrates. However, seawater is highly saline [brine], which may impair the formation/dissociation kinetics and storage of CO2 hydrates. Therefore, it is essential to understand the liquid CO2 [LCO2] hydrate formation and dissociation kinetics in static brine systems. In this experimental study, we have examined the formation/dissociation kinetics and morphology of high-pressure LCO2 hydrates in brine using a static [unstirred] high-pressure crystallizer at deep oceanic [1 km] thermodynamic conditions [10 MPa, 1–2 °C]. The results are compared with [unstirred/stirred] freshwater systems with/without hydrate promoters. Three key stages have been identified in the experiments: nucleation [stage 1], LCO2-hydrate-brine film formation [stage 2], and LCO2-hydrate-brine film breakage [stage 3]. In the absence of stirring, the formation of the LCO2-hydrate-brine film resists the mass transfer of LCO2 into the brine, and most likely, the volume expansion during hydrate formation causes the LCO2-hydrate-brine film to break. New hydrate morphological growth patterns have been identified. It was estimated that the hydrate conversion in the freshwater system was higher [27.5% (±3.04%) in 21.1 (±1.26) h] compared to the brine system [25.0% in 24.2 (±0.58) h]. LCO2 hydrates dissociate faster in brine [1.7 (±0.14) h] compared to the freshwater system [5.7 (±1.77) h]. Finally, the presence of the eco-friendly hydrate promoter 500 ppm l-tryptophan can delay the dissociation process.

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As the most successful commercialized thermoplastic vulcanizates (TPVs), polypropylene (PP)/ethylene propylene rubber (EPDM) TPVs exhibit poor oil resistance. In this work, we prepared PP/EPDM/butadiene acrylonitrile rubber (NBR) ternary TPVs with good oil resistance using core‐shell dynamic vulcanization. According to the theoretical analysis of the spreading coefficient and the transmission electron microscopy results, the rubber phases exhibited a special core‐shell structure, in which the cross‐linkedNBR‐core was encapsulated by the EPDM‐shell. The core‐shell structure effectively improved the interfacial compatibility between PP and NBR phase as the EPDM‐shell could avoid the direct contact of them, thus improving the mechanical properties of the TPVs. For example, the PP/EPDM/NBR (40/30/30) ternary TPV showed enhanced tensile strength of 12.57 MPa, compared with 10.71 MPa of PP/EPDM (40/60) TPV and 11.11 MPa of PP/NBR (40/60) TPV, respectively. Moreover, the oil resistance of the TPVs was also improved. Compared with PP/EPDM TPV, the change rates in mass, volume, tensile strength and elongation at break of PP/EPDM/NBR TPV after oil immersion decreased by 42.18%, 48.69%, 52.68% and 28.77%, respectively.