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Streams of intergalactic gas enriched by previous star formation were observed spiraling toward a massive galaxy. 

1,3-Pentadiene (piperylene) is an important monomer in the manufacturing of adhesives, plastics, and resins. It can be derived from biomass by the tandem ring-opening and dehydration (dehydra-decyclization) of 2-methyltetrahydrofuran (2-MTHF), but competing reaction pathways and the formation of another isomer (1,4-pentadiene) have limited piperylene yields to <60%. In this report, using detailed kinetic measurements of 2-MTHF dehydra-decyclization on zeolites with disparate acidities (boro-, and alumino-silicates) and micropore environments (MFI, MWW, and BEA), weakly acidic borosilicates were shown to exhibit ca. 10–30% higher selectivity to dienes at about five-to-sixty times lower proton-normalized rates than aluminosilicates (453–573 K). Dehydra-decyclization site time yields (STYs) were invariant for aluminosilicates within the investigated frameworks, indicating the absence of pore-confinement influence. However, individual site-normalized reaction rates varied by almost an order of magnitude on borosilicates in the order MWW > MFI > BEA at a given temperature (523 K), indicating the non-identical nature of active sites in these weak solid acids. The diene distribution remained far from equilibrium and was tuned towards the desirable conjugated diene (1,3-pentadiene) by facile isomerization of 1,4-pentadiene. This tuning capability was facilitated by high bed residence times, as well as the smaller micropore sizes among the zeolite frameworks considered. The suppression of competing pathways, and promotion of 1,4-pentadiene isomerization events lead to a hitherto unreported ∼86% 1,3-pentadiene yield and an overall ∼89% combined linear C5 dienes’ yield at near quantitative (∼98%) 2-MTHF conversion on the borosilicate B-MWW, without a significant reduction in diene selectivities for at least 80 hours time-on-stream under low space velocity (0.85 g reactant per g cat. per h) and high temperature (658 K) conditions. Finally, starting with iso-conversion levels ( ca. 21–26%) and using total turnover numbers (TONs) accrued over the entire catalyst lifetime as the stability criterion, borosilicates were demonstrated to be significantly more stable than aluminosilicates under reaction conditions (∼3–6× higher TONs). 

ABSTRACT We study the evolutionary trend of the total density profile of early-type galaxies (ETGs) in IllustrisTNG. To this end, we trace ETGs from z = 0 to 4 and measure the power-law slope γ′ of the total density profile for their main progenitors. We find that their slopes γ′ steepen on average during z ∼ 4–2, then becoming shallower until z = 1, after which they remain almost constant, aside from a residual trend of becoming shallower towards z = 0. We also compare to a statistical sample of ETGs at different redshifts, selected based on their luminosity profiles and stellar masses. Due to different selection effects, the average slopes of the statistical samples follow a modified evolutionary trend. They monotonically decrease since z = 3, and after z ≈ 1, they remain nearly invariant with a mild increase towards z = 0. These evolutionary trends are mass dependent for both samples, with low-mass galaxies having in general steeper slopes than their more massive counterparts. Galaxies that transitioned to ETGs more recently have steeper mean slopes as they tend to be smaller and more compact at any given redshift. By analysing the impact of mergers and AGN feedback on the progenitors’ evolution, we conjecture a multiphase path leading to isothermality in ETGs: dissipation associated with rapid wet mergers tends to steepen γ′ from z = 4 to 2, whereas subsequent AGN feedback (especially in the kinetic mode) makes γ′ shallower again from z = 2 to 1. Afterwards, passive evolution from z = 1 to 0, mainly through gas-poor mergers, mildly decreases γ′ and maintains the overall mass distribution close to isothermal. 

ABSTRACT We explore the isothermal total density profiles of early-type galaxies (ETGs) in the IllustrisTNG simulation. For the selected 559 ETGs at z = 0 with stellar masses $10^{10.7}\, \mathrm{M}_{\odot } \leqslant M_{\ast } \leqslant 10^{11.9}\, \mathrm{M}_{\odot }$, the total power-law slope has a mean of 〈γ′〉 = 2.011 ± 0.007 and a scatter of $\sigma _{\gamma ^{\prime }} = 0.171$ over the radial range 0.4–4 times the stellar half-mass radius. Several correlations between γ′ and galactic properties including stellar mass, effective radius, stellar surface density, central velocity dispersion, central dark matter fraction, and in situ-formed stellar mass ratio are compared to observations and other simulations, revealing that IllustrisTNG reproduces many correlation trends, and in particular, γ′ is almost constant with redshift below z = 2. Through analysing IllustrisTNG model variations, we show that black hole kinetic winds are crucial to lowering γ′ and matching observed galaxy correlations. The effects of stellar winds on γ′ are subdominant compared to active galactic nucleus (AGN) feedback, and differ due to the presence of AGN feedback from previous works. The density profiles of the ETG dark matter haloes are well described by steeper than NFW profiles, and they are steeper in the full physics (FP) run than their counterparts in the dark matter-only (DMO) run. Their inner density slopes anticorrelate (remain constant) with the halo mass in the FP (DMO) run, and anticorrelate with the halo concentration parameter c200 in both the types of runs. The dark matter haloes of low-mass ETGs are contracted whereas high-mass ETGs are expanded, suggesting that variations in the total density profile occur through the different halo responses to baryons. 

Commonly used methods to assess crystallinity, micro‐/mesoporosity, Brønsted acid site density and distribution (in micro‐ vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two‐dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro‐ and mesoporosity, and micropore reaction rates.

 

Commonly used methods to assess crystallinity, micro‐/mesoporosity, Brønsted acid site density and distribution (in micro‐ vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two‐dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro‐ and mesoporosity, and micropore reaction rates.

 

Micro/meso/macroporous (hierarchical) zeolites show remarkable catalytic performance for reactions involving bulky reactants. However, quantitative assessment of the microstructural characteristics contributing to the observed performance remains elusive. Here, structure–activity relationships are established for a set of micro/mesoporous self‐pillared pentasil (SPP) zeolites using two parallel liquid‐phase reactions (benzyl alcohol alkylation and self‐etherification) based on analysis of mass transport and reaction kinetics. A reaction–diffusion mathematical model is developed that quantitatively assigns the catalytic contributions of the external surface and micropores of SPP zeolites for these reactions. In addition, the effect of the zeolite external surface structure on the corresponding catalytic activity is quantitatively assessed by comparing SPP zeolites (with MFI structure) with MCM‐22 (with MWW structure). This work demonstrates that reaction–diffusion modeling allows quantitative description of the catalytic performance of hierarchical zeolites and provides a model reaction to assess nm‐sized characteristic diffusion lengths in MFI. © 2018 American Institute of Chemical EngineersAIChE J, 65: 1067–1075, 2019