An official website of the United States government
A novel internal conditioning (InCon) technique based on saturated sodium montmorillonite (sMT) functionalized with two non-ionic surfactants, polyoxyethylene (9) nonylphenylether and t-octyl phenoxy poly ethoxyethanol, is investigated in this study. With the integration of water for internal curing and pozzolanic reactivity in a single system, the role of InCon in modifying cement hydration kinetics is comprehensively elucidated. The results indicate that, in the presence of InCon, both silicate reaction and secondary aluminate reaction rates are enhanced, and the apparent activation energy (Ea) of cement hydration was decreased from 34.3 KJ/mol to 28.7 KJ/mol indicating a lower temperature sensitivity and threshold of the cement hydration reactions. In addition, decreased CH contents, improved degree of hydration, increased chemical shrinkage, and the formation of additional Csingle bondSsingle bondH and aluminum-containing phases were obtained from the cement with InCon. The autogenous shrinkage of cement and the negative impact of dry sMT on the early age strength of cement can be offset by InCon paving a new path to improve the overall properties of concrete.
more »
« less
Kinetics Study of the Hydrodeoxygenation of Xylitol over a ReOx-Pd/CeO2 Catalyst
In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170 °C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170 °C and a sub-Arrhenius relation was elucidated with activation energy being dependent on temperature, and ranging from 10.2–51.8 kJ/mol in the temperature range investigated. Internal and external mass transfer were investigated through evaluating the Weisz–Prater criterion and the effect of varying stirring rate on the reaction rate, respectively. There were no internal or external mass transfer limitations present in the reaction.
more »
« less
- Award ID(s):
- 1632824
- PAR ID:
- 10284077
- Date Published:
- Journal Name:
- Catalysts
- Volume:
- 11
- Issue:
- 1
- ISSN:
- 2073-4344
- Page Range / eLocation ID:
- 108
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Many computational studies of catalytic surface reaction kinetics have demonstrated the existence of linear scaling relationships between physical descriptors of catalysts and reaction barriers on their surfaces. In this work, the relationship between catalyst activity, electronic structure, and alloy composition was investigated experimentally using a AgxPd1−x Composition Spread Alloy Film (CSAF) and a multichannel reactor array that allows measurement of steady-state reaction kinetics at 100 alloy compositions simultaneously. Steady-state H2 −D2 exchange kinetics were measured at atmospheric pressure on AgxPd1−x catalysts over a temperature range of 333−593 K and a range of inlet H2 and D2 partial pressures. X-ray photoelectron spectroscopy (XPS) was used to characterize the CSAF by determining the local surface compositions and the valence band electronic structure at each composition. The valence band photoemission spectra showed that the average energy of the valence band, ε̅v, shifts linearly with composition from −6.2 eV for pure Ag to −3.4 eV for pure Pd. At all reaction conditions, the H2 −D2 exchange activity was found to be highest on pure Pd and gradually decreased as the alloy was diluted with Ag until no activity was observed for compositions with xPd < 0.58. Measured H2 −D2 exchange rates across the CSAF were fit using the Dual Subsurface Hydrogen (2H′) mechanism to extract estimates for the activation energy barriers to dissociative adsorption, ΔEads ‡ , associative desorption, ΔEdes ‡ , and the surface-to-subsurface diffusion energy, ΔEss, as a function of alloy composition, xPd. The 2H′ mechanism predicts ΔEads ‡ = 0−10 kJ/mol, ΔEdes ‡ = 30−65 kJ/mol, and ΔEss = 20−30 kJ/mol for all alloy compositions with xPd ≥ 0.64, including for the pure Pd catalyst (i.e., xPd = 1). For these Pd-rich catalysts, ΔEdes ‡ and ΔEss appeared to increase by ∼5 kJ/mol with decreasing xPd. However, due to the coupling of kinetic parameters in the 2H′ mechanism, we are unable to exclude the possibility that the kinetic parameters predicted when xPd ≥ 0.64 are identical to those predicted for pure Pd. This suggests that H2 −D2 exchange occurs only on bulk-like Pd domains, presumably due to the strong interactions between H2 and Pd. In this case, the decrease in catalytic activity with decreasing xPd can be explained by a reduction in the availability of surface Pd at high Ag compositions.more » « less
-
The growing global plastic waste challenge requires development of new plastic waste management strategies, such as pyrolysis, that will help to enable a circular plastic economy. Developing optimized, scalable pyrolysis reactors capable of maximizing the yield of desired products requires a fundamental understanding of plastic pyrolysis chemistry. Accordingly, the intrinsic reaction kinetics of polypropylene pyrolysis have been evaluated by the method of pulse-heated analysis of solid reactions (PHASR), which enables time-resolved measurement of pyrolysis kinetics at high temperature absent heat and mass transfer limitations on the millisecond scale. Polypropylene pyrolysis product evolution curves were generated at 525°C–625°C, and the overall reaction kinetics were described by a lumped first-order model with an activation energy of 242.0 ± 2.9 kJ mol−1 and a pre-exponential factor of 35.5 ± 0.6 ln(s−1). Additionally, the production of solid residues formed during polypropylene pyrolysis was investigated, revealing a secondary kinetic regime.more » « less
-
Abstract Recently, slow molecular dynamics of poly(l‐lactic acid) (PLLA) by using 1D and 2D exchange NMR are investigated. In this work, slow molecular dynamics of PLLA chains in the α′, a stereocomplex (SC) with poly(d‐lactic acid), and glassy states are investigated in terms of centerband‐only detection of exchange (CODEX) NMR. The mixing‐time dependence of the CODEX data demonstrates that the molecular dynamics of stems become slower in the order of α′, α, and SC. The temperature dependence of the correlation time 〈τc〉 of the helical jump motions in the α and SC phases simply exhibits Arrhenius behaviors, with activation energy,Ea, values of 91 ± 1 and 97 ± 1 kJ mol−1, respectively. In contrast, the temperature dependence of 〈τc〉 in the α′ sample exhibits two Arrhenius lines with substantially differentEavalues of 273 ± 12 and 16 ± 14 kJ mol−1at temperatures below and above 84 °C. The obtained kinetics of molecular dynamics not only establish the relationship between packing structure and dynamics in PLLA polymorphs and in the SC, but also allow for an understanding of the coupled dynamics between the crystalline and amorphous regions at approximatelyTg.more » « less
-
Ga-and In-exchanged chabazite (CHA) zeolites with same Si/Al and metal/Al ratios were prepared via the incipient wetness impregnation method, were characterized using N-2 adsorption, electron microscopy, temperature-programed reactions and were evaluated for the ethane dehydrogenation reaction using flow microreactors. Ga-CHA has higher reaction rates and a lower activation energy of 107 kJ/mol than In-CHA (E-a = 175 kJ/mol). Rietveld refinement of the X-ray powder diffraction pattern shows that the In+ cation is predominantly located above the 6-ring of the CHA cage. It is proposed that the reaction proceeds through the alkyl mechanism based on stability of alkyl hydride intermediates as determined using DFT calculations. The oxidative addition of ethane to the metal shows much lower Gibbs free energy for Ga-CHA (+27.95 kJ/mol) vs In-CHA (+124.85 kJ/mol). These results indicate that oxidative addition may be the rate-limiting step of ethane dehydrogenation in these materials.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/catal11010108
