scholarly journals Formation of interstellar propanal and 1-propanol ice: a pathway involving solid-state CO hydrogenation

2019 ◽  
Vol 627 ◽  
pp. A1 ◽  
Author(s):  
D. Qasim ◽  
G. Fedoseev ◽  
K.-J. Chuang ◽  
V. Taquet ◽  
T. Lamberts ◽  
...  

Context. 1-propanol (CH3CH2CH2OH) is a three carbon-bearing representative of the primary linear alcohols that may have its origin in the cold dark cores in interstellar space. To test this, we investigated in the laboratory whether 1-propanol ice can be formed along pathways possibly relevant to the prestellar core phase. Aims. We aim to show in a two-step approach that 1-propanol can be formed through reaction steps that are expected to take place during the heavy CO freeze-out stage by adding C2H2 into the CO + H hydrogenation network via the formation of propanal (CH3CH2CHO) as an intermediate and its subsequent hydrogenation. Methods. Temperature programmed desorption-quadrupole mass spectrometry (TPD-QMS) was used to identify the newly formed propanal and 1-propanol. Reflection absorption infrared spectroscopy (RAIRS) was used as a complementary diagnostic tool. The mechanisms that can contribute to the formation of solid-state propanal and 1-propanol, as well as other organic compounds, during the heavy CO freeze-out stage are constrained by both laboratory experiments and theoretical calculations. Results. Here it is shown that recombination of HCO radicals formed upon CO hydrogenation with radicals formed via C2H2 processing – H2CCH and H3CCH2 – offers possible reaction pathways to solid-state propanal and 1-propanol formation. This extends the already important role of the CO hydrogenation chain to the formation of larger complex organic molecules. The results are compared with ALMA observations. The resulting 1-propanol:propanal ratio concludes an upper limit of <0.35−0.55, which is complemented by computationally derived activation barriers in addition to the experimental results.

Author(s):  
John L. Edridge ◽  
Kati Freimann ◽  
Daren J. Burke ◽  
Wendy A. Brown

We have recorded reflection–absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) data for a range of CO 2 -bearing model astrophysical ices adsorbed on a graphitic dust grain analogue surface. Data have been recorded for pure CO 2 , for CO 2 adsorbed on top of amorphous solid water, for mixed CO 2 :H 2 O ices and for CO 2 adsorbed on top of a mixed CH 3 OH:H 2 O ice. For the TPD data, kinetic parameters for desorption have been determined, and the trapping behaviour of the CO 2 in the H 2 O (CH 3 OH) ice has been determined. Data of these types are important as they can be used to model desorption in a range of astrophysical environments. RAIR spectra have also shown the interaction of the CO 2 with H 2 O and CH 3 OH and can be used to compare with astronomical observations, allowing the accurate assignment of spectra.


2018 ◽  
Vol 612 ◽  
pp. A83 ◽  
Author(s):  
D. Qasim ◽  
K.-J. Chuang ◽  
G. Fedoseev ◽  
S. Ioppolo ◽  
A. C. A. Boogert ◽  
...  

Context. The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. Aims. This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. Methods. CH4, O2, and hydrogen atoms are co–deposited in an ultrahigh vacuum chamber at 10–20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption – quadrupole mass spectrometry (TPD–QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. Results. CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH → CH3 + H2O and CH3 + OH → CH3OH at 10–20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation Lamberts et al. (2017, A&A, 599, A132). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.


2020 ◽  
Vol 16 ◽  
pp. 3059-3068
Author(s):  
Giovanna Zanella ◽  
Martina Petrović ◽  
Dina Scarpi ◽  
Ernesto G Occhiato ◽  
Enrique Gómez-Bengoa

The tandem gold(I)-catalyzed rearrangement/Nazarov reaction of enynyl acetates in which the double bond is embedded in a piperidine ring was computationally and experimentally studied. The theoretical calculations predict that the position of the propargylic acetate substituent has a great impact on the reactivity. In contrast to our previous successful cyclization of the 2-substituted substrates, where the nitrogen favors the formation of the cyclized final product, the substitution at position 3 was computed to have a deleterious effect on the electronic properties of the molecules, increasing the activation barriers of the Nazarov reaction. The sluggish reactivity of 3-substituted piperidines predicted by the calculations was further confirmed by the results obtained with some designed substrates.


2021 ◽  
pp. 174751982098472
Author(s):  
Jun Yu ◽  
Ying Han ◽  
Guoqing Chen ◽  
Xiuzhen Xiao ◽  
Haifang Mao ◽  
...  

The effect of carbon nanotubes on the catalytic properties of Rh-Mn-Li/SiO2 catalysts was investigated for CO hydrogenation. The catalysts were comprehensively characterized by means of X-ray power diffraction, N2 sorption, transmission electron microscope, H2–temperature-programmed reduction, CO–temperature-programmed desorption, temperature-programmed surface reaction, and X-ray photoelectron spectroscopy. The results showed that an appropriate amount of carbon nanotubes can be attached to the surface of the SiO2 sphere and can improve the Rh dispersion. Moderate Rh-Mn interaction can be obtained by doping with the appropriate amount of carbon nanotubes, which promotes the formation of strongly adsorbed CO and facilitates the progress of CO insertion, resulting in the increase in the selectivity of C2+ oxygenate synthesis.


2021 ◽  
Author(s):  
Liam Howard-Fabretto ◽  
Timothy Gorey ◽  
Guangjing Li ◽  
Siriluck Tesana ◽  
Gregory F Metha ◽  
...  

Small Ru clusters are efficient catalysts for chemical reactions such as CO hydrogenation. In this study 3-atom Ru3 clusters were deposited onto radio frequency (RF)-deposited TiO2 which is an inexpensive,...


2021 ◽  
Vol 601 ◽  
pp. 120514 ◽  
Author(s):  
Rahamatullah Shaikh ◽  
Saeed Shirazian ◽  
Sarah Guerin ◽  
Eoin Sheehan ◽  
Damien Thompson ◽  
...  

Author(s):  
Senka Djaković ◽  
Silvija Maračić ◽  
Jasmina Lapić ◽  
Eduard Kovalski ◽  
Alexander Hildebrandt ◽  
...  

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