Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection–absorption spectroscopy and temperature programmed desorption study

Dostert, Karl‐Heinz; O’Brien, Casey P.; Mirabella, Francesca; Ivars‐Barceló, Francisco; Schauermann, Swetlana

doi:10.1039/c6cp00877a

Cited by 53 publications

(45 citation statements)

References 45 publications

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“…To answer this question, Figs 4(a) and (b) show the infrared spectra of solid propanal before and after H-bombardments, respectively. The two spectra are similar showing structured signals between 3000 and 2750 cm −1 corresponding to CH stretching modes, a very huge absorption band at 1730 cm −1 characteristic of the CO functional group and three sets of signals between 1500 and 750 cm −1 corresponding to CH 3 bending and rocking modes (Dostert et al 2016). Fig.…”

Section: Hydrogenation Of Propanal (Ch 3 Ch 2 Cho)mentioning

confidence: 82%

“…corresponding to CH 2 bending modes, in addition to the C-C stretching signal at 1161 cm −1 (Dostert et al 2016). Fig.…”

Section: Hydrogenation Of Propenal (H 2 C=chcho)mentioning

confidence: 91%

“…3.1 H-addition reaction on unsaturated alcohols involving double or triple CC bonds: the case of allyl (H 2 C=CHCH 2 OH) and propargyl (HC≡CCH 2 OH) alcohols 3.1.1 Hydrogenation of allyl alcohol (H 2 C=CHCH 2 OH) Fig. 2(a) shows the infrared spectrum of pure allyl alcohol (H 2 C=CHCH 2 OH) ice formed on a mirror maintained at 10 K, with OH and CH stretching modes located in 3600-2500 cm −1 spectral region, C=C and C-O vibrations at 1644 and 1110 cm −1 , respectively and CH 2 , OH and CH=CH 2 deformations at 1430, 1240 and 994 cm −1 , respectively (Dostert et al 2016). After IR-analysis, the allyl alcohol ice has been bombarded during 45 min by H atoms.…”

Section: R E S U Lt Smentioning

confidence: 99%

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Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

Jonusas

Guillemin

Krim

2017

Monthly Notices of the Royal Astronomical Society

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The knowledge of the H-addition reactions on unsaturated organic molecules bearing a triple or a double carbon-carbon bond such as propargyl or allyl alcohols and a CO functional group such as propynal, propenal or propanal may play an important role in the understanding of the chemical complexity of the interstellar medium. Why different aldehydes like methanal, ethanal, propynal and propanal are present in dense molecular clouds while the only alcohol detected in those cold regions is methanol? In addition, ethanol has only been detected in hot molecular cores. Are those saturated and unsaturated aldehyde and alcohol species chemically linked in molecular clouds through solid phase H-addition surface reactions or are they formed through different chemical routes? To answer such questions, we have investigated a hydrogenation study of saturated and unsaturated aldehydes and alcohols at 10 K. We prove through this experimental study that while pure unsaturated alcohol ices bombarded by H atoms lead to the formation of the corresponding fully or partially saturated alcohols, surface H-addition reactions on unsaturated aldehyde ices exclusively lead to the formation of fully saturated aldehyde. Such results show that in addition to a chemoselective reduction of C≡C and C=C bonds over the C=O group, there is no link between aldehydes and their corresponding alcohols in reactions involving H atoms in dense molecular clouds. Consequently, this could be one of the reasons why some aldehydes such as propanal are abundant in dense molecular clouds in contrast to the non-detection of alcohol species larger than methanol.

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Section: Hydrogenation Of Propanal (Ch 3 Ch 2 Cho)mentioning

confidence: 82%

“…corresponding to CH 2 bending modes, in addition to the C-C stretching signal at 1161 cm −1 (Dostert et al 2016). Fig.…”

Section: Hydrogenation Of Propenal (H 2 C=chcho)mentioning

confidence: 91%

Section: R E S U Lt Smentioning

confidence: 99%

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Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

Jonusas

Guillemin

Krim

2017

Monthly Notices of the Royal Astronomical Society

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“…This band could be assigned to the surface terminal OH groups . Simultaneously, the bands at 2966, 2923, and 1024 cm −1 could be assigned to the asymmetrical and symmetrical vibrations of the C−H bands and the C−O stretching vibrations of the adsorbed butoxides . The presence of the negative O−H stretching bands and butoxides bands indicates that BDO reacts with the surface hydroxyl groups to generate surface butoxide species as intermediates.…”

Section: Resultsmentioning

confidence: 90%

Catalytic Dehydration of 1,4‐Butanediol over Mg−Yb Binary Oxides and the Mechanism Study

et al. 2020

ChemCatChem

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In this study, MgÀ Yb binary oxides were synthesized using different MgO concentrations and investigated for the catalytic dehydration of 1,4-butanediol (BDO) into 3-buten-1-ol (BTO). The physicochemical properties of the catalysts were characterized by N 2 physisorption, X-ray diffraction, Raman spectroscopy, temperature-programmed techniques, and diffuse reflectance infrared Fourier transform spectroscopy. The MgÀ Yb binary oxides exhibited superior catalytic activity and better BTO selectivity compared with the pristine Yb 2 O 3 or MgO. Structures of MgÀ OÀ Yb were generated in the binary oxides via the interchange of Yb or Mg in the MgO or Yb 2 O 3 crystalline phases. Extra basic and acidic sites were formed over the MgÀ Yb binary oxides because of the formation of surface defects and the presence of MgÀ OÀ Yb structures, respectively. The acidic as well as basic sites were observed to influence the catalytic performance: BDO reactivity was enhanced by the more acidic sites, while BTO selectivity was favored by the basic sites. The highest BTO yield of 71.1 % was achieved over the Mg7Yb3 catalyst with 90.4 % BDO conversion and 78.6 % BTO selectivity at 350°C. The in situ DRIFTS results indicated that BDO was first adsorbed on the catalyst and then reacted with the acidic sites to generate butoxides. The β-H of the surface butoxides was abstracted by the basic oxygen anions to produce aldehyde species, which dissociated to form BTO.[a] R.

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“…This correlated appearance and development of the surface adsorbates related to the vibration at 1120 cm -1 and the formation rates of molecular propenol monitored in the gas phase strongly suggest that the related surface species must be a direct reaction intermediate (RI). Several other bands, appearing at 1090 cm -1 , 1463-1450 cm -1 , 2966 cm -1 and 2980 cm -1 , follow an identical time evolution pattern [12][13][14] and therefore can be also associated with RI. The vibrations at 2966 cm -1 and 2980 cm -1 are characteristic to C-H stretching modes with the band at 2980 cm -1 being typically assigned to a C-H fragment, in which the carbon atom is involved into the C=C bond.…”

Section: Spectroscopic Identification Of the Surface Species Formed Umentioning

confidence: 94%

Partial Hydrogenation of Unsaturated Carbonyl Compounds: Toward Ligand-Directed Heterogeneous Catalysis

Schauermann

2018

J. Phys. Chem. Lett.

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In this Perspective, we report on the recent progress in atomistic-level understanding of selective partial hydrogenation of α,β-unsaturated carbonyl compounds, particularly acrolein, toward unsaturated alcohols over model single crystalline and nanostructured Pd catalysts. This reaction was observed to proceed with nearly 100% selectivity over Pd(111) but not over supported Pd nanoparticles. The origin of the high selectivity was related to formation of a dense overlayer of oxopropyl surface species occurring at the early reaction stages via partial hydrogenation of the C=C bond in acrolein with only one H atom. This oxopropyl overlayer strongly modifies the adsorption and reactive properties of Pd(111), turning it 100% selective toward C=O bond hydrogenation. The underlying reaction mechanism represents a particular case of ligand-directed heterogeneous catalysis, in which the surface adsorbates do not directly participate in the catalytic process as the reaction intermediates but strongly affect the elementary reaction steps via specific adsorbate-adsorbate interactions.

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Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection–absorption spectroscopy and temperature programmed desorption study

Abstract: We present a mechanistic study on adsorption of acrolein and its partial hydrogenation products propanal and allyl alcohol over Pd(111) to understand the factors governing the selectivity in acrolein hydrogenation.

Cited by 53 publications

References 45 publications

Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

Catalytic Dehydration of 1,4‐Butanediol over Mg−Yb Binary Oxides and the Mechanism Study

Partial Hydrogenation of Unsaturated Carbonyl Compounds: Toward Ligand-Directed Heterogeneous Catalysis

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