The adsorption and reaction of 1,2-propanediol on Ag(110) under oxygen lean conditions

Ayre, Caroline R.; Madix, Robert J.

doi:10.1016/0039-6028(94)90776-5

Cited by 28 publications

(28 citation statements)

References 15 publications

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“…This adsorption process has been observed for several other alcohols at, or below the reaction temperature used in the ECCL process. [21][22][23][24][25] Nonetheless, information on the adsorption of diols or higher polyols is very scarce.…”

Section: Figurementioning

confidence: 99%

Liquid-Phase H-Transfer from 2-Propanol to Phenol on Raney Ni: Surface Processes and Inhibition

et al. 2017

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is perhaps the most widely used catalyst for the transformation of biogenic molecules in industrial practice (e.g., as in the production of sugar alcohols and hardening vegetable oils). Currently, Raney Ni has found another key application; the catalytic upstream biorefining (CUB) of lignocellulose in which the soluble products released from the lignocellulosic matrix undergo reductive processes, rendering depolymerized lignin oils in addition to high-quality holocellulosic pulps. Despite the industrial importance of Raney Ni, its surface chemistry is poorly understood. In this study, using the H-transfer reaction between 2-propanol (2-PrOH) and phenol as a model reaction, we studied the influence of various alcohols on the catalytic performance of Raney Ni. For the H-transfer hydrogenation of phenol to cyclohexanol, the inhibition of the catalyst increases in the order of secondary alcohols << primary alcohols < polyols at 130 °C. To better understand the observed inhibition, we also studied the molecular interactions of the various alcohols at the catalytic solid-liquid interface using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. The in situ spectroscopic data revealed that 2-PrOH adsorbs on at least two chemically different sites on the surface of Raney Ni. One of these two adsorption sites was attributed to the Ni site responsible for the saturation of the phenolic ring. The ATR-IR spectroscopic data also shows that the adsorption of phenol involves its hydroxyl group. Notably, the phenolic ring was found to be tilted with respect to the surface. Competitive adsorption of various other alcohols was also investigated at the catalytic solid-liquid interface. The presence of methanol inhibited the adsorption of 2-PrOH to a significantly greater degree than phenol. Therefore, it is proposed that hydrogen transfer hydrogenation of the phenolic ring be inhibited in the presence of additional alcohols mainly due to the competitive adsorption with 2-PrOH. Several polyols were found to interact through a bidentate interaction with the catalyst surface explaining their stronger inhibition, compared to primary alcohols. In a broader context, this study proposes the effect of hemicellulose sugars and sugar alcohols, formed in the CUB process, upon the product selectivity of CUB catalyzed by Raney Ni and using 2-PrOH as an Hdonor.

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Section: Figurementioning

confidence: 99%

Liquid-Phase H-Transfer from 2-Propanol to Phenol on Raney Ni: Surface Processes and Inhibition

et al. 2017

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“…Finally, we present a discussion on the implementation of the scheme. Concretely, we consider 1,2-propanediol molecules [65,66] as an example to realize our scheme. We choose three working states of the cyclic three-…”

Section: Enantiodiscrimination Of Chiral Moleculesmentioning

confidence: 99%

Enantiodiscrimination of chiral molecules via quantum correlation function

Zou,

Chen,

Liu

et al. 2022

Preprint

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We propose a scheme to realize enantiodiscrimination of chiral molecules based on quantum correlation function in a driven cavity-molecule system, where the chiral molecule is coupled with a quantized cavity field and two classical light fields to form a cyclic three-level model. According to the inherent properties of electric-dipole transition moments of chiral molecules, there is a π-phase difference in the overall phase of the cyclic three-level model for the left-and right-handed chiral molecules. Thus, the correlation function depends on this overall phase and is chirality-dependent. The analytical and numerical results indicate that the left-and right-handed chiral molecules can be discriminated by detecting the quantum correlation function. Our work opens up a promising route to discriminate molecular chirality, which is an extremely important task in pharmacology and biochemistry.

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“…Experimental studies of the PG selective oxidation into carbonyl/carboxylic compounds (methylglyoxal, hydroxyacetone, etc.) are known in the literature for catalysts with supported metal nanoparticles, including Ag [ 5 , 6 , 7 ], Pt [ 8 ] and Pd [ 9 , 10 , 11 , 12 ]. The mechanism of PG conversion was theoretically studied over the Ag 4 cluster [ 13 ].…”

Section: Introductionmentioning

confidence: 99%

“…The mechanism of PG conversion was theoretically studied over the Ag 4 cluster [ 13 ]. As in the case of ethylene glycol oxidation [ 9 , 14 , 15 ], the PG adsorption on the surface of single crystal Ag (110) and Pd (111) coated with oxygen led to the breaking of O–H bonds with the formation of the intermediate 1,2-propanedioxy (–OCH(CH 3 )CH 2 O–, PDO) [ 5 , 6 , 9 ]. As the temperature increased, the PDO transformations yielded a number of products, including hydroxyacetone or acetol (CH 3 COCH 2 OH), lactaldehyde (CH 3 CH(OH)CHO), and methylglyoxal or pyruvaldehyde (CH 3 COCHO).…”

Section: Introductionmentioning

confidence: 99%

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Modifier Effect in Silica-Supported FePO4 and Fe-Mo-O Catalysts for Propylene Glycol Oxidation

et al. 2022

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Currently, catalytic processing of biorenewable raw materials into valuable products attracts more and more attention. In the present work, silica-supported FePO4 and Fe-Mo-O catalysts are prepared, their phase composition, and catalytic properties are studied in the process of selective oxidation of propylene glycol into valuable mono- and bicarbonyl compounds, namely, hydroxyacetone and methylglyoxal. A comparative analysis of the main routes of propylene glycol adsorption with its subsequent oxidative conversion into carbonyl products is carried out. The DFT calculations show that in the presence of adsorbed oxygen atom, the introduction of the phosphate moiety to the Fe-containing site strengthens the alcohol adsorption on the catalyst surface with the formation of the 1,2-propanedioxy (–OCH(CH3)CH2O–) intermediate at the active site. The introduction of the molybdenum moiety to the Fe-containing site in the presence of the adsorbed oxygen atom is also energetically favorable, however, the interaction energy is found by 100 kJ/mol higher compared to the case with phosphate moiety that leads to an increase in the propylene glycol conversion while maintaining high selectivity towards C3 products. The catalytic properties of the synthesized iron-containing catalysts are experimentally compared with those of Ag/SiO2 sample. The synthesized FePO4/SiO2 and Fe-Mo-O/SiO2 catalysts are not inferior to the silver-containing catalyst and provide ~70% selectivity towards C3 products, while the main part of propylene glycol is converted into methylglyoxal in contrast to the Ag/SiO2 catalyst featuring the selective transformation of only the secondary C-OH group in the substrate molecule under the studied conditions with the formation of hydroxyacetone. Thus, supported Fe-Mo-O/SiO2 catalysts are promising for the selective oxidation of polyatomic alcohols under low-temperature conditions.

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The adsorption and reaction of 1,2-propanediol on Ag(110) under oxygen lean conditions

Cited by 28 publications

References 15 publications

Liquid-Phase H-Transfer from 2-Propanol to Phenol on Raney Ni: Surface Processes and Inhibition

Liquid-Phase H-Transfer from 2-Propanol to Phenol on Raney Ni: Surface Processes and Inhibition

Enantiodiscrimination of chiral molecules via quantum correlation function

Modifier Effect in Silica-Supported FePO4 and Fe-Mo-O Catalysts for Propylene Glycol Oxidation

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