Adsorption structure of adenine on cerium oxide

Bercha, Sofiia; Bhasker-Ranganath, Suman; Zheng, Xiaohui; Beranová, Klára; Vorokhta, Mykhailo; Acres, Robert G.; Škála, Tomáš; Matolín, Vladimı́r; Xu, Ye; Tsud, Nataliya

doi:10.1016/j.apsusc.2020.147257

Cited by 8 publications

(8 citation statements)

References 56 publications

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“…Previously, we studied the adsorption of a primary nucleobase, adenine, on CeO 2 (111) as a model system for organic/inorganic interfaces. 52 Adenine can be viewed as a cyclic amidine in which the C=NH group is a part of an aromatic ring. In nature, adenine deaminase catalyzes the conversion of adenine to NH 3 and hypoxanthine.…”

Section: Resultsmentioning

confidence: 99%

“…Our prior work 52,84 suggests that vdW interactions contribute to the stability of organic molecules as small as acetaldehyde when they are adsorbed on ceria. Thus, we have recalculated the minimum-energy reaction energy profiles on the three lowindex facets using the optB86b-vdW functional (red dashed traces, Figures 5a−c).…”

Section: Effects Of Vdw Interaction and Solvationmentioning

confidence: 99%

“…Our results shed light on the fundamental properties that endow ceria with versatile reactivity toward biologically and environmentally relevant organic molecules, including peptides and nucleobases. They make ceria a promising enzyme-mimetic material for the development of novel diagnostic, pharmaceutical, and therapeutic technologies, among others. − The main challenge for ambient temperature hydrolysis applications is identified to be the desorption of the carboxylate product.…”

Section: Introductionmentioning

confidence: 99%

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Hydrolysis of Acetamide on Low-Index CeO₂ Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Bhasker-Ranganath

2022

ACS Catal.

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Using DFT calculations and acetamide as the main example, we show that ceria is a potential catalyst for the hydrolysis of amide and similar bonds. The overall reaction is endergonic in the gas phase, yielding acetic acid and ammonia, but is slightly exergonic in the aqueous phase, which facilitates ionization of the products (CH 3 COO – and NH 4 + ). Neighboring Ce and O sites on the CeO 2 (111), (110), and (100) facets are conducive to the formation of an activated metastable tetrahedral intermediate (TI) complex, followed by C–N bond scission. With van der Waals and solvation effects taken into account, the overall reaction energetics is found to be most favorable on the (111) facet as desorption of acetic acid is much more uphill energetically on (110) and (100). We further suggest that the Ce–O–Ce sites on ceria surfaces can activate X(=Y)–Z type bonds in amides, amidines, and carboxylate and phosphate esters, among many others that we term “generalized esters”. A Brønsted-Evans–Polanyi relationship is identified correlating the stability of the transition and final states of the X–Z generalized ester bond scission. A simple descriptor (ΣΔχ) based on the electronegativity of the atoms that constitute the bond (X, Y, Z) versus those of the catalytic site (O, Ce, Ce) captures the trend in the stability of the transition state of generalized ester bond scission and suggests a direction for modifying ceria for targeting specific organic substrates.

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Section: Resultsmentioning

confidence: 99%

Section: Effects Of Vdw Interaction and Solvationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydrolysis of Acetamide on Low-Index CeO₂ Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Bhasker-Ranganath

2022

ACS Catal.

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“…This could be tentatively explained by partial C-N bond splitting in glycinate with the formation of the adsorbed acetate (-CH 3 forms component F and the -COO À group contributes to component C) and volatile ammonia. 53 This suggestion was also supported by Gong et al, 54 who reported that oxidation of the Au(111) surface leads to dehydrogenation of the propylamines with further C-N bond cleavage. At low oxygen coverage, this decomposition channel was not activated, i.e., only N-H bond splitting with the formation of propionitrile and water was observed.…”

Section: Srpesmentioning

confidence: 62%

Role of the redox state of cerium oxide on glycine adsorption: an experimental and theoretical study

Kosto

Barcaro

Kalinovych

et al. 2023

Phys. Chem. Chem. Phys.

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“…However, as the Pd/Ceria x /C catalysts were fabricated under a controlled-synthesis approach, it enables us to rule out most of the reasons that have been suggested by previous literature. One factor, which can be considered next, is the interaction between ceria and the reactant or intermediate to facilitate the formic acid dehydrogenation over Pd because ceria is an amphoteric oxide so both acidic and basic chemicals could adsorb on ceria surface . For example, amine-functional groups grafted on supports are known to promote the formic acid dehydrogenation reaction by scavenging the proton (H + ) from formic acid to produce formate anion (HCOO – ), an initial reactant of formic acid dehydrogenation. ,− There are two ways for ceria to facilitate formic acid dehydrogenation: (i) The oxygen sites of ceria could interact with protons to produce the formate anion near or far away from Pd.…”

Section: Resultsmentioning

confidence: 99%

Hydrogen Production via Cerium-Promoted Dehydrogenation of Formic Acid Catalyzed by Carbon-Supported Palladium Nanoparticles

Kim

Jang

Kim

2023

ACS Appl. Nano Mater.

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Formic acid is a promising hydrogen carrier owing to its high hydrogen density and liquid phase. Therefore, the production of hydrogen from formic acid via catalytic dehydrogenation reaction has been extensively studied. Various methods such as alloying of the active Pd metal with other metals and adding dopants (e.g., the amine-functional group, nitrogen, or metal oxide) have been suggested to enhance the catalytic activities for formic acid dehydrogenation. In this study, we synthesized carbon-supported palladium nanoparticles coexisting with ceria particles and investigated the role of cerium in this reaction over Pd/C catalysts. We made an effort not to change the particle size and the electronic state of Pd significantly while varying Ceria/Pd molar ratios in the catalysts, ruling out their effects on the reaction. Ceria was impregnated on carbon by incipient wetness impregnation; subsequently, Pd was impregnated on Ceria/C by deposition–precipitation. The catalytic tests demonstrated that ceria improved the reaction rate by producing formate anions, the main reactant of this reaction, as it was dissolved by formic acid during the reaction. More importantly, the dissolved cerium ions accelerated the reaction by interacting with the formate anion to change its electronic charge, thereby reducing the activation barrier for C–H bond cleavage. The carbon-supported palladium nanoparticles promoted by cerium could be used to develop a highly efficient hydrogen extraction system from formic acid.

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Adsorption structure of adenine on cerium oxide

Cited by 8 publications

References 56 publications

Hydrolysis of Acetamide on Low-Index CeO₂ Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Hydrolysis of Acetamide on Low-Index CeO₂ Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Role of the redox state of cerium oxide on glycine adsorption: an experimental and theoretical study

Hydrogen Production via Cerium-Promoted Dehydrogenation of Formic Acid Catalyzed by Carbon-Supported Palladium Nanoparticles

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Adsorption structure of adenine on cerium oxide

Cited by 8 publications

References 56 publications

Hydrolysis of Acetamide on Low-Index CeO2 Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Hydrolysis of Acetamide on Low-Index CeO2 Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Role of the redox state of cerium oxide on glycine adsorption: an experimental and theoretical study

Hydrogen Production via Cerium-Promoted Dehydrogenation of Formic Acid Catalyzed by Carbon-Supported Palladium Nanoparticles

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Product

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About

Hydrolysis of Acetamide on Low-Index CeO₂ Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Hydrolysis of Acetamide on Low-Index CeO₂ Surfaces: Ceria as a Deamidation and General De-esterification Catalyst