The CO oxidation mechanism on small Pd clusters. A theoretical study

González-Torres, Julio César; Bertin, V.; Poulain, E.; Olvera-Neria, Oscar

doi:10.1007/s00894-015-2828-5

Cited by 10 publications

(7 citation statements)

References 32 publications

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“…Finally, the formed CO 2 molecule gets desorbed from the Pd cluster. [52] Experimental findings of the present work reveal that depending on the oxidation state, and the moisture plays a critical role in Pd catalytic properties. Sun et al [40] investigated the role of water and hydroxyl (OH) groups to promote the CO oxidation reaction on the gold surface and proposed different reaction pathways and studied the corresponding micro kinetic activity.…”

Section: Theoretical Calculationsmentioning

confidence: 60%

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An Experimental and Theoretical Investigation on the Oxidation of CO over Pd/C Derived from the Spent Pd Catalyst

et al. 2021

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Development of novel materials and methodologies for removal of toxic and poisonous carbon monoxide (CO) gas is important to solve serious health and environmental related problems. Existing materials used for the removal of CO gas are quite expensive and therefore, the synthesis of low‐cost and earth‐abundant catalyst for CO oxidation is urgently needed. In the present work, we report the preparation of Pd nanoparticles loaded on porous carbon supports from the spent Pd/C and the subsequent catalytic oxidation of CO. Different Pd based catalysts are prepared by using various reducing agents with different reduction potential such as formaldehyde, green tea, ascorbic acid, and sodium borohydride. The prepared catalysts are characterized and employed for the oxidation of CO. All the prepared catalysts show excellent activity towards CO oxidation at room temperature either in presence or absence of moisture depending on the Pd0/Pd+2 ratio in Pd/C which follows the order Pd/C−NaBH4>Pd/C−HCHO>Pd/C−Ascorbic acid>Pd/C−Green tea. Experimental findings of the present work also reveal that depending on the oxidation state, and moisture plays a critical role in Pd catalytic properties on the oxidation of CO. Theoretical calculations performed using Vienna ab initio Simulation Package (VASP) support the experimental observations and further confirm that the reaction proceeds through Langmuir‐Hinshelwood mechanism.

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Section: Theoretical Calculationsmentioning

confidence: 60%

“…In the third step, one of the dissociated O atoms reacts with CO and makes CO 2 molecule. Finally, the formed CO 2 molecule gets desorbed from the Pd cluster [52] . Experimental findings of the present work reveal that depending on the oxidation state, and the moisture plays a critical role in Pd catalytic properties.…”

Section: Introductionmentioning

confidence: 62%

An Experimental and Theoretical Investigation on the Oxidation of CO over Pd/C Derived from the Spent Pd Catalyst

et al. 2021

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“…Such TS structure has also been observed previously in the CO oxidation by small Pd clusters. [64] Contrary to the previous pathway, Pt 4 has to overcome now larger barriers of ~1.0 eV in both steps. Surprisingly, on Pt 4 Ge the first step proceeds almost barrierless, although the second oxidation is highly unfavorable.…”

Section: Langmuir-hinshelwood Mechanismmentioning

confidence: 87%

Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**

Ugartemendia,

Mercero,

de Cózar

et al. 2024

ChemCatChem

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Control of CO emissions raises serious environmental concerns in the current chemical industry, as well as in nascent technologies based on hydrogen such as electrolyzers and fuel cells. Pt remains one of the state‐of‐art catalysts for the CO oxidation reaction, but suffers from CO self–poisoning. Recently, PtGe alloys were proposed as an excellent alternative to reduce CO poisoning. In this work we investigate the impact of Ge content on the CO oxidation kinetics of P4Gen subnanoclusters supported on MgO. Pt−Ge nanoalloys act as a bifunctional catalyst by displaying dual adsorption sites; i.e., CO is adsorbed on Pt whereas oxygen binds to Ge, forming an alternative oxygen source GeOx. Besides, Ge alloying modifies the electronic structure of Pt (ligand effects) and reduces the affinity to CO. In this way, the competition between CO and O2 adsorption and the overbinding of CO is alleviated, achieving a CO poisoning−free kinetic regime. Our calculations suggest that Pt4Ge3 is the optimal catalyst, evidencing that alloying composition is a parameter of extreme importance in nanocatalyst design. The work relies on global optimization search techniques to determine the accessibility of multiple structures at different conditions, mechanistic studies and microkinetic modelling

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“…[ 10,26 ] The LH mechanism involves three stages: the coadsorption of O 2 and CO molecules, the formation and dissociation of a peroxide‐like (OCOO) complex intermediate, and the final desorption of CO 2 . [ 27 ]…”

Section: Introductionmentioning

confidence: 99%

“…[10,26] The LH mechanism involves three stages: the coadsorption of O 2 and CO molecules, the formation and dissociation of a peroxide-like (OCOO) complex intermediate, and the final desorption of CO 2 . [27] For catalysts with surface oxygen atoms available, the Marsvan Krevelen (MvK) mechanism is another possible route, [28][29][30][31] in which the surface oxygen atoms are directly involved in the catalytic reaction. This usually occurs through the reaction of a surface oxygen atom with an entering CO molecule, leaving an oxygen vacancy (V O ), which is then filled with dissociated adsorbed oxygen.…”

Section: Introductionmentioning

confidence: 99%

A New Mars‐van Krevelen Mechanism for CO Oxidation on a Ti‐Decorated MXene

Zhang

Peng

Chen

et al. 2023

Adv Materials Inter

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First‐principles computations are performed to investigate the catalytic oxidation of CO on a Ti‐decorated Cr2TiC2O2 MXene monolayer, through comprehensive analysis of charge transfer, electronic density of states, and charge density difference of the interacting systems. By comparing the reaction energy barriers, it is found that, rather than the traditional Langmuir–Hinshelwood, Eley–Rideal, and Mars‐van Krevelen (MvK) mechanisms, the CO oxidation favours a new variant of the MvK mechanism, in which the anchored Ti atom activates the surface oxygen to spill over from the substrate and take part in the CO oxidation. This work highlights the importance of activating the surface oxygen atoms of MXene by foreign metal atoms to improve the catalytic activity, and suggests that further studies into the new MvK mechanism for CO oxidation may prove worthwhile.

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The CO oxidation mechanism on small Pd clusters. A theoretical study

Cited by 10 publications

References 32 publications

An Experimental and Theoretical Investigation on the Oxidation of CO over Pd/C Derived from the Spent Pd Catalyst

An Experimental and Theoretical Investigation on the Oxidation of CO over Pd/C Derived from the Spent Pd Catalyst

Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**

A New Mars‐van Krevelen Mechanism for CO Oxidation on a Ti‐Decorated MXene

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