Acetylene hydrogenation catalyzed by bare and Ni doped CeO<sub>2</sub>(110): the role of frustrated Lewis pairs

Zhou, Shulan; Wan, Qiang; Lin, Sen; Guo, Hua

doi:10.1039/d2cp00925k

Cited by 18 publications

(16 citation statements)

References 65 publications

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“…Extensive experimental and theoretical investigations have demonstrated the heterolytic dissociation of H 2 on FLP sites. , Compared with the ideal CeO 2 surface, the FLP sites also exhibited a significantly reduced energy barrier for the rate-determining step of hydrogenation of acetylene, theoretically suggesting the high activity for the CeO 2 catalysts with FLP sites. In addition, doping with other heteroatoms (such as Cu, Ni, , Ga, etc .) in CeO 2 was also an effective approach to improve the capacity of H 2 activation on FLP sites as well as the activity of hydrogenation of unsaturated compounds.…”

Section: Embedded Adsorption Configuration Of Small Molecules On Flp ...mentioning

confidence: 99%

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Zhang

Tian

et al. 2023

ACS Catal.

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Adsorption of molecules on active sites of heterogeneous catalysts significantly affects their catalytic performance, which provides a perspective to understand the catalytic process/mechanism at the atomic level and to establish structure–function relationships. This Perspective illustrates a strong correlation between the adsorption of reactants on CeO2-based catalysts and their improved catalytic activity and/or selectivity for various transformations. Regulating the oxygen defect of CeO2 provides an effective approach to construct two typical active sites of a frustrated Lewis pair (FLP) and dual-active site. Benefiting from the unique spatial and electronic structures, the FLP sites exhibit an “embedded” adsorption configuration of small molecules, promoting their effective activation and transformation. The dual-active sites constructed by metal clusters and oxygen vacancy of CeO2 could break the competitive adsorption of various molecules and thereafter enable highly active and selective hydrogenations. Finally, the possibilities and challenges in the adsorption behaviors of various molecules on CeO2-based catalysts are outlined. The tailorability of adsorption strength and selective configuration of molecules on active sites are anticipated to stimulate and guide the design of high-performing catalysts.

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Section: Embedded Adsorption Configuration Of Small Molecules On Flp ...mentioning

confidence: 99%

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Zhang

Tian

et al. 2023

ACS Catal.

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“…Ceria (CeO 2 ) has long been used as a support for metal catalysts, thanks to its strong reducibility [68]. The recent discovery by Vilé et al that ceria alone is capable of catalyzing selective hydrogenation of unsaturated hydrocarbons [47,69,70] has stimulated considerable interest in understanding its reactivity and selectivity [71]. The initial proposal of the mechanism for partial acetylene hydrogenation contained a relatively high barrier (2.86 eV) [69], which is kinetically unattainable.…”

Section: Flps Based On Metal Oxidesmentioning

confidence: 99%

“…Other dopants include copper [77,78]. DFT results show that atomic Cu promotes the formation of O v [71], leading to Cu/O FLPs catalyzing the cleavage of the H-H bond. These Ce-O FLPs were also found to be active for CH 4 activation, thanks to the strong interaction between the CH 4 molecule and FLPs.…”

Section: Flps Based On Metal Oxidesmentioning

confidence: 99%

Frustrated Lewis Pairs in Heterogeneous Catalysis: Theoretical Insights

2022

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Frustrated Lewis pair (FLP) catalysts have attracted much recent interest because of their exceptional ability to activate small molecules in homogeneous catalysis. In the past ten years, this unique catalysis concept has been extended to heterogeneous catalysis, with much success. Herein, we review the recent theoretical advances in understanding FLP-based heterogeneous catalysis in several applications, including metal oxides, functionalized surfaces, and two-dimensional materials. A better understanding of the details of the catalytic mechanism can help in the experimental design of novel heterogeneous FLP catalysts.

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“…In addition to be employed as supports for metal catalysts, metal oxides were somewhile used as catalysts for hydrogenations due to the ability of activating hydrogen molecules. , The abundant metal cations and oxygen anions in those metal oxides functionalize as Lewis acid sites and Lewis base sites, respectively, according to their own electronic characteristic. Creating oxygen vacancies in metal oxides to achieve sterically separated metal sites and oxygen sites can form the well-known frustrated Lewis pairs (FLPs), which was shown to be active for selective hydrogenations. − As exemplified by CeO 2 catalysts, the FLPs composed of sterically separated Ce and O sites surrounding the oxygen vacancy on the surface promotes the H 2 heterolytic dissociation, the barrier of which is much lower than that of homolytic dissociation.…”

Section: Atomic-level Regulation For Active Sitesmentioning

confidence: 99%

Mechanistic and Atomic-Level Insights into Semihydrogenation Catalysis to Light Olefins

Yan

Cao

et al. 2022

ACS Catal.

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Semihydrogenations of alkynes and alkadienes to light olefins catalyzed by a heterogeneous catalyst are widely applied in the chemical industry, but it remains challenging to design high-performance catalysts for these processes. The well-developed synthesis methodologies, characterization techniques for catalyst structures, and theoretical calculations in recent decades render opportunities for understanding mechanisms and elaborating the structures of active sites at the atomic level. This Review summarizes recent advances in the mechanistic and atomic-level insights into semihydrogenation catalysis for alkynes and alkadienes to light olefins. The structure-sensitivity, information on active sites, and reaction kinetics are initially discussed to demonstrate the knowledge on the mechanistic and kinetics details of the hydrogenations of alkynes and alkadienes. We then introduce the regulations for the active sites, especially at the atomic level, based on three categories, i.e., site-isolation, local environment regulation, and oxygen vacancy and interfacial sites. Followed by the discussion on the conventional thermocatalytic hydrogenations, the emerging photocatalytic and electrocatalytic semihydrogenations of alkynes and alkadienes are further covered. Finally, we provide a brief overview on the current status of this field and a perspective for future study on the atomic-level design and regulation of catalysts for controlling the selectivity to target products.

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Acetylene hydrogenation catalyzed by bare and Ni doped CeO₂(110): the role of frustrated Lewis pairs

Abstract: Ceria (CeO2) has recently been found to catalyze the selective hydrogenation of alkynes, which has stimulated much discussion on the catalytic mechanism on various facets of the reducible oxide. In...

Cited by 18 publications

References 65 publications

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Frustrated Lewis Pairs in Heterogeneous Catalysis: Theoretical Insights

Mechanistic and Atomic-Level Insights into Semihydrogenation Catalysis to Light Olefins

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Acetylene hydrogenation catalyzed by bare and Ni doped CeO2(110): the role of frustrated Lewis pairs

Abstract: Ceria (CeO2) has recently been found to catalyze the selective hydrogenation of alkynes, which has stimulated much discussion on the catalytic mechanism on various facets of the reducible oxide. In...

Cited by 18 publications

References 65 publications

Adsorption of Molecules on Defective CeO2 for Advanced Catalysis

Adsorption of Molecules on Defective CeO2 for Advanced Catalysis

Frustrated Lewis Pairs in Heterogeneous Catalysis: Theoretical Insights

Mechanistic and Atomic-Level Insights into Semihydrogenation Catalysis to Light Olefins

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Resources

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Acetylene hydrogenation catalyzed by bare and Ni doped CeO₂(110): the role of frustrated Lewis pairs

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis

Adsorption of Molecules on Defective CeO₂ for Advanced Catalysis