Atomically dispersed palladium catalyzes H/D exchange and isomerization of alkenes via reversible insertion and elimination

Liu, Kunlong; Qin, Ruixuan; Li, Kaijia; Zhang, Weijie; Ruan, Pengpeng; Fu, Gang

doi:10.1016/j.checat.2021.11.002

Cited by 20 publications

(9 citation statements)

References 72 publications

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“…It is more interesting that many high-activity Cu 2 O-based SACs and SCCs have been synthesized by experiments recently, which can support our predicted high-stability models. For example, SACs can be synthesized by Pd atom-doped second layer copper on the Cu 2 O(111) surface; SCCs can be synthesized by Co atom-doped first layer oxygen on the Cu 2 O(111) surface; SACs can be synthesized by Rh atom-doped copper on the Cu 2 O(100) surface . The high stability and reactivity of explored single-atom configurations doped into Cu 2 O surfaces are of topical interest in the framework of SAC and SCC catalysts, and studies of high reactivity of Cu 2 O-based SACs and SCCs are ongoing in our group.…”

Section: Resultsmentioning

confidence: 99%

Exploring Stability of Transition-Metal Single Atoms on Cu₂O Surfaces

Yu-Xian

et al. 2022

J. Phys. Chem. C

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Single-atom catalysts (SACs) and single-cluster catalysts (SCCs) have aroused significant interest in heterogeneous catalysis. Transition metal (TM) atoms doped on metal-oxide surfaces provide an opportunity for tuning their electronic, magnetic, and catalytic properties. Herein, the structural, energetic, electrochemical, electronic, and magnetic properties of TMs doped at copper and oxygen vacancies on Cu 2 O surfaces are systemically studied using density functional theory calculation with dispersion correction. Among the 174 systems studied, we found 60 new stable potential SACs and SCCs. It is found that SACs prefer to form on the Cu 2 O(111) surface by replacing the second-layer coordination-saturated copper atom, while SCCs prefer to form on the Cu 2 O(110) surface by replacing the second-layer oxygen atom. Binding and formation energies of SACs and SCCs along d-series TMs show a shape of two peaks, which is caused by respective majority-and minority-spin electron occupancy of d orbitals, and formation of SACs is much more favorable than formation of SCCs on three low-index Cu 2 O surfaces. The charge transfer decreases along the d-series from left to right across the periodic table due to the orbital energy decrease, while the spin states of TMs for SACs and SCCs on Cu 2 O surfaces show periodic variation trends along d-series. Our results provide fundamental knowledge of TMs doped on Cu 2 O surfaces, which helps design new atomically precise heterogeneous catalysts via SACs and SCCs.

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Section: Resultsmentioning

confidence: 99%

Exploring Stability of Transition-Metal Single Atoms on Cu₂O Surfaces

Yu-Xian

et al. 2022

J. Phys. Chem. C

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“…In particular, during the process of H 2 treatment, Pd(II) species are first reduced to Pd(0), and then PdH x combined with Pd δ + and H δ − is formed. [ 32 , 33 ] The electronic states of Pd atoms annealed in hydrogen atmosphere can be proved by temperature‐programmed reduction of H 2 (H 2 ‐TPR) technique (Figure 3c ). With temperature gradually increased from 25 to 500 °C, the consumption of H 2 was recorded and showed obvious variations.…”

Section: Resultsmentioning

confidence: 99%

Potassium Titanate Supported Atomically Dispersed Palladium for Catalytic Oxidation

Zhou

et al. 2022

Advanced Science

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Single‐atom catalysts based on noble metals provide efficient atomic utilization along with enhanced reactivity. Herein, a convenient strategy to construct atomically dispersed palladium catalyst on layered potassium titanate (KTO), which has enhanced interaction between the TiO6 layer and the palladium atoms, is presented. Due to the presence of K+ ions in the interlayers of KTO, the TiO6 octahedron layers have negative charge, which increases the interaction between Pd atoms and the substrate, thus preventing their agglomeration. In addition, the provision of charge of K+ ion makes the molecular oxygen in the system easier to be activated and promotes catalytic oxidation activity.

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“…However, the breaking of C=C during the hydrogenation process allows the rotation of the C–C bond for the stereoselective production of the trans -alkane. Therefore, the catalyst was also highly effective for the selective H/D exchange of alkenes as well as cis-to-trans transformation of alkenes via hydrogen-mediated isomerization (HMI) (Figure c) . The same mechanism was also extended to the Pd 1 /Cu 3 N catalyst which exhibited about an order of magnitude higher HMI activity than the reported homogeneous and heterogeneous catalysts by virtue of its high temperature stability. , Thus, with the fine control over the local chemical environment of catalytic metal sites, increasing opportunities are available for ADMCs to catalyze reactions that are difficult to achieve using conventional heterogeneous metal catalysts.…”

Section: Atomically Dispersed Metal Catalysts As Model Catalystsmentioning

confidence: 90%

“…Copyright 2019 Chinese Chemical Society. (c) The hydrogen-mediated isomerization mechanism of cis-to-trans transformation of alkenes by Pd 1 /Cu 2 O. Reproduced with permission from ref . Copyright 2021 Elsevier Inc.…”

Section: Atomically Dispersed Metal Catalysts As Model Catalystsmentioning

confidence: 99%

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

et al. 2022

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The surface and interface coordination structures of heterogeneous metal catalysts are crucial to their catalytic performance. However, the complicated surface and interface structures of heterogeneous catalysts make it challenging to identify the molecular-level structure of their active sites and thus precisely control their performance. To address this challenge, atomically dispersed metal catalysts (ADMCs) and ligand-protected atomically precise metal clusters (APMCs) have been emerging as two important classes of model heterogeneous catalysts in recent years, helping to build bridge between homogeneous and heterogeneous catalysis. This review illustrates how the surface and interface coordination chemistry of these two types of model catalysts determines the catalytic performance from multiple dimensions. The section of ADMCs starts with the local coordination structure of metal sites at the metal–support interface, and then focuses on the effects of coordinating atoms, including their basicity and hardness/softness. Studies are also summarized to discuss the cooperativity achieved by dual metal sites and remote effects. In the section of APMCs, the roles of surface ligands and supports in determining the catalytic activity, selectivity, and stability of APMCs are illustrated. Finally, some personal perspectives on the further development of surface coordination and interface chemistry for model heterogeneous metal catalysts are presented.

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Atomically dispersed palladium catalyzes H/D exchange and isomerization of alkenes via reversible insertion and elimination

Cited by 20 publications

References 72 publications

Exploring Stability of Transition-Metal Single Atoms on Cu₂O Surfaces

Exploring Stability of Transition-Metal Single Atoms on Cu₂O Surfaces

Potassium Titanate Supported Atomically Dispersed Palladium for Catalytic Oxidation

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

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Atomically dispersed palladium catalyzes H/D exchange and isomerization of alkenes via reversible insertion and elimination

Cited by 20 publications

References 72 publications

Exploring Stability of Transition-Metal Single Atoms on Cu2O Surfaces

Exploring Stability of Transition-Metal Single Atoms on Cu2O Surfaces

Potassium Titanate Supported Atomically Dispersed Palladium for Catalytic Oxidation

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

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Exploring Stability of Transition-Metal Single Atoms on Cu₂O Surfaces

Exploring Stability of Transition-Metal Single Atoms on Cu₂O Surfaces