Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Xiong, Haifeng; Lin, Sen; Goetze, Joris; Pletcher, Paul; Guo, Hua; Kovařík, Libor; Artyushkova, Kateryna; Weckhuysen, Bert M.; Datye, Abhaya K.

doi:10.1002/ange.201701115

Cited by 86 publications

(95 citation statements)

References 38 publications

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“…This figure predicts the minimum required binding energies of single atoms (examples given for Pt, Pd, and Ni) on a support to obtain stable SACs for a day at the two indicated temperatures. In this study, we focused on idealized surfaces without defects (except for steps), hydroxyl groups or dopants, which may act as nucleation sites for sintering and in this way alter diffusion processes of metal adatoms [35][36][37] . Despite this simplification, the framework introduced is general and the correlations provide a guiding tool for initial materials selection.…”

Section: Stability Assessmentmentioning

confidence: 99%

Stability of heterogeneous single-atom catalysts: a scaling law mapping thermodynamics to kinetics

Zhang

Wang

et al. 2020

npj Comput Mater

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Heterogeneous single-atom catalysts (SACs) hold the promise of combining high catalytic performance with maximum utilization of often precious metals. We extend the current thermodynamic view of SAC stability in terms of the binding energy (Ebind) of single-metal atoms on a support to a kinetic (transport) one by considering the activation barrier for metal atom diffusion. A rapid computational screening approach allows predicting diffusion barriers for metal–support pairs based on Ebind of a metal atom to the support and the cohesive energy of the bulk metal (Ec). Metal–support combinations relevant to contemporary catalysis are explored by density functional theory. Assisted by machine-learning methods, we find that the diffusion activation barrier correlates with (Ebind)2/Ec in the physical descriptor space. This diffusion scaling-law provides a simple model for screening thermodynamics to kinetics of metal adatom on a support.

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Section: Stability Assessmentmentioning

confidence: 99%

Stability of heterogeneous single-atom catalysts: a scaling law mapping thermodynamics to kinetics

Zhang

Wang

et al. 2020

npj Comput Mater

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“…Actually, despite the superior catalytic performance of single‐atom catalysts in many reactions of commercial importance, 13,21‐32 the nature of the active phase is not always clear, which is due primarily to the increased complexity in the electronic structure that arises from the change in surface composition 33 . For instance, it has been demonstrated that coadsorption of a pair of amphoteric species (e.g., propyl and H in PDH) could be significantly more stable than the adsorption of the isolated species on many oxide surfaces due to Lewis acid–base interaction, 34‐36 which makes it possible to tailor the catalytic properties of oxides to a particular chemical reaction by doping the surfaces with single metal atoms.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, much industrial chemical research has being devoted to the search for new and more effective catalysts because Pt is rather costly and hexavalent Cr is environmentally unfriendly. Hence, many oxides such as Ga 2 O 3 , 4‐6 VO x , 7‐9 ZrO 2 , 10‐12 CeO 2 , 13,14 ZnO, 15 TiO 2 , 16 and Al 2 O 3 17 have been extensively studied for PDH, among which Ga 2 O 3 is a very promising candidate.…”

Section: Introductionmentioning

confidence: 99%

Dual‐function catalysis in propane dehydrogenation over Pt₁–Ga₂O₃ catalyst: Insights from a microkinetic analysis

Chang

Wang

et al. 2020

AIChE Journal

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The kinetics of propane dehydrogenation over single‐Pt‐atom‐doped Ga2O3 catalyst has been examined by combining density functional theory calculations and microkinetic analysis. The doping of Pt not only can improve the selectivity of the Ga2O3 catalyst by hindering the deep dehydrogenation reactions but also helps to achieve a long‐term stability by improving the resistance of Ga2O3 to hydrogen reduction. Microkinetic analysis indicates that upon Pt doping the turnover frequency for propane consumption is increased by a factor of 2.8 under typical operating conditions, as compared to the data on the pristine Ga2O3 surface. The calculated results suggest that the Pt1–Ga2O3 catalyst shows a bifunctional character in this reaction where the Pt–O site brings about dehydrogenation while the Ga–O site is active for desorbing H2, which provides a beautiful explanation for the previous experimental observation that even trace amounts of Pt can dramatically improve the catalytic performance of Ga2O3.

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“…27 − 30 Very recently, a method based on atomic trapping was developed for the preparation of highly dispersed Pt, even at atomic level. 31 − 33 It was reported that the oxidized Pt species can disperse as single atoms on a CeO 2– x support upon calcination at 800 °C under air. The obtained catalyst showed excellent catalytic performance in the low-temperature oxidation of CO and in the conversion of methane into C 2 hydrocarbons.…”

Section: Introductionmentioning

confidence: 99%

Pt/ZrO₂ Prepared by Atomic Trapping: An Efficient Catalyst for the Conversion of Glycerol to Lactic Acid with Concomitant Transfer Hydrogenation of Cyclohexene

et al. 2019

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A series of heterogeneous catalysts consisting of highly dispersed Pt nanoparticles supported on nanosized ZrO 2 (20 to 60 nm) was synthesized and investigated for the one-pot transfer hydrogenation between glycerol and cyclohexene to produce lactic acid and cyclohexane, without any additional H 2 . Different preparation methods were screened, by varying the calcination and reduction procedures with the purpose of optimizing the dispersion of Pt species (i.e., as single-atom sites or extra-fine Pt nanoparticles) on the ZrO 2 support. The Pt/ZrO 2 catalysts were characterized by means of transmission electron microscopy techniques (HAADF-STEM, TEM), elemental analysis (ICP-OES, EDX mapping), N 2 -physisorption, H 2 temperature-programmed-reduction (H 2 -TPR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Based on this combination of techniques it was possible to correlate the temperature of the calcination and reduction treatments with the nature of the Pt species. The best catalyst consisted of subnanometer Pt clusters (<1 nm) and atomically dispersed Pt (as Pt 2+ and Pt 4+ ) on the ZrO 2 support, which were converted into extra-fine Pt nanoparticles (average size = 1.4 nm) upon reduction. These nanoparticles acted as catalytic species for the transfer hydrogenation of glycerol with cyclohexene, which gave an unsurpassed 95% yield of lactic acid salt at 96% glycerol conversion (aqueous glycerol solution, NaOH as promoter, 160 °C, 4.5 h, at 20 bar N 2 ). This is the highest yield and selectivity of lactic acid (salt) reported in the literature so far. Reusability experiments showed a partial and gradual loss of activity of the Pt/ZrO 2 catalyst, which was attributed to the experimentally observed aggregation of Pt nanoparticles.

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Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Cited by 86 publications

References 38 publications

Stability of heterogeneous single-atom catalysts: a scaling law mapping thermodynamics to kinetics

Stability of heterogeneous single-atom catalysts: a scaling law mapping thermodynamics to kinetics

Dual‐function catalysis in propane dehydrogenation over Pt₁–Ga₂O₃ catalyst: Insights from a microkinetic analysis

Pt/ZrO₂ Prepared by Atomic Trapping: An Efficient Catalyst for the Conversion of Glycerol to Lactic Acid with Concomitant Transfer Hydrogenation of Cyclohexene

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Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Cited by 86 publications

References 38 publications

Stability of heterogeneous single-atom catalysts: a scaling law mapping thermodynamics to kinetics

Stability of heterogeneous single-atom catalysts: a scaling law mapping thermodynamics to kinetics

Dual‐function catalysis in propane dehydrogenation over Pt1–Ga2O3 catalyst: Insights from a microkinetic analysis

Pt/ZrO2 Prepared by Atomic Trapping: An Efficient Catalyst for the Conversion of Glycerol to Lactic Acid with Concomitant Transfer Hydrogenation of Cyclohexene

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About

Dual‐function catalysis in propane dehydrogenation over Pt₁–Ga₂O₃ catalyst: Insights from a microkinetic analysis

Pt/ZrO₂ Prepared by Atomic Trapping: An Efficient Catalyst for the Conversion of Glycerol to Lactic Acid with Concomitant Transfer Hydrogenation of Cyclohexene