Revealing hydrogen spillover pathways in reducible metal oxides

Shun, Kazuki; Mori, Kohsuke; Masuda, Seizo; Hashimoto, Naoki; Hinuma, Yoyo; Kobayashi, Hisayoshi; Yamashita, Hiromi

doi:10.1039/d2sc00871h

Cited by 66 publications

(55 citation statements)

References 61 publications

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“…The associated surface reaction was 2H ad + O lat −D → HD (g) + O lat −H, where H ad is an adsorbed H atom, O lat is lattice oxygen in the CeO 2 and HD (g) is gaseous HD generated via hydrogen spillover. 39 The Pd/CeO 2 -NRs produced the most intense HD peak in the temperature range of 0 to 150 °C (Figure 1h), exceeding those produced by the Pd/CeO 2 -NPs and Pd/CeO 2 -NCs by factors of 1.7 and 4.4, respectively.…”

Section: Resultsmentioning

confidence: 94%

Sub-nanometric high entropy alloy cluster: hydrogen spillover-driven synthesis on CeO2 and structural reversibility

Hashimoto

Mori

Matsuzaki

et al. 2023

Preprint

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High-entropy alloy (HEA) nanoparticles (NPs) have attracted significant attention as promising catalysts, as a consequence of the various unique synergistic effects originating from the nanometer-scale, near-equimolar mixing of five or more components to produce single-phase solid solutions. However, the study of sub-nanometer HEA clusters having sizes of less than 1 nm remains incomplete despite the possibility of novel functions related to borderline molecular states with discrete quantum energy levels. The present work demonstrates the synthesis of CeO2 nanorods (CeO2-NRs) on which sub-nanometer CoNiCuZnPd HEA clusters consisting of 13 atoms were formed with the aid of a pronounced hydrogen spillover effect on readily reducible CeO2 (110) facets. The CoNiCuZnPd HEA sub-nanoclusters exhibited higher activity during the reduction of NO by H2 even at low temperatures compared with the corresponding monometallic catalysts. These clusters also showed a unique structural reversibility in response to repeated exposure to oxidative/reductive conditions, based on the sacrificial oxidation of the non-noble metals. Both experimental and theoretical analyses established that multi-element mixing in quantum-sized regions endowed the HEA clusters with entirely novel catalytic properties.

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Section: Resultsmentioning

confidence: 94%

Sub-nanometric high entropy alloy cluster: hydrogen spillover-driven synthesis on CeO2 and structural reversibility

Hashimoto

Mori

Matsuzaki

et al. 2023

Preprint

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“…In the present work, the comparison of oxide materials with the same surface loading of platinum allows in comparison to other studies direct quantitative evaluation of different behavior. For iron oxide, ceria, and titania, the major findings of this work are schematically depicted in Scheme , which highlights the diverse nature of hydrogen interaction with platinum–metal oxide catalysts . Iron oxide has the lowest uptake temperature for hydrogen in the presence of platinum via spillover and is an excellent hydrogenation catalyst for aromatic nitrocompounds .…”

Section: Discussionmentioning

confidence: 90%

“…For iron oxide, ceria, and titania, the major findings of this work are schematically depicted in Scheme 1 , which highlights the diverse nature of hydrogen interaction with platinum–metal oxide catalysts. 13 Iron oxide has the lowest uptake temperature for hydrogen in the presence of platinum via spillover and is an excellent hydrogenation catalyst for aromatic nitrocompounds. 45 However, easily induced phase transition may be an unwanted effect in catalysis since it may corrupt the catalyst’s lifetime.…”

Section: Discussionmentioning

confidence: 99%

“…A high energy barrier generally hampers hydrogen activation on perfect metal oxide surfaces; e.g., hydrogen dissociation on iron oxide surfaces has an activation barrier of 4.4 eV . In contrast, hydrogen dissociation on noble metals like platinum is barrier-free (<0.1 eV) and readily occurs below room temperature. ,− As a consequence, the presence of platinum on the metal oxide surface drastically influences the oxide by hydrogen spillover. , In the present study, we systematically investigated the hydrogen uptake behavior of iron(III) oxide, cerium(IV) oxide (ceria), zirconium(IV) oxide (zirconia), and aluminum(III) oxide (alumina) in the presence and absence of platinum. Platinum has, in all cases, an influence on the temperature of hydrogen uptake.…”

Section: Introductionmentioning

confidence: 99%

“… 9 In contrast, hydrogen dissociation on noble metals like platinum is barrier-free (<0.1 eV) and readily occurs below room temperature. 7 , 10 − 13 As a consequence, the presence of platinum on the metal oxide surface drastically influences the oxide by hydrogen spillover. 14 , 15 In the present study, we systematically investigated the hydrogen uptake behavior of iron(III) oxide, cerium(IV) oxide (ceria), zirconium(IV) oxide (zirconia), and aluminum(III) oxide (alumina) in the presence and absence of platinum.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Hydrogen Interaction with Oxide Supports in the Presence and Absence of Platinum

Beck

Rzepka

Marshall³

et al. 2022

J. Phys. Chem. C

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Oxides are essential catalysts and supports for noble metal catalysts. Their interaction with hydrogen enables, e.g., their use as a hydrogenation catalyst. Among the oxides considered reducible, substantial differences exist in their capability to activate hydrogen and how the oxide structure transforms due to this interaction. Noble metals, like platinum, generally enhance the oxide reduction by hydrogen spillover. This work presents a systematic temperature-programmed reduction study (300 to 873 K) of iron oxide, ceria, titania, zirconia, and alumina, with and without supported platinum. For all catalysts, platinum enhances the reducibility of the oxide. However, there are pronounced differences among all catalysts.

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Recent Advances and Perspectives on Supported Catalysts for Heterogeneous Hydrogen Production from Ammonia Borane

et al. 2023

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Ammonia borane (AB), a liquid hydrogen storage material, has attracted increasing attention for hydrogen utilization because of its high hydrogen content. However, the slow kinetics of AB hydrolysis and the indefinite catalytic mechanism remain significant problems for its large-scale practical application. Thus, the development of efficient AB hydrolysis catalysts and the determination of their catalytic mechanisms are significant and urgent. A summary of the preparation process and structural characteristics of various supported catalysts is presented in this paper, including graphite, metal-organic frameworks (MOFs), metal oxides, carbon nitride (CN), molybdenum carbide (MoC), carbon nanotubes (CNTs), boron nitride (h-BN), zeolites, carbon dots (CDs), and metal carbide and nitride (MXene). In addition, the relationship between the electronic structure and catalytic performance is discussed to ascertain the actual active sites in the catalytic process. The mechanism of AB hydrolysis catalysis is systematically discussed, and possible catalytic paths are summarized to provide theoretical considerations for the designing of efficient AB hydrolysis catalysts. Furthermore, three methods for stimulating AB from dehydrogenation by-products and the design of possible hydrogen product-regeneration systems are summarized. Finally, the remaining challenges and future research directions for the effective development of AB catalysts are discussed.

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Revealing hydrogen spillover pathways in reducible metal oxides

Abstract: Hydrogen spillover, the migration of dissociated hydrogen atoms from noble metal to their support materials, is a ubiquitous phenomenon and is widely utilized in heterogeneous catalysis and hydrogen storage materials....

Cited by 66 publications

References 61 publications

Sub-nanometric high entropy alloy cluster: hydrogen spillover-driven synthesis on CeO2 and structural reversibility

Sub-nanometric high entropy alloy cluster: hydrogen spillover-driven synthesis on CeO2 and structural reversibility

Hydrogen Interaction with Oxide Supports in the Presence and Absence of Platinum

Recent Advances and Perspectives on Supported Catalysts for Heterogeneous Hydrogen Production from Ammonia Borane

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