The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO‐CeO<sub>2</sub> Catalysts

Kang, Liqun; Wang, Bolun; Güntner, Andreas T.; Xu, Siyuan; Wan, Xuhao; Liu, Yiyun; Marlow, Sushila; Ren, Yifei; Gianolio, Diego; Tang, Chiu C.; Murzin, Vadim; Asakura, Hiroyuki; He, Qian; Guan, Shaoliang; Velasco-Vélez, Juan-Jesús; Pratsinis, Sotiris E.; Guo, Yuzheng; Wang, Ryan

doi:10.1002/anie.202102570

Cited by 28 publications

(17 citation statements)

References 70 publications

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“…In particular, the metal interaction with third row (MgO 5 , Al 2 O 3 6 and SiO 2 7 ) oxides and fourth row 3 d metal oxides (TiO 2 1 , 4 , 8 – 12 , FeO x 13 – 15 , Co 3 O 4 16 , 17 ) have been widely explored and discussed in terms of electron transfer process 18 , 19 , oxygen vacancies 1 , 11 , 12 , 20 and surface wetting 4 . In comparison, fifth or sixth row oxides, such as rare earth oxides, are seldom used as catalysts support except for CeO 2 2 , 3 , 20 – 25 . These early transition rare earth cations are strong Lewis acid and have strong binding to Lewis base such as H 2 O and NH 3 .…”

Section: Introductionmentioning

confidence: 99%

Catalytically efficient Ni-NiOx-Y2O3 interface for medium temperature water-gas shift reaction

Yan

Wang

et al. 2022

Nat Commun

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The metal-support interfaces between metals and oxide supports have long been studied in catalytic applications, thanks to their significance in structural stability and efficient catalytic activity. The metal-rare earth oxide interface is particularly interesting because these early transition cations have high electrophilicity, and therefore good binding strength with Lewis basic molecules, such as H2O. Based on this feature, here we design a highly efficient composite Ni-Y2O3 catalyst, which forms abundant active Ni-NiOx-Y2O3 interfaces under the water-gas shift (WGS) reaction condition, achieving 140.6 μmolCO gcat−1 s−1 rate at 300 °C, which is the highest activity for Ni-based catalysts. A combination of theory and ex/in situ experimental study suggests that Y2O3 helps H2O dissociation at the Ni-NiOx-Y2O3 interfaces, promoting this rate limiting step in the WGS reaction. Construction of such new interfacial structure for molecules activation holds great promise in many catalytic systems.

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Section: Introductionmentioning

confidence: 99%

Catalytically efficient Ni-NiOx-Y2O3 interface for medium temperature water-gas shift reaction

Yan

Wang

et al. 2022

Nat Commun

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“…What happens when a single metal atom is added onto a metal oxide surface? Taking Cu 2+ as an example, the 3d of 4sp of Cu 2+ will first hybridize with the conduction and valence bands of metal oxides, forming four Cu–O–M bonds. − Due to the different energies of Cu and M valence orbitals, the resultant Cu–O and O–M bonds in the atomic site usually have less bond strength than those in bulk CuO and MO. Those bridging O 2– in Cu–O–M should be more reactive and can be easily taken away by reducing agents compared with lattice O 2– .…”

Section: Introductionmentioning

confidence: 99%

Designing Reactive Bridging O^2– at the Atomic Cu–O–Fe Site for Selective NH₃ Oxidation

et al. 2022

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Surface oxidation chemistry involves the formation and breaking of metal−oxygen (M−O) bonds. Ideally, the M−O bonding strength determines the rate of oxygen absorption and dissociation. Here, we design reactive bridging O 2− species within the atomic Cu−O−Fe site to accelerate such oxidation chemistry. Using in situ X-ray absorption spectroscopy at the O K-edge and density functional theory calculations, it is found that such bridging O 2− has a lower antibonding orbital energy and thus weaker Cu− O/Fe−O strength. In selective NH 3 oxidation, the weak Cu−O/ Fe−O bond enables fast Cu redox for NH 3 conversion and direct NO adsorption via Cu−O−NO to promote N−N coupling toward N 2 .As a result, 99% N 2 selectivity at 100% conversion is achieved at 573 K, exceeding most of the reported results. This result suggests the importance to design, determine, and utilize the unique features of bridging O 2− in catalysis.

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“…In contrast, there is no CO 2 produced when H 2 O is introduced for the reference 5Cu/Al 2 O 3 catalyst (Figure S5), indicating that it does not have the exchange capability. Thus, compared with stable carbonate species on other oxide surfaces, , the accessibility of the carbonate layer on the surface of Sm 2 O 2 CO 3 provides favorable conditions for the exchange with hydroxyl. In conclusion, the combination of theory and experimental study demonstrates that the rare-earth oxycarbonates are naturally beneficial to the dissociation of H 2 O and produce *OH for exchange with the *CO 3 formed by CO 2 adsorption, realizing the efficient circulation of reactants and product molecules, which creates favorable conditions for accelerating the progress of the WGS reaction.…”

Section: Resultsmentioning

confidence: 99%

Promoting Molecular Exchange on Rare-Earth Oxycarbonate Surfaces to Catalyze the Water–Gas Shift Reaction

Zhou

et al. 2023

J. Am. Chem. Soc.

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It is highly desirable to fabricate an accessible catalyst surface that can efficiently activate reactants and desorb products to promote the local surface reaction equilibrium in heterogeneous catalysis. Herein, rare-earth oxycarbonates (Ln2O2CO3, where Ln = La and Sm), which have molecular-exchangeable (H2O and CO2) surface structures according to the ordered layered arrangement of Ln2O2 2+ and CO3 2– ions, are unearthed. On this basis, a series of Ln2O2CO3-supported Cu catalysts are prepared through the deposition precipitation method, which provides excellent catalytic activity and stability for the water–gas shift (WGS) reaction. Density functional theory calculations combined with systematic experimental characterizations verify that H2O spontaneously dissociates on the surface of Ln2O2CO3 to form hydroxyl by eliminating the carbonate through the release of CO2. This interchange efficiently promotes the WGS reaction equilibrium shift on the local surface and prevents the carbonate accumulation from hindering the active sites. The discovery of the unique layered structure provides a so-called “self-cleaning” active surface for the WGS reaction and opens new perspectives about the application of rare-earth oxycarbonate nanomaterials in C1 chemistry.

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO‐CeO₂ Catalysts

Cited by 28 publications

References 70 publications

Catalytically efficient Ni-NiOx-Y2O3 interface for medium temperature water-gas shift reaction

Catalytically efficient Ni-NiOx-Y2O3 interface for medium temperature water-gas shift reaction

Designing Reactive Bridging O^2– at the Atomic Cu–O–Fe Site for Selective NH₃ Oxidation

Promoting Molecular Exchange on Rare-Earth Oxycarbonate Surfaces to Catalyze the Water–Gas Shift Reaction

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO‐CeO2 Catalysts

Cited by 28 publications

References 70 publications

Catalytically efficient Ni-NiOx-Y2O3 interface for medium temperature water-gas shift reaction

Catalytically efficient Ni-NiOx-Y2O3 interface for medium temperature water-gas shift reaction

Designing Reactive Bridging O2– at the Atomic Cu–O–Fe Site for Selective NH3 Oxidation

Promoting Molecular Exchange on Rare-Earth Oxycarbonate Surfaces to Catalyze the Water–Gas Shift Reaction

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The Electrophilicity of Surface Carbon Species in the Redox Reactions of CuO‐CeO₂ Catalysts

Designing Reactive Bridging O^2– at the Atomic Cu–O–Fe Site for Selective NH₃ Oxidation