Selective Oxidative Coupling of Methane to Ethylene in a Solid Oxide Electrolyser Based on Porous Single‐Crystalline CeO<sub>2</sub> Monoliths

Ye, Lingting; Shang, Zhibo; Xie, Kui

doi:10.1002/anie.202207211

Cited by 17 publications

(17 citation statements)

References 53 publications

(16 reference statements)

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“…No energy loss peak appears after the zero-loss peak collected in the interior of either (111)/(100)CeO 2 or (111)/(100)CeO 2– x (Figure f), suggesting the high purity of (111)/(100)CeO 2 and (111)/(100)CeO 2– x interiors. In addition, some other techniques such as X-ray photoelectron spectroscopy (XPS), Raman spectrum, and electron paramagnetic resonance (EPR) plots shown in Figures S12–S15 all help distinguish the difference in oxygen vacancy counts (richer oxygen vacancies in (111)/(100)CeO 2– x than in (111)/(100)CeO 2 ) over these two samples from a macro perspective. − More information with analysis are provided in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

“X-Scheme” Charge Separation Induced by Asymmetrical Localized Electronic Band Structures at the Ceria Oxide Facet Junction

Rao

Huang

et al. 2023

ACS Catal.

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Photogenerated charge transfer can be tuned by crystal face controlling and heterostructure engineering. However, it is exceptionally challenging to understand the separation and transfer process of charge carriers, especially on the facet junction. Here, we show a separation pathway of the charge carriers in (111)/(100)CeO 2−x nanomaterials as the "X-Scheme junction" using selected region electron energy-loss spectroscopies. The driving force for the "X-Scheme junction" can be attributed to the localized electronic band structures' asymmetry of the ceria, which gathers the photogenerated electrons on the surface of the (111) plane and accumulates the photogenerated holes on the (100) face. Surface oxygen vacancies channel the photogenerated electrons and holes further to the Ce 3+ of the (111) plane and the Ce 4+ of the (100) plane, respectively, resulting in an enhanced photo-oxidative nitric oxide removal efficiency under visible-light irradiation. Furthermore, the system is found to integrate metal nanoparticles to form Pd− CeO 2−x , including Pd-(111)CeO 2−x and Pd-(100)CeO 2−x , which significantly restricts nitric dioxide production as a byproduct. This work provides a unique approach to understanding single-crystal photocatalysts based on the facet junction.

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Section: Resultsmentioning

confidence: 99%

“X-Scheme” Charge Separation Induced by Asymmetrical Localized Electronic Band Structures at the Ceria Oxide Facet Junction

Rao

Huang

et al. 2023

ACS Catal.

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“…Chem., Int. Ed.202261e202207211 This paper reports the tailoring of the chemical states and flux of active oxygen species at well-defined interfaces.…”

Section: Key Referencesmentioning

confidence: 99%

“…(a) Schematic illustration of symmetric SOE. Reproduced with permission from ref , copyright 2022 Wiley. (b) SEM and XRD pattern of PSC CeO 2 monoliths with in situ exsolved single-crystalline Ni nanoparticles.…”

Section: Functionalities and Applicationsmentioning

confidence: 99%

Section: Functionalities and Applicationsmentioning

confidence: 99%

“…Here we fabricate the PSC Ni x Ce 1– x O 2 electrode at the centimeter scale and exsolve Ni nanoparticles anchored onl the surface to construct well-defined metal–oxide interfaces for functioning three-phase boundaries as shown in Figure (b–d). , The average size of Ni nanoparticles is ∼4 nm. We use in situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) to investigate both the anode ( p CH 4 = 0.5 mbar) and cathode ( p CO 2 = 0.5 mbar) as shown in Figure (e–h).…”

Section: Functionalities and Applicationsmentioning

confidence: 99%

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Porous Single Crystals at the Macroscale: From Growth to Application

Xie

2023

Acc. Chem. Res.

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Conspectus Porous materials have wide applications in the fields of catalysis, separation, and energy conversion and storage. Porous materials contain pores that are specifically designed to achieve expectant performance. The solid phases in porous materials are normally completely continuous to form the basic porous frame while the pores are fluid phase within the solid phase. Single crystals are macroscopic materials in three spatial dimensions with the constituent atoms, ions, molecules, or molecular assemblies arranged in an orderly repeating pattern with the ordered structures. The growth of single crystals is indeed a process to arrange these constituents in three dimensions into a repeating pattern within the materials. Today the applications of single crystals are exponentially growing in wide fields, and single crystals are therefore unacknowledged as the pillars of our modern technology. Introducing porosity into single crystals would be expected to create a new kind of porous material in which the basic porous frames are single-crystalline and free of grain boundaries. The structural symmetry is completely maintained within the basic porous frames which are a continuous solid phase, but it is completely lost inside the pores. The porous architecture is free of grain boundaries, and the fully interconnected skeletons are in single-crystalline states within the basic porous frames. Single crystals with porosities can therefore be considered to be a new kind of porous material, but they are single-crystal-like because the structural symmetry is maintained only in the skeletons and completely lost within the pores. We therefore call them porous single crystals or consider them in porous single-crystalline states to stand out with their structural features. Porous single crystals at the macroscale combine the advantages of porous materials and single crystals to incorporate both porosity and structural coherence in a porous architecture, leading to invaluable opportunities to alter the material’s properties by controlling the unique structural features to enhance its performance. However, the growth of single crystals in three dimensions reduces the formation of porosities, leading to a fundamental challenge for introducing porosity into single crystals in a traditional process of crystal growth. In this Account, we report the rational design, growth methodology, and microstructural engineering of porous single crystals in a solid–solid transformation. We rationally design a high-density mother phase in a single-crystalline state and transform it into a low-density new phase in a single-crystalline state to introduce porosities into single crystals even incorporating the removal of specific compositions from the mother phase during the growth of porous single crystals. The porosity can be tailored by controlling the change in relative densities from the mother phase to the porous single crystals while the pore size can be engineered by controlling the fabrication conditions. Considering the unique structura...

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Chelated Ion‐Exchange Strategy toward BiOCl Mesoporous Single‐Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation

Mao

Liu

et al. 2023

Advanced Materials

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The photoresponse and photocatalytic efficiency of bismuth oxychloride (BiOCl) are greatly limited by rapid recombination of photogenerated carriers. The construction of porous single‐crystal BiOCl photocatalyst can effectively alleviate this issue and provide accessible active sites. Herein, a facile chelated ion‐exchange strategy is developed to synthesize BiOCl mesoporous single‐crystalline nanosheets (BiOCl MSCN) using acetic acid and ammonia solution respectively as chelating agent and ionization promoter. The strong chelation between acetate ions and Bi3+ ions introduces acetate ions into the precipitated product to exchange with Cl‐ ions, resulting in large lattice mismatch, strain release, and formation of void‐like mesopores. The prepared BiOCl MSCN photocatalyst exhibits excellent catalytic performance with 99% conversion and 98% selectivity for oxidation of benzyl alcohol to benzaldehyde and superior general adaptability for various aromatic alcohols. The theoretical calculations and characterizations confirm that the superior performance is mainly attributed to the abundant oxygen vacancies, plenty of accessible adsorption/active sites and fast charge transport path without grain boundaries.

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Selective Oxidative Coupling of Methane to Ethylene in a Solid Oxide Electrolyser Based on Porous Single‐Crystalline CeO₂ Monoliths

Cited by 17 publications

References 53 publications

“X-Scheme” Charge Separation Induced by Asymmetrical Localized Electronic Band Structures at the Ceria Oxide Facet Junction

“X-Scheme” Charge Separation Induced by Asymmetrical Localized Electronic Band Structures at the Ceria Oxide Facet Junction

Porous Single Crystals at the Macroscale: From Growth to Application

Chelated Ion‐Exchange Strategy toward BiOCl Mesoporous Single‐Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation

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Selective Oxidative Coupling of Methane to Ethylene in a Solid Oxide Electrolyser Based on Porous Single‐Crystalline CeO2 Monoliths

Cited by 17 publications

References 53 publications

“X-Scheme” Charge Separation Induced by Asymmetrical Localized Electronic Band Structures at the Ceria Oxide Facet Junction

“X-Scheme” Charge Separation Induced by Asymmetrical Localized Electronic Band Structures at the Ceria Oxide Facet Junction

Porous Single Crystals at the Macroscale: From Growth to Application

Chelated Ion‐Exchange Strategy toward BiOCl Mesoporous Single‐Crystalline Nanosheets for Boosting Photocatalytic Selective Aromatic Alcohols Oxidation

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Product

Resources

About

Selective Oxidative Coupling of Methane to Ethylene in a Solid Oxide Electrolyser Based on Porous Single‐Crystalline CeO₂ Monoliths