Surface characterization and methane activation on SnOx/Cu2O/Cu(111) inverse oxide/metal catalysts

Kang, Jindong; Rui, Ning; Huang, Enyu; Tian, Yi; Mahapatra, Mausumi; Rosales, Rina; Orozco, Ivan; Senanayake, Sanjaya D.; Liu, Ping; Rodríguez, José A.

doi:10.1039/d1cp02829d

Cited by 12 publications

(55 citation statements)

References 58 publications

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“…This finding demonstrates the relevant role played by an inverse ZnO/Cu configuration . In subsequent works, a substantial enhancement in the rate of methanol synthesis on Cu(111) was found after growing islands of zinc oxide onto this substrate. , In a ZnO/Cu configuration, the oxide overlayer and the oxide-metal interface have structural and electronic properties not seen for a regular Cu/ZnO configuration. ,, In general, the dispersion of oxide nanoparticles (ZnO, TiO 2 , SnO 2 , CeO 2 ) on a Cu(111) substrate generates very good catalysts for C1 chemistry (CO and CO 2 conversion, methanol synthesis, forward and reverse water–gas shift reactions, methane activation). − …”

Section: Introductionmentioning

confidence: 72%

“…The AP-XPS measurements were done using a SPECS instrument equipped with a PHOIBOS 150 EP MCD-9 analyzer and a Mg Kα X-ray source. 13,15,19 The experiments examining the catalytic activity of the ZrO 2 /CuO x /Cu(111) systems were performed in a setup that combines an ultrahigh vacuum (UHV) chamber for surface characterization and a batch microreactor for catalytic tests. 13,15,17 The UHV chamber was equipped with instrumentation for XPS (Al/Mg K alpha), Auger electron spectroscopy (AES), ion-scattering spectroscopy (ISS), and temperature-programmed desorption (TDS).…”

Section: ■ Methodsmentioning

confidence: 99%

“…An Omicron STM instrument was used to study the catalysts morphology. ,,, All the STM images were collected at room temperature, after the preparation and manipulation of the ZrO 2 /CuO x /Cu(111) surfaces, using a Pt–Ir tip. The AP-XPS measurements were done using a SPECS instrument equipped with a PHOIBOS 150 EP MCD-9 analyzer and a Mg Kα X-ray source. ,, …”

Section: Methodsmentioning

confidence: 99%

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CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Rui

Gutiérrez

Rosales

et al. 2021

Ind. Eng. Chem. Res.

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The conversion and utilization of carbon dioxide is a critical challenge for the reduction of greenhouse gas pollution and in the production of high value chemicals in C1 chemistry. ZrO2/Cu(111) is an inverse oxide/metal catalyst that displays high activity and stability for the hydrogenation of CO2 into methanol at 500–600 K. At elevated temperatures, ZrO2 grows on a CuO x /Cu(111) substrate forming islands of 10–12 nm in size and an average height of ∼3 Å. Reaction with H2 leads to the removal of the copper oxide producing ZrO2/Cu(111) surfaces which are very active for the binding and dissociation of CO2 into CO and C. After exposing ZrO2/Cu(111) to moderate or elevated pressures of a CO2/H2 mixture at 300 K, atomic C and minor amounts of CH x O and CO x are deposited on the catalyst surface. The adsorbed CH x O and CO x disappear upon heating above 400 K. The catalytic tests for CO2 hydrogenation give CO as the main reaction product and CH4 and CH3OH as secondary products. The relative yields of methane and methanol change with time and track the amount of atomic C deposited on the active ZrO2/Cu(111) surface. The formation of methane stops once the catalyst surface is saturated with C. Under steady-state conditions, ZrO2/Cu(111) is a much better catalyst for methanol synthesis than ZnO/Cu(111). This trend reflects variations in the size of the oxide islands and in the strength of oxide-metal interactions. The use of an inverse oxide/metal configuration is an important synthetic tool when preparing active, selective, and stable catalysts for CO2 hydrogenation.

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Section: Introductionmentioning

confidence: 72%

Section: ■ Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Rui

Gutiérrez

Rosales

et al. 2021

Ind. Eng. Chem. Res.

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“…Sn and SnO x have been studied and employed in the past for use as gas sensors − and are used in diverse types of catalytic reactions such as ethanol oxidation for fuel cells, CO oxidation, electrochemical CO 2 reduction, dry reforming and steam reforming of methane, partial oxidation of methane, and methane chlorination. − Additionally, in a previous study, our group investigated methane activation on highly dispersed SnO x nanoparticles (NPs) that were grown on Cu 2 O/Cu(111) using reactive deposition . This study demonstrated that SnO x /CuO x /Cu(111) catalysts activate methane even at room temperature and enhance the activity upon creation of a SnO x –Cu 2 O interface . However, the contribution of pure SnO x without any interfacial sites cannot be distinguished by such a system due to the existence of an active SnO x –Cu 2 O interface.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Surface Structure and Catalytic Activity of SnO_x/Au(111) Inverse Catalysts for CO₂ and H₂ Activation

et al. 2022

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Carbon dioxide hydrogenation is a promising approach for the reduction of greenhouse gas pollution via the production of fuels and high-value chemicals utilizing C1 chemistry. In this process, the activation of nonpolar molecules, CO 2 and H 2 , at mild conditions is challenging. Herein, we report a well-defined inverse SnO x /Au(111) catalyst that shows the ability to activate both CO 2 and H 2 at room temperature. Scanning tunneling microscopy (STM) and ambient pressure X-ray photoemission spectroscopy (AP-XPS) are combined to understand the surface structure, growth mode, chemical state, and activity of SnO x /Au(111) surfaces. Nanostructures of SnO x at the sub-monolayer level were prepared by depositing Sn on Au(111) followed by O 2 oxidation. For the as-prepared SnO x /Au(111), twodimensionally formed SnO x thin films on a Au(111) substrate were observed with STM of two different moieties, discernible based on their height: clusters (∼0.4 Å) and nanoparticles (NPs, 1−2.5 Å), which are assigned to Sn−Au alloys and SnO x , respectively, in corroboration with XPS analysis. Furthermore, SnO x /Au(111) was annealed under UHV to test its thermal stability. Upon annealing at 400−600 K, a disappearance of SnO x NPs and reappearance of highly dispersed Sn clusters were clearly noticeable from the STM and XPS results, identifying the thermal decomposition of SnO x and subsequent formation of Sn−Au alloys on the surface due to the recombination of Sn clusters with Au. We investigated the reactivity of the SnO x /Au(111) surfaces toward CH 4 , CO 2 , and H 2 . The SnO x /Au(111) surfaces have excellent CO 2 and H 2 activation abilities even at room temperature with negligible reactivity for methane activation. Our AP-XPS results show that H 2 can be activated on the SnO x NPs by the reduction to Sn. For CO 2 , the activation and further dissociation are identified by a reoxidation of Sn with newly formed Sn−O bonds and the formation of surface carbon. Therefore, we propose that SnO x is a potential catalyst or additive to achieve CO 2 hydrogenation under mild conditions.

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“…They are more conductive , and more resistant to electromigration . They can serve as a platform for investigating catalytic mechanisms and enhancing catalytic performance − and also for growing epitaxial foreign materials such as graphene − and transition metal dichalcogenides. − Specific interest has been placed on the (111) orientation. Rodriguez et al reported that TiO 2– x /Au(111) and CeO 2– x /Au(111) catalysts shows high water–gas shift performance .…”

Section: Introductionmentioning

confidence: 99%

Pseudoequilibrium between Etching and Selective Grain Growth: Chemical Conversion of a Randomly Oriented Au Film into a (111)-Oriented Ultrathin Au Film

et al. 2021

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Metal thin films with a specific orientation play vital roles in electronics, catalysts, and epitaxial templates. Although oriented metal films have been produced in the recent years, ultrathin oriented metal films (<10 nm) have not been achieved owing to the interfacial instability of the ultrathin films during the thermal annealing process. This study investigates chemical conversion of randomly oriented multigrain Au ultrathin films into (111)-oriented Au ultrathin films. A novel chemical process, termed pseudoequilibrium of etching and selective grain growth, is presented for the chemical conversion by using a quaternary ammonium halide. The reaction variables (reaction time, reaction temperature, species of halide ions) for the chemical conversion process are systematically investigated. This study reveals the inplane rotational degeneracy in the Au(111) thin film epitaxially grown on a Si(111) substrate. The chemical process can be applied to a broad range of thicknesses from 9 to 100 nm.

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Surface characterization and methane activation on SnO_x/Cu₂O/Cu(111) inverse oxide/metal catalysts

Abstract: To activate methane at low or medium temperatures is a difficult task and a pre-requisite for the conversion of this light alkane into high value chemicals. Herein, we report the...

Cited by 12 publications

References 58 publications

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Understanding the Surface Structure and Catalytic Activity of SnO_x/Au(111) Inverse Catalysts for CO₂ and H₂ Activation

Pseudoequilibrium between Etching and Selective Grain Growth: Chemical Conversion of a Randomly Oriented Au Film into a (111)-Oriented Ultrathin Au Film

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Surface characterization and methane activation on SnOx/Cu2O/Cu(111) inverse oxide/metal catalysts

Abstract: To activate methane at low or medium temperatures is a difficult task and a pre-requisite for the conversion of this light alkane into high value chemicals. Herein, we report the...

Cited by 12 publications

References 58 publications

CO2 Hydrogenation on ZrO2/Cu(111) Surfaces: Production of Methane and Methanol

CO2 Hydrogenation on ZrO2/Cu(111) Surfaces: Production of Methane and Methanol

Understanding the Surface Structure and Catalytic Activity of SnOx/Au(111) Inverse Catalysts for CO2 and H2 Activation

Pseudoequilibrium between Etching and Selective Grain Growth: Chemical Conversion of a Randomly Oriented Au Film into a (111)-Oriented Ultrathin Au Film

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Surface characterization and methane activation on SnO_x/Cu₂O/Cu(111) inverse oxide/metal catalysts

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Understanding the Surface Structure and Catalytic Activity of SnO_x/Au(111) Inverse Catalysts for CO₂ and H₂ Activation