Arephin Islam, Erwei Huang, Yi Tian, Pedro J Ramírez, Kasala Prabhakar Reddy, Hojoon Lim, Nathaniel White, Adrian Hunt, Iradwikanari Waluyo, Ping Liu, José A Rodriguez
{"title":"Low-Temperature Activation and Coupling of Methane on MgO Nanostructures Embedded in Cu<sub>2</sub>O/Cu(111).","authors":"Arephin Islam, Erwei Huang, Yi Tian, Pedro J Ramírez, Kasala Prabhakar Reddy, Hojoon Lim, Nathaniel White, Adrian Hunt, Iradwikanari Waluyo, Ping Liu, José A Rodriguez","doi":"10.1021/acsnano.4c10811","DOIUrl":null,"url":null,"abstract":"<p><p>The efficient conversion of methane into valuable hydrocarbons, such as ethane and ethylene, at relatively low temperatures without deactivation issues is crucial for advancing sustainable energy solutions. Herein, AP-XPS and STM studies show that MgO nanostructures (0.2-0.5 nm wide, 0.4-0.6 Å high) embedded in a Cu<sub>2</sub>O/Cu(111) substrate activate methane at room temperature, mainly dissociating it into CH<sub><i>x</i></sub> (<i>x</i> = 2 or 3) and H adatoms, with minimal conversion to C adatoms. These MgO nanostructures in contact with Cu<sub>2</sub>O/Cu(111) enable C-C coupling into ethane and ethylene at 500 K, a significantly lower temperature than that required for bulk MgO catalysts (>700 K), with negligible carbon deposition and no deactivation. DFT calculations corroborate these experimental findings. The CH<sub>4,gas</sub> → *CH<sub>3</sub> + *H reaction is a downhill process on MgO/Cu<sub>2</sub>O/Cu(111) surfaces. The activation of methane is facilitated by electron transfer from copper to MgO and the existence of Mg and O atoms with a low coordination number in the oxide nanostructures. The formation of O-CH<sub>3</sub> and O-H bonds overcomes the energy necessary for the cleavage of a C-H bond in methane. DFT studies reveal that smaller Mg<sub>2</sub>O<sub>2</sub> model clusters provide stronger binding and lower activation barriers for C-H dissociation in CH<sub>4</sub>, while larger Mg<sub>3</sub>O<sub>3</sub> clusters promote C-C coupling due to weaker *CH<sub>3</sub> binding. All of these results emphasize the importance of size when optimizing the catalytic performance of MgO nanostructures in the selective conversion of methane.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8000,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Nano","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acsnano.4c10811","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The efficient conversion of methane into valuable hydrocarbons, such as ethane and ethylene, at relatively low temperatures without deactivation issues is crucial for advancing sustainable energy solutions. Herein, AP-XPS and STM studies show that MgO nanostructures (0.2-0.5 nm wide, 0.4-0.6 Å high) embedded in a Cu2O/Cu(111) substrate activate methane at room temperature, mainly dissociating it into CHx (x = 2 or 3) and H adatoms, with minimal conversion to C adatoms. These MgO nanostructures in contact with Cu2O/Cu(111) enable C-C coupling into ethane and ethylene at 500 K, a significantly lower temperature than that required for bulk MgO catalysts (>700 K), with negligible carbon deposition and no deactivation. DFT calculations corroborate these experimental findings. The CH4,gas → *CH3 + *H reaction is a downhill process on MgO/Cu2O/Cu(111) surfaces. The activation of methane is facilitated by electron transfer from copper to MgO and the existence of Mg and O atoms with a low coordination number in the oxide nanostructures. The formation of O-CH3 and O-H bonds overcomes the energy necessary for the cleavage of a C-H bond in methane. DFT studies reveal that smaller Mg2O2 model clusters provide stronger binding and lower activation barriers for C-H dissociation in CH4, while larger Mg3O3 clusters promote C-C coupling due to weaker *CH3 binding. All of these results emphasize the importance of size when optimizing the catalytic performance of MgO nanostructures in the selective conversion of methane.
期刊介绍:
ACS Nano, published monthly, serves as an international forum for comprehensive articles on nanoscience and nanotechnology research at the intersections of chemistry, biology, materials science, physics, and engineering. The journal fosters communication among scientists in these communities, facilitating collaboration, new research opportunities, and advancements through discoveries. ACS Nano covers synthesis, assembly, characterization, theory, and simulation of nanostructures, nanobiotechnology, nanofabrication, methods and tools for nanoscience and nanotechnology, and self- and directed-assembly. Alongside original research articles, it offers thorough reviews, perspectives on cutting-edge research, and discussions envisioning the future of nanoscience and nanotechnology.