Cooperativity and Dynamics Increase the Performance of NiFe Dry Reforming Catalysts

The dry reforming of methane (DRM), i.e., the reaction of methane and CO2 to form a synthesis gas, converts two major greenhouse gases into a useful chemical feedstock. In this work, we probe the effect and role of Fe in bimetallic NiFe dry reforming catalysts. To this end, monometallic Ni, Fe, and...

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Veröffentlicht in:Journal of the American Chemical Society 2017-02, Vol.139 (5), p.1937-1949
Hauptverfasser: Kim, Sung Min, Abdala, Paula Macarena, Margossian, Tigran, Hosseini, Davood, Foppa, Lucas, Armutlulu, Andac, van Beek, Wouter, Comas-Vives, Aleix, Copéret, Christophe, Müller, Christoph
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container_end_page 1949
container_issue 5
container_start_page 1937
container_title Journal of the American Chemical Society
container_volume 139
creator Kim, Sung Min
Abdala, Paula Macarena
Margossian, Tigran
Hosseini, Davood
Foppa, Lucas
Armutlulu, Andac
van Beek, Wouter
Comas-Vives, Aleix
Copéret, Christophe
Müller, Christoph
description The dry reforming of methane (DRM), i.e., the reaction of methane and CO2 to form a synthesis gas, converts two major greenhouse gases into a useful chemical feedstock. In this work, we probe the effect and role of Fe in bimetallic NiFe dry reforming catalysts. To this end, monometallic Ni, Fe, and bimetallic Ni-Fe catalysts supported on a Mg x Al y O z matrix derived via a hydrotalcite-like precursor were synthesized. Importantly, the textural features of the catalysts, i.e., the specific surface area (172–178 m2/gcat), pore volume (0.51–0.66 cm3/gcat), and particle size (5.4–5.8 nm) were kept constant. Bimetallic, Ni4Fe1 with Ni/(Ni + Fe) = 0.8, showed the highest activity and stability, whereas rapid deactivation and a low catalytic activity were observed for monometallic Ni and Fe catalysts, respectively. XRD, Raman, TPO, and TEM analysis confirmed that the deactivation of monometallic Ni catalysts was in large due to the formation of graphitic carbon. The promoting effect of Fe in bimetallic Ni-Fe was elucidated by combining operando XRD and XAS analyses and energy-dispersive X-ray spectroscopy complemented with density functional theory calculations. Under dry reforming conditions, Fe is oxidized partially to FeO leading to a partial dealloying and formation of a Ni-richer NiFe alloy. Fe migrates leading to the formation of FeO preferentially at the surface. Experiments in an inert helium atmosphere confirm that FeO reacts via a redox mechanism with carbon deposits forming CO, whereby the reduced Fe restores the original Ni-Fe alloy. Owing to the high activity of the material and the absence of any XRD signature of FeO, it is very likely that FeO is formed as small domains of a few atom layer thickness covering a fraction of the surface of the Ni-rich particles, ensuring a close proximity of the carbon removal (FeO) and methane activation (Ni) sites.
doi_str_mv 10.1021/jacs.6b11487
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In this work, we probe the effect and role of Fe in bimetallic NiFe dry reforming catalysts. To this end, monometallic Ni, Fe, and bimetallic Ni-Fe catalysts supported on a Mg x Al y O z matrix derived via a hydrotalcite-like precursor were synthesized. Importantly, the textural features of the catalysts, i.e., the specific surface area (172–178 m2/gcat), pore volume (0.51–0.66 cm3/gcat), and particle size (5.4–5.8 nm) were kept constant. Bimetallic, Ni4Fe1 with Ni/(Ni + Fe) = 0.8, showed the highest activity and stability, whereas rapid deactivation and a low catalytic activity were observed for monometallic Ni and Fe catalysts, respectively. XRD, Raman, TPO, and TEM analysis confirmed that the deactivation of monometallic Ni catalysts was in large due to the formation of graphitic carbon. The promoting effect of Fe in bimetallic Ni-Fe was elucidated by combining operando XRD and XAS analyses and energy-dispersive X-ray spectroscopy complemented with density functional theory calculations. Under dry reforming conditions, Fe is oxidized partially to FeO leading to a partial dealloying and formation of a Ni-richer NiFe alloy. Fe migrates leading to the formation of FeO preferentially at the surface. Experiments in an inert helium atmosphere confirm that FeO reacts via a redox mechanism with carbon deposits forming CO, whereby the reduced Fe restores the original Ni-Fe alloy. 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Am. Chem. Soc</addtitle><description>The dry reforming of methane (DRM), i.e., the reaction of methane and CO2 to form a synthesis gas, converts two major greenhouse gases into a useful chemical feedstock. In this work, we probe the effect and role of Fe in bimetallic NiFe dry reforming catalysts. To this end, monometallic Ni, Fe, and bimetallic Ni-Fe catalysts supported on a Mg x Al y O z matrix derived via a hydrotalcite-like precursor were synthesized. Importantly, the textural features of the catalysts, i.e., the specific surface area (172–178 m2/gcat), pore volume (0.51–0.66 cm3/gcat), and particle size (5.4–5.8 nm) were kept constant. Bimetallic, Ni4Fe1 with Ni/(Ni + Fe) = 0.8, showed the highest activity and stability, whereas rapid deactivation and a low catalytic activity were observed for monometallic Ni and Fe catalysts, respectively. XRD, Raman, TPO, and TEM analysis confirmed that the deactivation of monometallic Ni catalysts was in large due to the formation of graphitic carbon. The promoting effect of Fe in bimetallic Ni-Fe was elucidated by combining operando XRD and XAS analyses and energy-dispersive X-ray spectroscopy complemented with density functional theory calculations. Under dry reforming conditions, Fe is oxidized partially to FeO leading to a partial dealloying and formation of a Ni-richer NiFe alloy. Fe migrates leading to the formation of FeO preferentially at the surface. Experiments in an inert helium atmosphere confirm that FeO reacts via a redox mechanism with carbon deposits forming CO, whereby the reduced Fe restores the original Ni-Fe alloy. Owing to the high activity of the material and the absence of any XRD signature of FeO, it is very likely that FeO is formed as small domains of a few atom layer thickness covering a fraction of the surface of the Ni-rich particles, ensuring a close proximity of the carbon removal (FeO) and methane activation (Ni) sites.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNptkE1PwzAMhiMEYmNw44xy5EBHnDZJe0Qdg0kTID7OlZe60GltR9Ih9d_TaQMunCxbj1_LD2PnIMYgJFwv0fqxXgBEsTlgQ1BSBAqkPmRDIYQMTKzDATvxftm3kYzhmA1kLHQMQg_ZS9o0a3LYll9l23Gscz7paqxK6_msto7QE28_iD-RKxpXYW2JNwV_KKfEJ67jz7Qdl_U7T7HFVedbf8qOClx5OtvXEXub3r6m98H88W6W3swDjKRpA6Ul6DzXhkBAUiiwSmGhkxwUEpA2ICnBMDEmhqiQpMlYE1mlIywQk0U4Ype73LVrPjfk26wqvaXVCmtqNj6DWJnQ9DmiR692qHWN946KbO3KCl2Xgci2GrOtxmyvsccv9smbRUX5L_zj7e_0dmvZbFzdP_p_1jdeCXrc</recordid><startdate>20170208</startdate><enddate>20170208</enddate><creator>Kim, Sung Min</creator><creator>Abdala, Paula Macarena</creator><creator>Margossian, Tigran</creator><creator>Hosseini, Davood</creator><creator>Foppa, Lucas</creator><creator>Armutlulu, Andac</creator><creator>van Beek, Wouter</creator><creator>Comas-Vives, Aleix</creator><creator>Copéret, Christophe</creator><creator>Müller, Christoph</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-7002-1582</orcidid><orcidid>https://orcid.org/0000-0001-9660-3890</orcidid></search><sort><creationdate>20170208</creationdate><title>Cooperativity and Dynamics Increase the Performance of NiFe Dry Reforming Catalysts</title><author>Kim, Sung Min ; Abdala, Paula Macarena ; Margossian, Tigran ; Hosseini, Davood ; Foppa, Lucas ; Armutlulu, Andac ; van Beek, Wouter ; Comas-Vives, Aleix ; Copéret, Christophe ; Müller, Christoph</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a427t-56216dd67e1019f51c55af69d15ae1e6712e9a3977814f2e6e7c74c564afaa9b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kim, Sung Min</creatorcontrib><creatorcontrib>Abdala, Paula Macarena</creatorcontrib><creatorcontrib>Margossian, Tigran</creatorcontrib><creatorcontrib>Hosseini, Davood</creatorcontrib><creatorcontrib>Foppa, Lucas</creatorcontrib><creatorcontrib>Armutlulu, Andac</creatorcontrib><creatorcontrib>van Beek, Wouter</creatorcontrib><creatorcontrib>Comas-Vives, Aleix</creatorcontrib><creatorcontrib>Copéret, Christophe</creatorcontrib><creatorcontrib>Müller, Christoph</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kim, Sung Min</au><au>Abdala, Paula Macarena</au><au>Margossian, Tigran</au><au>Hosseini, Davood</au><au>Foppa, Lucas</au><au>Armutlulu, Andac</au><au>van Beek, Wouter</au><au>Comas-Vives, Aleix</au><au>Copéret, Christophe</au><au>Müller, Christoph</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Cooperativity and Dynamics Increase the Performance of NiFe Dry Reforming Catalysts</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. 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Bimetallic, Ni4Fe1 with Ni/(Ni + Fe) = 0.8, showed the highest activity and stability, whereas rapid deactivation and a low catalytic activity were observed for monometallic Ni and Fe catalysts, respectively. XRD, Raman, TPO, and TEM analysis confirmed that the deactivation of monometallic Ni catalysts was in large due to the formation of graphitic carbon. The promoting effect of Fe in bimetallic Ni-Fe was elucidated by combining operando XRD and XAS analyses and energy-dispersive X-ray spectroscopy complemented with density functional theory calculations. Under dry reforming conditions, Fe is oxidized partially to FeO leading to a partial dealloying and formation of a Ni-richer NiFe alloy. Fe migrates leading to the formation of FeO preferentially at the surface. Experiments in an inert helium atmosphere confirm that FeO reacts via a redox mechanism with carbon deposits forming CO, whereby the reduced Fe restores the original Ni-Fe alloy. Owing to the high activity of the material and the absence of any XRD signature of FeO, it is very likely that FeO is formed as small domains of a few atom layer thickness covering a fraction of the surface of the Ni-rich particles, ensuring a close proximity of the carbon removal (FeO) and methane activation (Ni) sites.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>28068106</pmid><doi>10.1021/jacs.6b11487</doi><tpages>13</tpages><orcidid>https://orcid.org/0000-0002-7002-1582</orcidid><orcidid>https://orcid.org/0000-0001-9660-3890</orcidid></addata></record>
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