Dynamic multinuclear sites formed by mobilized copper ions in NOₓ selective catalytic reduction
Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NOₓ) with ammonia (NH₃), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinet...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2017-09, Vol.357 (6354), p.898-903 |
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| creator | Paolucci, Christopher Khurana, Ishant Parekh, Atish A. Li, Sichi Shih, Arthur J. Li, Hui Di Iorio, John R. Albarracin-Caballero, Jonatan D. Yezerets, Aleksey Miller, Jeffrey T. Delgass, W. Nicholas Ribeiro, Fabio H. Schneider, William F. Gounder, Rajamani |
| description | Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NOₓ) with ammonia (NH₃), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O₂)–mediated CuI→CuII redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst. |
| doi_str_mv | 10.1126/science.aan5630 |
| format | Article |
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Nicholas ; Ribeiro, Fabio H. ; Schneider, William F. ; Gounder, Rajamani</creator><creatorcontrib>Paolucci, Christopher ; Khurana, Ishant ; Parekh, Atish A. ; Li, Sichi ; Shih, Arthur J. ; Li, Hui ; Di Iorio, John R. ; Albarracin-Caballero, Jonatan D. ; Yezerets, Aleksey ; Miller, Jeffrey T. ; Delgass, W. Nicholas ; Ribeiro, Fabio H. ; Schneider, William F. ; Gounder, Rajamani ; Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)</creatorcontrib><description>Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NOₓ) with ammonia (NH₃), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O₂)–mediated CuI→CuII redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst.</description><identifier>ISSN: 0036-8075</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.aan5630</identifier><language>eng</language><publisher>Washington: American Association for the Advancement of Science</publisher><subject>Absorption spectroscopy ; Aluminum ; Ammonia ; Catalysis ; Catalysts ; Copper ; Diesel engines ; First principles ; Heavy metals ; Ion pairs ; Ions ; Low temperature ; Nitrogen oxides ; Oxides ; Oxygen ; Photochemicals ; Selective catalytic reduction ; Spectroscopy ; Spectrum analysis ; Tethering ; X-ray absorption spectroscopy ; X-ray spectroscopy ; Zeolites</subject><ispartof>Science (American Association for the Advancement of Science), 2017-09, Vol.357 (6354), p.898-903</ispartof><rights>Copyright © 2017 by the American Association for the Advancement of Science</rights><rights>Copyright © 2017, American Association for the Advancement of Science</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>000000031347534X ; 0000000275195100 ; 0000000262690620 ; 0000000225655906 ; 000000017752461X ; 0000000245069306 ; 0000000306642138 ; 0000000345155826 ; 0000000161835085 ; 0000000224140644 ; 0000000162917912 ; 0000000254440103 ; 0000000193887170 ; 0000000251916655</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/26399742$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/26399742$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>230,314,780,784,803,885,27924,27925,58017,58250</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1463731$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Paolucci, Christopher</creatorcontrib><creatorcontrib>Khurana, Ishant</creatorcontrib><creatorcontrib>Parekh, Atish A.</creatorcontrib><creatorcontrib>Li, Sichi</creatorcontrib><creatorcontrib>Shih, Arthur J.</creatorcontrib><creatorcontrib>Li, Hui</creatorcontrib><creatorcontrib>Di Iorio, John R.</creatorcontrib><creatorcontrib>Albarracin-Caballero, Jonatan D.</creatorcontrib><creatorcontrib>Yezerets, Aleksey</creatorcontrib><creatorcontrib>Miller, Jeffrey T.</creatorcontrib><creatorcontrib>Delgass, W. Nicholas</creatorcontrib><creatorcontrib>Ribeiro, Fabio H.</creatorcontrib><creatorcontrib>Schneider, William F.</creatorcontrib><creatorcontrib>Gounder, Rajamani</creatorcontrib><creatorcontrib>Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)</creatorcontrib><title>Dynamic multinuclear sites formed by mobilized copper ions in NOₓ selective catalytic reduction</title><title>Science (American Association for the Advancement of Science)</title><description>Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NOₓ) with ammonia (NH₃), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O₂)–mediated CuI→CuII redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst.</description><subject>Absorption spectroscopy</subject><subject>Aluminum</subject><subject>Ammonia</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Copper</subject><subject>Diesel engines</subject><subject>First principles</subject><subject>Heavy metals</subject><subject>Ion pairs</subject><subject>Ions</subject><subject>Low temperature</subject><subject>Nitrogen oxides</subject><subject>Oxides</subject><subject>Oxygen</subject><subject>Photochemicals</subject><subject>Selective catalytic reduction</subject><subject>Spectroscopy</subject><subject>Spectrum analysis</subject><subject>Tethering</subject><subject>X-ray absorption spectroscopy</subject><subject>X-ray spectroscopy</subject><subject>Zeolites</subject><issn>0036-8075</issn><issn>1095-9203</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNotkM1KxDAUhYMoOI6uXQlB1x2T5qfNUsZfGJyNrkuaudUMbTImqVCXvoJv6JMYGFeHe8_H4XAQOqdkQWkpr6Ox4AwstHZCMnKAZpQoUaiSsEM0I4TJoiaVOEYnMW4JyZ5iM6RvJ6cHa_Aw9sm60fSgA442QcSdDwNscDvhwbe2t1_5MH63g4CtdxFbh5_Xv98_OEIPJtlPwEYn3U8p5wXYjPnn3Sk66nQf4exf5-j1_u5l-Vis1g9Py5tV8VZKlQouFKUVNaI1irdVR0hNmCYlb2nVClELWtPK8FoaIYGzsgVJSceBVUobbjibo8t9ro_JNnmNBObdeOdytYZyySpGM3S1h3bBf4wQU7P1Y3C5V0NVxZWSXIpMXeypbUw-NLtgBx2mppRMZahkf722bqk</recordid><startdate>20170901</startdate><enddate>20170901</enddate><creator>Paolucci, Christopher</creator><creator>Khurana, Ishant</creator><creator>Parekh, Atish A.</creator><creator>Li, Sichi</creator><creator>Shih, Arthur J.</creator><creator>Li, Hui</creator><creator>Di Iorio, John R.</creator><creator>Albarracin-Caballero, Jonatan D.</creator><creator>Yezerets, Aleksey</creator><creator>Miller, Jeffrey T.</creator><creator>Delgass, W. 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Nicholas</au><au>Ribeiro, Fabio H.</au><au>Schneider, William F.</au><au>Gounder, Rajamani</au><aucorp>Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Dynamic multinuclear sites formed by mobilized copper ions in NOₓ selective catalytic reduction</atitle><jtitle>Science (American Association for the Advancement of Science)</jtitle><date>2017-09-01</date><risdate>2017</risdate><volume>357</volume><issue>6354</issue><spage>898</spage><epage>903</epage><pages>898-903</pages><issn>0036-8075</issn><eissn>1095-9203</eissn><abstract>Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NOₓ) with ammonia (NH₃), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O₂)–mediated CuI→CuII redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst.</abstract><cop>Washington</cop><pub>American Association for the Advancement of Science</pub><doi>10.1126/science.aan5630</doi><tpages>6</tpages><orcidid>https://orcid.org/000000031347534X</orcidid><orcidid>https://orcid.org/0000000275195100</orcidid><orcidid>https://orcid.org/0000000262690620</orcidid><orcidid>https://orcid.org/0000000225655906</orcidid><orcidid>https://orcid.org/000000017752461X</orcidid><orcidid>https://orcid.org/0000000245069306</orcidid><orcidid>https://orcid.org/0000000306642138</orcidid><orcidid>https://orcid.org/0000000345155826</orcidid><orcidid>https://orcid.org/0000000161835085</orcidid><orcidid>https://orcid.org/0000000224140644</orcidid><orcidid>https://orcid.org/0000000162917912</orcidid><orcidid>https://orcid.org/0000000254440103</orcidid><orcidid>https://orcid.org/0000000193887170</orcidid><orcidid>https://orcid.org/0000000251916655</orcidid></addata></record> |
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| ispartof | Science (American Association for the Advancement of Science), 2017-09, Vol.357 (6354), p.898-903 |
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| source | JSTOR Archive Collection A-Z Listing; American Association for the Advancement of Science |
| subjects | Absorption spectroscopy Aluminum Ammonia Catalysis Catalysts Copper Diesel engines First principles Heavy metals Ion pairs Ions Low temperature Nitrogen oxides Oxides Oxygen Photochemicals Selective catalytic reduction Spectroscopy Spectrum analysis Tethering X-ray absorption spectroscopy X-ray spectroscopy Zeolites |
| title | Dynamic multinuclear sites formed by mobilized copper ions in NOₓ selective catalytic reduction |
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