Dinitrogen dissociation on an isolated surface tantalum atom

P. Avenier; M. Taoufik; A. Lesage; X. Solans-Monfort; A. Baudouin; A. De Mallmann; L. Veyre; J. M. Basset; O. Eisenstein; L. Emsley; E. A. Quadrelli

doi:10.1126/science.1143078

Dinitrogen dissociation on an isolated surface tantalum atom

P. Avenier, M. Taoufik^*, A. Lesage, X. Solans-Monfort, A. Baudouin, A. De Mallmann, L. Veyre, J. M. Basset, O. Eisenstein, L. Emsley, E. A. Quadrelli

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

Both industrial and biochemical ammonia syntheses are thought to rely on the cooperation of multiple metals in breaking the strong triple bond of dinitrogen. Such multimetallic cooperation for dinitrogen cleavage is also the general rule for dinitrogen reductive cleavage with molecular systems and surfaces. We have observed cleavage of dinitrogen at 250°C and atmospheric pressure by dihydrogen on isolated silica surface-supported tantalum(III) and tantalum(V) hydride centers [(≡Si-O)₂Ta^III-H] and [(≡Si-O)₂Ta^VH₃], leading to the Ta ^V amido imido product [(≡SiO)₂Ta(=NH)(NH ₂)]: We assigned the product structure based on extensive characterization by infrared and solid-state nuclear magnetic resonance spectroscopy, isotopic labeling studies, and supporting data from x-ray absorption and theoretical simulations. Reaction intermediates revealed by in situ monitoring of the reaction with infrared spectroscopy support a mechanism highly distinct from those previously observed in enzymatic, organometallic, and heterogeneous N₂ activating systems.

Original language	English (US)
Pages (from-to)	1056-1060
Number of pages	5
Journal	SCIENCE
Volume	317
Issue number	5841
DOIs	https://doi.org/10.1126/science.1143078
State	Published - Aug 24 2007
Externally published	Yes

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title = "Dinitrogen dissociation on an isolated surface tantalum atom",

abstract = "Both industrial and biochemical ammonia syntheses are thought to rely on the cooperation of multiple metals in breaking the strong triple bond of dinitrogen. Such multimetallic cooperation for dinitrogen cleavage is also the general rule for dinitrogen reductive cleavage with molecular systems and surfaces. We have observed cleavage of dinitrogen at 250°C and atmospheric pressure by dihydrogen on isolated silica surface-supported tantalum(III) and tantalum(V) hydride centers [(≡Si-O)2TaIII-H] and [(≡Si-O)2TaVH3], leading to the Ta V amido imido product [(≡SiO)2Ta(=NH)(NH 2)]: We assigned the product structure based on extensive characterization by infrared and solid-state nuclear magnetic resonance spectroscopy, isotopic labeling studies, and supporting data from x-ray absorption and theoretical simulations. Reaction intermediates revealed by in situ monitoring of the reaction with infrared spectroscopy support a mechanism highly distinct from those previously observed in enzymatic, organometallic, and heterogeneous N2 activating systems.",

author = "P. Avenier and M. Taoufik and A. Lesage and X. Solans-Monfort and A. Baudouin and {De Mallmann}, A. and L. Veyre and Basset, {J. M.} and O. Eisenstein and L. Emsley and Quadrelli, {E. A.}",

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month = aug,

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doi = "10.1126/science.1143078",

language = "English (US)",

volume = "317",

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journal = "SCIENCE",

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T1 - Dinitrogen dissociation on an isolated surface tantalum atom

AU - Avenier, P.

AU - Taoufik, M.

AU - Lesage, A.

AU - Solans-Monfort, X.

AU - Baudouin, A.

AU - De Mallmann, A.

AU - Veyre, L.

AU - Basset, J. M.

AU - Eisenstein, O.

AU - Emsley, L.

AU - Quadrelli, E. A.

PY - 2007/8/24

Y1 - 2007/8/24

N2 - Both industrial and biochemical ammonia syntheses are thought to rely on the cooperation of multiple metals in breaking the strong triple bond of dinitrogen. Such multimetallic cooperation for dinitrogen cleavage is also the general rule for dinitrogen reductive cleavage with molecular systems and surfaces. We have observed cleavage of dinitrogen at 250°C and atmospheric pressure by dihydrogen on isolated silica surface-supported tantalum(III) and tantalum(V) hydride centers [(≡Si-O)2TaIII-H] and [(≡Si-O)2TaVH3], leading to the Ta V amido imido product [(≡SiO)2Ta(=NH)(NH 2)]: We assigned the product structure based on extensive characterization by infrared and solid-state nuclear magnetic resonance spectroscopy, isotopic labeling studies, and supporting data from x-ray absorption and theoretical simulations. Reaction intermediates revealed by in situ monitoring of the reaction with infrared spectroscopy support a mechanism highly distinct from those previously observed in enzymatic, organometallic, and heterogeneous N2 activating systems.

AB - Both industrial and biochemical ammonia syntheses are thought to rely on the cooperation of multiple metals in breaking the strong triple bond of dinitrogen. Such multimetallic cooperation for dinitrogen cleavage is also the general rule for dinitrogen reductive cleavage with molecular systems and surfaces. We have observed cleavage of dinitrogen at 250°C and atmospheric pressure by dihydrogen on isolated silica surface-supported tantalum(III) and tantalum(V) hydride centers [(≡Si-O)2TaIII-H] and [(≡Si-O)2TaVH3], leading to the Ta V amido imido product [(≡SiO)2Ta(=NH)(NH 2)]: We assigned the product structure based on extensive characterization by infrared and solid-state nuclear magnetic resonance spectroscopy, isotopic labeling studies, and supporting data from x-ray absorption and theoretical simulations. Reaction intermediates revealed by in situ monitoring of the reaction with infrared spectroscopy support a mechanism highly distinct from those previously observed in enzymatic, organometallic, and heterogeneous N2 activating systems.

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DO - 10.1126/science.1143078

M3 - Article

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AN - SCOPUS:34548260410

SN - 0036-8075

VL - 317

SP - 1056

EP - 1060

JO - SCIENCE

JF - SCIENCE

IS - 5841

ER -

Dinitrogen dissociation on an isolated surface tantalum atom

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