On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

Kozyra, Paweł; Radoń, Mariusz; Dátka, Jerzy; Brocławik, Ewa

doi:10.1007/s11224-012-0050-y

Cited by 15 publications

(25 citation statements)

References 55 publications

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“…4 depicts respective contour plots analogous to those presented in Ref. 5, but for consistency with those in Fig. 3, they were recalculated with the PBE0 functional (see the Computational protocol).…”

Section: Computational Protocolmentioning

confidence: 99%

“…As pointed out previously, much care is needed when choosing the occupation of the NO fragment, where a single unpaired electron is to be arbitrarily distributed in a doubly-degenerate * singly occupied molecular orbital (SOMO). 5 To keep the local electronic structure on NO in the promolecule similar to that in the T1Cu(I/II)-NO adducts, the unpaired electron was placed on the NO * orbital lying in the Cu-N-O plane (denoted as * ʈ ), with the perpendicular one (denoted as * Ќ ) remaining unoccupied. Figures 3 and 4 show contour plots of significant electron density transfer channels between NO and copper sites for NO adducts with Cu(II) and Cu(I) sites, respectively, while Tables 1 and 2 list calculated populations, main geometry parameters, and characteristics of independent density transfer channels for the studied systems.…”

Section: Computational Protocolmentioning

confidence: 99%

“…4 On the other hand, the adsorption of NO on a Cu(I) site in a zeolite, represented by a simple CuAlO 4 cluster model, has been recently studied by DFT calculations aided with the resolution of the deformation density (electron density transferred between NO and a cluster upon bond formation) into independent electron transfer channels. 5 We have shown in Ref. 5 that the comparison of spin-and orbital-resolved charge transfer channels for models of the gas phase Cu + -NO and a Cu(I) site in zeolites partially resolved queries concerning the bonding between Cu(I) and NO from the electronic, orbital interaction perspective, especially in the context of the impact of embedding on NO activation.…”

Section: Introductionmentioning

confidence: 99%

“…5 We have shown in Ref. 5 that the comparison of spin-and orbital-resolved charge transfer channels for models of the gas phase Cu + -NO and a Cu(I) site in zeolites partially resolved queries concerning the bonding between Cu(I) and NO from the electronic, orbital interaction perspective, especially in the context of the impact of embedding on NO activation. Therefore, it was tempting to apply the same protocol to the analogous model of a Cu(II) site to better understand and rationalize differences between the two forms of copper sites.…”

Section: Introductionmentioning

confidence: 99%

“…Indeed, our discussion of the identity and roles of electron density transfer channels to and from copper monocationic systems in the case of nitric oxide appeared highly complicated due to elusive electronic structure of NO adducts. 5 Only spin-resolved analysis of the deformation density with preselected electronic configuration on the NO fragment allowed the extraction of the two electron transfer channels strongly related to the changes of the NO bond. Unpaired electron transfer from the antibonding * NO orbital, apparently strengthening the bond, dominated the Cu + -NO gas phase system.…”

Section: Introductionmentioning

confidence: 99%

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Electronic propensity of Cu(II) versus Cu(I) sites in zeolites to activate NO — Spin- and orbital-resolved Cu–NO electron transfer

et al. 2013

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Electronic factors responsible for the notable decline of NO activation by Cu(II) with respect to Cu(I) sites in zeolites are investigated within spin-resolved analysis of electron transfer channels between the copper center and the substrate. The results of natural orbitals for chemical valence (NOCV) charge transfer analysis for a minimal model of Cu(II) sites in zeolite ZSM-5 ({T1Cu} + NO) are compared with those for Cu(I)-NO and referenced to an interaction of NO with bare Cu + cations. The bonding of NO, which is an open-shell and non-innocent ligand, gives rise to a noticeable nondynamical correlation in the adduct with Cu(II) (reflected in a broken-symmetry solution obtained at the density functional theory (DFT) level). Four distinct components of electron transfer between the copper and NO are identified: (i) donation of an unpaired electron from the NO ʈ * antibonding orbital to the Cu species, (ii) backdonation from copper d Ќ to the NO antibonding orbital, (iii) "covalent" donation from NO ʈ and Cu d ʈ orbitals to the bonding region, and (iv) donation from the nitrogen lone pair to Cu s,d . Large variations in channel identity and significance may be noted among studied systems and between spin manifolds: channel i is effective only in the bonding of NO with either a naked Cu + cation or Cu(II) site. Channel ii comes into prominence only for the model of the Cu(I) site: it strongly activates the NO bond by populating antibonding *, which weakens the N-O bond, in contrast to channel i depopulating the antibonding orbital and strengthening the N-O bond. Channels iii and iv, however, may contribute to the strength of the bonding between NO and copper, and are of minor importance for the activation of the NO bond. This picture perfectly matches the IR experiment: interaction with either Cu(II) sites or a naked Cu + cation imposes a comparable blue-shift of NO stretching frequency, while the frequency becomes strongly red-shifted for a Cu(I) site in ZSM-5 due to enhanced * backdonation.Résumé : Pour étudier les facteurs électroniques à l'origine de la diminution notable de l'activation de NO par les sites à Cu(II) comparativement aux sites à Cu(I) dans les zéolites, on procède à une analyse résolue en spin des mécanismes de transfert d'électrons entre le centre cuivre et le substrat. On compare les résultats de l'analyse du transfert de charge selon la théorie de la valence chimique des orbitales naturelles (VCON) pour le modèle minimal des sites à Cu(II) dans ZSM-5 ({T1Cu} + NO) à ceux obtenus pour Cu(I)-NO en prenant pour référence une interaction de NO avec les cations Cu + nus. La liaison de NO, qui est un ligand à couches ouvertes et non innocent, donne lieu à une corrélation non dynamique appréciable dans l'adduit formé avec le Cu(II) (ce que reflète la solution à symétrie brisée au niveau de la DFT). On distingue quatre composantes distinctes du transfert d'électrons entre le cuivre et NO : i) donation d'un électron non apparié de l'orbitale antiliante * de NO à l'espèce Cu, ii) rétrodonation de l'o...

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Section: Computational Protocolmentioning

confidence: 99%

Section: Computational Protocolmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electronic propensity of Cu(II) versus Cu(I) sites in zeolites to activate NO — Spin- and orbital-resolved Cu–NO electron transfer

et al. 2013

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Built‐in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra‐Low Concentration and Electroreduction to Ammonia

Sun

et al. 2021

Angewandte Chemie

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Ab uilt-in electric field in electrocatalyst can significantly accumulate higher concentration of NO 3 À ions near electrocatalyst surface region, thus facilitating mass transfer for efficient nitrate removal at ultra-lowconcentration and electroreduction reaction (NO 3 RR). Am odel electrocatalyst is created by stacking CuCl (111) and rutile TiO 2 (110) layers together,i nw hich ab uilt-in electric field induced from the electron transfer from TiO 2 to CuCl (CuCl_BEF) is successfully formed .T his built-in electric field effectively triggers interfacial accumulation of NO 3 À ions around the electrocatalyst. The electric field also raises the energy of key reaction intermediate *NO to lower the energy barrier of the rate determining step.ANH 3 product selectivity of 98.6 %, alow NO 2 À production of < 0.6 %, and mass-specific ammonia production rate of 64.4 h À1 is achieved, whicha re all the best among studies reported at 100 mg L À1 of nitrate concentration to date.

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Built‐in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra‐Low Concentration and Electroreduction to Ammonia

et al. 2021

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On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

Cited by 15 publications

References 55 publications

Electronic propensity of Cu(II) versus Cu(I) sites in zeolites to activate NO — Spin- and orbital-resolved Cu–NO electron transfer

Electronic propensity of Cu(II) versus Cu(I) sites in zeolites to activate NO — Spin- and orbital-resolved Cu–NO electron transfer

Built‐in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra‐Low Concentration and Electroreduction to Ammonia

Built‐in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra‐Low Concentration and Electroreduction to Ammonia

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