Geometry and electronic structure of lead phthalocyanine: Quantum calculations via density-functional theory and photoemission measurements

Papageorgiou, Nicolas; Ferro, Y.; Salomon, Éric; Allouche, A.; Layet, J. M.; Giovanelli, Luca; Lay, G. Le

doi:10.1103/physrevb.68.235105

Cited by 92 publications

(92 citation statements)

References 35 publications

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“…Evidence for the presence of surface nitrogen (N1s peak, see Fig. 9b) is a single peak centered at 399.0 eV, in agreement with the literature [68][69][70]; there is little separation (e.g., 0.28 eV as a shift in Pb-Pc [71]) between the four equivalent aza-type nitrogens and four equivalent pyrrole-type nitrogens (for both Co-and Cu-Pc). The decrease in surface nitrogen content with HTT is consistent with the disappearance of the C1s peak at 285.7 eV (attributed to carbon-nitrogen bonding, as mentioned above) and is practically undetected at 850°C and above.…”

Section: Effect Of Httsupporting

confidence: 76%

Pyrolyzed phthalocyanines as surrogate carbon catalysts: Initial insights into oxygen-transfer mechanisms

Vallejos-Burgos

Utsumi

Hattori

et al. 2012

Fuel

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a b s t r a c tDeposited and heat-treated phthalocyanines are promising electrocatalysts for replacing platinum in the oxygen reduction reaction (ORR), the most important process in energy conversion systems such as fuel cells; and yet its key mechanistic features are not well understood. To optimize their use, it is necessary to understand their behavior in the absence of an electric field. In the pursuit of this goal, we pyrolyzed metal-free, cobalt and copper phthalocyanines between 550 and 1000°C and studied their structural and chemical changes by elemental analysis, N 2 and CO 2 adsorption, X-ray diffraction (XRD), Raman spectroscopy, X-ray analysis fine structure (XAFS) and X-ray photoelectron spectroscopy (XPS). Their catalytic activity was assessed by non-isothermal O 2 gasification and NO reduction reactions. A comparison of these results with their other properties allowed us to reach the following conclusions: (i) the loss of reactivity of metal-free phthalocyanine with heat treatment is attributed to its structural annealing and heteroatom loss, with the porosity changes having no effect; (ii) for metal phthalocyanines at intermediate heat treatment temperatures, the optimum in reactivity correlates with the micropore surface area and the presence of metal particles, with no influence of nitrogen content; (iii) the coordination metal increases phthalocyanine thermal stability in an inert atmosphere, but in an oxidizing atmosphere it acts as a gasification catalyst even below decomposition temperatures. The implications of these findings for catalytic oxygen-transfer mechanisms are discussed.

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Section: Effect Of Httsupporting

confidence: 76%

Pyrolyzed phthalocyanines as surrogate carbon catalysts: Initial insights into oxygen-transfer mechanisms

Vallejos-Burgos

Utsumi

Hattori

et al. 2012

Fuel

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“…Indeed, two opposite phenylene rings bend up and the perpendicular ones bend down with respect to the surface, causing a breaking of the fourfold molecular symmetry. 16 This angular deformation has been previously observed for MPcs on semiconductor surfaces, 39,[45][46][47] where the molecular distortion induced by the substrate covalent bondings is more pronounced. This slight molecular distortion can explain the energy shift between the benzene and pyrrole components of the C 1s core-levels when the central metal atoms of FePc and CoPc interact with Au.…”

Section: Resultsmentioning

confidence: 74%

“…The fifth component (B v ) is related to the excitation of a vibrational mode for carbon atoms belonging to the benzene rings. 39,[42][43][44] Fit parameters are reported in Table III. An overall energy shift by a few tenths of eV towards higher BE is observed comparing both SLs with respect to their corresponding TFs, shift observed also for the shake-up satellites.…”

Section: Resultsmentioning

confidence: 99%

“…The N-1s core level is due the photoexcitation from the two non-equivalent nitrogen atoms (N 1 and N 2 ) in the pyrrole rings and in the bridge position, respectively, in agreement with previous observations on a variety of MPcs. [37][38][39][40][41][42] We fit the N-1s core-level with pseudo-Voigtprofiled peaks, all presenting a gaussian width of 0.19 eV (representing the overall energy resolution). The two main components with 0.4 eV energy difference, and the broad shake-up satellite structure (N s ) at higher BE, are in agreement with the literature on MPcs, 38,41,42 and the fit parameters are reported in Table II.…”

Section: Resultsmentioning

confidence: 99%

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Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

Massimi

Angelucci

Gargiani

et al. 2014

The Journal of Chemical Physics

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Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption, and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K. © 2014 AIP Publishing LLC

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“…The shoulder S B and the feature S P are the satellites of the B and P components, respectively. [21][22][23][24][25][26][27] The ratio of the B to P components, taking into account the satellites, is very close to theoretically expected value of 3. The main N 1 s peak of the lowest spectrum in Fig.…”

Section: -2mentioning

confidence: 99%

Morphology and properties of a hybrid organic-inorganic system: Al nanoparticles embedded into CuPc thin film

Молодцова

Аристова

Babenkov

et al. 2014

Journal of Applied Physics

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The evolution of the morphology and the electronic structure of the hybrid organic-inorganic system composed of aluminum nanoparticles (NPs) distributed in an organic semiconductor matrix—copper phthalocyanine (CuPc)—as a function of nominal aluminum content was studied by transmission electron microscopy and by photoemission spectroscopy methods. The aluminum atoms deposited onto the CuPc surface diffuse into the organic matrix and self-assemble to NPs in a well-defined manner with a narrow diameter distribution, which depends on the amount of aluminum that is evaporated onto the CuPc film. We find clear evidence of a charge transfer from Al to CuPc and we have been able to determine the lattice sites where Al ions sit. The finally at high coverage about 64 Å the formation of metallic aluminum overlayer on CuPc thin film takes place.

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Geometry and electronic structure of lead phthalocyanine: Quantum calculations via density-functional theory and photoemission measurements

Cited by 92 publications

References 35 publications

Pyrolyzed phthalocyanines as surrogate carbon catalysts: Initial insights into oxygen-transfer mechanisms

Pyrolyzed phthalocyanines as surrogate carbon catalysts: Initial insights into oxygen-transfer mechanisms

Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

Morphology and properties of a hybrid organic-inorganic system: Al nanoparticles embedded into CuPc thin film

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