Influence of substrate on molecular order for self‐assembled adlayers of CoPc and FePc

Kumar, Abhishek; Naumenko, Denys; Cozzarini, Luca; Barba, Luisa; Cassetta, Alberto; Pedio, M.

doi:10.1002/jrs.5344

Cited by 17 publications

(14 citation statements)

References 27 publications

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“…In the SHINERS test, SiO 2 -coated Au nanoparticles were used to enhance the Raman signal. In the open-circuit potential state, the Raman spectra of molecular FePc agree with previous reports (Figure a). The single sharp peak at 1532 cm –1 is associated with the −CN–C– groups of molecular FePc. , Following a potential step to 0.5 V, where FePc molecules catalyze the ORR, the pristine peak shows an apparent attenuation, while a new peak appears at 1512 cm –1 .…”

Section: Resultssupporting

confidence: 91%

Molecular Degradation of Iron Phthalocyanine during the Oxygen Reduction Reaction in Acidic Media

et al. 2022

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Molecular iron phthalocyanine (FePc) possesses an FeN4 active site structure similar to practical pyrolyzed Fe/N/C catalysts for the acidic oxygen reduction reaction (ORR), making it an ideal model system to derive the degradation mechanism of such catalysts. However, the degradation mechanism of FePc during the acidic ORR has been largely unclear to date. Herein, five most likely degradation factors affecting FePc-based ORR activity are individually investigated and compared. The attack by free radicals is found to be the main reason for the instability of FePc. Assisted by the combination of several spectroscopic methods, we successfully identify the degradation products and then propose a full structural evolution of molecular FePc degradation. Finally, high similarity in the decay mechanism between molecular FePc and practical Fe/N/C catalysts was present. This study provides a clear picture of the currently missing degradation mechanism of molecular FePc during acidic ORR, which will assist future investigations on the performance degradation of practical Fe/N/C catalysts.

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Section: Resultssupporting

confidence: 91%

Molecular Degradation of Iron Phthalocyanine during the Oxygen Reduction Reaction in Acidic Media

et al. 2022

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“…In particular, the peak at 751 cm −1 is less intense than that at 682 cm −1 , indicating that the molecular film is in the structural α-phase. [57,58] This finding is confirmed by X-ray diffractometry, where a single peak at 6.7° is observed (Figure S2, Supporting Information). This diffraction pattern is analogous to that reported by Serri et al for CoPc molecules arranged in the α-phase with an edge-on configuration on SiO 2 .…”

Section: Resultssupporting

confidence: 61%

Exchange Bias in Molecule/Fe₃GeTe₂ van der Waals Heterostructures via Spinterface Effects

Calavalle

Martín‐García

et al. 2022

Advanced Materials

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a Curie temperature close to the room temperature and strong out-of-plane anisotropy. [7][8][9][10] Moreover, the magnetic properties of FGT are tunable, as they can be modified either electrically, applying a gate voltage [11] and a large electrical current, [12] or through magnetic proximity effects. [13][14][15][16] In particular, when interfaced with antiferromagnetic layered materials, FGT displays an increased coercivity and exchange bias, [13][14][15][16] which are the prototypical manifestation of magnetic proximity [17][18][19] and are key elements in spintronic devices. [20] Another attractive approach to tune the properties of a magnetic surface is molecular functionalization. [21,22] The interfaces between magnetic materials and molecules, often named spinterfaces, [21,22] host hybrid states or magnetic interactions which lead to radical changes on the magnetic properties of both the molecular layer [23][24][25][26][27][28][29][30] and the magnetic material. [27][28][29][30][31][32][33] So far, the ferromagnetic layers used for investigating spinterface effects are typically films of 3d metals or oxides with dangling bonds on the surface, which result in nonideal interfaces with molecules. Moreover, until recently, the molecular side of a spinterface has been the main target of research due to its easily tunable electronic properties, [23][24][25][26][27][28][29] whereas the possibility of tailoring the magnetism of ferromagnetic materials has yet to be fully exploited.Layered magnetic materials are excellent candidates for developing a spinterface in view of their tunable magnetism and their single crystalline nature, which offer the possibility to form highly controllable interfaces with molecules [34,35] via the so-called van der Waals epitaxy. [36][37][38][39] Indeed, hybrid heterostructures based on atomically sharp 2D material/molecule interfaces have been widely used to tailor the optoelectronic and transport properties of nonmagnetic layered materials. [40][41][42][43][44][45] However, so far the possibility to tune the properties of a layered magnetic material through the magnetic interactions at a van der Waals spinterface has not yet been experimentally demonstrated.Here, we report on the emergence of spinterface effects between molecular films of Co-phthalocyanine (CoPc) and a few-nm-thick FGT flakes. The molecular layer induces a negative magnetic exchange bias in FGT, indicating that the The exfoliation of layered magnetic materials generates atomically thin flakes characterized by an ultrahigh surface sensitivity, which makes their magnetic properties tunable via external stimuli, such as electrostatic gating and proximity effects. Another powerful approach to engineer magnetic materials is molecular functionalization, generating hybrid interfaces with tailored magnetic interactions, called spinterfaces. However, spinterface effects have not yet been explored on layered magnetic materials. Here, the emergence of spinterface effects is demonstrated at the interface between flakes of the ...

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“…Their work confirms the validity, promise, and power of the TERS technique for the analysis of various electro‐optic materials . Kumar et al used Raman scattering to study the influence of substrate on molecular order for self‐assembled adlayers of CoPc and FePc (metal phthalocyanine) thin films of about 50 nm thickness on technolically relevant substrates such as SiOx/Si, indium tin oxide, and polycrystalline gold . Schipporeit and Mergel studied the spectral decomposition of Raman spectra of mixed‐phase TiO 2 thin films on Si and silicate substrates …”

Section: Solid‐state Studiesmentioning

confidence: 83%

“…[174] Kumar et al used Raman scattering to study the influence of substrate on molecular order for self-assembled adlayers of CoPc and FePc (metal phthalocyanine) thin films of about 50 nm thickness on technolically relevant substrates such as SiOx/Si, indium tin oxide, and polycrystalline gold. [175] Schipporeit and Mergel studied the spectral decomposition of Raman spectra of mixed-phase TiO 2 thin films on Si and silicate substrates. [176] 16 | LIQUIDS, SOLUTIONS, AND LIQUID INTERACTIONS Understanding molecule-molecule interactions in the liquid and solution phase remains important in the areas of Raman theory and application.…”

Section: Metals Carbons and Other Crystalline Materialsmentioning

confidence: 99%

Recent advances in linear and nonlinear Raman spectroscopy. Part XIII

Nafie

2019

J Raman Spectroscopy

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This article is an overview of advances in Raman spectroscopy published in 2018 in the Journal of Raman Spectroscopy (JRS) and, in addition, trends over the past decade across journals that have published papers important to the field of Raman spectroscopy. The trends are based on statistical data of article counts obtained from Clarivate Analytic's Web of Science Core Collection byyear and by subfield of Raman spectroscopy. Coverage is provided for presentations involving Raman spectroscopy at four international conferences this published in JRS in 2018 are highlighted and arragned by topics at the frontier of Raman spectroscopy. Based on these data, presentations, and publications, it is clear that Raman spectroscopy continues as an expanding field of research across a wide range of novel disciplines and applications that provide sensitive photonic information at the molecular level.KEYWORDS advances in Raman spectroscopy, applications of Raman spectroscopy, developments in Raman spectroscopy, review

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Influence of substrate on molecular order for self‐assembled adlayers of CoPc and FePc

Cited by 17 publications

References 27 publications

Molecular Degradation of Iron Phthalocyanine during the Oxygen Reduction Reaction in Acidic Media

Molecular Degradation of Iron Phthalocyanine during the Oxygen Reduction Reaction in Acidic Media

Exchange Bias in Molecule/Fe₃GeTe₂ van der Waals Heterostructures via Spinterface Effects

Recent advances in linear and nonlinear Raman spectroscopy. Part XIII

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Influence of substrate on molecular order for self‐assembled adlayers of CoPc and FePc

Cited by 17 publications

References 27 publications

Molecular Degradation of Iron Phthalocyanine during the Oxygen Reduction Reaction in Acidic Media

Molecular Degradation of Iron Phthalocyanine during the Oxygen Reduction Reaction in Acidic Media

Exchange Bias in Molecule/Fe3GeTe2 van der Waals Heterostructures via Spinterface Effects

Recent advances in linear and nonlinear Raman spectroscopy. Part XIII

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Exchange Bias in Molecule/Fe₃GeTe₂ van der Waals Heterostructures via Spinterface Effects