<sup>207</sup>Pb and<sup>119</sup>Sn Solid-State NMR and Relativistic Density Functional Theory Studies of the Historic Pigment Lead–Tin Yellow Type I and Its Reactivity in Oil Paintings

Catalano, Jaclyn; Murphy, Arthur; Yao, Yao; Alkan, Fahri; Zumbulyadis, Nicholas; Centeno, Silvia A.; Dybowski, Cecil

doi:10.1021/jp505908j

Cited by 35 publications

(19 citation statements)

References 51 publications

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“…3A, curve a) with clear chemical shifts at -608, -670 and -728 ppm. The first one (at -608 ppm) is assigned to SnOx clusters and is in agreement with previous reports for SnO2 species, 21 with the magnitude of this peak being dependent on the degree of SnOx oligomerization. However, the other two chemical shifts (at -670 and -728 ppm) are ascribed to hydrated, Sn(IV) species in Td sites (closed and/or open sites).…”

Section: Sn Mas Nmrsupporting

confidence: 92%

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Design and control of Lewis acid sites in Sn-substituted microporous architectures

et al. 2016

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Monometallic and bimetallic tin-containing framework architectures have been prepared by hydrothermal methods. Structural and spectroscopic techniques were used to probe the nature of the solid-acid sites, at the molecular level, using a combination of XRD, DR UV-Vis, solid state MAS NMR ( 119 Sn, 27 Al and 31 P) and XAFS. The nature and strength of the solidacid sites were experimentaly probed by FT-IR spectroscopy using CD3CN as a probe molecule. To elucidate further the localstructure, the structural characteristics of the Sn sites were probed using DFT calculations, with a view to rationalising the experimental findings. These detailed structural and spectroscopic studies revealed the presence of multiple Sn environments, with the monometallic SnAlPO-5 catalyst displaying a greater number of tetrahedral Sn(IV) active centres. These framework Sn(IV) centres generated stong Lewis acid sites, when compared with their bimetallic Co-Sn analogue, thereby affording attractive possibilities for modulating catalytic reactivity. IntroductionTetrahedral (Td) sites in microporous solids are widely reported as catalytic active centres in selective oxidation and acidcatalysed transformations, 1-4 of which Ti in TS-1, 5 Fe in ZSM-5 6 and Co in AlPO-5 7 are significant examples. Controlling the nature of these active sites allows one to tune the Lewis 8 and Brønsted acidity, 9 and regulate redox 10 centres for oxidation catalysis. The addition of a second heteroatom allows for further optimisation of these properties, as well as influencing the coordination geometry of the initial heteroatom. [2][3][4] The incorporation of Sn into zeolitic 11 and non-zeolitic 1,4 architectures has received significant attention for its promising performance in Baeyer-Villiger oxidations. 11 The activity of these systems was correlated with the presence of Sn in Td sites, with well isolated Lewis acidic centres, which can be used for a wide range of catalytic reactions. [11][12][13] The synthetic findings were supported by a large number of characterization techniques, including DR UV-Vis, 119 Sn MAS NMR and in situ IR spectroscopy. 11,14 Although such materials could be expected to show significant catalytic functionality, the incorporation of Sn into AlPO-5 frameworks in Td sites is, however, very limited and poorly understood.This work focuses on the isomorphous substitution of P(V) with Sn (IV) within AlPO-5 using a modified hydrothermal preparation method. 4 Cobalt (Co 2+ /Co 3+ ) ions can be simultaneously introduced into the AlPO-5 architecture 2,3,15 by the substitution of (Al 3+ ) sites. Recently, a combined DFT and EXAFS study demonstrated the potential of effecting catalytic synergy in Co−Ti bimetallic nanoporous frameworks. 16 However, the prospects of introducing a relatively heavier element like Sn, alongside a redox transition-metal such as Co, could pave the way for probing bifunctional catalytic transformations. Nevertheless, the structural and spectroscopic features of such a system needs to be probed in meticulous detail...

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Section: Sn Mas Nmrsupporting

confidence: 92%

“…119 Sn MAS-NMR has been used extensively for probing the nature of Sn species in zeolites, [21][22][23] and these interpretations can be rationally extended for probing analogous species in AlPO-5. In Fig.…”

Section: Sn Mas Nmrmentioning

confidence: 99%

Design and control of Lewis acid sites in Sn-substituted microporous architectures

et al. 2016

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“…reproduction of historical recipes is fundamental to assess these different aspects, and determine if the painter prepared the soaps him/herself on purpose or if they appeared naturally. Different works report the study of reactions of lead compounds with organic binders (usually oil, sometimes egg yolk, beeswax, or resin), ranging from the preparation of simple binary mixtures, up to the accurate reproduction of historical recipes (Meilunas et al, 1990;Mecklenburg & S., 2001;Erhardt et al, 2005;Carlyle, 2006;Cotte et al, 2006Cotte et al, , 2007Boon et al, 2007;Carlyle et al, 2008;Mazzeo et al, 2008;Salvadó et al, 2009;Bonaduce et al, 2012aBonaduce et al, , 2012bDuce et al, 2013;Pratali, 2013;Catalano et al, 2014a;Osmond, 2014;Pallipurath et al, 2015;de Viguerie et al, 2016). An interesting observation is given by Mazzeo et al who reported the FTIR analysis of model paintings prepared by mixing oil and egg yolk with 42 different pigments, among which included eight lead-based compounds, after 10 years of natural aging (Mazzeo et al, 2008).…”

Section: Confrontation Of Historical Texts With Experimental Observatmentioning

confidence: 99%

Lead soaps in paintings: Friends or foes?

Cotte

Checroun

Nolf

et al. 2016

Studies in Conservation

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The origin(s) and role(s) of metal soaps in paints are a worldwide concern today. These hybrid compounds, containing both fatty acid chains and metals associated with a carboxylate function, are increasingly identified in paints. As reviewed in the first part of this work, the presence of metal soaps in paints is differently interpreted in scientific publications: metal soaps are sometimes considered to play a positive role as anchor points, during paint drying processes; they can also be considered as responsible for many degradation processes (protrusions, efflorescences, darkening, etc.). Their origins are also interpreted in various ways. In some paintings (in particular from the twentieth century), they have sometimes introduced on purpose, as additives, to modify the physical properties of the painting materials. In older paintings, metal soaps are usually thought to result from an uncontrolled reaction of oil with lead-based pigments, in particular lead white, red lead, and lead tin yellow. In the second part of this work, the review of historical recipes of lead-based paint shows an important number of recipes based on controlled mixing of oil with lead driers. In the third part, the experimental reproduction of such traditional recipes using walnut oil and litharge (PbO) shows that lead soaps can be formed, both in about one hour at ∼100°C, or in about one month at room temperature. It shows as well that after a few years, litharge is no longer detected in the paint medium, while different lead carbonates are. Finally, the micro-infrared spectroscopy and micro-X-ray diffraction re-analysis of protrusions from a nine-year model painting shows together with lead soaps, the presence of Pb 5 (CO 3 ) 3 (OH) 2 O ('synthetic plumbonacrite'), an unusual phase recently observed in a protrusion from a painting by Vincent Van Gogh. This work highlights (i) the multiple origins and roles of metal soaps in paints and (ii) the importance of combining the analysis of fragments from historical paintings with the analysis and reproduction of historical recipes. In particular, we show that the components detected today in historical paintings may severely differ from those originally used or prepared by the painter, complicating the assessment of the painter's intentions. More than the presence of metal soaps, the key questions to be tackled should be about their origins and (re)mobilization.

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“…[18] When these soaps aggregate,m igrate,a nd crystallize,s ignificant damage can occur to paint layers. [18] When these soaps aggregate,m igrate,a nd crystallize,s ignificant damage can occur to paint layers.…”

Section: Angewandte Chemiementioning

confidence: 99%

Modeling the Evolution of Crosslinked and Extractable Material in an Oil‐Based Paint Model System

et al. 2018

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The construction of mechanistic models for the autoxidation of fatty acid or ester substrates found in oil paint binders is a challenging undertaking due to the complexity of the large crosslinked species that form, and the small molecules that volatilize. Building models that capture this product diversity are made possible by automating the process of network generation. This work presents a microkinetic model for the autoxidation of ethyl linoleate catalyzed by cobalt(II) 2-ethyl hexanoate. The mechanism size was controlled by using a rate-based criterion to include the most kinetically relevant reactions from among the millions of possible reactions generated. The resulting model was solved and compared to experimental metrics. Quantities such as hexanal production and the consumption of unsaturated moieties were in good agreement with experiment. Finally, the model was used to explore the effect of the catalyst concentration and temperature on key measurables.

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²⁰⁷Pb and¹¹⁹Sn Solid-State NMR and Relativistic Density Functional Theory Studies of the Historic Pigment Lead–Tin Yellow Type I and Its Reactivity in Oil Paintings

Cited by 35 publications

References 51 publications

Design and control of Lewis acid sites in Sn-substituted microporous architectures

Design and control of Lewis acid sites in Sn-substituted microporous architectures

Lead soaps in paintings: Friends or foes?

Modeling the Evolution of Crosslinked and Extractable Material in an Oil‐Based Paint Model System

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207Pb and119Sn Solid-State NMR and Relativistic Density Functional Theory Studies of the Historic Pigment Lead–Tin Yellow Type I and Its Reactivity in Oil Paintings

Cited by 35 publications

References 51 publications

Design and control of Lewis acid sites in Sn-substituted microporous architectures

Design and control of Lewis acid sites in Sn-substituted microporous architectures

Lead soaps in paintings: Friends or foes?

Modeling the Evolution of Crosslinked and Extractable Material in an Oil‐Based Paint Model System

Contact Info

Product

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²⁰⁷Pb and¹¹⁹Sn Solid-State NMR and Relativistic Density Functional Theory Studies of the Historic Pigment Lead–Tin Yellow Type I and Its Reactivity in Oil Paintings