Layered α-TiCl3: Microsheets on YSZ Substrates for Ethylene Polymerization with Enhanced Activity

Groenke M, Arrozi USF, Bronkalla N, Schmidt P, Valldor M, Oswald S, Woodcock TG, Eckert V, Hao Q, Plueschke L, Lederer A, Nielsch K, Buechner B, Kaskel S, Hampel S (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Chemistry of Materials American Chemical Society

Book Volume: 31

Pages Range: 5305-5313

Journal Issue: 14

DOI: 10.1021/acs.chemmater.9b01818

Abstract

The transition metal halide α-titanium(III) chloride (α-TiCl3) is a layered two-dimensional compound and a well-established Ziegler-Natta catalyst for the polymerization of ethylene. A new synthesis technique is used to obtain thin sheets of α-TiCl3 that show exceptional physical properties in contrast to their bulk counterparts, due to an enlarged surface-to-volume ratio. Chemical vapor transport (CVT) of α-titanium(III) chloride directly on substrates results in microsheets that exhibit an improved catalytic effect. For rational planning of synthesis conditions, thermodynamic simulations of occurring gas-phase equilibria were performed. Based on these calculation results, crystal growth was achieved by adding GaCl3 via pure short term CVT in a temperature gradient of 700-600 K on yttrium-stabilized zirconia (YSZ) substrates. Phase pure, as-grown, single crystal sheets with high crystallinity and a thickness of around 4 μm were obtained. These thin sheets of α-TiCl3 on YSZ substrates were implemented as catalysts for the ethylene polymerization reaction. A significant improvement of catalytic activity of 16% was achieved, probably due to an increased surface-to-volume ratio. As a highlight, the as-grown microsheets were exfoliated subsequently to a thickness lower than 200 nm and an even higher catalytic activity of up to 24% was confirmed experimentally due to delamination effects. This is the first time that an improved catalytic effect of α-TiCl3 is observed as a result of downscaling from bulk to microsheets by CVT.

Involved external institutions

Leibniz-Institut für Festkörper- und Werkstoffforschung Dresden e.V. (IFW) / Leibniz Institute for Solid State and Materials Research Dresden

Germany (DE) Brandenburgische Technische Universität Cottbus-Senftenberg (BTU)

Germany (DE) Technische Universität Dresden

Germany (DE)

How to cite

APA:

Groenke, M., Arrozi, U.S.F., Bronkalla, N., Schmidt, P., Valldor, M., Oswald, S.,... Hampel, S. (2019). Layered α-TiCl3: Microsheets on YSZ Substrates for Ethylene Polymerization with Enhanced Activity. Chemistry of Materials, 31(14), 5305-5313. https://doi.org/10.1021/acs.chemmater.9b01818

MLA:

Groenke, Martin, et al. "Layered α-TiCl3: Microsheets on YSZ Substrates for Ethylene Polymerization with Enhanced Activity." Chemistry of Materials 31.14 (2019): 5305-5313.

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