Interplay between surface chemistry and performance of rutile-type catalysts for halogen production

Chemical Science
Maximilian MoserJavier Pérez-Ramírez

Abstract

Catalytic HBr oxidation is an integral step in the bromine-mediated functionalisation of alkanes to valuable chemicals. This study establishes the relationships between the mechanism of HBr oxidation over rutile-type oxides (RuO2, IrO2, TiO2) and their apparent catalytic performance. Comparison with the well-studied HCl oxidation revealed distinct differences in surface chemistry between HBr and HCl oxidation that impact the stability and activity of the catalysts. The kinetic fingerprints of both oxidation reactions over the three rutile-type oxides investigated are compared using temporal analysis of products, which substantiates the energy profiles derived from density functional theory. The quantitative determination of the halogen uptake under operando conditions using prompt gamma activation analysis demonstrates that RuO2 suffers from extensive subsurface bromination upon contact with hydrogen bromide, particularly at low temperature and low O2 : HBr ratios, which negatively affects the stability of the catalyst. TiO2 exhibits intrinsically low halogen coverage (30-50%) under all the conditions investigated, due to its unique defect-driven mechanism that renders it active and stable for Br2 production. On the contrary, f...Continue Reading

References

Dec 15, 1994·Physical Review. B, Condensed Matter·P E Blöchl
Oct 15, 1996·Physical Review. B, Condensed Matter·G Kresse, J Furthmüller
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
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May 24, 2013·The Journal of Chemical Physics·Gerard Novell-LeruthNúria López
Feb 2, 2012·The Journal of Physical Chemistry Letters·Youngmin LeeYang Shao-Horn

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Citations

Jun 2, 2017·Angewandte Chemie·Vladimir PaunovićJavier Pérez-Ramírez
Aug 2, 2017·Chemical Communications : Chem Comm·Zhong-Kang HanYi Gao
Feb 6, 2017·Chemical Reviews·Ronghe LinJavier Pérez-Ramírez
Sep 21, 2021·Physical Chemistry Chemical Physics : PCCP·Pan DengWenlong Jiang

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Methods Mentioned

BETA
transmission electron microscopy
X-ray
neutron capture

Software Mentioned

Vienna ab initio simulation package ( VASP )

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