Efficient debromination of tetrabromobisphenol A in protic solvents by supported nickel catalysts: Effect of metal-support interactions

Paavo Auvinen; Eerika Olkkonen; Konstantin Tamarov; Ida M. Uotila; Ville H. Nissinen; Jani Pelto; Vesa Pekka Lehto; Mika Suvanto; Janne Jänis; Jarkko J. Saarinen

doi:10.1016/j.apcata.2026.120818

Efficient debromination of tetrabromobisphenol A in protic solvents by supported nickel catalysts: Effect of metal-support interactions

Paavo Auvinen^*
, Eerika Olkkonen
, Konstantin Tamarov
, Ida M. Uotila
, Ville H. Nissinen
, Jani Pelto
, Vesa Pekka Lehto
, Mika Suvanto
, Janne Jänis
, Jarkko J. Saarinen

^*Corresponding author for this work

University of Eastern Finland

Research output: Contribution to journal › Article › Scientific › peer-review

Abstract

Toxic and environmentally hazardous brominated flame retardants (BFR) hinder the recycling of plastic waste, which has led to the development of various extraction processes to remove them. These processes can be further advanced by debrominating BFRs into less harmful compounds with potential commercial value, thus supporting the principles of a circular economy. Herein, Ni/Al₂O₃ was employed for the catalytic debromination of tetrabromobisphenol A flame retardant in mixtures of H₂O, isopropanol and NaOH at modest reaction temperatures. Activity experiments conducted in an autoclave indicated that studied catalyst exhibits impressive debromination activity and complete selectivity towards C−Br bond scission. The catalyst reduction temperature was found to correlate with debromination activity, with higher temperatures yielding improved performance. Debromination proceeded under H₂ and also under N₂ in protic solvents via transfer hydrogenation. Catalyst characterization, coupled with high-resolution mass-spectrometry product analytics and deuterium labelling, suggested that the enhanced catalytic activity can be attributed to the activation of the metal-support interface and subsequent interactions with adsorbed solvent molecules and associated dissociation products on the alumina support. Used experimental conditions also provided high tolerance against bromine poisoning of the catalyst, in contrast to reference debromination experiments conducted in toluene. The study demonstrates the capability of Ni/Al₂O₃ as an efficient and affordable debromination catalyst in solvents of low environmental impact. Furthermore, the results provide additional insights into structure-activity relationships of supported nickel catalysts in protic solvents, which can be leveraged for the development of more efficient and sustainable dehalogenation and heteroatom removal processes for environmental applications.

Original language	English
Article number	120818
Journal	Applied Catalysis A: General
Volume	713
DOIs	https://doi.org/10.1016/j.apcata.2026.120818
Publication status	Published - 5 Mar 2026
MoE publication type	A1 Journal article-refereed

Funding

This work was supported by the European Union from the Horizon Europe Programme through the European Health and Digital Executive Agency (HADEA) under Grant Agreement No. 101057067. The mass spectrometry facility is supported by the Biocenter Kuopio, Biocenter Finland/FINStruct and the Research Council of Finland infrastructure funding (FIRI). The Pohjois-Savon Liitto DeepSurface projects (A78280 & A78303) support is acknowledged for XPS instrument acquisition and measurements.

Keywords

Brominated flame retardant
Dehalogenation
Green solvents
Heteroatom removal
Plastics recycling
Protic solvents

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10.1016/j.apcata.2026.120818Licence: CC BY

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Auvinen, P., Olkkonen, E., Tamarov, K., Uotila, I. M., Nissinen, V. H., Pelto, J., Lehto, V. P., Suvanto, M., Jänis, J., & Saarinen, J. J. (2026). Efficient debromination of tetrabromobisphenol A in protic solvents by supported nickel catalysts: Effect of metal-support interactions. Applied Catalysis A: General, 713, Article 120818. https://doi.org/10.1016/j.apcata.2026.120818

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title = "Efficient debromination of tetrabromobisphenol A in protic solvents by supported nickel catalysts: Effect of metal-support interactions",

abstract = "Toxic and environmentally hazardous brominated flame retardants (BFR) hinder the recycling of plastic waste, which has led to the development of various extraction processes to remove them. These processes can be further advanced by debrominating BFRs into less harmful compounds with potential commercial value, thus supporting the principles of a circular economy. Herein, Ni/Al2O3 was employed for the catalytic debromination of tetrabromobisphenol A flame retardant in mixtures of H2O, isopropanol and NaOH at modest reaction temperatures. Activity experiments conducted in an autoclave indicated that studied catalyst exhibits impressive debromination activity and complete selectivity towards C−Br bond scission. The catalyst reduction temperature was found to correlate with debromination activity, with higher temperatures yielding improved performance. Debromination proceeded under H2 and also under N2 in protic solvents via transfer hydrogenation. Catalyst characterization, coupled with high-resolution mass-spectrometry product analytics and deuterium labelling, suggested that the enhanced catalytic activity can be attributed to the activation of the metal-support interface and subsequent interactions with adsorbed solvent molecules and associated dissociation products on the alumina support. Used experimental conditions also provided high tolerance against bromine poisoning of the catalyst, in contrast to reference debromination experiments conducted in toluene. The study demonstrates the capability of Ni/Al2O3 as an efficient and affordable debromination catalyst in solvents of low environmental impact. Furthermore, the results provide additional insights into structure-activity relationships of supported nickel catalysts in protic solvents, which can be leveraged for the development of more efficient and sustainable dehalogenation and heteroatom removal processes for environmental applications.",

keywords = "Brominated flame retardant, Dehalogenation, Green solvents, Heteroatom removal, Plastics recycling, Protic solvents",

author = "Paavo Auvinen and Eerika Olkkonen and Konstantin Tamarov and Uotila, \{Ida M.\} and Nissinen, \{Ville H.\} and Jani Pelto and Lehto, \{Vesa Pekka\} and Mika Suvanto and Janne J{\"a}nis and Saarinen, \{Jarkko J.\}",

note = "Publisher Copyright: {\textcopyright} 2026 The Authors. Published by Elsevier B.V. ",

year = "2026",

month = mar,

day = "5",

doi = "10.1016/j.apcata.2026.120818",

language = "English",

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journal = "Applied Catalysis A: General",

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T1 - Efficient debromination of tetrabromobisphenol A in protic solvents by supported nickel catalysts

T2 - Effect of metal-support interactions

AU - Auvinen, Paavo

AU - Olkkonen, Eerika

AU - Tamarov, Konstantin

AU - Uotila, Ida M.

AU - Nissinen, Ville H.

AU - Pelto, Jani

AU - Lehto, Vesa Pekka

AU - Suvanto, Mika

AU - Jänis, Janne

AU - Saarinen, Jarkko J.

PY - 2026/3/5

Y1 - 2026/3/5

N2 - Toxic and environmentally hazardous brominated flame retardants (BFR) hinder the recycling of plastic waste, which has led to the development of various extraction processes to remove them. These processes can be further advanced by debrominating BFRs into less harmful compounds with potential commercial value, thus supporting the principles of a circular economy. Herein, Ni/Al2O3 was employed for the catalytic debromination of tetrabromobisphenol A flame retardant in mixtures of H2O, isopropanol and NaOH at modest reaction temperatures. Activity experiments conducted in an autoclave indicated that studied catalyst exhibits impressive debromination activity and complete selectivity towards C−Br bond scission. The catalyst reduction temperature was found to correlate with debromination activity, with higher temperatures yielding improved performance. Debromination proceeded under H2 and also under N2 in protic solvents via transfer hydrogenation. Catalyst characterization, coupled with high-resolution mass-spectrometry product analytics and deuterium labelling, suggested that the enhanced catalytic activity can be attributed to the activation of the metal-support interface and subsequent interactions with adsorbed solvent molecules and associated dissociation products on the alumina support. Used experimental conditions also provided high tolerance against bromine poisoning of the catalyst, in contrast to reference debromination experiments conducted in toluene. The study demonstrates the capability of Ni/Al2O3 as an efficient and affordable debromination catalyst in solvents of low environmental impact. Furthermore, the results provide additional insights into structure-activity relationships of supported nickel catalysts in protic solvents, which can be leveraged for the development of more efficient and sustainable dehalogenation and heteroatom removal processes for environmental applications.

AB - Toxic and environmentally hazardous brominated flame retardants (BFR) hinder the recycling of plastic waste, which has led to the development of various extraction processes to remove them. These processes can be further advanced by debrominating BFRs into less harmful compounds with potential commercial value, thus supporting the principles of a circular economy. Herein, Ni/Al2O3 was employed for the catalytic debromination of tetrabromobisphenol A flame retardant in mixtures of H2O, isopropanol and NaOH at modest reaction temperatures. Activity experiments conducted in an autoclave indicated that studied catalyst exhibits impressive debromination activity and complete selectivity towards C−Br bond scission. The catalyst reduction temperature was found to correlate with debromination activity, with higher temperatures yielding improved performance. Debromination proceeded under H2 and also under N2 in protic solvents via transfer hydrogenation. Catalyst characterization, coupled with high-resolution mass-spectrometry product analytics and deuterium labelling, suggested that the enhanced catalytic activity can be attributed to the activation of the metal-support interface and subsequent interactions with adsorbed solvent molecules and associated dissociation products on the alumina support. Used experimental conditions also provided high tolerance against bromine poisoning of the catalyst, in contrast to reference debromination experiments conducted in toluene. The study demonstrates the capability of Ni/Al2O3 as an efficient and affordable debromination catalyst in solvents of low environmental impact. Furthermore, the results provide additional insights into structure-activity relationships of supported nickel catalysts in protic solvents, which can be leveraged for the development of more efficient and sustainable dehalogenation and heteroatom removal processes for environmental applications.

KW - Brominated flame retardant

KW - Dehalogenation

KW - Green solvents

KW - Heteroatom removal

KW - Plastics recycling

KW - Protic solvents

UR - https://www.scopus.com/pages/publications/105030273564

U2 - 10.1016/j.apcata.2026.120818

DO - 10.1016/j.apcata.2026.120818

M3 - Article

AN - SCOPUS:105030273564

SN - 0926-860X

VL - 713

JO - Applied Catalysis A: General

JF - Applied Catalysis A: General

M1 - 120818

ER -

Efficient debromination of tetrabromobisphenol A in protic solvents by supported nickel catalysts: Effect of metal-support interactions

Abstract

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Keywords

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