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The authors thank Dr. M. V. Shashkov for the GC-MS measurements and Prof. E. P. Talsi for discussions. This work was partially supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental order for the Boreskov Institute of Catalysis (BIC, project AAAA-A21-121011390008-4). The studies were carried out using facilities of the shared research center "National Center of Investigation of Catalysts" at BIC. J.J.C., J.M.P., A.S.-D., and J.P.-J. are grateful for grants PID2021-128128NB-I00 and PID2020-112762GB-I00 funded by MINECO/AEI/10.13039/501100011033 and by "ERDF A way of making Europe" and the Generalitat de Catalunya (2021SGR00110). A.S.-D. also acknowledges the Spanish Ministry of Universities and the European Union - Next Generation EU for financial support through a Margarita Salas grant.

Analysis of institutional authors

Puiggali-Jou, JordiAuthorSole-Daura, AlbertAuthorPoblet, Josep MAuthorCarbo, Jorge JCorresponding Author

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August 21, 2023
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Article
Hybrid Gold

Resolving the Mechanism for H2O2 Decomposition over Zr(IV)-Substituted Lindqvist Tungstate: Evidence of Singlet Oxygen Intermediacy

Publicated to:Acs Catalysis. 13 (15): 10324-10339 - 2023-07-24 13(15), DOI: 10.1021/acscatal.3c02416

Authors: Maksimchuk, Nataliya V; Puiggali-Jou, Jordi; Zalomaeva, Olga V; Larionov, Kirill P; Evtushok, Vasilii Yu; Soshnikov, Igor E; Sole-Daura, Albert; Kholdeeva, Oxana A; Poblet, Josep M; Carbo, Jorge J

Affiliations

Boreskov Inst Catalysis, Novosibirsk 630090, Russia - Author
Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Tarragona 43005, Spain - Author

Abstract

The decomposition of hydrogen peroxide (H2O2) is the main undesired side reaction in catalytic oxidationprocessesof industrial interest that make use of H2O2 as a terminal oxidant, such as the epoxidation of alkenes. However,the mechanism responsible for this reaction is still poorly understood,thus hindering the development of design rules to maximize the efficiencyof catalytic oxidations in terms of product selectivity and oxidantutilization efficiency. Here, we thoroughly investigated the H2O2 decomposition mechanism using a Zr-monosubstituteddimeric Lindqvist tungstate, (Bu4N)(6)[{W5O18Zr(& mu;-OH)}(2)] ({ZrW ( 5 ) } ( 2 )),which revealed high activity for this reaction in acetonitrile. Themechanism of the {ZrW ( 5 ) } ( 2 )-catalyzed H2O2 degradationin the absence of an organic substrate was investigated using kinetic,spectroscopic, and computational tools. The reaction is first orderin the Zr catalyst and shows saturation behavior with increasingH(2)O(2) concentration. The apparent activationenergy is 11.5 kcal & BULL;mol(-1), which is significantlylower than the values previously found for Ti- and Nb-substitutedLindqvist tungstates (14.6 and 16.7 kcal & BULL;mol(-1), respectively). EPR spectroscopic studies indicated the formationof superoxide radicals, while EPR with a specific singlet oxygen trap,2,2,6,6-tetramethyl-piperidone (4-oxo-TEMP), revealed the generationof O-1(2). The interaction of test substrates,& alpha;-terpinene and tetramethylethylene, with H2O2 in the presence of {ZrW ( 5 ) } ( 2 ) corroborated the formationof products typical of the oxidation processes that engage O-1(2) (endoperoxide ascaridole and 2,3-dimethyl-3-butene-2-hydroperoxide,respectively). While radical scavengers (BuOH)-Bu- t and p-benzoquinone produced no effect on theperoxide product yield, the addition of 4-oxo-TEMP significantly reducedit. After optimization of the reaction conditions, a 90% yield ofascaridole was attained. DFT calculations provided an atomistic descriptionof the H2O2 decomposition mechanism by Zr-substitutedLindqvist tungstate catalysts. Calculations showed that the reactionproceeds through a Zr-trioxidane [Zr-& eta;(2)-OO(OH)] keyintermediate, whose formation is the rate-determining step. The Zr-substitutedPOM activates heterolytically a first H2O2 moleculeto generate a Zr-peroxo species, which attacks nucleophilically toa second H2O2, causing its heterolytic O-Ocleavage to yield the Zr-trioxidane complex. In agreement with spectroscopicand kinetic studies, the lowest-energy pathway involves dimeric Zrspecies and an inner-sphere mechanism. Still, we also found monomericinner- and outer-sphere pathways that are close in energy and couldcoexist with the dimeric one. The highly reactive Zr-trioxidane intermediatecan evolve heterolytically to release singlet oxygen and also decomposehomolytically, producing superoxide as the predominant radical species.For H2O2 decomposition by Ti- and Nb-substitutedPOMs, we also propose the formation of the TM-trioxidane key intermediate,finding good agreement with the observed trends in apparent activationenergies.

Keywords

ActivationDftGenerationHydrogen peroxide decompositionHydrogen trioxide hooohHydroxyl radicalsIsopropyl-alcoholLindqvist tungstateLindqvisttungstateLow-temperature ozonationMolecular-orbital methodsOxidationPeroxo intermediateSinglet oxygenSuperoxide ionZirconium

Quality index

Bibliometric impact. Analysis of the contribution and dissemination channel

The work has been published in the journal Acs Catalysis due to its progression and the good impact it has achieved in recent years, according to the agency WoS (JCR), it has become a reference in its field. In the year of publication of the work, 2023, it was in position 21/178, thus managing to position itself as a Q1 (Primer Cuartil), in the category Chemistry, Physical.

From a relative perspective, and based on the normalized impact indicator calculated from World Citations provided by WoS (ESI, Clarivate), it yields a value for the citation normalization relative to the expected citation rate of: 1.4. This indicates that, compared to works in the same discipline and in the same year of publication, it ranks as a work cited above average. (source consulted: ESI Nov 14, 2024)

This information is reinforced by other indicators of the same type, which, although dynamic over time and dependent on the set of average global citations at the time of their calculation, consistently position the work at some point among the top 50% most cited in its field:

  • Weighted Average of Normalized Impact by the Scopus agency: 1.55 (source consulted: FECYT Feb 2024)
  • Field Citation Ratio (FCR) from Dimensions: 8.77 (source consulted: Dimensions Nov 2025)

Specifically, and according to different indexing agencies, this work has accumulated citations as of 2025-11-04, the following number of citations:

  • WoS: 14
  • Scopus: 17
  • Europe PMC: 1
  • Google Scholar: 5

Impact and social visibility

From the perspective of influence or social adoption, and based on metrics associated with mentions and interactions provided by agencies specializing in calculating the so-called "Alternative or Social Metrics," we can highlight as of 2025-11-04:

  • The use, from an academic perspective evidenced by the Altmetric agency indicator referring to aggregations made by the personal bibliographic manager Mendeley, gives us a total of: 18.
  • The use of this contribution in bookmarks, code forks, additions to favorite lists for recurrent reading, as well as general views, indicates that someone is using the publication as a basis for their current work. This may be a notable indicator of future more formal and academic citations. This claim is supported by the result of the "Capture" indicator, which yields a total of: 18 (PlumX).

With a more dissemination-oriented intent and targeting more general audiences, we can observe other more global scores such as:

  • The Total Score from Altmetric: 4.4.
  • The number of mentions on the social network X (formerly Twitter): 5 (Altmetric).

It is essential to present evidence supporting full alignment with institutional principles and guidelines on Open Science and the Conservation and Dissemination of Intellectual Heritage. A clear example of this is:

  • The work has been submitted to a journal whose editorial policy allows open Open Access publication.
  • Assignment of a Handle/URN as an identifier within the deposit in the Institutional Repository: http://hdl.handle.net/20.500.11797/imarina9327205

Leadership analysis of institutional authors

This work has been carried out with international collaboration, specifically with researchers from: Russia.

There is a significant leadership presence as some of the institution’s authors appear as the first or last signer, detailed as follows: Last Author (Carbó Martin, Jorge Juan).

the author responsible for correspondence tasks has been Carbó Martin, Jorge Juan.