Influence of Preparation and Activation on the Speciation of Carbon‐Supported Mo–W Carbides.

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Title: Influence of Preparation and Activation on the Speciation of Carbon‐Supported Mo–W Carbides.
Authors: Azimov, Parviz1 (AUTHOR), Sayag, Céline1 (AUTHOR), Guibert, Clement1 (AUTHOR), Wilson, Axel1 (AUTHOR), Nassereddine, Abdallah2 (AUTHOR), Aguilar‐Tapia, Antonio3 (AUTHOR), Hazemann, Jean‐Louis2 (AUTHOR), Carrier, Xavier1,4 (AUTHOR) xavier.carrier@sorbonne-universite.fr
Source: ChemCatChem. 2/25/2026, Vol. 18 Issue 4, p1-13. 13p.
Subjects: Catalyst synthesis, Carburization, Chemical reactions, X-ray absorption spectra, Molybdenum compounds, Chemical precursors, Catalysts
Abstract: Carbon‐supported Mo–W carbides were synthesized by two different methods (co‐impregnation and sequential impregnation of W and Mo precursors) to unravel how precursor impregnation controls carburization pathways. In situ W L3‐edge HERFD‐XAS and Mo K‐edge XAS, quantitatively analyzed by MCR‐ALS reveals that all samples follow a 3‐component sequence "oxide → reduced oxide → carbide" upon temperature‐programmed carburization. However, the temperature window of the reduced MoO2–WO3‐x coexistence is route‐dependent. Co‐impregnation and preliminary carburization of W generate extended overlapping domains (300°C‐420°C) in which both reduced oxides are simultaneously formed, promoting cooperative oxide‐oxide transformations and leading to mixed Mo–W carbidic environments, consistent with XRD and TEM. In contrast, in the route where Mo is carburized first, pre‐reduced molybdenum domains trigger early W reduction and shorten the MoO2–WO3‐x overlap window, leading to independent transformation paths for the two metal precursors and to the formation of separate Mo‐rich and W‐rich carbide phases. These results demonstrate that impregnation and carburization orders are decisive synthetic levers for directing the speciation of Mo–W carbide towards mixed bicarbides or phase‐segregated Mo‐rich/W‐rich carbides providing actionable guidelines for designing bifunctional carbide catalysts. [ABSTRACT FROM AUTHOR]
Copyright of ChemCatChem is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Influence of Preparation and Activation on the Speciation of Carbon‐Supported Mo–W Carbides.
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  Data: <searchLink fieldCode="AR" term="%22Azimov%2C+Parviz%22">Azimov, Parviz</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Sayag%2C+Céline%22">Sayag, Céline</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Guibert%2C+Clement%22">Guibert, Clement</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wilson%2C+Axel%22">Wilson, Axel</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Nassereddine%2C+Abdallah%22">Nassereddine, Abdallah</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Aguilar‐Tapia%2C+Antonio%22">Aguilar‐Tapia, Antonio</searchLink><relatesTo>3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Hazemann%2C+Jean‐Louis%22">Hazemann, Jean‐Louis</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Carrier%2C+Xavier%22">Carrier, Xavier</searchLink><relatesTo>1,4</relatesTo> (AUTHOR)<i> xavier.carrier@sorbonne-universite.fr</i>
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  Data: <searchLink fieldCode="JN" term="%22ChemCatChem%22">ChemCatChem</searchLink>. 2/25/2026, Vol. 18 Issue 4, p1-13. 13p.
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  Data: <searchLink fieldCode="DE" term="%22Catalyst+synthesis%22">Catalyst synthesis</searchLink><br /><searchLink fieldCode="DE" term="%22Carburization%22">Carburization</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22X-ray+absorption+spectra%22">X-ray absorption spectra</searchLink><br /><searchLink fieldCode="DE" term="%22Molybdenum+compounds%22">Molybdenum compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+precursors%22">Chemical precursors</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink>
– Name: Abstract
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  Data: Carbon‐supported Mo–W carbides were synthesized by two different methods (co‐impregnation and sequential impregnation of W and Mo precursors) to unravel how precursor impregnation controls carburization pathways. In situ W L3‐edge HERFD‐XAS and Mo K‐edge XAS, quantitatively analyzed by MCR‐ALS reveals that all samples follow a 3‐component sequence "oxide → reduced oxide → carbide" upon temperature‐programmed carburization. However, the temperature window of the reduced MoO2–WO3‐x coexistence is route‐dependent. Co‐impregnation and preliminary carburization of W generate extended overlapping domains (300°C‐420°C) in which both reduced oxides are simultaneously formed, promoting cooperative oxide‐oxide transformations and leading to mixed Mo–W carbidic environments, consistent with XRD and TEM. In contrast, in the route where Mo is carburized first, pre‐reduced molybdenum domains trigger early W reduction and shorten the MoO2–WO3‐x overlap window, leading to independent transformation paths for the two metal precursors and to the formation of separate Mo‐rich and W‐rich carbide phases. These results demonstrate that impregnation and carburization orders are decisive synthetic levers for directing the speciation of Mo–W carbide towards mixed bicarbides or phase‐segregated Mo‐rich/W‐rich carbides providing actionable guidelines for designing bifunctional carbide catalysts. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of ChemCatChem is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1002/cctc.202600006
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        Text: English
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        PageCount: 13
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      – SubjectFull: Carburization
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      – SubjectFull: Chemical reactions
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      – SubjectFull: X-ray absorption spectra
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      – SubjectFull: Molybdenum compounds
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      – SubjectFull: Chemical precursors
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      – SubjectFull: Catalysts
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      – TitleFull: Influence of Preparation and Activation on the Speciation of Carbon‐Supported Mo–W Carbides.
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              Text: 2/25/2026
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