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Synergistic promotion over Cu+-Ov-Ce3+ interface dehydrogenative lactonization of 1,6-hexanediol to ε-CL.

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Title: Synergistic promotion over Cu+-Ov-Ce3+ interface dehydrogenative lactonization of 1,6-hexanediol to ε-CL.
Authors: Wang, Zheng1 (AUTHOR), Li, Yongwang1 (AUTHOR), Wang, Wanli1 (AUTHOR), Zhu, Binxin1 (AUTHOR), Zhang, Jiaxing1 (AUTHOR), Wang, Xingtao1 (AUTHOR), Liu, Qingzhao2 (AUTHOR), Li, Kaihao1 (AUTHOR), Yin, Yancong1 (AUTHOR), Shi, Jinhua1 (AUTHOR), Zhang, Zhiwei1,3 (AUTHOR) zhiweiz@ipe.ac.cn, Wang, Fumin1,4 (AUTHOR) wangfumin@tju.edu.cn, Zhang, Xubin1 (AUTHOR) tjzxb@tju.edu.cn
Source: Chemical Engineering Science. Sep2026, Vol. 333, pN.PAG-N.PAG. 1p.
Subjects: Catalysis, Caprolactones, Glycols, Ab-initio calculations, Biodegradable materials, Abstraction reactions
Abstract: [Display omitted] • Cu+-O v -Ce3+ interface site catalyzes 1,6-HDO dehydrogenation lactonization to ɛ-CL. • Mechanism of 1,6-HDO dehydrogenation lactonization revealed via experiments and DFT. • Kinetics and DFT reveal α‑H abstraction as rate-determining step. ε-Caprolactone (ε-CL) is a key monomer for biodegradable polyesters, but its green synthesis remains challenging. Rational design of interfacial active sites to promote α‑H abstraction, intermediate cyclization, and stabilizing Cu(I) species is significant for the formation of ε-CL in Cu‑based catalysts. In this work, a series of catalysts with stable Cu+-O v -Ce3+ hetero‑interfacial structures, which are confirmed by XPS spectra, Raman spectra, and XAFS spectra, are designed for the dehydrogenative lactonization of 1,6‑hexanediol (1,6-HDO). As confirmed by experimental and spectroscopic data, the catalytically critical Cu+-O v -Ce3+ hetero‑interface, not Lewis‑base or isolated Cu sites, enables 1,6‑HDO dehydrogenative lactonization, a role for which density functional theory (DFT) calculations elucidate its dual function in promoting adsorption/activation and mapping the pathway, thereby allowing the α‑H abstraction to be identified by combined DFT and kinetic modeling as the rate‑determining surface step. Under optimal reaction conditions, the maximum conversion of 1,6‑HDO reaches 76.23%, with ε-CL selectivity of 59.30%. This insight into the active center for diol dehydrogenative lactonization provides new perspectives for the design of high‑performance catalysts. [ABSTRACT FROM AUTHOR]
Copyright of Chemical Engineering Science is the property of Pergamon Press - An Imprint of Elsevier Science 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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  Label: Title
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  Data: Synergistic promotion over Cu+-Ov-Ce3+ interface dehydrogenative lactonization of 1,6-hexanediol to ε-CL.
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  Data: <searchLink fieldCode="AR" term="%22Wang%2C+Zheng%22">Wang, Zheng</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Li%2C+Yongwang%22">Li, Yongwang</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wang%2C+Wanli%22">Wang, Wanli</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhu%2C+Binxin%22">Zhu, Binxin</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhang%2C+Jiaxing%22">Zhang, Jiaxing</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wang%2C+Xingtao%22">Wang, Xingtao</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Liu%2C+Qingzhao%22">Liu, Qingzhao</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Li%2C+Kaihao%22">Li, Kaihao</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Yin%2C+Yancong%22">Yin, Yancong</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Shi%2C+Jinhua%22">Shi, Jinhua</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhang%2C+Zhiwei%22">Zhang, Zhiwei</searchLink><relatesTo>1,3</relatesTo> (AUTHOR)<i> zhiweiz@ipe.ac.cn</i><br /><searchLink fieldCode="AR" term="%22Wang%2C+Fumin%22">Wang, Fumin</searchLink><relatesTo>1,4</relatesTo> (AUTHOR)<i> wangfumin@tju.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Zhang%2C+Xubin%22">Zhang, Xubin</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> tjzxb@tju.edu.cn</i>
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  Data: <searchLink fieldCode="JN" term="%22Chemical+Engineering+Science%22">Chemical Engineering Science</searchLink>. Sep2026, Vol. 333, pN.PAG-N.PAG. 1p.
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  Data: <searchLink fieldCode="DE" term="%22Catalysis%22">Catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Caprolactones%22">Caprolactones</searchLink><br /><searchLink fieldCode="DE" term="%22Glycols%22">Glycols</searchLink><br /><searchLink fieldCode="DE" term="%22Ab-initio+calculations%22">Ab-initio calculations</searchLink><br /><searchLink fieldCode="DE" term="%22Biodegradable+materials%22">Biodegradable materials</searchLink><br /><searchLink fieldCode="DE" term="%22Abstraction+reactions%22">Abstraction reactions</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: [Display omitted] • Cu+-O v -Ce3+ interface site catalyzes 1,6-HDO dehydrogenation lactonization to ɛ-CL. • Mechanism of 1,6-HDO dehydrogenation lactonization revealed via experiments and DFT. • Kinetics and DFT reveal α‑H abstraction as rate-determining step. ε-Caprolactone (ε-CL) is a key monomer for biodegradable polyesters, but its green synthesis remains challenging. Rational design of interfacial active sites to promote α‑H abstraction, intermediate cyclization, and stabilizing Cu(I) species is significant for the formation of ε-CL in Cu‑based catalysts. In this work, a series of catalysts with stable Cu+-O v -Ce3+ hetero‑interfacial structures, which are confirmed by XPS spectra, Raman spectra, and XAFS spectra, are designed for the dehydrogenative lactonization of 1,6‑hexanediol (1,6-HDO). As confirmed by experimental and spectroscopic data, the catalytically critical Cu+-O v -Ce3+ hetero‑interface, not Lewis‑base or isolated Cu sites, enables 1,6‑HDO dehydrogenative lactonization, a role for which density functional theory (DFT) calculations elucidate its dual function in promoting adsorption/activation and mapping the pathway, thereby allowing the α‑H abstraction to be identified by combined DFT and kinetic modeling as the rate‑determining surface step. Under optimal reaction conditions, the maximum conversion of 1,6‑HDO reaches 76.23%, with ε-CL selectivity of 59.30%. This insight into the active center for diol dehydrogenative lactonization provides new perspectives for the design of high‑performance catalysts. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Chemical Engineering Science is the property of Pergamon Press - An Imprint of Elsevier Science 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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      – Type: doi
        Value: 10.1016/j.ces.2026.124219
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      – Code: eng
        Text: English
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        PageCount: 1
        StartPage: N.PAG
    Subjects:
      – SubjectFull: Catalysis
        Type: general
      – SubjectFull: Caprolactones
        Type: general
      – SubjectFull: Glycols
        Type: general
      – SubjectFull: Ab-initio calculations
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      – SubjectFull: Biodegradable materials
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      – SubjectFull: Abstraction reactions
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      – TitleFull: Synergistic promotion over Cu+-Ov-Ce3+ interface dehydrogenative lactonization of 1,6-hexanediol to ε-CL.
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              Text: Sep2026
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