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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]
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Database: Engineering Source
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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]
ISSN:00092509
DOI:10.1016/j.ces.2026.124219