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<p>The growing demand for γ‑butyrolactone (GBL) as an essential solvent for lithium‑ion battery electrolytes has attracted considerable interest in its high efficiency synthesis. The dehydrogenation of 1,4‑butanediol (BDO) offers an atom‑economical and environmentally friendly pathway to produce GBL. However, the lack of investigation into the dehydrogenation mechanism and structure–activity relationships hinders further optimization of the industrially predominant CuZnAl catalyst. Herein, a series of CuO-ZnO-Al<sub>2</sub>O<sub>3</sub> catalysts with Cu/Zn molar ratios of 0.5, 1 and 2 were prepared and evaluated using dehydrogenation of BDO to GBL as a model reaction. The results indicate that C<sub>1</sub>ZA with an equimolar Cu/Zn ratio achieved the optimal performance with 99.6% BDO conversion and 98.7% GBL yield at 220&#xa0;°C (LHSV = 1.0&#xa0;h<sup>− 1</sup>, H<sub>2</sub>/BDO = 5), along with outstanding reaction stability over 240&#xa0;h. Structural characterization results show that the Cu/Zn ratio governs the Cu<sup>+</sup>/Cu<sup>0</sup> proportion, the generation of Cu-ZnO<sub>x</sub> interfacial species and the distribution of Lewis acid, Brønsted acid as well as basic sites. With a Cu/Zn ratio of 1, the C<sub>1</sub>ZA catalyst delivered the highest Cu<sup>+</sup>/Cu<sup>0</sup> ratio, the most abundant Cu-ZnOₓ interfacial sites, and a Lewis‑acid‑dominated surface bearing very few Brønsted acid and strong base sites. This combination of characteristics accelerated the desired two‑step dehydrogenation-hemiacetalization cascade while inhibiting competing dehydration and acetalization pathways, thus yielding the highest GBL selectivity. These findings highlight a cooperative interaction between interfacial electronic structure and surface acid-base properties that collectively governs dehydrogenation selectivity, thus offering design principles for highly selective Cu‑based dehydrogenation catalysts.</p> Graphical Abstract <p></p>

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Tailoring the Surface Chemistry and Interfacial Architecture of CuZnAl Catalysts Via the Cu/Zn Ratio for Highly Selective Dehydrogenation of 1,4-Butanediol to γ-Butyrolactone

  • 期刊论文

  • 发表日期：

    2026年7月10日

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  • Siqi Zhang,
  • Huiling Wu,
  • Lingchen Meng,
  • Haodong Li,
  • Bofan Liu,
  • Dechen Wang,
  • Shenghua Yuan

摘要

The growing demand for γ‑butyrolactone (GBL) as an essential solvent for lithium‑ion battery electrolytes has attracted considerable interest in its high efficiency synthesis. The dehydrogenation of 1,4‑butanediol (BDO) offers an atom‑economical and environmentally friendly pathway to produce GBL. However, the lack of investigation into the dehydrogenation mechanism and structure–activity relationships hinders further optimization of the industrially predominant CuZnAl catalyst. Herein, a series of CuO-ZnO-Al2O3 catalysts with Cu/Zn molar ratios of 0.5, 1 and 2 were prepared and evaluated using dehydrogenation of BDO to GBL as a model reaction. The results indicate that C1ZA with an equimolar Cu/Zn ratio achieved the optimal performance with 99.6% BDO conversion and 98.7% GBL yield at 220 °C (LHSV = 1.0 h− 1, H2/BDO = 5), along with outstanding reaction stability over 240 h. Structural characterization results show that the Cu/Zn ratio governs the Cu+/Cu0 proportion, the generation of Cu-ZnOx interfacial species and the distribution of Lewis acid, Brønsted acid as well as basic sites. With a Cu/Zn ratio of 1, the C1ZA catalyst delivered the highest Cu+/Cu0 ratio, the most abundant Cu-ZnOₓ interfacial sites, and a Lewis‑acid‑dominated surface bearing very few Brønsted acid and strong base sites. This combination of characteristics accelerated the desired two‑step dehydrogenation-hemiacetalization cascade while inhibiting competing dehydration and acetalization pathways, thus yielding the highest GBL selectivity. These findings highlight a cooperative interaction between interfacial electronic structure and surface acid-base properties that collectively governs dehydrogenation selectivity, thus offering design principles for highly selective Cu‑based dehydrogenation catalysts.

Graphical Abstract