基于密度泛函理论计算Cu价态对1,4-丁二醇脱氢制备<italic style="font-style: italic">γ</italic>-丁内酯反应的影响

贺洋; 曹媛; 王馨艺; 刘宇飞; 李美其; 王康军; 刘蝈蝈

doi:10.12434/j.issn.2097-2547.20250012

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基于密度泛函理论计算Cu价态对1,4-丁二醇脱氢制备γ-丁内酯反应的影响

低碳分子转化合成 | 更新时间：2025-12-25

- 基于密度泛函理论计算Cu价态对1,4-丁二醇脱氢制备γ-丁内酯反应的影响
- Influence of Cu valence states on dehydrogenation of 1,4-butanediol to γ-butyrolactone based on density functional theory calculation
- 低碳化学与化工 2025, 50(12): 48-58.
- 作者机构：
  
  沈阳化工大学化学工程学院，辽宁沈阳 110142
- 作者简介：
  
  贺洋（1998—），硕士研究生，研究方向为低碳化工催化剂，E-mail：1048367034@qq.com。
  王康军（1979—），博士，教授，研究方向为能源转化与催化材料，E-mail：wangkj_dut@syuct.edu.cn；
  刘蝈蝈（1988—），博士，副教授，研究方向为碳一化工与低碳化工催化剂，E-mail：lguoguo@syuct.edu.cn。
- 基金信息：
  
  辽宁省自然科学基金(2021-NLTS-12-03);辽宁省教育厅面上项目(LJKZ0439);辽宁省教育厅青年项目(LJKQ2021068);沈阳化工大学优青托举计划(2019YQ01)
- DOI：10.12434/j.issn.2097-2547.20250012
  中图分类号： TQ426.8
- 收稿：2025-01-09，
  
  修回：2025-03-02，
  
  纸质出版：2025-12-25
- 稿件说明：
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贺洋,曹媛,王馨艺等.基于密度泛函理论计算Cu价态对1,4-丁二醇脱氢制备γ-丁内酯反应的影响[J].低碳化学与化工,2025,50(12):48-58.

HE Yang,CAO Yuan,WANG Xinyi,et al.Influence of Cu valence states on dehydrogenation of 1,4-butanediol to γ-butyrolactone based on density functional theory calculation[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(12):48-58.
贺洋,曹媛,王馨艺等.基于密度泛函理论计算Cu价态对1,4-丁二醇脱氢制备γ-丁内酯反应的影响[J].低碳化学与化工,2025,50(12):48-58. DOI： 10.12434/j.issn.2097-2547.20250012.

HE Yang,CAO Yuan,WANG Xinyi,et al.Influence of Cu valence states on dehydrogenation of 1,4-butanediol to γ-butyrolactone based on density functional theory calculation[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(12):48-58. DOI： 10.12434/j.issn.2097-2547.20250012.

摘要

-丁内酯（GBL）作为重要的工业原料，其需求量日益增大。Cu基催化剂上的1

4-丁二醇（BDO）脱氢是目前主要采用的GBL制备方法。然而，该方法中Cu基催化剂上的脱

氢反应机制及Cu价态对反应的影响亟待深入研究。采用密度泛函理论计算并分析了Cu基催化剂上BDO脱氢制GBL的反应过程，对比了不同反应路径的能垒，并对Cu

-完美型催化剂、Cu

-缺陷型催化剂、Cu

催化剂和Cu

/Cu

复合型催化剂上物质的吸附能、过渡态等进行了研究。结果表明，最可能发生的反应路径（路径A）为BDO先脱去两个氢原子后环化生成2-羟基四氢呋喃（2-HTHF），随后2-HTHF脱去两个氢原子生成GBL，路径A的决速步能垒为287.67 kJ/mol。在路径A下，Cu

对BDO、2-HTHF等分子具有较强的吸附性能，而Cu

则更易于活化 H

；Cu

、氧空位均能有效促进O—H键与C—H键的断裂，并活化BDO和2-HTHF；在H

覆盖率较低的情况下，Cu

对 H

合成有明显的促进作用。与其他3种催化剂相比，Cu

/Cu

复合型催化剂的催化性能更好。

Abstract

As an important industrial raw material

-butyrolactone (GBL) is in increasing demand day by day. Currently

the dehydrogenation of 1

4-butanediol (BDO) on Cu-based catalysts represents the predominant method for GBL preparation. However

the dehydrogenation reaction mechanism on Cu-based catalysts and the influence of the Cu valence states on the reaction remain to be thoroughly investigated. The reaction process of BDO dehydrogenation to GBL on Cu-based catalysts was calculated and analyzed by density functional theory. The energy barriers of different reaction pathways were compared

and the adsorption energies

transition states

etc. of substances on Cu

-perfect type catalyst

-defect type catalyst

catalyst and Cu

/Cu

composite type catalyst were studied. The results show that the most probable reaction pathway (pathway A) involves BDO first eliminating two hydrogen atoms follows by cyclization to form 2-hydroxytetrahydrofuran (2-HTHF)

which then loses two additional hydrogen atoms to produce GBL

with the energy barrier of rate-determining step of pathway A of 287.67 kJ/mol. Under pathway A

demonstrates strong adsorption towards BDO and 2-HTHF molecules

while Cu

exhibits greater aptitude for H

activation. Both Cu

and oxygen vacancy effectively facilitate the breaking of O—H

and C—H bonds

activating BDO and 2-HTHF

and Cu⁰ significantly promotes H

synthesis under low H

coverage conditions. Notably

Cu⁰/Cu

composite catalyst outperforms the other three catalysts in terms of catalytic performance.

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references

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DOI：10.12434/j.issn.2097-2547.20250012

摘要

Abstract

关键词

Keywords

references