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Influence of Cu valence states on dehydrogenation of 1,4-butanediol to
γ -butyrolactone based on density functional theory calculation- Low-Carbon Chemistry and Chemical Engineering Vol. 50, Issue 12, Pages: 48-58(2025)
- 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：
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20250012
CLC： TQ426.8Received：09 January 2025，
Revised：2025-03-02，
Published：25 December 2025
- 稿件说明：
移动端阅览
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
γ
-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
0
催化剂和Cu
0
/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
0
则更易于活化 H
2
；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
2
覆盖率较低的情况下，Cu
0
对 H
2
合成有明显的促进作用。与其他3种催化剂相比，Cu
0
/Cu
+
复合型催化剂的催化性能更好。
Abstract
As an important industrial raw material
γ
-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
Cu
+
-defect type catalyst
Cu
0
catalyst and Cu
0
/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
Cu
+
demonstrates strong adsorption towards BDO and 2-HTHF molecules
while Cu
0
exhibits greater aptitude for H
2
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
2
synthesis under low H
2
coverage conditions. Notably
Cu⁰/Cu
+
composite catalyst outperforms the other three catalysts in terms of catalytic performance.
关键词
Keywords
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