低碳化学与化工2025，Vol.50Issue(12)：48-58,11.DOI:10.12434/j.issn.2097-2547.20250012
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
摘要
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,Cu0 catalyst and Cu0/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 Cu0 exhibits greater aptitude for H2 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 H2 synthesis under low H2 coverage conditions.Notably,Cu0/Cu+composite catalyst outperforms the other three catalysts in terms of catalytic performance.关键词
1,4-丁二醇/γ-丁内酯/密度泛函理论/Cu价态/氧空位Key words
1,4-butanediol/γ-butyrolactone/density functional theory/Cu valence states/oxygen vacancy分类
化学化工引用本文复制引用
贺洋,曹媛,王馨艺,刘宇飞,李美其,王康军,刘蝈蝈..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):48-58,11.基金项目
辽宁省自然科学基金(2021-NLTS-12-03) （2021-NLTS-12-03）
辽宁省教育厅面上项目(LJKZ0439) （LJKZ0439）
辽宁省教育厅青年项目(LJKQ2021068) （LJKQ2021068）
沈阳化工大学优青托举项目(2019YQ01). （2019YQ01）
