摘要
采用密度泛函理论方法,构建了Ag,Zn,Pd原子掺杂的Cu(111)和Cu_(2)O(111)活性晶面,探讨了不同金属掺杂对Cu(111)和Cu_(2)O(111)催化剂的草酸二甲酯(DMO)加氢反应活性和选择性的影响.研究结果显示,掺杂Zn可有效阻止乙醇酸甲酯(MG)进一步加氢,提高MG的选择性,Ag助剂可以有效提高加氢活性;而Pd助剂的添加使MG的生成能垒增高,降低了MG的选择性.Ag-Cu(111)表面具有适宜的d带中心,生成CH_(3)OOCCH_(2)OH的活性最高.在Ag,Zn,Pd原子掺杂的Cu_(2)O(111)表面,Ag-Cu_(2)O(111)能带带隙小、价带强度高,在DMO加氢反应中具有最佳的催化活性.基于上述结果,提出铜基催化剂结构调变和性能调控的理论方法,为高效催化剂的设计提供可靠的理论指导.
The active crystal planes of Cu(111)and Cu_(2)O(111)doped with Ag,Zn and Pd atoms were constructed using a density functional theory to investigate the effects of different metal doping on the activity and selectivity for dimethyl oxalate(DMO)hydrogenation to methyl glycolate(MG).The results showed that Zn-doping can prohibit the deep hydrogenation of MG effectively,and Ag additves could effectively improve hydrogenation activity for DMO.Conversely,the addition of Pd increased the energy barrier of MG generation,thus reduced MG selectivity.The Ag-Cu(111)surface has a suitable d-center and has the highest activity to generate CH_(3)OOCCH_(2)OH.On the surface of Ag,Zn,Pd atom doped Cu_(2)O(111),Ag-Cu_(2)O(111)has a small band gap and high valence band strength,and has the best catalytic activity in DMO hydrogenation reaction.Based on the above results,theoretical methods for structural modulation and performance regulation of copper-based catalysts are proposed,which provide reliable theoretical guidance for the design of highly efficient catalysts.
作者
宋有为
安江伟
王征
王旭慧
权燕红
任军
赵金仙
SONG Youwei;AN Jiangwei;WANG Zheng;WANG Xuhui;QUAN Yanhong;REN Jun;ZHAO Jinxian(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,China)
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2022年第6期268-277,共10页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:21808154)
山西省应用基础研究项目(批准号:201901D211059)资助.
关键词
草酸二甲酯
选择性加氢
铜基催化剂
金属掺杂
Dimethyl oxalate(DMO)
Selective hydrogenation
Cu-based catalyst
Metal-doping
