The electron-donating effect of pyridinic N sites in covalent triazine frameworks on the molecular ruthenium catalyzing CO2 hydrogenation to formate

被引：0
作者：
Luo, Maowei [1 ]
Zhang, Pengfei [1 ]
Zhou, Xu [2 ]
Ran, Zepeng [2 ]
Zhang, Ping [2 ]
Sui, Ran [2 ]
Fan, Zhu [2 ]
Wu, Minghao [2 ]
Hu, Xiaowei [1 ]
Wang, Shengping [1 ,3 ]
机构：
[1] Tianjin Univ, Collaborat Innovat Ctr Chem Sci & Engn, Sch Chem Engn & Technol, Key Lab Green Chem Technol, Tianjin 300072, Peoples R China
[2] Purificat Equipment Res Inst CSIC, Handan 056027, Peoples R China
[3] Ningxia Univ, Sch Chem & Chem Engn, State Key Lab High Efficiency Utilizat Coal & Gree, Yinchuan 750021, Peoples R China
来源：
MOLECULAR CATALYSIS | 2024年 / 562卷
基金：
中国国家自然科学基金;
关键词：
Pyridinic n; CTFs; DFT calculations; CO2; activation; Formate; CARBON-DIOXIDE HYDROGENATION; FORMIC-ACID; CATALYTIC-HYDROGENATION; SELECTIVE OXIDATION; MECHANISTIC INSIGHT; ORGANIC FRAMEWORKS; CONVERSION; COMPLEXES; METHANOL; PROTON;
D O I：
10.1016/j.mcat.2024.114213
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
In this study, molecular ruthenium (Ru3+) was immobilized onto pyridine-functionalized covalent triazine frameworks (CTFs) to catalyze the hydrogenation of CO2 to formate efficiently. The energy barrier for this process on N3-Ru, coordinated by both pyridinic N and triazinic-N, was found to be 29.91 kcal/mol, significantly lower than the 38.07 kcal/mol on N2-Ru, coordinated only by triazinic-N. Increasing the content of pyridine ring in the catalyst (RuCl3@CTF-1<RuCl3@CTF-2< RuCl3@CTF-3) led to a higher ratio of N3-Ru to N2-Ru. The higher the N3-Ru content, the denser the electron cloud density of Ru species, favoring Ru-H nucleophilic attack on C atoms in CO2, as confirmed by XPS. RuCl3@CTF-3, with the highest content of N3-Ru structure, exhibited the best performance (TOF=1274 h(-)(1) at 120 degrees C, 6 Mpa) and the lowest apparent activation energy (Ea=36.53 KJ<middle dot>mol(-1)) in CO2 hydrogenation, consistent with DFT calculations.
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页数：10
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