Junxing Han , Chenhao Gong , Can He , Yue Shan , Hui Lou , Zhongguo Zhang
{"title":"功能化三聚氰胺基 Dendron-OMS 混合物作为硝基醛(Henry)反应的高效催化剂","authors":"Junxing Han , Chenhao Gong , Can He , Yue Shan , Hui Lou , Zhongguo Zhang","doi":"10.1016/j.jcat.2024.115566","DOIUrl":null,"url":null,"abstract":"<div><p>Controllable synthesis of organic–inorganic hybrid materials with functional sites and tunable structures is of great significance. Herein, novel melamine-based G<sub>n</sub>-Dendron-OMS (G represents Generation; n = 1, 2, 3; Dendron = DMEDA, PIP, AMP, TMDP; OMS = FDU-12, MCM-41, SBA-15, KIT-6) hybrids with various terminal diamine groups, Dendron generations and ordered mesoporous silica hosts were synthesized, characterized and used to catalyze the nitroaldol (Henry) reaction. Among these hybrids, G<sub>1</sub>-DMEDA-FDU-12 shows outstanding catalytic performance with 4-nitrobenzaldehyde conversion of 96 %, β-nitroalcohol selectivity of 94 % and TOF of 20.4 h<sup>−1</sup> under mild and solvent-free conditions. HMDS and HCl intervening active-site deactivation, in situ Raman spectra, Mulliken charge distribution and DFT calculations suggest that the triazine N atom (N<sub>T</sub>) in the Dendron chain functions as the active site, the dehydrogenation of nitromethane is the rate determining step (RDS) and the Gibbs free energy change of the RDS on the triazine N atom decreased to as low as 30.2 kcal mol<sup>−1</sup>. The formation of the deuterated β-nitroalcohol (R-OD) detected by FTIR and NMR indicates that nitroaldol (Henry) reaction undergoes an ion-pair mechanism. This work for the first time reveals the triazine-based active site for the nitroaldol (Henry) reaction and highlights a novel strategy to construct uniform, functional and tunable active sites for potential applications in catalysis, CO<sub>2</sub> capture and pollutant removal.</p></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":6.5000,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Functionalized melamine-based Dendron-OMS hybrids as highly-efficient catalysts for the nitroaldol (Henry) reaction\",\"authors\":\"Junxing Han , Chenhao Gong , Can He , Yue Shan , Hui Lou , Zhongguo Zhang\",\"doi\":\"10.1016/j.jcat.2024.115566\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Controllable synthesis of organic–inorganic hybrid materials with functional sites and tunable structures is of great significance. Herein, novel melamine-based G<sub>n</sub>-Dendron-OMS (G represents Generation; n = 1, 2, 3; Dendron = DMEDA, PIP, AMP, TMDP; OMS = FDU-12, MCM-41, SBA-15, KIT-6) hybrids with various terminal diamine groups, Dendron generations and ordered mesoporous silica hosts were synthesized, characterized and used to catalyze the nitroaldol (Henry) reaction. Among these hybrids, G<sub>1</sub>-DMEDA-FDU-12 shows outstanding catalytic performance with 4-nitrobenzaldehyde conversion of 96 %, β-nitroalcohol selectivity of 94 % and TOF of 20.4 h<sup>−1</sup> under mild and solvent-free conditions. HMDS and HCl intervening active-site deactivation, in situ Raman spectra, Mulliken charge distribution and DFT calculations suggest that the triazine N atom (N<sub>T</sub>) in the Dendron chain functions as the active site, the dehydrogenation of nitromethane is the rate determining step (RDS) and the Gibbs free energy change of the RDS on the triazine N atom decreased to as low as 30.2 kcal mol<sup>−1</sup>. The formation of the deuterated β-nitroalcohol (R-OD) detected by FTIR and NMR indicates that nitroaldol (Henry) reaction undergoes an ion-pair mechanism. This work for the first time reveals the triazine-based active site for the nitroaldol (Henry) reaction and highlights a novel strategy to construct uniform, functional and tunable active sites for potential applications in catalysis, CO<sub>2</sub> capture and pollutant removal.</p></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-05-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951724002793\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951724002793","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Functionalized melamine-based Dendron-OMS hybrids as highly-efficient catalysts for the nitroaldol (Henry) reaction
Controllable synthesis of organic–inorganic hybrid materials with functional sites and tunable structures is of great significance. Herein, novel melamine-based Gn-Dendron-OMS (G represents Generation; n = 1, 2, 3; Dendron = DMEDA, PIP, AMP, TMDP; OMS = FDU-12, MCM-41, SBA-15, KIT-6) hybrids with various terminal diamine groups, Dendron generations and ordered mesoporous silica hosts were synthesized, characterized and used to catalyze the nitroaldol (Henry) reaction. Among these hybrids, G1-DMEDA-FDU-12 shows outstanding catalytic performance with 4-nitrobenzaldehyde conversion of 96 %, β-nitroalcohol selectivity of 94 % and TOF of 20.4 h−1 under mild and solvent-free conditions. HMDS and HCl intervening active-site deactivation, in situ Raman spectra, Mulliken charge distribution and DFT calculations suggest that the triazine N atom (NT) in the Dendron chain functions as the active site, the dehydrogenation of nitromethane is the rate determining step (RDS) and the Gibbs free energy change of the RDS on the triazine N atom decreased to as low as 30.2 kcal mol−1. The formation of the deuterated β-nitroalcohol (R-OD) detected by FTIR and NMR indicates that nitroaldol (Henry) reaction undergoes an ion-pair mechanism. This work for the first time reveals the triazine-based active site for the nitroaldol (Henry) reaction and highlights a novel strategy to construct uniform, functional and tunable active sites for potential applications in catalysis, CO2 capture and pollutant removal.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.