{"title":"Rational design of ligand-immobilized Rh/IRMOFs catalysts for 1-butene hydroformylation with high regioselectivity","authors":"","doi":"10.1016/j.jece.2024.114163","DOIUrl":null,"url":null,"abstract":"<div><div>The diverse pore structures and excellent tunable proprieties of IRMOFs materials made the possibility to explore the effect of the mode of ligand-immobilization on its catalytic performance for 1-butene hydroformylation. In this work, we report a successful case of theory-guided rational design of a highly active ligand-immobilized Rh/IRMOF catalyst based on previous work. Density functional theory calculations of elementary reaction barriers for 1-butene hydroformylation over 1Rh/IRMOFs-PPh<sub>3</sub> models (IRMOF-1, -8, -10, -14, and -16) were performed. The calculation results and topographic steric maps analysis predicted that 1Rh/IRMOF-10-PPh<sub>3</sub> have superior catalytic performance. This can be attributed to the “shape-selective” effect of phosphine ligands grafted in the backbone on the reactive transition state. In addition, the anchoring positions of the phenyl phosphine ligand grafting on the skeleton of 1Rh/IRMOF-10-PPh<sub>3</sub> was identified in details. The 1Rh/IRMOF-10-PPh<sub>3</sub>[3‐3] was predicted to have the highest n/i ratio. In order to verify the theoretical prediction, 1Rh/IRMOF-10–32PPh<sub>3</sub> catalyst was prepared by post-synthesis strategy and the n/i ratio was experimentally confirmed to be 3.49, which outperform the previous 1Rh/MOF-5-PPh<sub>3</sub> catalyst. This work suggests that the 1Rh/IRMOF-10-PPh<sub>3</sub> catalyst can be a promising catalyst for hydroformylation reactions.</div></div>","PeriodicalId":15759,"journal":{"name":"Journal of Environmental Chemical Engineering","volume":null,"pages":null},"PeriodicalIF":7.4000,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Environmental Chemical Engineering","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2213343724022942","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The diverse pore structures and excellent tunable proprieties of IRMOFs materials made the possibility to explore the effect of the mode of ligand-immobilization on its catalytic performance for 1-butene hydroformylation. In this work, we report a successful case of theory-guided rational design of a highly active ligand-immobilized Rh/IRMOF catalyst based on previous work. Density functional theory calculations of elementary reaction barriers for 1-butene hydroformylation over 1Rh/IRMOFs-PPh3 models (IRMOF-1, -8, -10, -14, and -16) were performed. The calculation results and topographic steric maps analysis predicted that 1Rh/IRMOF-10-PPh3 have superior catalytic performance. This can be attributed to the “shape-selective” effect of phosphine ligands grafted in the backbone on the reactive transition state. In addition, the anchoring positions of the phenyl phosphine ligand grafting on the skeleton of 1Rh/IRMOF-10-PPh3 was identified in details. The 1Rh/IRMOF-10-PPh3[3‐3] was predicted to have the highest n/i ratio. In order to verify the theoretical prediction, 1Rh/IRMOF-10–32PPh3 catalyst was prepared by post-synthesis strategy and the n/i ratio was experimentally confirmed to be 3.49, which outperform the previous 1Rh/MOF-5-PPh3 catalyst. This work suggests that the 1Rh/IRMOF-10-PPh3 catalyst can be a promising catalyst for hydroformylation reactions.
期刊介绍:
The Journal of Environmental Chemical Engineering (JECE) serves as a platform for the dissemination of original and innovative research focusing on the advancement of environmentally-friendly, sustainable technologies. JECE emphasizes the transition towards a carbon-neutral circular economy and a self-sufficient bio-based economy. Topics covered include soil, water, wastewater, and air decontamination; pollution monitoring, prevention, and control; advanced analytics, sensors, impact and risk assessment methodologies in environmental chemical engineering; resource recovery (water, nutrients, materials, energy); industrial ecology; valorization of waste streams; waste management (including e-waste); climate-water-energy-food nexus; novel materials for environmental, chemical, and energy applications; sustainability and environmental safety; water digitalization, water data science, and machine learning; process integration and intensification; recent developments in green chemistry for synthesis, catalysis, and energy; and original research on contaminants of emerging concern, persistent chemicals, and priority substances, including microplastics, nanoplastics, nanomaterials, micropollutants, antimicrobial resistance genes, and emerging pathogens (viruses, bacteria, parasites) of environmental significance.