2014 Fiscal Year Annual Research Report
非食性バイオマスからの化成品生産に向けた固体触媒グリーンエンジニアリングの構築
| Project/Area Number |
14J12396
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| Research Institution | Japan Advanced Institute of Science and Technology |
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Principal Investigator |
CHOUDHARY Hemant 北陸先端科学技術大学院大学, マテリアルサイエンス研究科, 特別研究員(DC2)
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| Project Period (FY) |
2014-04-25 – 2016-03-31
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| Keywords | Biomass / Metal Organic Framework / Heterogeneous Catalyst / Organic Transformation / Acid Catalyst |
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| Outline of Annual Research Achievements |
In the event of engineering greener methodologies for converting inedible-biomass into commodity chemicals over heterogeneous catalysts, succinic acid (SA, a C4 building block) was chosen as the chemical of interest. According to my previous report, the oxidative dissociation of furan carbonyls in the presence of acid catalyst can successfully produce SA. Thereby to further extend the scope, the preparation of metal-organic framework (MOF) based acid catalyst through two methods, namely- a) ligand design and b) post-synthetic modification were undertaken. Although, the prepared catalyst possessed acidic properties (and catalytic activity for esterification reaction), however, these were not enough to achieve the transformation of furans to SA. Since, the prime target was to develop sustainable catalytic process for SA synthesis utilizing biomass-resources, another approach, “one-pot two-step”, involving the production of HCO2H (from biomass-derived sugar) and in-situ usage of generated HCO2H for the hydrogenation of maleic anhydride to produce SA over heterogeneous catalyst.
The research also proposed the functionalization of MOFs to afford not only acid catalysts but also to immobilize metals like palladium (Pd) through amine functionalization. The successful incorporation of amine functionality was achieved through ligand design methodology and Pd was grafted on such material to afford a potent heterogeneous catalyst. Such catalyst demonstrated remarkable stability and catalytic performances for hydrogenation and coupling (Suzuki-Miyaura & Mizoroki-Heck) reactions.
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| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
The preparation of solid acid catalyst for synthesis of SA using biomass-resources was proposed in addition to the creation of amine functionalized MOFs to bind metals like palladium. In this one year, MOF based acid catalyst were successfully prepared with acidic properties to carry out acid-catalyzed esterification reactions. However, the transformation of furan carbonyls to SA over MOF based acid catalyst could not be achieved. For this, an alternative pathway was developed to utilize biomass-resources for the production of SA over heterogeneous catalyst. The amine functionalized MOFs were successfully prepared to afford unprecedented catalysis over it for hydrogenation and C-C coupling reactions.
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| Strategy for Future Research Activity |
Based on the past achievement and current research progress, the future work is planned as the engineering of catalytic processes involving the prepared MOF based acid catalyst. Another future plan includes the extension of the catalytic scope of Pd immobilized amino-functionalized MOF to C-X coupling (X=C, O, N, S, etc.) reactions. MOF based acid catalyst will be mainly prepared by post-synthetic modification such as oxidation or addition reaction. A variety of organic linker molecule and different metal ion center will be investigated for the generation of desired acidic properties in the catalyst. In addition to it, the screening of synthetic conditions (such as temperature and solvent) to realize the stable MOF structure will be also considered.
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Research Products
(7 results)
