Molecular mechanism comparison of decarbonylation with deoxygenation and hydrogenation of 5-hydroxymethylfurfural catalyzed by palladium acetate.
Molecular mechanism comparison of decarbonylation with deoxygenation and hydrogenation of 5-hydroxymethylfurfural catalyzed by palladium acetate.
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DOI：
10.1039/c8cp07723a
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发表时间：
2019-02
期刊：
影响因子：
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通讯作者：
Hong-Yan Xie;Ting Qi;Ya Lyu;Jin-Feng Zhang;Zhen-Bing Si;Li-Juan Liu;Liangfang Zhu;Huaqing Yang-Huaqing-Y
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文献类型：
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作者：
Hong-Yan Xie;Ting Qi;Ya Lyu;Jin-Feng Zhang;Zhen-Bing Si;Li-Juan Liu;Liangfang Zhu;Huaqing Yang-Huaqing-Y
The selective removal of oxygen from 5-hydroxymethylfurfural (HMF) is challenging for the effective utilization of biomass. The catalytic mechanisms of palladium acetate toward the conversion of HMF to furfuryl alcohol (FFA), 5-methylfurfural (5-MF) and 2,5-dihydroxymethyl furan (DHMF) have been theoretically investigated. The decarbonylation of HMF to FFA includes (i) migratory extrusion, (ii) metal-acetate-co-assisted deprotonation, (iii) decarbonylation, (iv) metal-assisted deprotonation, and (v) migratory extrusion and catalyst regeneration. Both hydrogenation and deoxidation of HMF with HCOOH as the H-source involve (i) migratory extrusion, (ii) oxidative addition, (iii) reductive elimination, (iv) metal-assisted deprotonation, and (v) migratory extrusion and catalyst regeneration. The C-H bond cleavage is the crucial reaction step, in which the metal-acetate-co-assisted deprotonation is kinetically more preferable than the oxidative addition. Both FFA and DHMF are kinetically superior to 5-MF. In terms of selectivity, increasing the temperature is beneficial to decarbonylation and decreasing the temperature is advantageous to hydrogenation. The present finding provides molecular-level insight into the functions of both the metal-center and coordinated-ligand in the Pd(OAc)2 catalyst, which may drive the novel design of catalytic systems toward both decarbonylation and hydrogenation reactions.
