A multicentre synergistic polyoxometalate-based metal–organic framework for one-step selective oxidative cleavage of β-O-4 lignin model compounds†,Green Chemistry

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A multicentre synergistic polyoxometalate-based metal–organic framework for one-step selective oxidative cleavage of β-O-4 lignin model compounds†
Green Chemistry ( IF 9.3 ) Pub Date : 2019-11-29 , DOI: 10.1039/c9gc03626a
Hong-Rui Tian _{1,

2,

3,

4,

5} , Yi-Wei Liu _{1,

2,

3,

4,

5} , Zhong Zhang _{1,

2,

3,

4,

5} , Shu-Mei Liu _{1,

2,

3,

4,

5} , Tian-Yi Dang _{1,

2,

3,

4,

5} , Xiao-Hui Li _{1,

2,

3,

4,

5} , Xiu-Wei Sun _{1,

2,

3,

4,

5} , Ying Lu _{1,

2,

3,

4,

5} , Shu-Xia Liu _{1,

2,

3,

4,

5}

Affiliation

A novel mixed-valence polyoxovanadate-based copper–organic framework, [Cu^I(bbi)]₂{[Cu^I(bbi)]₂V^IV₂V^V₈O₂₆}·2H₂O (NENU-MV-5, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)), was facilely synthesized from routine reagents under mild hydrothermal conditions. Using NENU-MV-5 as a heterogeneous catalyst without any co-catalyst, one-step oxidative cleavage of β-O-4 lignin into phenols and aromatic acids with high catalytic activity and selectivity was realized under an oxygen atmosphere. No obvious decrease in activity was observed after five cycles, which indicates the excellent stability and sustainability of NENU-MV-5. The perfect catalytic performance of NENU-MV-5 can be attributed to the multi-site synergistic effect of the mixed-valence V^V–O–V^IV sites on polyoxovanadate for the oxidation of β-O-4 alcohol to β-O-4 ketone and the Cu(I) sites on the framework for the rapid cleavage of the C_α–C_β bond of β-O-4 ketone. This system represented the first co-catalyst-free example for the one-step selective degradation of lignin catalyzed by a well-defined crystalline catalyst with definite composition and structure in a single solvent.

中文翻译：

基于多中心协同多金属氧酸盐的金属-有机骨架，可一步选择性氧化裂解β- O-4木质素模型化合物†

一种新颖的基于混合价多氧钒酸盐的铜-有机骨架，[Cu ^I（bbi）] ₂ {[Cu ^I（bbi）] ₂ V ^IV₂ V ^V₈ O ₂₆ }·2H ₂O（NENU-MV-5，bbi = 1,1'-（1,4-丁二基）双（咪唑））是在温和的水热条件下从常规试剂轻松合成的。使用NENU-MV-5作为不具有任何助催化剂的非均相催化剂，在氧气气氛下实现了β-O-4木质素的一步氧化裂解为具有高催化活性和选择性的酚和芳族酸。在五个循环后未观察到活性的明显降低，这表明NENU-MV-5具有优异的稳定性和可持续性。NENU-MV-5的完美催化性能可归因于聚氧钒酸盐上混合价V ^V –O–V ^IV位的多位点协同作用，可将β-O-4醇氧化为β-O- 4酮与铜（I上为C的快速切割的框架）站点_α -C _β β-O-4酮键。该系统代表了第一个不含助催化剂的实例，该实例是通过在单一溶剂中具有确定的组成和结构的明确定义的结晶催化剂，一步一步选择性降解木质素的方法。

更新日期：2020-01-02

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