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MOF catalysts in biomass upgrading towards value-added fine chemicals†
CrystEngComm ( IF 2.6 ) Pub Date : 2016-09-05 00:00:00 , DOI: 10.1039/c6ce01782g
Annika Herbst 1, 2, 3, 4 , Christoph Janiak 1, 2, 3, 4
CrystEngComm ( IF 2.6 ) Pub Date : 2016-09-05 00:00:00 , DOI: 10.1039/c6ce01782g
Annika Herbst 1, 2, 3, 4 , Christoph Janiak 1, 2, 3, 4
Affiliation
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The development of new synthetic routes from biomass sources towards already existing molecules, which are then called bio-based molecules, or the transformation of biomass into new building blocks and materials will be of great impact. The review presents a critical comparison between metal–organic frameworks (MOFs) and other catalysts (e.g. zeolites) for biomass transformation and valorization to platform chemicals: cellulose hydrolysis to glucose, fructose or sorbitol; fructose, glucose or maltose to 5-hydroxymethylfurfural (5-HMF); sucrose to methyl lactate; furans, levulinic acid, lignin or vanillin as feedstock; triglycerides to esters and glycerol. For example, in the case of cellulose hydrolysis as well as glucose isomerization MOF-based catalysts could not compete with zeolites and sulfonated carbon which display significantly higher activity. In DMSO, MIL-101Cr-SO3H-15% and NUS-6(Hf) are among the best heterogeneous catalysts reported so far for the conversion of fructose into 5-HMF. For the glucose-to-5-HMF transformation MIL-101Cr-SO3H is only a low-to-medium activity catalyst for 5-HMF while mesoporous tantalum phosphate as well as Sn montmorillonite display significantly higher activities. On the other hand, MIL-101Cr-SO3H preferentially transformed glucose to 5-HMF over levulinic acid while the catalysts Amberlyst-15 and sulfuric acid gave mostly levulinic acid. For levulinic acid conversion to ethyl levulinate UiO-66Zr catalysts can compete with other heterogeneous catalysts for the levulinic esterification reaction. For active MOF catalysts open metal sites (coordinatively unsaturated sites) are important as the activity increases with the amount of missing linkers. The two MOFs MIL-101Cr and UiO-66 and their derivatives are used in many studies. These MOFs did not only act as catalysts themselves but also served as hosts or support to embedded catalytic species, e.g., phosphotungstic acid (PTA), ruthenium and palladium nanoparticle (Ru-NP, Pd-NP) or poly(N-bromomaleimide) catalysts. For the conversion of vanillin into 2-methoxy-4-methylphenol the selectivity of Pd@UiO-66Zr-NH2 was quantitative compared with other supported Pd catalysts (selectivity 48%). Further, MOFs were used as precursors for decomposition and carbonization due to their high porosity and uniformly distributed metal centers to yield catalytically active metal–carbonaceous materials with high thermal and chemical stability. For example, metal nanoparticles supported on nanoporous carbon (M/NC) were synthesized by carbonization and carbothermal reduction of Ru, W, V, and Ti metal precursors loaded in IRMOF-1 or IRMOF-3. Fe–Co-based MOF-derived catalysts are a highly efficient system for the conversion of 5-HMF to 2,5-diformylfuran. In water-containing reactions, the water stability of MOFs is of high importance.
中文翻译：
财政部促进生物质向增值精细化学品升级的催化剂†
从生物质来源到已经存在的分子（后来称为生物基分子）的新合成路线的发展，或将生物质转化为新的构建基块和材料的方法，都将产生巨大的影响。审查提出了金属有机骨架（MOFs）和其他催化剂（例如沸石）用于将生物质转化和增值以形成平台化学品：将纤维素水解为葡萄糖，果糖或山梨糖醇；果糖，葡萄糖或麦芽糖转化为5-羟甲基糠醛（5-HMF）; 蔗糖为乳酸甲酯；以呋喃，乙酰丙酸，木质素或香草醛为原料；甘油三酸酯为酯和甘油。例如，在纤维素水解以及葡萄糖异构化的情况下，基于MOF的催化剂无法与显示出明显更高活性的沸石和磺化碳竞争。在DMSO中，MIL-101Cr-SO 3 H-15％和NUS-6（Hf）是迄今为止报道的将果糖转化为5-HMF的最佳多相催化剂。用于葡萄糖到5-HMF的转化MIL-101Cr-SO 3H只是5-HMF的中低活性催化剂，而介孔磷酸钽和Sn蒙脱土则显示出明显更高的活性。另一方面，MIL-101Cr-SO 3H优先于乙酰丙酸将葡萄糖转化为5-HMF，而催化剂Amberlyst-15和硫酸主要产生乙酰丙酸。为了将乙酰丙酸转化为乙酰丙酸乙酯，UiO-66Zr催化剂可与其他非均相催化剂竞争乙酰丙酸酯化反应。对于活性MOF催化剂，开放的金属位点（配位不饱和位点）非常重要，因为活性会随着缺失的连接基数量的增加而增加。许多研究使用了两个MOF MIL-101Cr和UiO-66及其衍生物。这些MOF不仅充当催化剂本身，而且还充当嵌入的催化物质的主体或载体，例如磷钨酸（PTA），钌和钯纳米粒子（Ru-NP，Pd-NP）或聚（N-溴马来酰亚胺）催化剂。为了将香兰素转化为2-甲氧基-4-甲基苯酚，Pd @ UiO-66Zr-NH 2的选择性与其他负载的Pd催化剂相比，该催化剂的定量（选择性48％）为定量。此外，由于MOF的高孔隙率和均匀分布的金属中心，因此被用作分解和碳化的前体，从而产生具有高热稳定性和化学稳定性的催化活性金属-碳质材料。例如，通过碳化和碳热还原负载在IRMOF-1或IRMOF-3中的Ru，W，V和Ti金属前驱体，可以合成负载在纳米孔碳（M / NC）上的金属纳米颗粒。Fe-Co基MOF衍生的催化剂是将5-HMF转化为2,5-二甲酰呋喃的高效体系。在含水反应中，MOF的水稳定性至关重要。
更新日期：2016-09-05
中文翻译：
财政部促进生物质向增值精细化学品升级的催化剂†
从生物质来源到已经存在的分子（后来称为生物基分子）的新合成路线的发展，或将生物质转化为新的构建基块和材料的方法，都将产生巨大的影响。审查提出了金属有机骨架（MOFs）和其他催化剂（例如沸石）用于将生物质转化和增值以形成平台化学品：将纤维素水解为葡萄糖，果糖或山梨糖醇；果糖，葡萄糖或麦芽糖转化为5-羟甲基糠醛（5-HMF）; 蔗糖为乳酸甲酯；以呋喃，乙酰丙酸，木质素或香草醛为原料；甘油三酸酯为酯和甘油。例如，在纤维素水解以及葡萄糖异构化的情况下，基于MOF的催化剂无法与显示出明显更高活性的沸石和磺化碳竞争。在DMSO中，MIL-101Cr-SO 3 H-15％和NUS-6（Hf）是迄今为止报道的将果糖转化为5-HMF的最佳多相催化剂。用于葡萄糖到5-HMF的转化MIL-101Cr-SO 3H只是5-HMF的中低活性催化剂，而介孔磷酸钽和Sn蒙脱土则显示出明显更高的活性。另一方面，MIL-101Cr-SO 3H优先于乙酰丙酸将葡萄糖转化为5-HMF，而催化剂Amberlyst-15和硫酸主要产生乙酰丙酸。为了将乙酰丙酸转化为乙酰丙酸乙酯，UiO-66Zr催化剂可与其他非均相催化剂竞争乙酰丙酸酯化反应。对于活性MOF催化剂，开放的金属位点（配位不饱和位点）非常重要，因为活性会随着缺失的连接基数量的增加而增加。许多研究使用了两个MOF MIL-101Cr和UiO-66及其衍生物。这些MOF不仅充当催化剂本身，而且还充当嵌入的催化物质的主体或载体，例如磷钨酸（PTA），钌和钯纳米粒子（Ru-NP，Pd-NP）或聚（N-溴马来酰亚胺）催化剂。为了将香兰素转化为2-甲氧基-4-甲基苯酚，Pd @ UiO-66Zr-NH 2的选择性与其他负载的Pd催化剂相比，该催化剂的定量（选择性48％）为定量。此外，由于MOF的高孔隙率和均匀分布的金属中心，因此被用作分解和碳化的前体，从而产生具有高热稳定性和化学稳定性的催化活性金属-碳质材料。例如，通过碳化和碳热还原负载在IRMOF-1或IRMOF-3中的Ru，W，V和Ti金属前驱体，可以合成负载在纳米孔碳（M / NC）上的金属纳米颗粒。Fe-Co基MOF衍生的催化剂是将5-HMF转化为2,5-二甲酰呋喃的高效体系。在含水反应中，MOF的水稳定性至关重要。
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