Metal organic frameworks for biomass conversion

Fang, Ruiqi; Dhakshinamoorthy, Amarajothi; Li, Yingwei; Garcı́a, Hermenegildo

doi:10.1039/d0cs00070a

Cited by 213 publications

(132 citation statements)

References 249 publications

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“…Besides, readers are referred to other reports providing the encapsulation of metal NPs within the cages of MOFs and their catalytic performance in broad ranges of reactions including biomass conversion. [69][70][71][72][73]…”

Section: Metal Nps@mofsmentioning

confidence: 99%

“…This section describes the shape selective catalysis achieved by metal NPs encapsulated within the pores of MOFs as heterogeneous catalysts and are categorized based on NPs. Besides, readers are referred to other reports providing the encapsulation of metal NPs within the cages of MOFs and their catalytic performance in broad ranges of reactions including biomass conversion …”

Section: Metal Nps@mofsmentioning

confidence: 99%

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Catalysis in Confined Spaces of Metal Organic Frameworks

2020

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Compared to homogeneous catalysis, heterogeneous catalysis can achieve product selectivity due to spatial constraints and differences in molecular dimensions of substrates and products by performing the reaction in a confined space. Shape selectivity for substrates, products or transition states is a wellestablished phenomenon observed in porous inorganic solids like zeolites with considerable impact in petrochemistry. More recently, metal organic frameworks (MOFs) have emerged as heterogeneous solid catalysts for a broad range of organic reactions due to their unique properties of large surface area, tuneable pore volume and high density of sites. The present mini-review aims to describe the current evidences showing MOFs as shape-selective catalysts. After a brief introduction on the concept, types and examples of shape-selectivity, the available data on MOFs as shape-selective catalysts have been organized according the nature of active sites promoting the reaction, starting from metal nodes as Lewis acid sites and commenting examples of encapsulated metal nanoparticles (NPs) and molecular guests as centers in various reactions such as addition to carbonyl compounds, hydrogenations, oxidations and oxidative dehydrogenations. The final section provides our view on the current achievements and prospective for future developments in the field.

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Section: Metal Nps@mofsmentioning

confidence: 99%

Section: Metal Nps@mofsmentioning

confidence: 99%

Catalysis in Confined Spaces of Metal Organic Frameworks

2020

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“…Fossil fuel consumption has been sharply increasing for the past decades due to human activity and the development of industry, the non-renewability of fossil energy, and the environmental pollution problems force researchers to seek green and renewable energy sources. [1][2][3][4] As a renewable energy, biodiesel is attracting worldwide attention. In the production of biodiesel, glycerol is obtained as a main byproduct, and the rapid development of biodiesel will inevitably lead to the excess production of glycerol.…”

Section: Introductionmentioning

confidence: 99%

Direct Transformation of Glycerol to Propanal using Zirconium Phosphate‐Supported Bimetallic Catalysts

et al. 2020

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Selective transformation of glycerol to propanal (PA) provides a feasible route towards the sustainable synthesis of high valueadded chemicals. In this work, zirconium phosphate (ZrP) was studied as support and Ru and Co as metal sites for glycerol hydrogenolysis in a continuous-flow reactor. It was found that ZrP-supported CoÀ O species had a moderate selectivity to PA (49.5 %) in glycerol hydrogenolysis. Notably, once Ru species were doped into CoO/ZrP, the resulting catalyst exhibited not only an outstanding catalytic performance for glycerol hydrogenolysis to PA (a selectivity of 80.2 % at full conversion), but also a high stability at least a 50 h long-term performance. The spent catalyst could be regenerated by calcining in air to remove carbonaceous deposits. Characterization indicated that the acid sites on ZrP played a very critical role in the dehydration of glycerol into acrolein (AE), that the distribution of Co was uniform, basically consistent with that of Zr, P and Ru, and that an especially close contact between CoÀ O and Ru species was formed on Ru/CoO/ZrP catalyst. The further activity tests and characterizations confirmed that there was a strong interaction between the dispersed CoÀ O species and Ru 0 nanoparticles, which endowed Ru sites with high electronic density. This effect could play a role in facilitating the dissociation of H 2 , and thus in promoting the hydrogenation reaction. Besides, DFT calculations suggested that the CoÀ O species can adsorb more strongly the C=C bond of the intermediate AE on a highly coordinatively unsaturated Co (Co cus) site and thus lead to preferential hydrogenation at the C=C bond of AE to PA.

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“…[4] An efficient strategy to obtain carbon supported metal NPs with regular size and their even dispersion on the supports is the pyrolysis of the metal containing inorganic-organic polymeric complexes. [5] In particular, metal-organic frameworks (MOFs), a class of porous inorganic-organic hybrid materials, have been found to be an extremely appealing type of precursors for fabricating various carbon supported metal NPs, which have been applied in many fields. [6] Since the metal cations in the MOFs are reduced by the in-situ generated carbon matrix from the decomposition of the organic ligands, strong interactions between the metal NPs and the carbon support exist in the thus-obtained carbon supported metal NPs.…”

Section: Introductionmentioning

confidence: 99%

Co−MOF‐74@Cu−MOF‐74 Derived Bifunctional Co−C@Cu−C for One‐Pot Production of 1, 4‐Diphenyl‐1, 3‐Butadiene from Phenylacetylene

et al. 2020

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Carbon‐supported metal nanoparticles (NPs) play important roles in heterogeneous catalysis. In particular, supported bimetallic catalytic systems can be promising multifunctional catalysts for one‐pot tandem/cascade reactions, in which two or more successive independent reactions are realized in one pot. In this manuscript, we report the preparation of a carbon‐supported bimetallic CoCu catalytic system (Co−C@Cu−C), with Co NPs wrapped by carbon‐supported Cu NPs, from the pyrolysis of a core‐shell structured Co−MOF‐74@Cu−MOF‐74. The as‐obtained Co−C@Cu−C acts as a bifunctional catalyst for the transformation of phenylacetylene to 1, 4‐diphenyl‐1, 3‐butadiene in one pot, in which supported metallic Cu NPs and Co NPs are active for the coupling and hydrogenation reaction respectively. By tuning the reaction rates of the coupling and the hydrogenation in this tandem reaction over the Co−C@Cu−C via changing the reaction medium and the reducing agent, an efficient direct transformation of phenylacetylene to 1, 4‐diphenyl‐1, 3‐butadiene was realized. This work not only highlights the important role of MOFs in the preparation of multifunctional carbon supported metal NPs for heterogeneous catalysis, but also demonstrates the possibility of tuning the reaction rates of different catalytic steps in a tandem reaction to realize an efficient overall reaction.

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Metal organic frameworks for biomass conversion

Abstract: This review narrates the recent developments on the catalytic applications of pristine metal–organic frameworks (MOFs), functionalized MOFs, guests embedded over MOFs and MOFs derived carbon composites for biomass conversion into platform chemicals.

Cited by 213 publications

References 249 publications

Catalysis in Confined Spaces of Metal Organic Frameworks

Catalysis in Confined Spaces of Metal Organic Frameworks

Direct Transformation of Glycerol to Propanal using Zirconium Phosphate‐Supported Bimetallic Catalysts

Co−MOF‐74@Cu−MOF‐74 Derived Bifunctional Co−C@Cu−C for One‐Pot Production of 1, 4‐Diphenyl‐1, 3‐Butadiene from Phenylacetylene

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