Recyclable Zr/Hf-Containing Acid-Base Bifunctional Catalysts for Hydrogen Transfer Upgrading of Biofuranics: A Review

The massive burning of a large amount of fossil energy has caused a lot of serious environmental issues (e.g., air pollution and climate change), urging people to efficiently explore and valorize sustainable alternatives. Biomass is being deemed as the only organic carbon-containing renewable resource for the production of net-zero carbon emission fuels and fine chemicals. Regarding this, the selective transformation of high-oxygen biomass feedstocks by catalytic transfer hydrogenation (CTH) is a very promising strategy to realize the carbon cycle. Among them, the important Meerwein-Ponndorf-Verley (MPV) reaction is believed to be capable of replacing the traditional hydrogenation strategy which generally requires high-pressure H2 and precious metals, aiming to upgrade biomass into downstream biochemical products and fuels. Employing bifunctional heterogeneous catalysts with both acidic and basic sites is needed to catalyze the MPV reaction, which is the key point for domino/cascade reaction in one pot that can eliminate the relevant complicated separation/purification step. Zirconium (Zr) and hafnium (Hf), belonging to transition metals, rich in reserves, can demonstrate similar catalytic efficiency for MPV reaction as that of precious metals. This review introduced the application of recyclable heterogeneous non-noble Zr/Hf-containing catalysts with acid-base bifunctionality for CTH reaction using the safe liquid hydrogen donor. The corresponding catalysts were classified into different types including Zr/Hf-containing metal oxides, supported materials, zeolites, metal-organic frameworks, metal-organic hybrids, and their respective pros and cons were compared and discussed comprehensively. Emphasis was placed on evaluating the bifunctionality of catalytic material and the key role of the active site corresponding to the structure of the catalyst in the MPV reaction. Finally, a concise summary and prospect were also provided centering on the development and suggestion of Zr/Hf-containing acid-base bifunctional catalysts for CTH.

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One-pot synthesis of bimetallic metal–organic frameworks (MOFs) as acid–base bifunctional catalysts for tandem reaction

Catalysis Science & Technology ◽

10.1039/c9cy01940e ◽

2020 ◽

Vol 10 (2) ◽

pp. 315-322 ◽

Cited By ~ 9

Author(s):

Yanjing Hu ◽

Jian Zhang ◽

Hang Huo ◽

Zhe Wang ◽

Xianzhu Xu ◽

...

Keyword(s):

Metal Organic Frameworks ◽

Bifunctional Catalysts ◽

Pore System ◽

Acid Base ◽

One Pot ◽

System P ◽

Synergistic Mechanism ◽

Metal Organic ◽

Hierarchical Pore System ◽

Hierarchical Pore

Bimetallic MIL-101(Al/Fe)–NH2 exhibits enhanced acid–base bifunctional catalytic activity due to its synergistic mechanism and hierarchical pore system.

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Hf-based metal organic frameworks as bifunctional catalysts for the one-pot conversion of furfural to γ-valerolactone

Molecular Catalysis ◽

10.1016/j.mcat.2019.04.010 ◽

2019 ◽

Vol 472 ◽

pp. 17-26 ◽

Cited By ~ 8

Author(s):

Wenke Li ◽

Zhe Cai ◽

Hang Li ◽

Yu Shen ◽

Yongqiang Zhu ◽

...

Keyword(s):

Metal Organic Frameworks ◽

Bifunctional Catalysts ◽

One Pot ◽

Metal Organic ◽

The One

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Application of an amino-functionalised metal–organic framework: an approach to a one-pot acid–base reaction

RSC Advances ◽

10.1039/c3ra44701d ◽

2013 ◽

Vol 3 (44) ◽

pp. 21582 ◽

Cited By ~ 46

Author(s):

Takashi Toyao ◽

Mika Fujiwaki ◽

Yu Horiuchi ◽

Masaya Matsuoka

Keyword(s):

Metal Organic Framework ◽

Acid Base ◽

One Pot ◽

Metal Organic ◽

Organic Framework

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One-Pot Synthesis of Core–Shell Structured Metal–Organic Coordination Polymer Microspheres with a Hierarchical Microporous–Mesoporous–Macroporous Structure

Australian Journal of Chemistry ◽

10.1071/ch18558 ◽

2019 ◽

Vol 72 (6) ◽

pp. 450

Author(s):

Yafang Zhou ◽

Yingxi Xu ◽

Jianyu Guo ◽

Siyong Zhang ◽

Yan Lu

Keyword(s):

Coordination Polymer ◽

Heterogeneous Catalysts ◽

Nitrogen Adsorption ◽

Core Shell ◽

Polymer Microspheres ◽

Nitrate Hexahydrate ◽

Macroporous Structure ◽

Hydrothermal Conditions ◽

One Pot ◽

Metal Organic

New core–shell structured metal–organic coordination polymer (CP) microspheres with a hierarchical microporous–mesoporous–macroporous structure are synthesized by a one-pot template-free method. The ligand L with a Schiff-base functional group is obtained by reacting 3-hydroxy-4-aminobenzoic acid with para-benzaldehyde. The coordination polymer microspheres (Zn-L-CP) are obtained by mixing the ligand L and zinc nitrate hexahydrate together under hydrothermal conditions. The resultant coordination polymer microspheres with a core–shell structure are characterized by FT-IR and solid state NMR spectroscopy, transmission and scanning electron microscopy, and nitrogen adsorption–desorption measurements. The obtained Zn-L-CP microspheres are proved to be effective heterogeneous catalysts for the deacetylation reaction with the merits of easy recycling and stability. The yield is 96% when using methanol as solvent, and the yield can remain at 90% after seven cycles.

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Efficient Catalytic Production of Biodiesel with Acid-Base Bifunctional Rod-Like Ca-B Oxides by the Sol-Gel Approach

Materials ◽

10.3390/ma12010083 ◽

2018 ◽

Vol 12 (1) ◽

pp. 83 ◽

Cited By ~ 6

Author(s):

Anping Wang ◽

Hu Li ◽

Heng Zhang ◽

Hu Pan ◽

Song Yang

Keyword(s):

Renewable Resources ◽

Sol Gel ◽

Acid Value ◽

Catalytic Performance ◽

Acid Base ◽

Reaction Conditions ◽

One Pot ◽

Catalytic Material ◽

Acid And Base ◽

Optimal Reaction

The search for acid-base bifunctional catalysts has become a hot topic in the preparation of biofuels from renewable resources. In the present work, a series of novel acid-base bifunctional metal-boron catalysts were successfully prepared by a sol-gel method and characterized by XRD, IR, SEM, TEM, TGA, BET, and TPD. Among those bifunctional solid materials, the Ca-B(700) catalyst had the highest density of both acid and base sites and showed excellent catalytic performance in the production of biodiesel from nonedible oils with high acid value. Under the optimal reaction conditions of 20/1 methanol/oil mole ratio and 4 wt % catalyst dosage at 105 °C for 2 h, a high biodiesel yield of 96.0% could be obtained from Jatropha curcas oil in one-pot. In addition, Ca-B(700) was also applicable to producing biodiesel from Firmiana platanifolia L.f. oil in a relatively low acid value, with an almost quantitative yield (98.5%) at 65 °C after 2 h. The Ca-B(700) catalyst had good stability and reusability, which is a promising acid-base bifunctional catalytic material for the preparation of biodiesel.

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A combination of experimental and computational methods to study the reactions during a Lignin-First approach

Pure and Applied Chemistry ◽

10.1515/pac-2019-1002 ◽

2020 ◽

Vol 92 (4) ◽

pp. 631-639

Author(s):

Ivan Kumaniaev ◽

Elena Subbotina ◽

Maxim V. Galkin ◽

Pemikar Srifa ◽

Susanna Monti ◽

...

Keyword(s):

Transition Metal ◽

Hydrogen Transfer ◽

Transfer Hydrogenation ◽

Metal Catalyst ◽

Main Role ◽

One Pot ◽

Transition Metal Catalyst ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

Metal Catalyzed

AbstractCurrent pulping technologies only valorize the cellulosic fiber giving total yields from biomass below 50 %. Catalytic fractionation enables valorization of both cellulose, lignin, and, optionally, also the hemicellulose. The process consists of two operations occurring in one pot: (1) solvolysis to separate lignin and hemicellulose from cellulose, and (2) transition metal catalyzed reactions to depolymerize lignin and to stabilized monophenolic products. In this article, new insights into the roles of the solvolysis step as well as the operation of the transition metal catalyst are given. By separating the solvolysis and transition metal catalyzed hydrogen transfer reactions in space and time by applying a flow-through set-up, we have been able to study the solvolysis and transition metal catalyzed reactions separately. Interestingly, the solvolysis generates a high amount of monophenolic compounds by pealing off the end groups from the lignin polymer and the main role of the transition metal catalyst is to stabilize these monomers by transfer hydrogenation/hydrogenolysis reactions. The experimental data from the transition metal catalyzed transfer hydrogenation/hydrogenolysis reactions was supported by molecular dynamics simulations using ReaXFF.

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Selective One-Pot Two-Step C−C Bond Formation using Metal-Organic Frameworks with Mild Basicity as Heterogeneous Catalysts

ChemCatChem ◽

10.1002/cctc.201700784 ◽

2017 ◽

Vol 9 (21) ◽

pp. 4019-4023 ◽

Cited By ~ 21

Author(s):

Francisco G. Cirujano ◽

Elena López-Maya ◽

Marleny Rodríguez-Albelo ◽

Elisa Barea ◽

Jorge A. R. Navarro ◽

...

Keyword(s):

Heterogeneous Catalysts ◽

Bond Formation ◽

Metal Organic Frameworks ◽

One Pot ◽

Metal Organic

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Facile synthesis of novel heterogenous Rh/COF catalyst and its application in tandem selective transfer hydrogenation and mono-methylation of Nitro compounds with Methanol

10.33774/chemrxiv-2021-6qtnd ◽

2021 ◽

Author(s):

Jianguo liu ◽

Mingyue Zhang ◽

Nan Wang ◽

Xiuzhi Wei ◽

Bo Yang ◽

...

Keyword(s):

Heterogeneous Catalysts ◽

Hydrogen Transfer ◽

Reaction Pathway ◽

Nitro Compounds ◽

Transfer Hydrogenation ◽

Facile Synthesis ◽

Detailed Mechanism ◽

Effective Synthesis ◽

First Time ◽

Better Than

The development of transition metal heterogeneous catalysts for economical and effective synthesis of N-methylamine, especially for the mono-methylation of amines is still challenging. Herein, two unprecedented Rh-supported COFs heterogeneous catalysts Rh/MelCOF was facile synthesized by Schiff base reaction using melamine as a precursor, and for the first time, it was successfully applied to the effective and high selective tandem reaction of transfer hydrogenation and mono-methylation of nitroaromatic hydrocarbons with methanol as C1 and hydrogenation source, with water as the only by-product. A series of nitroaromatic hydrocarbons, including heterocyclic or sterically hindered derivatives, can be well tolerated and the catalyst could also be reused 4 times without losing significant reactivity. At the same time, the study of the Rh/MelCOF mechanism supports the hydrogen borrowing mechanism and puts forward the reaction pathway of azobenzene as an intermediate, which is better than the hydrogen transfer pathway from N-phenylhydroxylamine to aniline directly. This work not only expands the COF family but also provides an effective way to obtain mono N-methylated amines from nitroaromatic hydrocarbons, as well as the detailed mechanism of Rh/COF catalyzed tandem transfer hydrogenation and mono-methylation of amines.

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Acid-Base Bifunctional Metal-Organic Frameworks: Green Synthesis and Application in One-Pot Glucose to 5-HMF Conversion

NANO ◽

10.1142/s1793292018501321 ◽

2018 ◽

Vol 13 (11) ◽

pp. 1850132 ◽

Cited By ~ 3

Author(s):

Yunlei Zhang ◽

Pei Jin ◽

Minjia Meng ◽

Lin Gao ◽

Meng Liu ◽

...

Keyword(s):

Active Sites ◽

Large Scale ◽

Direct Synthesis ◽

Metal Organic Frameworks ◽

Acid Base ◽

One Pot ◽

Ring Opening Reaction ◽

Metal Organic ◽

Base Strength ◽

Viable Approach

The direct synthesis of metal-organic frameworks (MOFs) with acidic and basic active sites is challenging due to the introduction of functional groups by post-functionalization method often jeopardize the framework integrity. Herein, we report the direct synthesis of acid-base bi-functional MOFs with tuning acid-base strength. Employing modulated hydrothermal (MHT) approach, microporous MOFs named UiO-66-NH2 was prepared. Through the ring-opening reaction of 1,3-propanesultone with amino group, UiO-66-NH2-SO3H-type catalysts can be obtained. The synthesized catalysts were well characterized and their catalytic performances were evaluated in one-pot glucose to 5-HMF conversion. Results revealed the acid-base bi-functional catalyst possessed high activity and excellent stability. This work provides a general and economically viable approach for the large-scale synthesis of acid-base bi-functional MOFs for their potential use in catalysis field.

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