MOF-derived cobalt nanoparticles catalyze a general synthesis of amines

Jagadeesh, Rajenahally V.; Murugesan, Kathiravan; Alshammari, Ahmad S.; Neumann, Helfried; Pohl, Marga‐Martina; Radnik, Jörg; Beller, Matthias

doi:10.1126/science.aan6245

Cited by 677 publications

(459 citation statements)

References 53 publications

Supporting

Mentioning

453

Contrasting

Unclassified

Order By: Relevance

“…In this work, published in Science by Beller's group, a MOF, Co‐1,4‐diazabicyclo[2.2.2]octane (DABCO)‐terephthalic acid (TPA), was first immobilized on a XC‐72R activated carbon support. After subsequent pyrolysis of this composite at 800 °C, the resulting catalyst, Co‐DABCO‐TPA@C‐800, was shown to be highly efficient in the synthesis of a large variety of amines under industrially viable and scalable conditions (Figure ) . It should be noted that altering the metal composition of the MOF (Fe‐, Mn‐, Cu‐, or Ni‐) showed insufficient activity.…”

Section: Mof‐derived Catalystsmentioning

confidence: 99%

“…White circles represent single Co atoms (right image). (C) Co‐DABCO‐TPA@C‐800 catalyzed the reductive amination of aldehydes for the synthesis of linear primary amines, the reductive amination of ketones, and the synthesis of secondary, tertiary, and N ‐methylamines . Copyright 2017 the American Association for the Advancement of Science.…”

Section: Mof‐derived Catalystsmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

Yang

Bulut

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

Owing to the almost boundless structural tunability, MOF and MOF-derived catalysts have recently exhibited structures of higher complexity, and hence, have demonstrated activity in a wide array of organic transformations. These reactions have a broad range of important applications ranging from pharmaceuticals to agriculture. Given the increasing number of publications in the area, this Minireview is focused on the most recent advancements in thermally driven organic transformations using both MOFs, nanoparticle@MOF (NP@MOF) composites, and several classes of MOF-derived materials. The most recent advancements made in materials design and the utility of these materials in a broad range of reactions are discussed.

show abstract

Section: Mof‐derived Catalystsmentioning

confidence: 99%

Section: Mof‐derived Catalystsmentioning

confidence: 99%

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

Yang

Bulut

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Liang Wang and Feng-Shou Xiao * Heterogeneous catalysts have played a crucial role in upgrading fuels, transforming biomass [1][2][3], removing pollutants [4][5][6], harvesting solar energy [7][8][9], and producing fine chemicals [10,11]. Compared with homogeneous catalysts, the heterogeneous catalysts have obvious advantages in easy separation and regeneration from the reaction systems [12][13][14][15], but still have unsatisfactory activity and/or selectivity.…”

Section: A Significant Enhancement Of Catalytic Performance By Adjustmentioning

confidence: 99%

A significant enhancement of catalytic performance by adjusting catalyst wettability

Wang

Xiao

2018

Sci. China Mater.

View full text Add to dashboard Cite

Heterogeneous catalysts have played a crucial role in upgrading fuels, transforming biomass [1][2][3], removing pollutants [4][5][6], harvesting solar energy [7][8][9], and producing fine chemicals [10,11]. Compared with homogeneous catalysts, the heterogeneous catalysts have obvious advantages in easy separation and regeneration from the reaction systems [12][13][14][15], but still have unsatisfactory activity and/or selectivity. These issues are reasonably assigned to the limited molecular diffusion on the heterogeneous catalysts. Therefore, it is in great demand to improve the catalytic performances of these catalysts by increasing mass transfer in the reactions, which is always a challenge in the heterogeneous catalysis.For a general reaction from A and B reactants to C and D products, the rate of a chemical reaction is sensitive to the concentration of the reactants and products, as shown in Equation (1) Therefore, it is reasonable to improve the reaction rate by increasing the concentration of reactants and reducing the concentration of products close to the active centers. Normally, a heterogeneous catalysis [16] mainly includes the adsorption of reactant, reactant transfer on the catalyst surface, reactant conversion from reactants to products, product transfer on the catalyst surface, and desorption of products, as presented in Scheme 1. In these steps, four steps are related to the molecular diffusion in the reaction.It is well known that the molecular diffusion is strongly influenced by catalyst wettability. The recent results have demonstrated that the adjustment of catalyst wettability would lead to (i) enrichment of the reactants for accelerating the reaction, (ii) fast diffusion of the products for shifting the reaction balance, (iii) formation of new reaction intermediates, (iv) isolation of undesired molecules for hindering the side reactions, and (v) stabilization of the catalyst structure. Enrichment of reactants for increasing catalytic activityAs illustrated in Equation (1), enhancement of reactant concentration should effectively increase the reaction rate. In the beginning, it was focused on the zeolite catalysts. One typical example is the industrial TS-1 zeolite with hydrophobic framework, which is not favorable for adsorption of H 2 O 2 in the oxidations of organic compounds with H 2 O 2 because the H 2 O 2 is polar and hydrophilic [17][18][19][20]. Obviously, the TS-1 zeolite with more hydrophilicity might be helpful to enrich the H 2 O 2 , leading to improvement of the catalytic activities. As expected, Wang et al. [21] synthesized hydrophilic TS-1 zeolite by employing organosilicon as precursor, followed by calcination to transform the organic groups into silanol groups. The TS-1 zeolite with more hydrophilic silanol groups exhibits much higher reaction rate (4.9 mmol L −1 min) in the oxidation of 1-hexene with H 2 O 2 , because the hydrophilic zeolite can effectively enrich the concentration of H 2 O 2 reactant in the zeolite micropores, as confirmed by the molecule adsorption and...

show abstract

“…[14] Furthermore, they also provide cavities as perfect platforms for immobilization of metal nanoparticles by virtue of their unusually large surface area, well-ordered crystalline structure, high porosity and tunable pore size. [16] Based on our longstanding interest in allene chemistry as well as synthesis and application of Pd nanoparticles, [17] we speculate that the combination of MOF and palladium nanoparticles may offer possibilities for allene transformations and targeted selectivities. [16] Based on our longstanding interest in allene chemistry as well as synthesis and application of Pd nanoparticles, [17] we speculate that the combination of MOF and palladium nanoparticles may offer possibilities for allene transformations and targeted selectivities.…”

Section: Introductionmentioning

confidence: 99%

Allenylphosphine Oxides as Starting Materials for the Synthesis of Conjugated Enynes: Boosting the Catalytic Performance by MOF Encapsulated Palladium Nanoparticles

Wang

Sun

et al. 2018

Adv Synth Catal

View full text Add to dashboard Cite

A direct coupling of allenylphosphine oxides and alkynes is disclosed here mediated by MOF encapsulated palladium nanocatalysts. The methodology using a-allenyl ethers as starting materials provides a heterogeneous approach to generate tri-conjugated enynes with medium to excellent yields. The reaction tolerates a variety of functional groups to afford a range of structurally diverse substituted conjugated enynes. MOF served as support plays a significant role in dispersing and stabilizing the Pd nanoparticles. When compared with the homogeneous system, the advantage is also witnessed exhibiting a steady and high TOF value as well as the efficient reusability. A remarkable pore-control effect of the MOF catalysts was also revealed, depending on the dimension of MOF, molecular size of allenylphosphine oxides, alkynes and enynes respectively. Benefitting from the heterogeneous manner, successful recycling of the MOF catalyst was further achieved with high reaction efficiency maintained.

show abstract

MOF-derived cobalt nanoparticles catalyze a general synthesis of amines

Cited by 677 publications

References 53 publications

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

Recent Advances of MOFs and MOF‐Derived Materials in Thermally Driven Organic Transformations

A significant enhancement of catalytic performance by adjusting catalyst wettability

Allenylphosphine Oxides as Starting Materials for the Synthesis of Conjugated Enynes: Boosting the Catalytic Performance by MOF Encapsulated Palladium Nanoparticles

Contact Info

Product

Resources

About