Phase Transfer Ceria-Supported Nanocatalyst for Nitrile Hydration Reaction

Gupta, Nikitra N.; Punekar, Amrin S.; Raj, Karthik Raja E. K.; Ghodekar, Medha M.; Patil, Vipul; Gopinath, Chinnakonda S.; Raja, Thirumalaiswamy

doi:10.1021/acsomega.9b02173

Cited by 8 publications

(8 citation statements)

References 39 publications

(58 reference statements)

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“…Up to now, various heterogeneous and homogeneous catalysts have been explored for this reaction, among them CeO 2 has been extensively reported as catalysts for the transformation of nitriles and amides . Hydration of nitriles to amides in water, − one-pot synthesis of ester from nitriles and alcohols, one-pot synthesis of N -alkylamides from nitriles with amines, dehydration of aldoximes to nitriles and one-pot synthesis of amides and esters, synthesis of amides from amides and amines (transamidation), , hydromethoxylation of acrylonitrile and esterification of acetamide by benzyl alcohol can be selectively catalyzed by CeO 2 or CeO 2 -based catalysts under aqueous, organic, or solvent-free conditions. Experimental and theoretical studies suggest that the Lewis acid sites (exposed oxygen atoms) and adjacent low-coordinated Ce sites (Ce LC ) (oxygen defect site) cooperatively contribute to these catalytic reactions.…”

Section: Transformations Of Nitriles and Amidesmentioning

confidence: 99%

“…Li et al realized the continual adjustment of surface intrinsic properties of CeO 2 nanorods, and the highest oxygen vacancy concentration and largest surface Ce 3+ content contributed to the significant catalytic performance in nitrile hydrolysis . In order to overcome drawbacks of CeO 2 such as easy aggregation and difficult dispersibility, it is necessary to support CeO 2 on other materials such as polymer. , …”

Section: Transformations Of Nitriles and Amidesmentioning

confidence: 99%

“…333 In order to overcome drawbacks of CeO 2 such as easy aggregation and difficult dispersibility, it is necessary to support CeO 2 on other materials such as polymer. 331,334 In addition, CeO 2 showed superior catalytic performance among various metal oxides in the one-pot selective synthesis of esters from various nitriles, alcohols and water in high yields (83% to >99%), 70 or N-alkyl amides (secondary amide) from nitriles, amines and water in high yields (73% to >99%). 335 The mechanism includes the following steps: (1) the dissociation of H 2 O and amines or alcohols on CeO 2 ; (2) hydration of adsorbed nitrile to form a primary amide via the nucleophilic addition of hydroxyl species (OH δ− ) and (3) reaction of the primary amide with amines or alkoxides (OR δ− ) as the rate-determining step, in which Lewis acidbase pair sites on CeO 2 are the active sites.…”

Section: Transformations Of Nitriles and Amidesmentioning

confidence: 99%

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Ceria-Based Materials for Thermocatalytic and Photocatalytic Organic Synthesis

et al. 2021

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Value-added chemicals, fuels, and pharmaceuticals synthesized by organic transformation from raw materials via catalytic techniques have attracted enormous attention in the past few decades. Heterogeneous catalysts with high stability, long cycling life, good environmental-friendliness, and economic efficiency are greatly desired to accomplish the catalytic organic transformations. With the advantages of reversible Ce3+/Ce4+ redox pairs, tailorable oxygen vacancies, and surface acid–base properties, ceria-based catalysts have been actively investigated in the fields of catalytic organic synthesis. In this Review, we summarize the fundamentals and latest applications of ceria-based heterogeneous catalysts for organic transformations via thermocatalytic and photocatalytic routes. The fabricating approaches of various ceria and ceria-based catalysts and their structure/composition–activity relationship are discussed and prospected. The advanced characterization techniques and theoretical methods for reaction mechanism studies over CeO2-based catalysts are summarized and discussed. This comprehensive Review provides a basic understanding of the structure–performance relationships of ceria-based catalysts for organic synthesis. In addition, it also provides some insights and outlooks in the design and research direction in the ceria-based catalysts with better performance.

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Section: Transformations Of Nitriles and Amidesmentioning

confidence: 99%

Section: Transformations Of Nitriles and Amidesmentioning

confidence: 99%

Section: Transformations Of Nitriles and Amidesmentioning

confidence: 99%

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Ceria-Based Materials for Thermocatalytic and Photocatalytic Organic Synthesis

et al. 2021

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“…Depending on the desorption temperature, for the Lewis acid/base sites, the desorption peaks at < 473 K, 473-673 K, and > 673 K which represents the weak, medium, and strong sites, respectively. [24] The NH 3 -TPD results are presented in Figure 4a, showing that the peaks of adsorbed analysis gases (NH 3 ) on the RD-POM assemblies were slightly shifted to a higher temperature. As a result, the ratio of strong Lewis acid sites in RD-POM assemblies are significantly increased compared to PTi 2 W 10 .…”

Section: Resultsmentioning

confidence: 99%

Self‐Assembly of Polyoxometalate‐Based Sub‐1 nm Polyhedral Building Blocks into Rhombic Dodecahedral Superstructures

Wang,

Chen,

Liu

et al. 2023

Angew Chem Int Ed

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Self‐assembly of subnanometer (sub‐1 nm) scale polyhedral building blocks can yield some superstructures with novel and interesting morphology as well as potential functionalities. However, achieving the self‐assembly of sub‐1 nm polyhedral building blocks is still a great challenge. Herein, through encapsulating the titanium‐substituted polyoxometalate (POM, K7PTi2W10O40) with tetrabutylammonium cations (TBA+), we first synthesized a sub‐1 nm rhombic dodecahedral building block by further tailoring the spatial distribution of TBA+ on the POM. Molecular dynamics (MD) simulations demonstrated the eight TBA+ cations interacted with the POM cluster and formed the sub‐1 nm rhombic dodecahedron. As a result of anisotropy, the sub‐1 nm building blocks have self‐assembled into rhombic dodecahedral POM (RD‐POM) assemblies at the microscale. Benefiting from the regular structure, Br− ions, and abundant active sites, the obtained RD‐POM assemblies exhibit excellent catalytic performance in the cycloaddition of CO2 with epoxides without co‐catalysts. This work provides a promising approach to tailor the symmetry and structure of sub‐1 nm building blocks by tuning the spatial distribution of ligands, which may shed light on the fabrication of superstructures with novel properties by self‐assembly.

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“…Thus, the biphasic system is regarded as a promising process technology for biomass conversion to high-value chemicals. 18,21 Rare earth metal-based Lewis acid catalysts have been shown to have excellent catalytic performance for reactions such as polyaddition, 22 hydration, 23 and polymerization. 24 Compared to d-series transition metals (such as Cr, Ti, and Fe), the rare earth metal possesses an abundant number of coordination sites.…”

Section: Introductionmentioning

confidence: 99%

High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis Acid HScCl₄ Catalyst

et al. 2021

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Lignocellulosic biorefineries have received considerable attention for the purpose of producing high-value chemicals and materials. Levulinic acid (LA) is an important biomass-derived platform chemical that is produced from sugar-based biomass. Unfortunately, the catalysts reported thus far have shortcomings, such as expensive starting materials, complicated synthesis or purification operations, and a low LA yield under harsh reaction conditions. Herein, we develop a novel dual-functional catalyst, HScCl 4 , by combining Brønsted acid (HCl) and Lewis acid (ScCl 3 ) sites. The as-prepared HScCl 4 catalyst shows high efficiency and high selectivity for converting 5-hydroxymethylfurfural (HMF) to LA in a biphasic system consisting of methyl isobutyl ketone (MIBK) and water. The density functional theory (DFT) results show that the synergistic catalytic effect, originating from the Brønsted and Lewis acidic sites of HScCl 4 , significantly decreases the energy barriers of reactants and intermediates, thus facilitating the conversion of HMF to LA. Moreover, the efficient separation of LA in the water-MIBK biphasic system by extracting LA to the MIBK phase minimizes the side reactions of LA and thus the formation of humins while significantly improving the LA yield. The conversion of HMF and the selectivity for LA are 100 and 95.6% at 120 °C for 35 min, respectively. The free energy (ΔG) and activation energy (E a ) of the reaction are −30 kcal mol −1 and 13.7 kJ mol −1 , respectively. The developed process provides a green, sustainable, and efficient pathway to produce LA from biomass-derived HMF under mild conditions.

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Phase Transfer Ceria-Supported Nanocatalyst for Nitrile Hydration Reaction

Cited by 8 publications

References 39 publications

Ceria-Based Materials for Thermocatalytic and Photocatalytic Organic Synthesis

Ceria-Based Materials for Thermocatalytic and Photocatalytic Organic Synthesis

Self‐Assembly of Polyoxometalate‐Based Sub‐1 nm Polyhedral Building Blocks into Rhombic Dodecahedral Superstructures

High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis Acid HScCl₄ Catalyst

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Phase Transfer Ceria-Supported Nanocatalyst for Nitrile Hydration Reaction

Cited by 8 publications

References 39 publications

Ceria-Based Materials for Thermocatalytic and Photocatalytic Organic Synthesis

Ceria-Based Materials for Thermocatalytic and Photocatalytic Organic Synthesis

Self‐Assembly of Polyoxometalate‐Based Sub‐1 nm Polyhedral Building Blocks into Rhombic Dodecahedral Superstructures

High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis Acid HScCl4 Catalyst

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Product

Resources

About

High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis Acid HScCl₄ Catalyst