Phosphorus‐Modified Mesoporous Inorganic Materials for Production of Hydrocarbon Fuels and Value‐Added Chemicals

Kasipandi, Saravanan; Ali, Mansoor; Li, Yongdan; Bae, Jong Wook

doi:10.1002/cctc.202000418

Cited by 12 publications

(11 citation statements)

References 100 publications

(346 reference statements)

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“…For all samples, the XPS peaks of P 2p appear at 129.4 and 130.3 eV (ascribed to P 2p3/2 and P 2p1/2 peaks in framework P) and 133.3 and 134.5 eV (ascribed to P 2p3/2 and P 2p1/2 in P 5+ of surface PO 4 3– ) . The binding energies of 778.1 and 792.9 eV in the Co 2p peaks of Co 2 P are characteristic of the 2p 3/2 and 2p 1/2 peaks of framework Co . CoP also shows additional binding energies of 778.6 and 796.6 eV (related to the 2p 3/2 and 2p 1/2 peaks of framework Co, respectively) and 798.5 and 782.1 eV (related to the 2p 3/2 and 2p 1/2 peaks of Co 2+ of Co 3 (PO 4 ) 2 , respectively).…”

Section: Resultsmentioning

confidence: 95%

“…Recently, transition-metal phosphide nanoparticles have been considered promising candidates to replace noble-metal catalysts in electrochemistry due to their high activities and acid compatibility . In thermochemistry, metal phosphides is mainly used in hydrotreating reactions, such as hydrogenation reactions, Fischer–Tropsch synthesis, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, and hydrodechlorination . Practically, they demonstrated their ability to selectively hydrogenate CO and CC for cinnamaldehyde by adjusting the adsorption configuration of the reactants on the surface .…”

Section: Introductionmentioning

confidence: 99%

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Adsorption Configuration-Determined Selective Hydrogenative Ring Opening and Ring Rearrangement of Furfural over Metal Phosphate

Tong

Dong

et al. 2021

ACS Catal.

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Developing an economic catalyst to upgrade furfural to alcohols (such as linear alcohol and cyclopentanol) is highly significant for fine chemical synthesis and biomass utilization. Here, a class of metal phosphate nanoparticles (such as CoP, Co 2 P, and Ni 2 P) with different metal compositions and topological structures is synthesized. The acidity and hydrogen activation ability were well adjusted according to the types. An 80.2% yield of 1,2,5-pentanetriol was reported for the first time via a hydrogenative ring-opening route over CoP, whereas Ni 2 P shows a high catalytic efficiency for cyclopentanol with a 62.8% yield via a hydrogenative ring-rearrangement route. Based on the catalytic performance of Pd/C and the result of attenuated total reflectance−infrared spectroscopy, the route difference is derived from the adsorption configuration of furfural on the catalyst. After loading on the insert support, the metal phosphate/support catalysts show high activity and stability during the recycling experiments. This work provides an effective strategy to regulate the reaction path through an adsorption mechanism and shows the precise synergistic effect of hydrogenation and acid catalysis.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Adsorption Configuration-Determined Selective Hydrogenative Ring Opening and Ring Rearrangement of Furfural over Metal Phosphate

Tong

Dong

et al. 2021

ACS Catal.

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“…Due to the mesoporous structure and adjustable surface acidity, they have been studied for biomass conversion, syngas conversion, biodiesel production, and butane oxidation over catalysts such as sodium phosphate and vanadium phosphate. [111] For the glycerol dehydration to acrylic acid, 92% acrolein selectivity was reported over an iron phosphate (FePO 4 ) catalyst. FePO 4 is a weak acid catalyst.…”

Section: Phosphate-containing Catalystmentioning

confidence: 99%

“…Phosphorus is a potential element for various compound formations, owing to its remarkable ability of bond formation, and hence, can be equated for carbon. [ 111 ] The group of phosphate catalysts mainly include phosphoric acid substituted composites and metal phosphates. Due to the mesoporous structure and adjustable surface acidity, they have been studied for biomass conversion, syngas conversion, biodiesel production, and butane oxidation over catalysts such as sodium phosphate and vanadium phosphate.…”

Section: Catalysts For Glycerol Oxydehydration Processmentioning

confidence: 99%

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A review on bi/multifunctional catalytic oxydehydration of bioglycerol to acrylic acid: Catalyst type, kinetics, and reaction mechanism

Abdullah

Ahmed

et al. 2021

Can J Chem Eng

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Acrylic acid, conventionally produced via propylene (non‐renewable fossil fuel route), is an industrially important chemical. The bio‐based feedstock process employing glycerol (a by‐product of biodiesel production) has attracted the attention of researchers due to its non‐polluting and renewable characteristics. Bi/multifunctional catalysts using a combination of zeolites, metal oxides, heteropoly acids, and phosphates have been mainly studied for the glycerol oxydehydration process. Brønsted acid sites favour acrolein generation over Lewis acid sites, whereas the redox sites convert the generated acrolein to acrylic acid. So far, the maximum acrylic acid yields of 60% and 59% have been reported on heteropoly acid and mixed metal oxide catalysts, respectively. Some DFT studies also revealed the deprotonation energy of acid sites and further helped in designing efficient catalysts. Despite these accomplishments, catalyst deactivation because of coking and stability remains a major problem. In this paper, various bi/multifunctional catalysts employed in glycerol oxydehydration to acrylic acid are critically reviewed. Different catalyst forms, preparation techniques, reaction kinetics, reaction mechanisms, deactivation, reactivation, process operating parameters, and sustainability are considered. In addition, the challenges associated with each catalyst type and strategies to overcome low yield, deactivation, and future directions are discussed.

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New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation

Méjri

Fliss

Essalah

et al. 2022

Int J of Quantum Chemistry

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Oxidative addition of aliphatic amine on monocyclic 2-R-1,3,2-dioxaphospholane (R = methyl or phenyl) leading to phosphoranes bearing a P H axial bond was investigated using a combined theoretical and experimental approach. The reaction followed first order kinetics for both reactants. The activation parameters were consistent with a concerted mechanism exhibiting stereo, enantio, and regio specificities.Systematic density functional theory studies including reactivity descriptors, structural parameters, determination of all possible phosphorane isomers, their transition states and their formation mechanisms were carried out to delineate the reaction pathway. Depending on the nature of the atom in the final apical position (H, N of the amine, or C of the methyl), three types of phosphoranes were identified. Energy profiles, using the intrinsic reaction coordinate technique for the formation of each isomer, were established. It was shown that the phosphorus biphilicity acts in three consecutive sequences, namely nitrogen nucleophilic attack leading to a supermolecule structure, nucleophilic behavior of phosphorus in the transition state zone of influence, and electrophilic approach of the nitrogen atom to complete the reaction. Phosphorane with an equatorial P H bond was found to be a kinetic product that transforms rapidly to the thermodynamically stable isomer with axial P H via two consecutive Berry pseudo-rotations. A new tool, referred to reactive internal reaction coordinates, was introduced to represent the reaction path more clearly.

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Phosphorus‐Modified Mesoporous Inorganic Materials for Production of Hydrocarbon Fuels and Value‐Added Chemicals

Cited by 12 publications

References 100 publications

Adsorption Configuration-Determined Selective Hydrogenative Ring Opening and Ring Rearrangement of Furfural over Metal Phosphate

Adsorption Configuration-Determined Selective Hydrogenative Ring Opening and Ring Rearrangement of Furfural over Metal Phosphate

A review on bi/multifunctional catalytic oxydehydration of bioglycerol to acrylic acid: Catalyst type, kinetics, and reaction mechanism

New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation

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