Zr-MOF-808@MCM-41 catalyzed phosgene-free synthesis of polyurethane precursors

Rojas‐Buzo, Sergio; García‐García, Pilar; Corma, Avelino

doi:10.1039/c8cy02235f

Cited by 50 publications

(22 citation statements)

References 58 publications

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“…14,15 Zr-and Hf-MOFs have attracted great attention for their inherent chemical, mechanical and hydrothermal stabilities, offering excellent properties for their wide application in different relevant catalytic processes. [16][17][18][19][20] Despite Hf and Zr should have similar physicochemical properties, the higher oxophilicity of Hf with respect to Zr, should imply a stronger Brønsted acidic character of the m3-OH groups present on the metallic node. 21,22 However, traditional solvothermal synthesis of Hf-MOFs usually ends up with amorphous materials or requires several weeks to crystallize.…”

Section: Introductionmentioning

confidence: 99%

Tailoring Lewis/Brønsted acid properties of MOF nodes via hydrothermal and solvothermal synthesis: simple approach with exceptional catalytic implications

et al. 2021

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Section: Introductionmentioning

confidence: 99%

Tailoring Lewis/Brønsted acid properties of MOF nodes via hydrothermal and solvothermal synthesis: simple approach with exceptional catalytic implications

et al. 2021

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“…Preparation methods based on homogeneous catalysts are mostly governed by Zn‐based materials [3] that, despite providing higher conversions and selectivities, their recovery and re‐use is difficult. These issues can be overcome by the use of heterogeneous systems (supported Zn(OAc) 2 , [4] CeO 2 , [5] Au@CeO 2 , [6, 5b] ZnAlPO 4 , [7] [Zn]SiO 2 , [8] AlSBA‐15, [9] [ZnCO 3 ] 2 ⋅[Zn(OH) 2 ] 3 ,] [10] (PbCO 3 ) 2 ⋅Pb(OH) 2 , [10] Bi/Yb/Ge/SiO 2 composite, [11] Zr‐MOF‐808@MCM‐41, [12] Zn/Al/Ce mixed oxide [13] ) at the expense of decreased yields.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Performance of Zirconium‐Doped Ceria Catalysts for the Methoxycarbonylation of Anilines

Núñez-Rico

Rellán‐Piñeiro

Puértolas

et al. 2020

Chemistry A European J

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The methoxycarbonylation of anilines stands as an attractive method for the phosgene-free production of carbamates. Despite the high yields obtained for ceria catalysts, the reduction of the amounto fs ide products and the prevention of catalyst deactivation still represent major hurdles in this chemistry.O ne advantage of ceria is the possibility of tuning its reactivity by doping its lattice with other metals. In the present work, as eries of dopedc eria-based materials, prepared by substitution with metals, are evaluated in the methoxycarbonylation of 2,4-diaminotoluene with dimethyl carbonate.A monga ll catalysts, containing Eu, Hf, La, Pr,S m, Tb, Yo rZ r, ceria promoted with 2mol %Z re xhibited 96 % selectivity towards the desired carbamates, improving the pure CeO 2 catalyst. Densityf unctional theoryd emonstrates that two descriptors are needed: 1) ag eometric factor that governs the reductiono fe nergy barriers for carbamate formationt hrough ureas;2)catalyst basicity as NÀHb onds need to be activated. Assessment in subsequent reaction cycles revealed that the CeO 2-ZrO 2 catalysti sm ore stable than bulk CeO 2 ,a long with the reduction of fouling processes.

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“…Conventionally, the production of urethanes involves the employment of phosgene, which is extremely toxic and harmful to the environment and human beings. Therefore, there have been tons of endeavors for producing carbamates via phosgene-free pathways [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. Among them, the catalytic reductive carbonylation of nitroarenes is regarded as one of the promising routes [6][7][8][20][21][22][23][24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

An Escape from Noble Metals for Generating Urethanes via Reductive Carbonylation of Nitroarenes over FeSe2/γ-Al2O3 †

Tran

Nguyen

et al. 2020

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The reaction of FeCl3, SeO2, and Pyridine (Py) in the presence of methanol (MeOH) under CO pressure generates a black precipitate, which has been confirmed as ferric di-selenide, FeSe2 through different structure characterization methods. Furthermore, impregnation of 5 wt% of FeSe2 onto γ-Al2O3 exhibits better catalytic performance than FeSe2 due to the highly dispersed and smaller particle sizes ca. 200–300 nm. The reductive carbonylation of nitrobenzene (NB) was investigated over FeSe2/γ-Al2O3 as a heterogeneous catalyst, delivering an excellent yield and high selectivity of methyl-N-phenyl carbamate (MPC). Moreover, a set of reactions was performed with variation in the reaction time, temperature, and pressure to investigate the effects of these factors. In particular, FeSe2/γ-Al2O3 is highly stable and can be recycled for up to five cycles without significant loss in catalytic performance. A mechanistic study was also conducted on this low-cost catalyst system, especially proposing a crucial role of FeSe2 (μ-CO) active species.

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Zr-MOF-808@MCM-41 catalyzed phosgene-free synthesis of polyurethane precursors

Abstract: Zr-MOF-808@MCM-41 exhibited high catalytic activity, selectivity and stability for the synthesis of aromatic carbamates from aromatic amines and dimethyl carbonate.

Cited by 50 publications

References 58 publications

Tailoring Lewis/Brønsted acid properties of MOF nodes via hydrothermal and solvothermal synthesis: simple approach with exceptional catalytic implications

Tailoring Lewis/Brønsted acid properties of MOF nodes via hydrothermal and solvothermal synthesis: simple approach with exceptional catalytic implications

Enhanced Performance of Zirconium‐Doped Ceria Catalysts for the Methoxycarbonylation of Anilines

An Escape from Noble Metals for Generating Urethanes via Reductive Carbonylation of Nitroarenes over FeSe2/γ-Al2O3 †

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