Acid-promoted Ir-La-S/AC-catalyzed methanol carbonylation on single atomic active sites

任周,; 吕元,; 冯四全,; 宋宪根,; 丁云杰,

doi:10.1016/s1872-2067(18)63019-0

Cited by 15 publications

(4 citation statements)

References 43 publications

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“…We calculated the volumetric and per metal site reaction rates of AA production on atomically dispersed ReO 4 /SiO 2 and Rh–ReO 4 /SiO 2 and compared these with other heterogeneous and homogeneous systems (see Table ). The AA production rates on a per g of metal basis observed for the Re-based catalysts reported here are competitive with Cu modified zeolites, , atomically dispersed Rh on polymer supports, and atomically dispersed Ir–La site pairs, , albeit in the absence of high operating pressure, high CO/MeOH feed ratios, and halide cofeeds. The volumetric AA production rates on our Rh–ReO 4 /SiO 2 catalyst in a fixed bed process are on par with those of the Monsanto process and a few-fold lower than those of the Cavita process …”

Section: Discussionmentioning

confidence: 99%

Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO₄/SiO₂ Catalysts

Finzel

Robatjazi

et al. 2020

J. Am. Chem. Soc.

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Methanol carbonylation to acetic acid (AA) is a large-scale commodity chemical production process that requires homogeneous liquid-phase organometallic catalysts with corrosive halide-based cocatalysts to achieve high selectivity and activity. Here, we demonstrate a heterogeneous catalyst based on atomically dispersed rhenium (ReO4) active sites on an inert support (SiO2) for the halide-free, gas phase carbonylation of methanol to AA. Atomically dispersed ReO4 species and nanometer sized ReO x clusters were deposited on a high surface area (700 m2/g) inert SiO2 using triethanolamine as a dispersion promoter and characterized using aberration corrected scanning transmission electron microscopy (AC-STEM), UV–vis spectroscopy, and X-ray absorption spectroscopy (XAS). Reactivity measurements at atmospheric pressure with 30 mbar of methanol and CO (1:1 molar ratio) showed that bulk Re2O7 and ReO x clusters on SiO2 (formed at >10 wt %) were selective for dimethyl ether formation, while atomically dispersed ReO4 on SiO2 (formed at <10 wt %) exhibited stable (for 60 h) > 93% selectivity to AA with single pass conversion >60%. Kinetic analysis, in situ FTIR, and in situ XAS measurements suggest that the AA formation mechanism involves methanol activation on ReO4, followed by CO insertion into the terminal methyl species. Further, the introduction of ∼0.2 wt % of atomically dispersed Rh to 10 wt % atomically dispersed ReO4 on SiO2 resulted in >96% selectivity toward AA production at volumetric reaction rates comparable to homogeneous processes. This work introduces a new class of promising heterogeneous catalysts based on atomically dispersed ReO4 on inert supports for alcohol carbonylation.

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Section: Discussionmentioning

confidence: 99%

Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO₄/SiO₂ Catalysts

Finzel

Robatjazi

et al. 2020

J. Am. Chem. Soc.

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“…This reaction is usually homogenously catalyzed using a square-planar nucleophilic Rh(I) anion. [34] To transfer this process to a heterogeneously catalyzed reaction, supported Rh [35][36][37] , Ir [38][39][40] , Au [41,42] or Ni carbonyl complexes [43][44][45] were investigated in the past due to their similarity to the in-depth analyzed homogenous systems. One of the most efficient ways to improve the carbonylation activity of the different complexes has been the enrichment of electron density of the applied transition metal.…”

Section: Introductionmentioning

confidence: 99%

Application of Prussian Blue Analogue‐Derived Mn−Co Catalysts in the Hydrogenation of CO to Higher Alcohols

et al. 2023

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MnxCo3‐x[Co(CN)6]2 Prussian blue analogues were synthesized with Mn : Co ratios in the range from 7 : 10 to 1 : 11 and pyrolyzed at 600 °C to obtain a highly nitrogen‐ and oxygen‐functionalized carbon matrix with embedded reduced Mn and Co species. These catalyst precursors were applied in the CO hydrogenation to higher alcohols at 260 °C and a pressure of 60 bar using a H2/CO ratio of 1. Metallic Co0 formed during pyrolysis was partially transformed into Co2C under reaction conditions. With increasing Co content CO conversion increased up to 10.6 % reaching a total alcohol selectivity of 19 %. Gas chromatograms revealed the expected formation of primary short‐chain alcohols, but also of secondary alcohols, acetic acid and propionaldehyde indicating olefin hydration, carbonylation and hydroformylation as reaction pathways, respectively. The obtained hydrocarbon fractions had a very high olefinicity, which is beneficial for both olefin hydration to secondary alcohols catalyzed by adsorbed carboxylic acids and for hydroformylation. Whereas the carbide‐based reaction pathway and the reductive hydroformylation are assumed to occur at the Co2C/Co0 interface, carbonylation is presumably catalyzed by an additional Co‐based active site. Thus, a unique class of multifunctional catalysts was obtained with highly promising properties bridging the gap between heterogeneous and homogeneous catalysis.

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“…[97][98][99] In another attempt, single-site La-Ir based catalysts were also rather active and stable for vapor-phase methanol carbonylation. [100][101][102] Besides the Rh and Ir catalytic systems, Cu, Co, Ni, and Au species were also loaded on different supports for methanol carbonylation indispensable halide additives. [103][104][105] Recently, an attractive halide-free catalyst of atomically dispersed ReO 4 on SiO 2 was developed for acetic acid production.…”

Section: Hydration Of Petroleum-derived Ethylene To Ethanolmentioning

confidence: 99%

Nonenzymatic ethanol production in sustainable ways

Feng,

Guo,

Pang

et al. 2024

Green Chem.

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Acid-promoted Ir-La-S/AC-catalyzed methanol carbonylation on single atomic active sites

Cited by 15 publications

References 43 publications

Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO₄/SiO₂ Catalysts

Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO₄/SiO₂ Catalysts

Application of Prussian Blue Analogue‐Derived Mn−Co Catalysts in the Hydrogenation of CO to Higher Alcohols

Nonenzymatic ethanol production in sustainable ways

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Acid-promoted Ir-La-S/AC-catalyzed methanol carbonylation on single atomic active sites

Cited by 15 publications

References 43 publications

Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO4/SiO2 Catalysts

Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO4/SiO2 Catalysts

Application of Prussian Blue Analogue‐Derived Mn−Co Catalysts in the Hydrogenation of CO to Higher Alcohols

Nonenzymatic ethanol production in sustainable ways

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Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO₄/SiO₂ Catalysts

Selective Methanol Carbonylation to Acetic Acid on Heterogeneous Atomically Dispersed ReO₄/SiO₂ Catalysts