First-principles-informed energy span and microkinetic analysis of ethanol catalytic conversion to 1,3-butadiene on MgO

Boje, Astrid; Taifan, William; Ström, Henrik; Baltrušaitis, Jonas; Hellman, Anders

doi:10.1039/d1cy00419k

Cited by 7 publications

(2 citation statements)

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“…The differential equations describing the surface kinetics were solved using the Python Catalysis Kinetics (PyCatKin) tool, 54 using the SciPy 55 lsoda wrapper to the Fortran ODEPACK library, 56 and backward differentiation formulas. The relative and absolute tolerances were set to 1 × 10 −8 and 1 × 10 −10 , respectively.…”

Section: S S Smentioning

confidence: 99%

Investigating the Composition of the Metal Dimer Site in Chabazite for Direct Methane-to-Methanol Conversion

Engedahl,

Boje,

Ström

et al. 2024

J. Phys. Chem. C

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Methanol is a liquid energy carrier that has the potential to reduce the use of fossil fuels. Industrial production of methanol is currently a multistep high-temperature/high-pressure synthesis route. Direct conversion of methane to methanol under low-temperature and low-pressure conditions is an interesting but challenging alternative, which presently lacks suitable catalysts.Here, the complete reaction cycle for direct methane-to-methanol conversion over transition-metal dimers in the chabazite zeolite is studied by using density functional theory calculations and microkinetic modeling. In particular, a reaction mechanism previously identified for the Cu 2 dimer is explored under dry and wet conditions for dimers composed of Ag, Au, Pd, Ni, Co, Fe, and Zn and the bimetallic dimers AuCu, PdCu, and AuPd. The densityfunctional-theory-based microkinetic modeling shows that Cu 2 , AuPd, and PdCu dimers have reasonable turnover frequencies under technologically relevant conditions. The adsorption energy of atomic oxygen is identified as a descriptor for the reaction landscape as it correlates with the adsorption and transition-state energies of the other reaction intermediates. Using the established scaling relations, a volcano plot of the rate is generated with its apex close to the Cu 2 , AuPd, and PdCu dimers.

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Section: S S Smentioning

confidence: 99%

Investigating the Composition of the Metal Dimer Site in Chabazite for Direct Methane-to-Methanol Conversion

Engedahl,

Boje,

Ström

et al. 2024

J. Phys. Chem. C

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“…The dopant metals, such as Na and Zn, help in the dehydrogenation reaction of ethanol to relative products such as acetaldehyde, and Zr helps in or supports the catalyzation of aldol condensation to produce 1,3-butadiene. Some papers demonstrated that the adequate loading of MgO on ZrO 2 could aid in a two-stage process of producing 1,3-butadiene from ethanol dehydration [1,[7][8][9][10]. To avoid the low yield and productivity of 1,3-butadiene from ethanol, ash, Mg, and Zr, catalysts are used in a fixed bed or dual fixed bed reactor, as the catalyst had different metal constituents and would provide enough support for different metal-supported catalysts.…”

Section: Introductionmentioning

confidence: 99%

1,3-Butadiene Production Using Ash-Based Catalyst

Bojang

2023

Catalysts

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The production of 1,3-butadiene from ethanol was carried out using ash as a catalyst in combination with Zr and Mg. The catalytic experiments were carried out at 350–400 °C with a different weight hourly space velocity (WHSV). The catalysts that were used were combined as follows: Ash, Ash:MgO (weight ratio 1:1), Ash:MgO (1:2), Ash:MgO (1:3), and Ash: MgO/ZrO2 (1:1:1). The characterization of the catalyst was carried out using BET, SEM, XRD, TGA, and XPS, respectively. The yield of 1,3-butadiene using bare ash was 65% at 400 °C and 2.5 h−1 of WHSV. Using the Ash:MgO (1:2) catalyst led to an ethanol conversion rate of 79 % at 350 °C; the yield and selectivity of 1,3-butadiene were 48% and 87.8 %, respectively. Using the Ash:MgO(1:3) catalyst led to a 1,3-butadiene yield of 25% and a selectivity of 82% at 350 °C. The Ash:MgO(1:2) catalyst had a 1,3-butadiene yield of 50% and selectivity of 83%, and the Ash:MgO(1:1) had a 1,3-butadiene yield of 30% and selectivity of 80%, while the Ash:MgO/ZrO2 (1:1:1) catalyst had a 1,3-butadiene yield of 50% and selectivity of 90.8% at 2.5 h−1 of WHSV.

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Mechanism of Preferential Hydrogenation of Hydroxymethyl Group to Aldehyde Group in 5‐Hydroxymethylfurfural over W₂C‐Based Catalyst

Tai

Liu

et al. 2022

ChemSusChem

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A W 4 C 2 cluster was used to model a W 2 C catalyst with the armchair model of activated carbon support, noted as W 4 C 2 /AC. Over W 4 C 2 /AC, the mechanism for the hydrogenation of both À H 2 OH and À CHO groups in 5-hydroxymethylfurfural (HMF) was theoretically studied in tetrahydrofuran at GGA-PBE/DNP level. 5-Methylfurfural was the major product from only hydrodehydration of the À CH 2 OH group, whereas 2,5-dihydroxymethylfuran was the minor product from the hydrogenation of both À CH 2 OH and À CHO groups. The rate-determining steps were concerned with the À C(H) 2 À H bond formation for the hydrodehydration of À CH 2 OH group, and the À (OH)(H)À H bond formation for the hydrogenation of À CHO group. Kinetically, Wsites promoted the hydrodehydration of À CH 2 OH group and inhibited the hydrogenation of À CHO group. This stemmed from the strong Lewis acidity of W-sites, which easily accepted the lone-pair electrons of the oxygen atom in the À C(OH)(H)À group, making À C(OH)(H)À H bond formation hard, and hampering the hydrogenation of the À CHO group.

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First-principles-informed energy span and microkinetic analysis of ethanol catalytic conversion to 1,3-butadiene on MgO

Abstract: Kinetic modeling of single-step catalytic conversion of ethanol to 1,3-butadiene is necessary to inform accurate process design. This paper uses first-principles-informed energy span and microkinetic analysis to explore the reaction...

Cited by 7 publications

References 59 publications

Investigating the Composition of the Metal Dimer Site in Chabazite for Direct Methane-to-Methanol Conversion

Investigating the Composition of the Metal Dimer Site in Chabazite for Direct Methane-to-Methanol Conversion

1,3-Butadiene Production Using Ash-Based Catalyst

Mechanism of Preferential Hydrogenation of Hydroxymethyl Group to Aldehyde Group in 5‐Hydroxymethylfurfural over W₂C‐Based Catalyst

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First-principles-informed energy span and microkinetic analysis of ethanol catalytic conversion to 1,3-butadiene on MgO

Abstract: Kinetic modeling of single-step catalytic conversion of ethanol to 1,3-butadiene is necessary to inform accurate process design. This paper uses first-principles-informed energy span and microkinetic analysis to explore the reaction...

Cited by 7 publications

References 59 publications

Investigating the Composition of the Metal Dimer Site in Chabazite for Direct Methane-to-Methanol Conversion

Investigating the Composition of the Metal Dimer Site in Chabazite for Direct Methane-to-Methanol Conversion

1,3-Butadiene Production Using Ash-Based Catalyst

Mechanism of Preferential Hydrogenation of Hydroxymethyl Group to Aldehyde Group in 5‐Hydroxymethylfurfural over W2C‐Based Catalyst

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Mechanism of Preferential Hydrogenation of Hydroxymethyl Group to Aldehyde Group in 5‐Hydroxymethylfurfural over W₂C‐Based Catalyst