DFT Study of Nickel‐Catalyzed Low‐Temperature Methanol Synthesis

McGuinness, David S.; Patel, Jim; Amin, Mohamad Hassan; Bhargava, Suresh K.

doi:10.1002/cctc.201700213

Cited by 4 publications

(3 citation statements)

References 46 publications

(54 reference statements)

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“…In addition to the facile Ni phyllosilicate formation, the use of Ni as a catalyst has a wide range of applications due to its high interaction with hydrogen and relatively low cost in comparison to precious metals . For CO 2 hydrogenation reactions, nickel catalysts are typically used for CH 4 production, although methanol synthesis catalysts have also been reported. , Indium, in addition to its use in semiconductor materials, has also attracted attention as a catalyst, and was recently shown to have activity for methanol synthesis from CO 2 /H 2 . Aluminum is a well-known structural promoter and was included to increase stability by protecting against sintering. , …”

Section: Introductionmentioning

confidence: 99%

Low-Pressure Hydrogenation of CO₂ to CH₃OH Using Ni-In-Al/SiO₂ Catalyst Synthesized via a Phyllosilicate Precursor

2017

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The overall objective of this research is to convert the increasingly concerning CO 2 and renewable H 2 to highly demanded methanol (CH 3 OH), which creates a win− win scenario for simultaneous climate change prevention and sustainable economic development. The key to the success of this targeted CO 2 utilization technology is the development of low-pressure methanol synthesis catalysts (Ni a In b Al/SiO 2 ; a = 0−8.3, b = 0−9.1) by means of a phyllosilicate precursor, allowing for formation of well-dispersed metallic particles with an average diameter of 2.5−3.5 nm. The catalysts were characterized with various methods including ICP-OES, N 2 physisorption, XRD, SEM, TEM, TGA, H 2 TPR, DRIFTS, and XPS. The performances of the Ni a In b Al/SiO 2 catalysts and conventional catalyst were compared under various evaluation temperatures at ambient pressure. It was found that catalysts with Ni/In ratios of 0.4−0.7 showed the highest activity. Ni 3.5 In 5.3 Al/SiO 2 (NIA-0.7) with 15% metal loading was the best among the tested Ni a In b Al/SiO 2 catalysts with an activity of 0.33 mol h −1 (mol catalyst metal) −1 in comparison to the benchmark Cu/ZnO/ Al 2 O 3 (CZA) catalyst at 0.17. Several Ni a In b Al/SiO 2 catalysts also showed similar CO 2 conversions in comparison to the CZA catalyst. Infrared studies using DRIFTS determined that CO 2 hydrogenation on Ni a In b Al/SiO 2 catalysts proceeds through monodentate carbonate before further conversion to monodentate and bidentate formate. With a feed of CO/H 2 instead of CO 2 /H 2 the primary hydrocarbon product changes from methanol to propane, accompanied by a lack of formate and monodentate carbonate IR signals.

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Section: Introductionmentioning

confidence: 99%

Low-Pressure Hydrogenation of CO₂ to CH₃OH Using Ni-In-Al/SiO₂ Catalyst Synthesized via a Phyllosilicate Precursor

2017

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“…Both bases gave similar computational results (see the Supporting Information, section 8). The alkali counter ion can sometimes play a significant role in the reaction mechanism, as reported, for example, by McGuinness . However, DFT calculations of the base‐catalyzed cycle with (Figure S20) and without (Figure ) the sodium counter ion revealed no significant differences in the reaction path and their relative energies.…”

Section: Resultsmentioning

confidence: 99%

Carbamate Synthesis Using a Shelf‐Stable and Renewable C₁ Reactant

et al. 2019

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4‐Propylcatechol carbonate is a shelf‐stable, renewable C1 reactant. It is easily prepared from renewable 4‐propylcatechol (derived from wood) and dimethyl carbonate (derived from CO2) using a reactive distillation system. In this work, the 4‐propylcatechol carbonate is used for the two‐step synthesis of carbamates under mild reaction conditions. In the first step, 4‐propylcatechol carbonate is treated with an alcohol at 50–80 °C in the presence of a Lewis acid catalyst, such as Zn(OAc)2⋅2 H2O. With liquid alcohols, no solvent is used and with solid alcohols 2‐methyltetrahydrofuran is used as solvent. In the second step, the alkyl 2‐hydroxy‐propylphenyl carbonate intermediates obtained react with amines at room temperature in 2‐methyltetrahydrofuran, forming the target carbamates and the byproduct 4‐propylcatechol, which can be recycled into a carbonate reactant.

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“…This result implied the applicability of cheap Ni catalysts for methanol formation from CO and H 2 . Later, McGuinness et al considered two different mechanisms of methanol synthesis (CO + 2H 2 → CH 3 OH) on the Ni catalyst surface [115]. They compared the possibility of direct (via formyl intermediates) and indirect (via methyl formate) routes of CO hydrogenation for methanol production, as shown in Figure 29.…”

Section: Nickelmentioning

confidence: 99%

A Review of Theoretical Studies on Carbon Monoxide Hydrogenation via Fischer–Tropsch Synthesis over Transition Metals

Jamaati,

Torkashvand,

Sarabadani Tafreshi

et al. 2023

Molecules

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The increasing demand for clean fuels and sustainable products has attracted much interest in the development of active and selective catalysts for CO conversion to desirable products. This review maps the theoretical progress of the different facets of most commercial catalysts, including Co, Fe, Ni, Rh, and Ru. All relevant elementary steps involving CO dissociation and hydrogenation and their dependence on surface structure, surface coverage, temperature, and pressure are considered. The dominant Fischer–Tropsch synthesis mechanism is also explored, including the sensitivity to the structure of H-assisted CO dissociation and direct CO dissociation. Low-coordinated step sites are shown to enhance catalytic activity and suppress methane formation. The hydrogen adsorption and CO dissociation mechanisms are highly dependent on the surface coverage, in which hydrogen adsorption increases, and the CO insertion mechanism becomes more favorable at high coverages. It is revealed that the chain-growth probability and product selectivity are affected by the type of catalyst and its structure as well as the applied temperature and pressure.

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DFT Study of Nickel‐Catalyzed Low‐Temperature Methanol Synthesis

Cited by 4 publications

References 46 publications

Low-Pressure Hydrogenation of CO₂ to CH₃OH Using Ni-In-Al/SiO₂ Catalyst Synthesized via a Phyllosilicate Precursor

Low-Pressure Hydrogenation of CO₂ to CH₃OH Using Ni-In-Al/SiO₂ Catalyst Synthesized via a Phyllosilicate Precursor

Carbamate Synthesis Using a Shelf‐Stable and Renewable C₁ Reactant

A Review of Theoretical Studies on Carbon Monoxide Hydrogenation via Fischer–Tropsch Synthesis over Transition Metals

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DFT Study of Nickel‐Catalyzed Low‐Temperature Methanol Synthesis

Cited by 4 publications

References 46 publications

Low-Pressure Hydrogenation of CO2 to CH3OH Using Ni-In-Al/SiO2 Catalyst Synthesized via a Phyllosilicate Precursor

Low-Pressure Hydrogenation of CO2 to CH3OH Using Ni-In-Al/SiO2 Catalyst Synthesized via a Phyllosilicate Precursor

Carbamate Synthesis Using a Shelf‐Stable and Renewable C1 Reactant

A Review of Theoretical Studies on Carbon Monoxide Hydrogenation via Fischer–Tropsch Synthesis over Transition Metals

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Product

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Low-Pressure Hydrogenation of CO₂ to CH₃OH Using Ni-In-Al/SiO₂ Catalyst Synthesized via a Phyllosilicate Precursor

Low-Pressure Hydrogenation of CO₂ to CH₃OH Using Ni-In-Al/SiO₂ Catalyst Synthesized via a Phyllosilicate Precursor

Carbamate Synthesis Using a Shelf‐Stable and Renewable C₁ Reactant