Lewis acid sites in MOFs supports promoting the catalytic activity and selectivity for CO esterification to dimethyl carbonate

Xu, Yu-Ping; Wang, Zhiqiao; Tan, Hai; Jing, Kaiqiang; Xu, Zhusheng; Guo, Guo‐Cong

doi:10.1039/c9cy02330e

Cited by 61 publications

(37 citation statements)

References 53 publications

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“…[37] XPS can analyze the electron density differences of the same metal in different environments. [38] We supplemented and verified the acidity difference of the catalyst through XPS analysis. By XPS, we tested the local environment of Zr and Hf under different ligands (Figure 8), and all the catalysts used were tested after activation.…”

Section: Nh 3 -Tpd and Xps Resultsmentioning

confidence: 99%

“…In Figure 9, the ~1070 cm À 1 and ~1042 cm À 1 bands belong to the v 18a and v 12 modes of pyridine adsorption on unsaturated metal sites (that is Lewis acidity sites), respectively. [38,40] The amount of the acid sites on the catalyst surface can be determined by the peak area. When the desorption temperature is 25 °C, it represents the total acidity amount of the catalyst surface.…”

Section: Py-ftir Adsorption-desorption Resultsmentioning

confidence: 99%

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Study of the Cycloaddition of CO₂ with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Jin

Qin

Dong

et al. 2021

Chemistry A European J

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A series of MOFs with a 6-connected spn topology were synthesized Hf), Hf), Hf)). Through the in situ DRIFTS of NH 3 adsorptiondesorption, we found that the activated catalyst mainly contains Lewis acid sites. The effects of different organic ligands on the Lewis acid of the Zr 6 cluster were analyzed by XPS and NH 3 -TPD, and the relative Lewis acidity of the same metal was obtained: PCN-777 > MOF-808 > MOF-818. In the Py-FTIR results, we confirmed that MOF-818 has a higher acid site density. In the activity test, MOFs with mesoporous structure showed better catalytic activity under normal temperature and pressure. Among them, MOF-818 can still maintain a high degree of crystallinity after catalysis. Finally, we use density functional theory to propose the mechanism of the cycloaddition reaction of carbon dioxide and styrene oxide. The results show that the metal is coordinated with styrene oxide and halogens attack the β carbon of the epoxide.

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Section: Nh 3 -Tpd and Xps Resultsmentioning

confidence: 99%

Section: Py-ftir Adsorption-desorption Resultsmentioning

confidence: 99%

Study of the Cycloaddition of CO₂ with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Jin

Qin

Dong

et al. 2021

Chemistry A European J

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“…The final NH 3 desorption peak above 330 °C was indexed to strong acid sites, which is associated with the NH 3 adsorbed on Brønsted acid sites. 78,79 In the cases of UiO-66(Zr) and 3.2%-PS/UiO-66(Zr), a broad desorption signal was observed between 150 and 330 °C, suggesting the presence of rich medium acid sites. The amount of NH 3 desorbed from these acid sites was calculated by integrating the area under the TPD curves.…”

Section: Resultsmentioning

confidence: 99%

Sulfonate-Grafted Metal–Organic Frameworks for Reductive Functionalization of CO₂ to Benzimidazoles and N-Formamides

Chen

2021

ACS Catal.

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Metal–organic frameworks (MOFs) with inner salt of 3-(pyridinylium)-1-propanesulfonate (PS) as the organic linkage were developed as catalysts (PS/MOFs) for reductive functionalization of carbon dioxide (CO2) to benzimidazoles and N-formamides. The pendant −SO3 – anion in the PS/MOFs acted as an organocatalytic active site for reductive cyclization of CO2 with 1,2-phenylenediamine to afford 1H-benzo[d]imidazole. A linear correlation was observed between the catalytic performance (in terms of turnover frequencies) and the specific surface area of PS/MOFs at a low conversion level of 1,2-phenylenediamine. Our theoretical investigation revealed significantly reduced energy barriers from 2.03 eV under catalyst-free conditions to 0.97 eV in the presence of the catalyst. The developed PS/MOFs can efficiently promote a broad range of benzimidazoles in 88–99% yields through reductive cyclization. Moreover, the PS/MOFs can readily catalyze N-formylation of various monoamines with CO2 as the carbonyl source for quantitative syntheses of N-formamides. The research thus highlights MOF-based catalysts for organocatalytic transformation of CO2 into high value-added chemicals.

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“…The understanding gained from this work can guide the design of selective solid catalysts and control reaction temperature to maximize the lactic acid yield. Moreover, the use of water‐tolerant Lewis acidic MIL‐101(Al)−NH 2 could be extended to other aqueous acid‐catalyzed biomass conversion reactions, such as isomerization, [72] Meerwein‐Ponndorf‐Verley reduction, [73] Fries rearrangement, [74] acetalization, [75] hydrolysis, [76] esterification, [77] condensation, [78] and dehydration [79]…”

Section: Discussionmentioning

confidence: 99%

Aluminum‐based Metal‐Organic Framework as Water‐tolerant Lewis Acid Catalyst for Selective Dihydroxyacetone Isomerization to Lactic Acid

et al. 2022

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Lactic acid is a renewable and versatile chemical for food, pharmaceuticals, cosmetics, and other chemicals. Lactic acid can be produced from biomass‐derived dihydroxyacetone. However, selective and recyclable water‐tolerant acid catalysts need to be developed for the specific production of lactic acid. Here we show that the MIL‐101(Al)−NH2 metal‐organic framework (MOF) is a water‐tolerant and selective solid Lewis acid catalyst for dihydroxyacetone isomerization to lactic acid. The Lewis acidic MIL‐101(Al)−NH2 catalyst promoted a high lactic acid selectivity of 91 % at 96 % dihydroxyacetone conversion at 120 °C in water. The reaction proceeded by temperature and/or MIL‐101(Al)−NH2 MOFs mediated dihydroxyacetone dehydration to pyruvaldehyde. Subsequently, the MIL‐101(Al)−NH2 facilitated rehydration of the pyruvaldehyde to lactic acid. The Lewis acidic MIL‐101(Al)−NH2 catalyst was stable and reusable four times without any decrease in catalytic performance.

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Lewis acid sites in MOFs supports promoting the catalytic activity and selectivity for CO esterification to dimethyl carbonate

Abstract: We studied the effect of Lewis acidity in metal–organic frameworks (MOFs) on their activity as catalyst supports for the esterification of CO to dimethyl carbonate.

Cited by 61 publications

References 53 publications

Study of the Cycloaddition of CO₂ with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Study of the Cycloaddition of CO₂ with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Sulfonate-Grafted Metal–Organic Frameworks for Reductive Functionalization of CO₂ to Benzimidazoles and N-Formamides

Aluminum‐based Metal‐Organic Framework as Water‐tolerant Lewis Acid Catalyst for Selective Dihydroxyacetone Isomerization to Lactic Acid

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Lewis acid sites in MOFs supports promoting the catalytic activity and selectivity for CO esterification to dimethyl carbonate

Abstract: We studied the effect of Lewis acidity in metal–organic frameworks (MOFs) on their activity as catalyst supports for the esterification of CO to dimethyl carbonate.

Cited by 61 publications

References 53 publications

Study of the Cycloaddition of CO2 with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Study of the Cycloaddition of CO2 with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Sulfonate-Grafted Metal–Organic Frameworks for Reductive Functionalization of CO2 to Benzimidazoles and N-Formamides

Aluminum‐based Metal‐Organic Framework as Water‐tolerant Lewis Acid Catalyst for Selective Dihydroxyacetone Isomerization to Lactic Acid

Contact Info

Product

Resources

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Study of the Cycloaddition of CO₂ with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Study of the Cycloaddition of CO₂ with Styrene Oxide Over Six‐Connected spn Topology MOFs (Zr, Hf) at Room Temperature

Sulfonate-Grafted Metal–Organic Frameworks for Reductive Functionalization of CO₂ to Benzimidazoles and N-Formamides