Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO<sub>2</sub> Hydrogenation to Methanol

Rungtaweevoranit, Bunyarat; Baek, Jayeon; Araújo, Joyce R.; Archanjo, Bráulio S.; Choi, Kyung Min; Yaghi, Omar M.; Somorjai, Gábor A.

doi:10.1021/acs.nanolett.6b03637

Cited by 380 publications

(318 citation statements)

References 38 publications

(36 reference statements)

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“…Varying the copper concentration in the zeolite or even the use of other sorbents than zeolites might circumvent this problem. In this respect, metal–organic frameworks have high potential in combining catalytic sites and high adsorption capabilities …”

Section: Discussionmentioning

confidence: 99%

Sorption‐Enhanced Methanol Synthesis

et al. 2019

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A small heat of reaction limits the efficiency of the catalytic hydrogenation of CO2 to form methanol; an improved efficiency can be achieved by shifting the thermodynamic equilibrium toward the formation of methanol. The exothermic adsorption of the products in sorption catalysts is shown to increase the reaction yield. The sorption catalysts consist of catalytically active Cu particles incorporated into a zeolite, which is known to strongly absorb water. In addition to high reaction yield of methanol, the sorption catalyst reduces CO2 to CO and dimethyl ether. An enhancement factor of up to 400% for CO and 130% for methanol and dimethyl ether at a relatively low pressure of 15 bar is shown. Furthermore, the following relevant parameters for future technical realization are derived: a high catalytic activity and the reversible adsorption of the products at reaction conditions. A key experiment that combines a catalytic reaction and a pressure swing desorption is presented and demonstrates the feasibility of sorption‐enhanced catalysis for efficient energy use in large‐scale reactors.

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Section: Discussionmentioning

confidence: 99%

Sorption‐Enhanced Methanol Synthesis

et al. 2019

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“…[103] Catalytic hydrogenation of CO 2 to methanol could be one of the key reactions in a possible scenario of low CO 2 emissions. [103] Catalytic hydrogenation of CO 2 to methanol could be one of the key reactions in a possible scenario of low CO 2 emissions.…”

Section: Cu Npsmentioning

confidence: 99%

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

et al. 2019

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frameworks (MOFs) are currently attracting considerable attention as heterogeneous catalysts at moderate temperatures, mainly for liquid-phase reactions. Since structural stability is one of the major concerns for the use of MOFs in catalysis, particularly considering that frequently some of the reported MOF materials are very unstable, the interest in this area has been focused on those MOFs exhibiting the highest structural robustness, UiO-66 being among the most widely used. Two introductory sections deal with the synthesis, structure and main properties of UiO-66, including its remarkable thermal (up to 350°C) and chemical (aqueous solution in a wide pH range) stability. The main body of the review summarizes those examples of using UiO-66 in catalysis grouped according to the nature of the active sites, starting with the use of UiO-66 as Lewis acids. In this section, emphasis has been made in the recent strategies to create structural defects in a controlled way that generate Lewis acidity. Other sections cover examples illustrating substituted terephthalate as active sites and the evidence that there is a synergy between acid and basic sites in close proximity that make some of these UiO-66 with substituents at the linker to act as dual acid-base catalysts. Other sections are focused on the use of UiO-66 as hosts of metal nanoparticles, metal oxides and other host, remarking the influence that the nature of UiO-66 and the possible presence of substituents in the framework play on the activity of the incorporated guest. The last section summarizes the current state of the art in the use of UiO-66 in catalysis and provides our views on future developments regarding the application of UiO-66 in industrial processes.

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“…Yaghi's group has also encapsulated Cu NPs into UiO‐66 to give Cu⊂UiO‐66 composite for the hydrogenation of CO 2 to methanol ( Figure ), which showed the best catalytic performance upon the other Cu‐based composites supported by mesoporous silica (MCF‐26), ZrO 2 , and Al 2 O 3 , and gave an eightfold enhanced yield over the benchmark Cu/ZnO/Al 2 O 3 catalyst with a 100% selectivity for methanol.…”

Section: Synthesis Strategies For Integration Of Active Mnps Into Mofsmentioning

confidence: 99%

Section: Synthesis Strategies For Integration Of Active Mnps Into Mofsmentioning

confidence: 99%

Integration of Metal Nanoparticles into Metal–Organic Frameworks for Composite Catalysts: Design and Synthetic Strategy

Cheng

2019

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Metal–organic frameworks (MOFs) are constructed by periodically alternate metal ions with organic ligands, which offer structural diversity and a wide range of interesting properties as an attractive classification of crystalline porous materials. Integration of MOFs with other size‐limited functional centers can supply new multifunctional composites, which exhibit both the properties of the components and new characteristics due to the combination of MOFs with the selected loadings. In recent years, integration of metal/metal oxide nanoparticles (MNPs) into MOFs to form the composite catalysts has attracted considerable attention due to the superior performance. In this review, the latest studies and up‐to‐date developments on the design and synthetic strategy of new MNP@MOF composite catalysts are specifically highlighted. Both the achievements and problems are evaluated and proposed, and the opportunities and challenges of MNP@MOF composite catalysts are discussed.

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Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO₂ Hydrogenation to Methanol

Cited by 380 publications

References 38 publications

Sorption‐Enhanced Methanol Synthesis

Sorption‐Enhanced Methanol Synthesis

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

Integration of Metal Nanoparticles into Metal–Organic Frameworks for Composite Catalysts: Design and Synthetic Strategy

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Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO2 Hydrogenation to Methanol

Cited by 380 publications

References 38 publications

Sorption‐Enhanced Methanol Synthesis

Sorption‐Enhanced Methanol Synthesis

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

Integration of Metal Nanoparticles into Metal–Organic Frameworks for Composite Catalysts: Design and Synthetic Strategy

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Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO₂ Hydrogenation to Methanol