Semi-Hydrogenation of Acetylene to Ethylene Catalyzed by Bimetallic CuNi/ZSM-12 Catalysts

Hu, Song; Zhang, Chong; Wu, Mingyu; Ye, Runping; Shi, Depan; Li, Mujin; Zhao, Peng; Zhang, Rongbin; Feng, Gang

doi:10.3390/catal12091072

Cited by 6 publications

(6 citation statements)

References 42 publications

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“…Previous studies on acetylene semihydrogenation to ethylene have shown that at a high H 2 /acetylene ratio, overhydrogenation of the formed ethylene leads to ethane formation. Hence, loss of reaction selectivity has been observed at high H 2 concentrations. , However, we do not expect this to happen for the UiO-67(Co) cluster. Since the presence of adsorbed ethylene at the active site hinders H 2 bond dissociation, loss of reaction selectivity due to over hydrogenation seems unlikely.…”

Section: Resultsmentioning

confidence: 82%

“…Hence, loss of reaction selectivity has been observed at high H 2 concentrations. 71,72 However, we do not expect this to happen for the UiO-67(Co) cluster. Since the presence of adsorbed ethylene at the active site hinders H 2 bond dissociation, loss of reaction selectivity due to over hydrogenation seems unlikely.…”

Section: Ethane Formation Via the Chch 3 Hydrogenationmentioning

confidence: 74%

“…At very low concentrations of H 2 , the acetylene conversion rate is expected to be low. This is because acetylene hydrogenation to ethylene is hampered due to unavailability of H atoms . Under these conditions, acetylene oligomerization to 1,3 butadiene is expected to be the dominant pathway.…”

Section: Resultsmentioning

confidence: 99%

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Unraveling the Role of Single-Atom Catalysts Immobilized onto Metal–Organic Frameworks in Selective Acetylene Hydrogenation: An Implementation of the Active Site Isolation Strategy

Ganai,

Sarkar

2024

J. Phys. Chem. C

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The active site isolation strategy has long been used to perform selective hydrogenation of acetylene. Out of all of the approaches available for isolating active sites, the use of single-atom catalysts (SACs) provides an attractive route to enhancing selectivity. Herein, SACs in the form of metal alkoxides (where the metal varies from Sc to Zn) have been immobilized onto the organic linkers of the UiO-67 metal−organic framework (MOF), and density functional theory (DFT) calculations have been used to thoroughly examine their hydrogenation ability. Given that there are four pathways detrimental to C 2 H 4 selectivity, namely, (a) C 2 H 4 hydrogenation pathway, (b) C 2 H 2 overhydrogenation pathway, (c) CHCH 3 hydrogenation pathway, and (d) C 2 oligomerization to 1,3-butadiene, UiO-67(Co) has been screened out to be the most efficient catalyst. Comparison with other studies shows that the hydrogenation ability of the UiO-67(Co) MOF is superior to that of many Pd-based catalysts and some non-Pd-based catalysts. Although isolation of active sites has been shown to effectively inhibit the production of green oils, our findings are contrary to the previously reported phenomena. Our study shows that the use of SACs does not guarantee inhibition of green oil formation�two C 2 molecules can adsorb at the same active site and can undergo C−C coupling. Selectivity of the reaction is hampered when C 2 oligomerization to 1,3-butadiene becomes more competent than the C 2 H 4 desorption pathway. In the realm of SACs, the choice of modulating the ethylene adsorption mode/energy is not available, and hence, we have reported a new strategy to enhance C 2 H 4 selectivity. Since the availability of H atoms is crucial for the hydrogenation process, the key to attaining selectivity is to reduce the availability of H atoms to an extent that ethylene hydrogenation can be prevented without hampering acetylene hydrogenation to ethylene. This criterion is accurately met by UiO-67(Co).

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Section: Resultsmentioning

confidence: 82%

Section: Ethane Formation Via the Chch 3 Hydrogenationmentioning

confidence: 74%

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Unraveling the Role of Single-Atom Catalysts Immobilized onto Metal–Organic Frameworks in Selective Acetylene Hydrogenation: An Implementation of the Active Site Isolation Strategy

Ganai,

Sarkar

2024

J. Phys. Chem. C

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“…In an attempt to replace Pd with an earth abundant metal, Hu et al created CuNi bimetallic catalysts of various ratios on ZSM-12 (pore window 6.0 × 5.6 Å) support. 66 First, they found that the combined bimetallic material had enhanced performance compared to its individual constituents. Fur-Figure 4.…”

Section: Synthesis Techniques and Their Impact On Catalyst Performancementioning

confidence: 99%

Challenges and Opportunities for Exploiting the Role of Zeolite Confinements for the Selective Hydrogenation of Acetylene

Vito,

Shetty

2023

ACS Appl. Mater. Interfaces

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Zeolites, with their ordered crystalline porous structure, provide a unique opportunity to confine metal catalysts, whether single atoms (e.g., transition metal ions (TMIs)) or metal clusters, when used as a catalyst support. The confined environment has been shown to provide rate and selectivity enhancement across a variety of reactions via both steric and electronic effects, such as size exclusion and transition state stabilization. In this review, we provide a survey of various zeolite confined catalysts used for the semihydrogenation of acetylene highlighting their performance, defined by ethylene selectivity at full acetylene conversion, in relationship to the synthesis technique employed. Synthesis methods that ensure confinement with the catalyst transition metal location in the extraframework positions are reported to have the highest selectivity to ethylene. However, the underlying molecular factors responsible for selective catalysis within confinement remain elusive due to the difficulty in deconvoluting individual effects. Through the careful use of a combination of characterization and spectroscopic methods, insights into the relationship between the properties of zeolite confined catalysts and their performance have been explored in other works for a variety of reactions. More specifically, operando spectroscopy studies have revealed the dynamic behavior of zeolite confined catalysts under various conditions implying that the structure and properties observed ex situ do not always match those of the active catalyst under reaction conditions. Applying this type of analysis to acetylene semihydrogenation, a simple gas phase reaction, can help elucidate the structure−function relationship of zeolite confined catalysts allowing for more informed design choices and consequently their application to a wider variety of more complex reactions such as the liquid phase hydrogenation of alkynols where solvent effects must also be considered in addition to those of confinement.

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“…In an attempt to replace Pd with an earth abundant metal, Hu et al created CuNi bimetallic catalysts of various ratios on ZSM-12 (5.7 Å) support. 46 Firstly, they found that the combined bimetallic material had enhanced performance compared to its individual constituents. Furthermore, at an optimal temperature of 250°C with a Ni/Cu ratio of 7, 100% acetylene conversion could be achieved with 82.5% ethylene selectivity as compared to the Ni/ZSM-12 catalyst which only achieved ~70% selectivity at full acetylene conversion.…”

Section: Post Synthesis Techniquesmentioning

confidence: 99%

Challenges and opportunities for exploiting the role of zeolite confinements for the selective hydrogenation of acetylene

Vito,

Shetty

2023

Preprint

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Zeolites, with their ordered crystalline porous structure, provide a unique opportunity to confine metal catalysts, whether single atoms (e.g., transition metal ions (TMIs)) or metal clusters when used as a catalyst support. The confined environment has been shown to provide rate and selectivity enhancement across a variety of reactions via both steric and electronic effects such as size exclusion and transition state stabilization. In this review, we provide a survey of various zeolite confined catalysts used for the semi-hydrogenation of acetylene highlighting their performance, defined by ethylene selectivity at full acetylene conversion, in relationship to the synthesis technique employed. Synthesis methods that ensure confinement with catalyst transition metal location in the extra-framework positions are observed to have the report the highest selectivity to ethylene. However, the underlying molecular factors responsible for selective catalysis within confinement remains elusive due to the difficulty of deconvoluting individual effects. Through the careful use of a combination of characterization and spectroscopic methods, insights into the relationship between the properties of zeolite confined catalysts and their performance have been explored in other works for a variety of reactions. More specifically, operando spectroscopy studies have revealed the dynamic behavior of zeolite confined catalysts under various conditions implying that the structure and properties observed ex-situ do not always match those of the active catalyst under reaction conditions. Applying this type of analysis to acetylene semi-hydrogenation, a simple gas phase reaction, can help elucidate the structure-function relationship of zeolite confined catalysts allowing for more informed design choices and consequently their application to a wider variety of more complex reactions such as the liquid phase hydrogenation of alkynols where solvent effects must also be considered in addition to those of confinement.

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Semi-Hydrogenation of Acetylene to Ethylene Catalyzed by Bimetallic CuNi/ZSM-12 Catalysts

Cited by 6 publications

References 42 publications

Unraveling the Role of Single-Atom Catalysts Immobilized onto Metal–Organic Frameworks in Selective Acetylene Hydrogenation: An Implementation of the Active Site Isolation Strategy

Unraveling the Role of Single-Atom Catalysts Immobilized onto Metal–Organic Frameworks in Selective Acetylene Hydrogenation: An Implementation of the Active Site Isolation Strategy

Challenges and Opportunities for Exploiting the Role of Zeolite Confinements for the Selective Hydrogenation of Acetylene

Challenges and opportunities for exploiting the role of zeolite confinements for the selective hydrogenation of acetylene

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