Comparative performance of Cu-zeolites in the isothermal conversion of methane to methanol

Knorpp, Amy J.; Newton, Mark A.; Mizuno, Stefanie Caroline Mayumi; Zhu, Jie; Mebrate, Hiwote; Pinar, Ana B.; Bokhoven, Jeroen A. van

doi:10.1039/c9cc05659a

Cited by 28 publications

(33 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…69 In spite of this, methanol conversion has been demonstrated for various zeolite framework types using this lower temperature approach to activation and reaction. 48,49,[75][76][77] This suggests that the nature of the copper active species might not be limited to dehydrated di-or tri-copper oxo sites, and that a wider spectrum of active site motifs might exist.…”

mentioning

confidence: 99%

Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 99%

Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…They provided better performance than the MFI , FER , and *BEA topologies during methanol production from CH 4 . [ 93 ] In recent years, Fe‐, Cu‐, and other metal‐containing zeolites with various framework topologies including LTL , [ 91 ] EON , [ 91 ] MEI , [ 91 ] BPH , [ 91 ] HEU , [ 91 ] SZR , [ 91 ] FAU , [ 91 ] AFX , [ 92 ] MFI , [ 94 ] MOR , [ 95 ] FER , [ 96 ] *BEA , [ 96a,97 ] CHA , [ 98 ] MAZ , [ 99 ] AEI , [ 100 ] and ERI [ 101 ] have been studied for direct CH 4 conversion to methanol. [ 102 ] Within these zeolite framework topologies, various active metal sites including mono‐, di‐, and trinuclear metal species and sub‐nanometer metal oxide clusters have been proposed and significantly affect the CH 4 activation barrier and methanol selectivity.…”

Section: Ch4 Conversion Over Zeolite‐based Catalystsmentioning

confidence: 99%

Applications of Zeolites to C1 Chemistry: Recent Advances, Challenges, and Opportunities

2020

View full text Add to dashboard Cite

However, due to growing concerns regarding crude oil depletion and increasing environmental requirements, finding abundant fossil hydrocarbons with high H 2 /C ratios as well as alternative carbon resources has become crucial to maintaining sustainable, environmentally benign systems that can aid human development. [2] Thus, one-carbon (C1) chemistry, which is the chemistry of C1 molecules that can be derived from sources other than fossil hydrocarbons, including carbon monoxide (CO), carbon dioxide (CO 2), methane (CH 4), methanol (CH 3 OH), and formic acid (HCOOH), has emerged and plays important roles in the energy supply and high-value chemical preparation. [1,3] These C1 resources can be obtained from natural gas, shale gas, coal, biomass, solid wastes, and CO 2 emissions. [3a,4] Extensive studies have been dedicated to the catalytic conversion of C1 molecules, including production of dimethyl ether (DME) and liquid fuels from syngas (a mixture of CO and H 2); production of methanol, light olefins, and even aromatics from CH 4 ; and production of hydrogen from HCOOH. [5] All of these transformations require metallic catalytic species such as single atoms; clusters; or oxides, carbides, or alloy particles (e.g., Rh-, AuPd-, Fe 3 O 4-, and Fe 5 C 2-based catalysts). However, these isolated metallic species suffer from severe sintering due to a lack of confinement effects from supports, which leads to poor catalytic stability and decreased selectivities toward their target products. The efficient production of a specific range of hydrocarbons or oxygenates remains a difficult scientific and technical challenge. Overcoming product selectivity limitations and improving catalyst stabilities via catalyst designs are important areas of research. Zeolites are an important class of shape-selective catalysts with uniform micropores, tunable acidities, and high thermal and hydrothermal stabilities. Over the past decade, they have gained broad popularity and been applied to various industrially important catalytic processes. [6] In particular, the design and development of zeolite-based mono-, bi-, and multifunctional catalysts that combine the advantages of zeolites with those of metallic catalytic species have boosted the application of zeolites to C1 chemistry. As shown in Figure 1, value-added hydrocarbons and oxygenates can be produced from C1 molecules via various catalytic routes over zeolite-based catalysts. By May of 2020, the Structure Commission of the International C1 chemistry, which is the catalytic transformation of C1 molecules including CO, CO 2 , CH 4 , CH 3 OH, and HCOOH, plays an important role in providing energy and chemical supplies while meeting environmental requirements. Zeolites are highly efficient solid catalysts used in the chemical industry. The design and development of zeolite-based mono-, bi-, and multifunctional catalysts has led to a booming application of zeolite-based catalysts to C1 chemistry. Combining the advantages of zeolites and metallic catalytic species has promoted the catal...

show abstract

“…In methane‐to‐methanol conversion, copper‐cation exchanged zeolite omega (framework type code MAZ, Figure 1 a) [21] can achieve high selectivity (no detectable products of over‐oxidation observed by FTIR) and methanol yields for both high (723 K) and low (473 K) activation temperatures with methanol yields of 200 μmol/gram‐zeolite, and 141 μmol/gram‐zeolite, respectively [22, 23] . The reason behind this superior performance must lie in the details of the zeolite's framework structure and the active sites that it stabilizes.…”

Section: Figurementioning

confidence: 99%

Paired Copper Monomers in Zeolite Omega: The Active Site for Methane‐to‐Methanol Conversion

et al. 2021

Self Cite

View full text Add to dashboard Cite

The direct conversion of methane to methanol using oxygen is a challenging but potentially rewarding pathway towards utilizing methane. By using a stepwise chemical looping approach, copper‐exchanged zeolites can convert methane to methanol, but productivity is still too low for viable implementation. However, if the nature of the active site could be elucidated, that information could be used to design more effective catalysts. By employing anomalous X‐ray powder diffraction with support from theory and other X‐ray techniques, we have derived a quantitative and spatial description of the highly selective, active copper sites in zeolite omega (Cu‐omega). This is the first comprehensive description of the structure of non‐copper‐oxo active species and will provide a pivotal model for future development for materials for methane to methanol conversion.

show abstract

Comparative performance of Cu-zeolites in the isothermal conversion of methane to methanol

Abstract: A series of zeolites were screened for the direct conversion of methane to methanol under isothermal low-temperature stepwise conditions; of the screened zeolites, omega zeolite (MAZ) showed superior performance.

Cited by 28 publications

References 35 publications

Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination

Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination

Applications of Zeolites to C1 Chemistry: Recent Advances, Challenges, and Opportunities

Paired Copper Monomers in Zeolite Omega: The Active Site for Methane‐to‐Methanol Conversion

Contact Info

Product

Resources

About