Boosting the activity of transition metal carbides towards methane activation by nanostructuring

Figueras, Marc; Gutiérrez, Ramón A.; Prats, Hèctor; Viñes, Francesc; Ramírez, Pedro José Rueda; Illas, Francesc; Rodríguez, José A.

doi:10.1039/d0cp00228c

Cited by 18 publications

(58 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, this biological system cannot be used in large industrial-scale operations . Thus, a significant amount of research has been aimed at examining fundamental and practical aspects associated with methane activation by transition metals, oxides, sulfides, carbides, and zeolites. − …”

Section: Introductionmentioning

confidence: 99%

“…Experimental surface science studies have historically offered a rich insight into the role of well-defined metal and oxide surfaces in catalytic reactions and have been used to study methane activation since the 1980s. , Initially, the major focus was on examining the interaction of methane with well-defined surfaces of metals, , but recent work has shifted to examining the binding and activation of methane on oxide, metal–oxide, and metal–carbide interfaces. − Today, facing new challenges, advanced surface science tools and approaches have offered a new perspective on low temperature pathways that can occur when catalytic phenomena are controlled in an atomically precise manner to unravel as yet unrealized chemical pathways. While theoretical and kinetic models predict, experimental surface science validates that metal–oxide and metal–carbide interfaces can facilitate efficient C–H activation, − often at very low temperatures through the manipulation of the last layers of atoms by combining a metal center with oxygen or carbon centers, or upon careful choice of a coreactant (CO 2 , O 2 , H 2 O) that can steer pathways through a series of complex reaction steps. Several key results of recent studies have revealed the importance of engineering active sites in model surfaces that can offer insights to validate and better understand such processes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

2020

Self Cite

View full text Add to dashboard Cite

The abundance of cheap, natural gas has transformed the energy landscape, whereby revealing new possibilities for sustainable chemical technologies or impacting those that have relied on traditional fossil fuels. The primary component, methane, is underutilized and wastefully exhausted, leading to anthropogenic global warming. Historically, the manipulation of methane remained "clavis aurea," an insurmountable yet rewarding challenge and thus the focus of intense research. This is primarily due to an inability to dissociate C−H bonds in methane selectively, which requires a high energy penalty and is an essential prerequisite for the direct conversion of methane into a large set of value-added products. The discovery of such processes would promise an energy gainful use of natural gas benefiting several essential chemical processes associated with C1 chemistry. This first C−H bond dissociation step of the methane molecule appears in numerous catalytic mechanisms as the rate-determining step or most essential barrier sequence for all subsequent steps that follow in the production of C−C, C−O, or C x −H y −O z bonds found in value added products. A main goal is to catalytically reduce the energy barrier for the first C−H bond dissociation to be able to achieve the activation of methane at low or moderate temperatures. As such there is great value in understanding the fundamental nature of the active sites responsible for bond breaking or formation and thus be able to facilitate better control of this chemistry, leading to the development of new technologies for fuel production and chemical conversion. Surface science studies offer enhanced perspectives for a careful manipulation of bonds over the last layer atoms of catalyst surfaces, an essential factor for the design of atomically precise catalysts and unravelling of the reaction mechanism. With the advent of new surface imaging, spectroscopy, and in situ tools, it has been possible to decipher the surface chemistry of complex materials systems and further our understanding of atomic active sites on the surfaces of metals, oxides, and carbides or metal−oxide and metal−carbide interfaces. The once considered near impossible step of C−H bond activation is now observed at low temperatures with high propensity over a collection of oxide, metal−oxide, and metal−carbide systems in a conventional or inverse configuration (oxide or carbide on metal). The enabling of C− H activation at low temperature has opened interesting possibilities for the specific production of chemicals such as methanol directly from methane, a step toward facile synthesis of liquid fuels. We highlight the most recent of these results and present the key aspects of active site configurations engineered from surface science studies which enable such a simple reactive event through careful manipulation of the last surface layer of atoms found in the catalyst structure. New concepts which help in the activation and conversion of methane are discussed.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…Transition-metal carbides and carbide-based surfaces were found to be able to activate methane at mild conditions. 25 − 29 In view of this, the reactivity of transition metal carbide ions with methane has been intensively investigated in the gas phase by mass spectrometry and quantum chemical calculations. 30 − 41 Mechanistic aspects of the C–H bond activation of methane by diatomic transition metal carbide cations were elucidated by quantum-chemical calculations and verified experimentally using mass spectrometry.…”

Section: Introductionmentioning

confidence: 99%

Quadruple C–H Bond Activations of Methane by Dinuclear Rhodium Carbide Cation [Rh₂C₃]⁺

Jin

et al. 2021

JACS Au

View full text Add to dashboard Cite

The structure of the [Rh 2 C 3 ] + ion and its reaction with CH 4 in the gas phase have been studied by infrared photodissociation spectroscopy and mass spectrometry in conjunction with quantum chemical calculations. The [Rh 2 C 3 ] + ion is characterized to have an unsymmetrical linear [Rh–C–C–C–Rh] + structure existing in two nearly isoenergetic spin states. The [Rh 2 C 3 ] + ion reacts with CH 4 at room temperature to form [Rh 2 C] + + C 3 H 4 and [Rh 2 C 2 H 2 ] + + C 2 H 2 as the major products. In addition to the [Rh 2 C] + ion, the [Rh 2 13 C] + ion is formed at about one-half of the [Rh 2 C] + intensity when the isotopic-labeled 13 CH 4 sample is used. The production of [Rh 2 13 C] + indicates that the linear C 3 moiety of [Rh 2 C 3 ] + can be replaced by the bare carbon atom of methane with all four C–H bonds being activated. The calculations suggest that the overall reactions are thermodynamically exothermic, and that the two Rh centers are the reactive sites for C–H bond activation and hydrogen atom transfer reactions.

show abstract

“…[8] Nanostructuring transition metal carbides increases their active surface area and enhances their catalytic activity. [9] Carbides are well known to catalyze hydrogenation, dehydrogenation, hydrogenolysis and isomerization [8c,10] and have been used effectively in the hydrogenolysis of biomass. [4,11] Initial studies by Boudart showed that W-carbide has properties similar to Pt and can readily carry out dehydrogenation and hydrogenation reactions.…”

Section: Introductionmentioning

confidence: 99%

“…In hydrodeoxygenation reaction, transition metal carbides can efficiently convert furfural to 2‐methylfuran at moderate temperatures [8] . Nanostructuring transition metal carbides increases their active surface area and enhances their catalytic activity [9] . Carbides are well known to catalyze hydrogenation, dehydrogenation, hydrogenolysis and isomerization [8c,10] and have been used effectively in the hydrogenolysis of biomass [4,11] .…”

Section: Introductionmentioning

confidence: 99%

Catalytic Activity of Ti‐based MXenes for the Hydrogenation of Furfural

et al. 2020

View full text Add to dashboard Cite

Herein we report on the catalytic activity of Ti-based MXenes (Ti 3 CNT z and Ti 3 C 2 T z) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either gaseous hydrogen or 2-propanol as solvent and hydrogen source. Both catalysts showed good activity in the conversion of furfural to furfuryl alcohol, with furfuryl ether as the main by-product. Stability tests indicated that Ti 3 CNT z is more stable than Ti 3 C 2 T z against deactivation. Ab initio calculations were used to examine the hydrogenation and etherification reactions pathways and their corresponding reaction energetics on the Ti 3 CNT z MXene. The results indicate that the hydrogenation of the carbonyl bond efficiently proceeds via the heterolytic activation of hydrogen over the metal-oxygen site pair followed by the addition of the proton and hydride to the C and O atoms of the carbonyl. The subsequent hydrogenation of the unsaturated furan ring via metal bound hydrogen, however, is calculated to be much more difficult. Protons bound to the oxygen of the MXene are acidic and can also catalyze the etherification of the resulting alcohols. The bifunctional acidmetal site pairs also selectively catalyze the hydrogenolysis of the furfuryl alcohol to form 2-methyl furan.

show abstract

Boosting the activity of transition metal carbides towards methane activation by nanostructuring

Abstract: Molybdenum carbide breaks methane by going nano.

Cited by 18 publications

References 52 publications

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

Quadruple C–H Bond Activations of Methane by Dinuclear Rhodium Carbide Cation [Rh₂C₃]⁺

Catalytic Activity of Ti‐based MXenes for the Hydrogenation of Furfural

Contact Info

Product

Resources

About

Boosting the activity of transition metal carbides towards methane activation by nanostructuring

Abstract: Molybdenum carbide breaks methane by going nano.

Cited by 18 publications

References 52 publications

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

Low Temperature Activation of Methane on Metal-Oxides and Complex Interfaces: Insights from Surface Science

Quadruple C–H Bond Activations of Methane by Dinuclear Rhodium Carbide Cation [Rh2C3]+

Catalytic Activity of Ti‐based MXenes for the Hydrogenation of Furfural

Contact Info

Product

Resources

About

Quadruple C–H Bond Activations of Methane by Dinuclear Rhodium Carbide Cation [Rh₂C₃]⁺