Active sites for tandem reactions of CO
 2
 reduction and ethane dehydrogenation

Yan, Binhang; Yao, Siyu; Kattel, Shyam; Wu, Qiyuan; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Su, Dong; Chen, Jingguang G.

doi:10.1073/pnas.1806950115

Cited by 121 publications

(103 citation statements)

References 31 publications

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“…However, on a surface that contained a greater amount of Ni than Fe, it was inferred that metallic Ni particles would be more pronounced. This could essentially dampen the catalytic effect observed with oxidized Fe, thereby changing the active site and promoting activity in favor of the dry reforming reaction, similar to those described previously for the reactions of CO 2 with ethane …”

Section: Resultssupporting

confidence: 61%

“…From previous synchrotron X‐ray diffraction experiments we have confirmed that the CeO 2 support is crystalline and approximately 33 nm in size . In addition, under reaction conditions for the reduction of CO 2 with ethane the CeO 2 lattice has been shown to undergo abrupt expansions indicating an increase of the average CeO bond length due to the partial reduction of Ce 4+ to Ce 3+ . The BET surface area of the support has been reported by our group to be 49.1 m 2 g −1 while the Ni 3 Pt 1 /CeO 2 catalyst has a surface area of 44.5 m 2 g −1 …”

Section: Methodsmentioning

confidence: 52%

“…In situ X‐ray absorption near‐edge spectroscopy (XANES) measurements for the Fe K edge (7,112 eV), Ni K edge (8,333 eV), Co K edge (7,709 eV), and Pd K edge (24,350 eV) were collected at the Beamline 9‐BM of the Advanced Photon Source (APS) at Argonne National Laboratory. For each experiment, ~200 mg of sieved sample (60–80 mesh) was loaded into a custom Cu microchannel cell and held in place with graphite paper, as described previously . Using similar procedures as flow reactor experiments, the catalysts were first reduced in a 50/50 mixture of Ar and He at 723 K for 60 min.…”

Section: Methodsmentioning

confidence: 99%

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The effects of bimetallic interactions for CO₂‐assisted oxidative dehydrogenation and dry reforming of propane

2019

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The catalytic reduction of CO 2 by propane may occur via dry reforming to produce syngas (CO + H 2 ) or oxidative dehydrogenation to yield propylene. Utilizing propane and CO 2 as coreactants presents several advantages over conventional methane dry reforming or direct propane dehydrogenation, including lower operating temperatures and less coke formation. Thus, it is of great interest to identify catalytic systems that can either effectively break the C C bond to generate syngas or selectively break C H bonds to produce propylene. In this study, several precious and nonprecious bimetallic catalysts supported on reducible CeO 2 were investigated using flow reactor studies at 823 K to identify selective catalysts for CO 2 -assisted reforming and dehydrogenation of propane. K E Y W O R D SCeO 2 , CO 2 soft oxidant, propane, propylene, synthesis gas | INTRODUCTIONCarbon dioxide management is a prominent issue facing society that requires a diverse portfolio of innovative technologies. High atmospheric concentrations of CO 2 contribute to adverse effects that impact human health and the climate. The need to reduce CO 2 is evident, and the International Panel on Climate Change has stated that climate stabilization (no more than a 2 C rise from preindustrial levels) will require a combination of mitigation, utilization, and even negative emission technologies. 1 Thus, one key approach will be to transform abundant CO 2 into a useful feedstock for processes that not only produce high value products but also match the scale necessary to impact anthropogenic emissions.The two most relevant reactions for the catalytic conversion of CO 2 to CO are reverse water gas shift (RWGS) and dry reforming of methane (DRM). The CO product can be utilized as feedstock for Fischer-Tropsch reactions or methanol synthesis. These two reduction chemistries are not without obstacles, beginning with the challenge that CO 2 is the most thermodynamically stable carbon/oxygen-based molecule (ΔG F = −394 kJ mol −1 ). 2 Current implementation of RWGS has limited feasibility since efforts to obtain large amounts of renewable and CO 2 -free hydrogen are still under development. 3 Furthermore, high coke deposition rates at the reaction temperatures required for DRM hinders further significant improvements in catalyst stability. 4,5 A viable alternative is to utilize other light hydrocarbons, such as ethane or propane, as feedstock for CO 2 reduction. In addition to reforming, these light alkanes contain the C C bond that can be advantageously utilized to build olefins. 6 Thus, the reduction of CO 2 via light alkanes offers two distinct reaction pathways: dry reforming and oxidative dehydrogenation. Specifically, it is of interest to explore the use of propane due to its increasing abundance, competitive pricing, and the demand for propylene, which is one of the most diverse petrochemical building blocks used in the production of various chemicals such as fibers and textiles for a variety of applications.Currently, propylene is primarily coproduced by...

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Section: Resultssupporting

confidence: 61%

Section: Methodsmentioning

confidence: 52%

Section: Methodsmentioning

confidence: 99%

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The effects of bimetallic interactions for CO₂‐assisted oxidative dehydrogenation and dry reforming of propane

2019

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“…The implementation of CO 2 reduction always requires sufficient energy inputs and appropriate catalysts. Depending on the form of energy inputs (heat, electricity, radiation), CO 2 reduction is generally divided into thermo‐, electro‐, and photocatalytic reactions . The energy cost is relatively high and the product selectivity is uncontrollable in the thermocatalytic reduction of CO 2 , whereas the conversion is low in both electro‐ or photocatalytic CO 2 reduction .…”

Section: Introductionmentioning

confidence: 99%

Coupling of Solar Energy and Thermal Energy for Carbon Dioxide Reduction: Status and Prospects

2020

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Enormous efforts have been devoted to the reduction of carbon dioxide (CO2) by utilizing various driving forces, such as heat, electricity, and radiation. However, the efficient reduction of CO2 is still challenging because of sluggish kinetics. Recent pioneering studies from several groups, including us, have demonstrated that the coupling of solar energy and thermal energy offers a novel and promising strategy to promote the activity and/or manipulate selectivity in CO2 reduction. Herein, we clarify the definition and principles of coupling solar energy and thermal energy, and comprehensively review the status and prospects of CO2 reduction by coupling solar energy and thermal energy. Catalyst design, reactor configuration, photo‐mediated activity/selectivity, and mechanism studies in photo‐thermo CO2 reduction will be emphasized. The aim of this Review is to promote understanding towards CO2 activation and provide guidelines for the design of new catalysts for the efficient reduction of CO2.

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“…Reaction 1), while pure dehydrogenation leads to H2 as a product (Reaction 3) 7,14,19,21,52 . However, the amount of hydrogen in the reactor effluent is also influenced by the extent of reverse water- In the case where direct dehydrogenation (Reaction 3) is the sole contributor to olefin formation, this ratio is expected to have a value equal to one.…”

Section: Effect Of Support and Active Sites On C2h6 Conversion Pathwaysmentioning

confidence: 99%

CO2 Assisted Ethane Oxidative Dehydrogenation over MoO3 and V2O5 Catalysts Supported on Reducible CeO2-TiO2

Nguyen¹,

Celik²,

Tsilomelekis

2020

Preprint

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Supported MOx (M= Mo, V) on mixed CeO2-TiO2 were investigated for the oxidative dehydrogenation of ethane (ODHE) using CO2 as a mild oxidant. Raman spectroscopic characterization of the synthesized catalysts under dehydrated conditions suggest that surface MoOx species prefer to anchor on the crystalline domains of TiO2. Upon increasing the amount of CeO2 in the mixed oxide support, an intense and broad band at ~930cm-1 underscored that the prevalent species tend to be polymeric (MoOx)n domains. On the other hand, in the case of VOx catalysts, a gradual shift in the symmetric stretching of the vanadyl (V=O) Raman band with increasing CeO2 content was observed that points at the gradual anchoring of the surface vanadia species on both TiO2 and CeO2 thus highlighting the possible existence of the amorphous VOx to be located at the interface of the two mixed oxides. The catalytic behavior of Mo and V were distinct. As the ceria content in the support increased, MoOx catalysts promoted the ODHE via Mars van Krevelen mechanism while VOx catalysts appeared to favor ethane direct dehydrogenation. Investigation of structure-function relationships via in-situ Raman spectroscopic efforts revealed that adding ceria not only changed the redox properties of the support but also improved those of the deposited metal oxide. We also show that upon incorporation of ceria into the support, CO2 directly participates in the reoxidation of the dispersed MoOx species during catalysis. This effect was distinct from the reaction of CO2 in the reverse water gas shift reaction. Operando Raman spectra revealed that the presence of CO2 enhances the stability of the bridging Mo–O–Mo bond of polymeric molybdena domains, which is proposed to affect the relative contribution of oxidative versus non-oxidative pathways in ethane dehydrogenation.

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Active sites for tandem reactions of CO ₂ reduction and ethane dehydrogenation

Cited by 121 publications

References 31 publications

The effects of bimetallic interactions for CO₂‐assisted oxidative dehydrogenation and dry reforming of propane

The effects of bimetallic interactions for CO₂‐assisted oxidative dehydrogenation and dry reforming of propane

Coupling of Solar Energy and Thermal Energy for Carbon Dioxide Reduction: Status and Prospects

CO2 Assisted Ethane Oxidative Dehydrogenation over MoO3 and V2O5 Catalysts Supported on Reducible CeO2-TiO2

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Active sites for tandem reactions of CO 2 reduction and ethane dehydrogenation

Cited by 121 publications

References 31 publications

The effects of bimetallic interactions for CO2‐assisted oxidative dehydrogenation and dry reforming of propane

The effects of bimetallic interactions for CO2‐assisted oxidative dehydrogenation and dry reforming of propane

Coupling of Solar Energy and Thermal Energy for Carbon Dioxide Reduction: Status and Prospects

CO2 Assisted Ethane Oxidative Dehydrogenation over MoO3 and V2O5 Catalysts Supported on Reducible CeO2-TiO2

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Product

Resources

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Active sites for tandem reactions of CO ₂ reduction and ethane dehydrogenation

The effects of bimetallic interactions for CO₂‐assisted oxidative dehydrogenation and dry reforming of propane

The effects of bimetallic interactions for CO₂‐assisted oxidative dehydrogenation and dry reforming of propane