Selective Activation of Methane on Single-Atom Catalyst of Rhodium Dispersed on Zirconia for Direct Conversion

Kwon, Yongwoo; Kim, Tae Yong; Kwon, Gihun; Yi, Jongheop; Lee, Hyunjoo

doi:10.1021/jacs.7b11010

Cited by 329 publications

(312 citation statements)

References 48 publications

(63 reference statements)

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“…[7][8][9][10] Fortunately, a mass of recent studies have demonstrated that Fe-N x -based carbon nanomaterials represent one of the most promising alternatives to PGM-based catalysts for ORR because of their extraordinary catalytic performance, together with a relatively cheap price and abundant reserves. [13][14][15][16] Due to the low coordination, maximum atom utilization efficiency, and most exposed active sites, isolated single atom (ISA) catalysts usually exhibit exceptional catalytic performances and thereby have triggered considerable interests. [13][14][15][16] Due to the low coordination, maximum atom utilization efficiency, and most exposed active sites, isolated single atom (ISA) catalysts usually exhibit exceptional catalytic performances and thereby have triggered considerable interests.…”

Section: Introductionmentioning

confidence: 99%

Isolated Fe Single Atomic Sites Anchored on Highly Steady Hollow Graphene Nanospheres as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

et al. 2018

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The rational design of economical and high‐performance nanocatalysts to substitute Pt for the oxygen reduction reaction (ORR) is extremely desirable for the advancement of sustainable energy‐conversion devices. Isolated single atom (ISA) catalysts have sparked tremendous interests in electrocatalysis due to their maximized atom utilization efficiency. Nevertheless, the fabrication of ISA catalysts remains a grand challenge. Here, a template‐assisted approach is demonstrated to synthesize isolated Fe single atomic sites anchoring on graphene hollow nanospheres (denoted as Fe ISAs/GHSs) by using Fe phthalocyanine (FePc) as Fe precursor. The rigid planar macrocycle structure of FePc molecules and the steric‐hindrance effect of graphene nanospheres are responsible for the dispersion of Fe–Nx species at an atomic level. The combination of atomically dispersed Fe active sites and highly steady hollow substrate affords the Fe ISAs/GHSs outstanding ORR performance with enhanced activity, long‐term stability, and better tolerance to methanol, SO2, and NOx in alkaline medium, outperforming the state‐of‐the‐art commercial Pt/C catalyst. This work highlights the great promises of cost‐effective Fe‐based ISA catalysts in electrocatalysis and provides a versatile strategy for the synthesis of other single metal atom catalysts with superior performance for diverse applications.

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Section: Introductionmentioning

confidence: 99%

Isolated Fe Single Atomic Sites Anchored on Highly Steady Hollow Graphene Nanospheres as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

et al. 2018

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“…Interestingly, methanol was the exclusive product on Rh 1 /TiO 2 single atom catalysts, which lacked the acidity of H-ZSM-5. Another synchronous work also found that the reaction of methane to methanol was facile on Rh 1 /ZrO 2 [11]. Thus through modulating the acidity of the support, the desired product of acetic acid or methanol can be tuned.…”

Section: Rh Single Atom Catalyst For Direct Conversion Of Methane To mentioning

confidence: 94%

Rh single atom catalyst for direct conversion of methane to oxygenates

Lin

Wang

2017

Sci. China Mater.

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Along with the fast development of economy and growth of world's population, the demand for energy is significantly enhanced. The conventional petroleum and coal resources are unrenewable and bring about severe pollution to the environment. In the past decade, the technological advances in drilling and exploitation lead to a significant increase in the production capacity of shale gas worldwide. The U.S. Energy Information Administration projects that the annual shale gas output would rise by 104% from 2012 to 2040, which could ignite "shale gas revolution" and change the energy landscape [1]. As we know, the main component in natural and shale gas is methane which contributes to 83%-99%. Consequently, technologies utilizing methane efficiently are more and more recognized and predicted as leading actor in the coming century of natural/shale gas chemical engineering.Up to now, the industrial approach of catalytic valorization of CH 4 mainly comes through the routes of steam reforming to syngas, which can then be converted into methanol and other value added chemicals by Fischer-Tropsch synthesis at a large scale [2]. Comparatively, the direct, one-step transformation of CH 4 to liquid oxygenates, which is more energy-effective and economic for the avoidance of expensive syngas intermediates, has been proven difficult due to low conversion, selectivity and yield of target product. Particularly, the selective oxidation of methane to methanol, which is famous as a "holy grail" reaction in catalysis science, has long time been studied but bloomed again only recently. The scientific challenge lies in the inertness of methane molecules with low electron affinity and high C-H bond energy of 439 kJ mol −1 , causing the cleavage of first C-H bond as the rate-determining step [3]. Various formulations of catalysts have been developed, particularly in mimic enzymatic systems of methane monooxygenases, among which the zeolites containing Cu or Fe species were reported as star catalysts to produce methanol from methane [4]. On these catalysts, the production of methanol originates from multi-steps of methane activation, conversion to methoxyl, then being extracted by H 2 O [5,6]. These processes can lead to satisfactory selectivity of nearly 100%, however, the rate of CH 4 conversion and the yield of methanol are too low due to the stoichiometric production of methoxyl from the activation of methane on Cu or Fe sites in either stepwise or chemical looping modes.The supported noble metal catalysts give another alternative but suffer from no serious consideration previously due to facile deep dissociation of C-H bond and over-oxidation to CO 2 on the metal sites. Nevertheless, the one-step conversion of CH 4 to CH 3 OH or CH 3 COOH was feasible on homogeneous Pt or Pd based catalysts despite of using corrosive oxidants or media [7,8]. Moreover, the theoretical studies found that the metal sites with lower coordination number can stabilize CH 3 species to avoid the successive dehydrogenation of CH 4 [9]. Recently, corresponding ...

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“…Further investigations suggest that a two‐step reaction pathway is responsible for the conversion of methane to oxygenates, in which methane is first activated to produce Rh‐CH 3 , followed by oxygen insertion to produce methanol or CO insertion to produce acetic acid. In another study, Lee and co‐workers introduced a single‐atom Rh catalyst using ZrO 2 as support materials for selective activation of methane . The reaction was performed using H 2 O 2 in the aqueous solution or using O 2 in gas phase as oxidant, producing methanol and ethane, respectively.…”

Section: Catalytic Heterogeneous Reactionsmentioning

confidence: 99%

“…In another study, Lee and co-workers introduced a single-atom Rh catalyst using ZrO 2 as support materials for selective activation of methane. [119] The reaction was performed using H 2 O 2 in the aqueous solution or using O 2 in gas phase as oxidant, producing methanol and ethane, respectively. In addition to acetic acid and methanol, the direct conversion of methane to methyl acetate is also attractive.…”

Section: Methane Conversionmentioning

confidence: 99%

Rh‐Based Nanocatalysts for Heterogeneous Reactions

Luo

Peng

et al. 2018

ChemNanoMat

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Rhodium (Rh) is well‐known for its catalytic application in diverse industrial reactions such as methane conversion, hydrogen generation, and olefin hydroformylation. Compared to homogeneous catalysts, heterogeneous Rh‐based nanocatalysts are facilely separated and collected after reactions, thus being more compatible for industrialization. To this end, the development of active and stable heterogeneous Rh‐based catalysts has received everlasting interest. In this review, we focus on the synthesis and catalytic application of Rh‐based nanocatalysts for heterogeneous catalysis. Recent efforts in the design and fabrication of Rh‐based nanocatalysts are highlighted. Various synthetic strategies and protocols for shape‐controlled synthesis of Rh‐based nanocrystals and supported Rh‐based nanocatalysts are overviewed. In addition, we introduce methane conversion, hydrogen generation, and olefin hydroformylation as three typical catalytic applications of the Rh‐based nanocatalysts, and provide insights into the catalytic mechanisms involved. The remaining challenges and future prospects for the Rh‐based heterogeneous nanocatalysts are also discussed. This review offers a guideline for future research on Rh‐based nanocatalysts for heterogeneous catalysis.

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Selective Activation of Methane on Single-Atom Catalyst of Rhodium Dispersed on Zirconia for Direct Conversion

Cited by 329 publications

References 48 publications

Isolated Fe Single Atomic Sites Anchored on Highly Steady Hollow Graphene Nanospheres as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

Isolated Fe Single Atomic Sites Anchored on Highly Steady Hollow Graphene Nanospheres as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

Rh single atom catalyst for direct conversion of methane to oxygenates

Rh‐Based Nanocatalysts for Heterogeneous Reactions

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