Gas‐Phase Dehydrogenation of Alkanes: C−H Activation by a Graphene‐Supported Nickel Single‐Atom Catalyst Model

2019 ◽  
Vol 58 (42) ◽  
pp. 14906-14910 ◽  
Author(s):  
Michael Borrome ◽  
Scott Gronert
Keyword(s):  
2019 ◽  
Vol 21 (13) ◽  
pp. 7147-7154
Author(s):  
Yang Wang ◽  
Shiwei Cao ◽  
Jicai Zhang ◽  
Fangli Fan ◽  
Jie Yang ◽  
...  

Two experiments prove Re pentacarbonyl could exist stably in the gas phase at the single-atom level.


1997 ◽  
Vol 161 ◽  
pp. 89-96 ◽  
Author(s):  
Steven B. Charnley

AbstractA theory for the origin of all organic molecules observed in regions of massive and low-mass star formation, as well as in dark molecular clouds is described. On dust grains, single atom addition reactions and stability of the intermediate radicals, mechanisms similar to those believed to form the organic component of the Murchison meteorite, lead to a very limited number of mantle compositions depending upon the degree of hydrogenation. The key step in the theory is the formation of the formyl radical by H atom addition (by quantum tunnelling) to CO. Subsequent H atom additions lead to formaldehyde and methanol, as previously suggested; C, N, and O atoms can also undergo additions to HCO. For increasing hydrogenation, the mantle types include one in which there is little contribution from formyl-initiated chemistry; one in which an acetylenic chain develops through C atom additions; and others where the acetylenic chain is increasingly hydrogenated to form aldehydes and alcohols. Following evaporation of grain mantles, such as occurs in protostellar «hot cores», these molecules can form new organics, for example, by alkyl cation transfer from alcohols. In dark clouds, different mantles lead to different gas phase organics. This scenario accounts naturally for the formation of many interstellar organics for which none presently exists, predicts observable correlations between specific interstellar molecules, indicates the presence of many new organic molecules and why several others are not observed.


2017 ◽  
Vol 7 (19) ◽  
pp. 4302-4314 ◽  
Author(s):  
Helmut Schwarz

Genuine, single-atom catalysis can be realized in the gas phase and probed by mass spectrometry combined with computational chemistry.


2019 ◽  
Author(s):  
Jingkun Li ◽  
Li Jiao ◽  
Evan Wegener ◽  
Lynne K. LaRochelle Richard ◽  
Ershuai Liu ◽  
...  

<div> <div> <div> <p>Pyrolysis is indispensable for synthesizing highly active Fe-N-C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap ob- scures the connections between the input precursors and output products, clouding the pathway toward Fe-N-C catalyst improve- ment. Herein, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single atom Fe1(II)- N4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C, and then to tetrahedral Fe1(II)-O4 via a crystal-to-melt-like transformation below 600 °C. The Fe1(II)-O4 releases a single Fe atom that flows into the N-doped carbon defect forming Fe1(II)-N4 above 600 °C. This vapor phase single Fe atom transport mechanism is verified by synthesizing Fe1(II)-N4 sites via “non-contact pyrolysis” wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis. </p> </div> </div> </div>


2019 ◽  
Author(s):  
Jingkun Li ◽  
Li Jiao ◽  
Evan Wegener ◽  
Lynne K. LaRochelle Richard ◽  
Ershuai Liu ◽  
...  

<div> <div> <div> <p>Pyrolysis is indispensable for synthesizing highly active Fe-N-C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap ob- scures the connections between the input precursors and output products, clouding the pathway toward Fe-N-C catalyst improve- ment. Herein, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single atom Fe1(II)- N4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C, and then to tetrahedral Fe1(II)-O4 via a crystal-to-melt-like transformation below 600 °C. The Fe1(II)-O4 releases a single Fe atom that flows into the N-doped carbon defect forming Fe1(II)-N4 above 600 °C. This vapor phase single Fe atom transport mechanism is verified by synthesizing Fe1(II)-N4 sites via “non-contact pyrolysis” wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis. </p> </div> </div> </div>


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Michael Götz ◽  
Stefan Götz ◽  
Jens-Volker Kratz ◽  
Jochen Ballof ◽  
Christoph E. Düllmann ◽  
...  

Abstract The formation of carbonyl complexes using atom-at-a-time quantities of short-lived transition metals from fusion and fission reactions was reported in 2012. Numerous studies focussing on this chemical system, which is also applicable for the superheavy elements followed. We report on a novel two-chamber approach for the synthesis of such complexes that allows spatial decoupling of thermalization and gas-phase carbonyl complex synthesis. Neutron induced fission on 235U and spontaneous fission of 248Cm were employed for the production of the fission products. These were stopped inside a gas volume behind the target and flushed with an inert-gas flow into a second chamber. This was flushed with carbon monoxide to allow the gas-phase synthesis of carbonyl complexes. Parameter studies of the transfer from the first into the second chamber as well as on the carbonyl complex formation and transport processes have been performed. High overall efficiencies of more than 50% were reached rendering this approach interesting for studies of superheavy elements. Our results show that carbonyl complex formation of thermalized fission products is a single-atom reaction, and not a hot-atom reaction.


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