CO2 reduction by group 6 transition metal suboxide cluster anions

The Journal of Chemical Physics
Ekram HossainCaroline Chick Jarrold

Abstract

Reactions between small group 6 transition metal suboxide clusters, M(x)O(y)(-) (M = (98)Mo or (186)W; x = 1-4; y < or = 3x) and both CO(2) and CO were studied in gas phase using mass spectrometric analysis of high-pressure, fast flow reaction products. Both Mo(2)O(y)(-) and W(2)O(y)(-) show evidence of sequential oxidation by CO(2) of the form, M(2)O(y)(-)+CO(2)-->M(2)O(y+1)(-)+CO for the more reduced species. Similar evidence is observed for the trimetallic clusters, although Mo(3)O(6)(-) appears uniquely unreactive. Lower mass resolution in the M(4)O(y)(-) range precludes definitive product mass assignments, but intensity patterns suggest the continued trend of sequential oxidation of the more reduced end of the M(4)O(y)(-) oxide series. Based on thermodynamic arguments, cluster oxidation by CO(2) is possible if D(0)(O-Mo(x)O(y)(-)) > 5.45 eV. Although simple bond energy analysis suggests that tungsten oxides may be more reactive toward CO(2) compared to molybdenum oxides, this is not born out experimentally, suggesting that the activation barrier for the reduction of CO(2) by tungsten suboxide clusters is very high compared to analogous molybdenum suboxide clusters. In reactions with CO, suboxides of both metal-based oxides...Continue Reading

References

Oct 18, 2006·Physical Chemistry Chemical Physics : PCCP·S Funk, U Burghaus
Jun 15, 2007·The Journal of Chemical Physics·Richard B WyrwasCaroline Chick Jarrold
Apr 29, 2008·Journal of the American Chemical Society·Emily E BartonAndrew B Bocarsly
Oct 16, 2008·The Journal of Physical Chemistry. a·Grant E JohnsonA W Castleman
Dec 18, 2008·Chemical Society Reviews·Eric E BensonJonathan M Smieja
Feb 19, 2009·The Journal of Chemical Physics·Ekram Hossain, Caroline Chick Jarrold
Apr 2, 2009·The Journal of Chemical Physics·David W RothgebKrishnan Raghavachari
Oct 17, 2009·The Journal of Chemical Physics·Nicholas J MayhallKrishnan Raghavachari
Nov 4, 2009·Chemical Communications : Chem Comm·Nathaniel K SzymczakJonas C Peters
Feb 16, 2010·The Journal of Chemical Physics·David W RothgebCaroline Chick Jarrold

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Citations

Sep 22, 2011·The Journal of Chemical Physics·David W RothgebCaroline Chick Jarrold
Feb 16, 2016·The Journal of Physical Chemistry. a·Manisha RayCaroline Chick Jarrold
Apr 14, 2017·Journal of the American Chemical Society·Shaodong ZhouHelmut Schwarz
Jun 28, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Yan-Xia ZhaoSheng-Gui He
Sep 12, 2018·Angewandte Chemie·Qiang ChenSheng-Gui He
Sep 24, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Hai-Yan ZhouJia-Bi Ma
Mar 1, 2018·Annual Review of Physical Chemistry·Leah G DodsonJ Mathias Weber
Nov 9, 2011·The Journal of Physical Chemistry. a·Mingfei ZhouXuming Zheng
Oct 14, 2014·The Journal of Physical Chemistry. a·Jeremy A FeltonCaroline Chick Jarrold
Mar 17, 2012·The Journal of Physical Chemistry. a·Jia ZhuangMingfei Zhou
Jan 16, 2015·The Journal of Physical Chemistry. a·Benjamin J Knurr, J Mathias Weber
Mar 26, 2014·The Journal of Physical Chemistry. a·Sarah E Waller, Caroline C Jarrold

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