skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Trends of Alkane Activation on Doped Cobalt (II, III) Oxide from First Principles

 [1];  [2]; ORCiD logo [1]
  1. Department of Chemistry, University of California, Riverside CA 92521 USA
  2. Department of Chemical and Petroleum Engineering and Department of Chemistry, University of Kansas, Lawrence KS 66045 USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
Grant/Contract Number:
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Related Information: CHORUS Timestamp: 2018-01-12 23:42:37; Journal ID: ISSN 1867-3880
Wiley Blackwell (John Wiley & Sons)
Country of Publication:

Citation Formats

Fung, Victor, Tao, Franklin Feng, and Jiang, De-en. Trends of Alkane Activation on Doped Cobalt (II, III) Oxide from First Principles. Germany: N. p., 2017. Web. doi:10.1002/cctc.201700960.
Fung, Victor, Tao, Franklin Feng, & Jiang, De-en. Trends of Alkane Activation on Doped Cobalt (II, III) Oxide from First Principles. Germany. doi:10.1002/cctc.201700960.
Fung, Victor, Tao, Franklin Feng, and Jiang, De-en. 2017. "Trends of Alkane Activation on Doped Cobalt (II, III) Oxide from First Principles". Germany. doi:10.1002/cctc.201700960.
title = {Trends of Alkane Activation on Doped Cobalt (II, III) Oxide from First Principles},
author = {Fung, Victor and Tao, Franklin Feng and Jiang, De-en},
abstractNote = {},
doi = {10.1002/cctc.201700960},
journal = {ChemCatChem},
number = 1,
volume = 10,
place = {Germany},
year = 2017,
month =

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on November 15, 2018
Publisher's Accepted Manuscript

Save / Share:
  • We report a consistent set of ab initio calculations of the electronic structures and electrical transport properties of p-type thermoelectric compounds RFe{sub 4}Sb{sub 12}, where R is a rattling filler selected from alkali metals (Na, K), alkaline earths (Ca, Sr, Ba), and rare earth metals (La, Ce, Pr, Yb). Different from the single Sb-dominated light band in the valence band edge of CoSb{sub 3}, the heavy bands from Fe d electronic states also fall in the energy range close to the valence band edges in the RFe{sub 4}Sb{sub 12}. These heavy bands dominate the band-edge density of states, pin themore » Fermi levels, and mostly determine the electrical transport properties of those p-type RFe{sub 4}Sb{sub 12}. The Seebeck coefficients can be roughly categorized into three groups based on the charge states of fillers, and the maxima are lower than those of n-type CoSb{sub 3} skutterudites. Effective carrier relaxation time in p-type RFe{sub 4}Sb{sub 12}, obtained from the combinations of calculations and experiments, is remarkably similar among different compounds with values around 7.5 x 10{sup -15} s and weak temperature dependence. The optimal doping levels of those RFe{sub 4}Sb{sub 12} are estimated to be around 0.6-0.8 holes per unit cell at 850 K, which is difficult to achieve in RFe{sub 4}Sb{sub 12} compounds. Prospects for further improving the performance of p-type skutterudites are also discussed.« less
  • We present a comprehensive, Density Functional Theory-based analysis of the direct synthesis of hydrogen peroxide, H2O2, on twelve transition metal surfaces. We determine the full thermodynamics and selected kinetics of the reaction network on these metals, and we analyze these energetics with simple, microkinetically motivated rate theories to assess the activity and selectivity of hydrogen peroxide production on the surfaces of interest. By further exploiting Brønsted-Evans-Polanyi relationships and scaling relationships between the binding energies of different adsorbates, we express the results in the form of a two dimensional contour volcano plot, with the activity and selectivity being determined as functionsmore » of two independent descriptors, the atomic hydrogen and oxygen adsorption free energies. We identify both a region of maximum predicted catalytic activity, which is near Pt and Pd in descriptor space, and a region of selective hydrogen peroxide production, which includes Au. The optimal catalysts represent a compromise between activity and selectivity and are predicted to fall approximately between Au and Pd in descriptor space, providing a compact explanation for the experimentally known performance of Au-Pd alloys for hydrogen peroxide synthesis, and suggesting a target for future computational screening efforts to identify improved direct hydrogen peroxide synthesis catalysts. Related methods of combining activity and selectivity analysis into a single volcano plot may be applicable to, and useful for, other aqueous phase heterogeneous catalytic reactions where selectivity is a key catalytic criterion.« less
  • We show that bulk moduli, determined from first-principles total-energy electronic calculations using the local-spin-density and atomic-sphere approximations in cubic structures, are in remarkable agreement with experiment for all of the nonmagnetic, ferromagnetic, and antiferromagnetic 3[ital d] and 4[ital d] transition and noble metals. Good agreement with experiment is achieved without relativistic corrections which, by themselves, introduce sizable errors in calculated bulk moduli.
  • We have developed a systematic method to investigate the phase stability of M{sub n+1}AX{sub n} phases, here applied for M=Sc, Ti, V, Cr, or Mn, A=Al, and X=C or N. Through a linear optimization procedure including all known competing phases, we identify the set of most competitive phases for n=1-3 in each system. Our calculations completely reproduce experimental occurrences of stable MAX phases. We also identify and suggest an explanation for the trend in stability as the transition metal is changed across the 3d series for both carbon- and nitrogen-based systems. Based on our results, the method can be usedmore » to predict stability of potentially existing undiscovered phases.« less