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Absolute band-edge energies are over-emphasized in the design of photoelectrochemical materials

Journal Article · · Nature Catalysis
 [1];  [2];  [3];  [4];  [5];  [6]
  1. University of Oregon, Eugene, OR (United States)
  2. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  3. University of North Carolina at Chapel Hill, NC (United States)
  4. University of Michigan, Ann Arbor, MI (United States)
  5. University of California, Irvine, CA (United States)
  6. University of Oregon, Eugene, OR (United States); University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations
The absolute band-edge potentials of semiconductors, i.e., the conduction-band minimum, valence-band maximum, and their relative positions to solution redox potentials, are often invoked as design principles for photoelectrochemical (PEC) devices, especially for particulate photocatalysts. Here we show that reliance on these criteria is not necessary and limits the exploration of materials that will advance the fields of photoelectrochemistry, photochemistry, and photocatalysis. We discuss how i) band-edge energies are not singular parameters and instead shift with pH, electrolyte type, and surface chemistry; ii) the free energy of electrons and holes in comparison to that of solution redox couples dictates overall reaction spontaneity and thus reactivity; and iii) favorable charge-transfer kinetics can occur even when the relevant electrolyte redox potential(s) appear ‘outside’ the bandgap, enabled by the inversion or accumulation of electronic charge at the semiconductor surface. As a result, this discussion informs design principles for photocatalyst systems engineering for both one-electron redox reactions as well as for more complex multi-electron transfer reactions (e.g, H2 evolution, H2O oxidation, CO2 reduction).
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of Oregon, Eugene, OR (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; SC0006628; SC0014279; SC0021173; SC0021266; SC0023431
OSTI ID:
2998451
Alternate ID(s):
OSTI ID: 2502066
Journal Information:
Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 6 Vol. 7; ISSN 2520-1158
Publisher:
Springer Science and Business Media LLCCopyright Statement
Country of Publication:
United States
Language:
English

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band-edge
chemical physics
electrocatalysis
electron transfer
photocatalysis
quasi-Fermi levels