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@ARTICLE{Kampmann:877280,
      author       = {Kampmann, Jonathan and Betzler, Sophia and Hajiyani,
                      Hamidreza and Häringer, Sebastian and Beetz, Michael and
                      Harzer, Tristan and Kraus, Jürgen and Lotsch, Bettina V.
                      and Scheu, Christina and Pentcheva, Rossitza and Fattakhova,
                      Dina and Bein, Thomas},
      title        = {{H}ow photocorrosion can trick you: a detailed study on
                      low-bandgap {L}i doped {C}u{O} photocathodes for solar
                      hydrogen production},
      journal      = {Nanoscale},
      volume       = {12},
      number       = {14},
      issn         = {2040-3372},
      address      = {Cambridge},
      publisher    = {RSC Publ.},
      reportid     = {FZJ-2020-02103},
      pages        = {7766 - 7775},
      year         = {2020},
      abstract     = {The efficiency of photoelectrochemical tandem cells is
                      still limited by the availability of stable low band gap
                      electrodes. In this work, we report a photocathode based on
                      lithium doped copper(II) oxide, a black p-type
                      semiconductor. Density functional theory calculations with a
                      Hubbard U term show that low concentrations of Li
                      (Li0.03Cu0.97O) lead to an upward shift of the valence band
                      maximum that crosses the Fermi level and results in a p-type
                      semiconductor. Therefore, Li doping emerged as a suitable
                      approach to manipulate the electronic structure of copper
                      oxide based photocathodes. As this material class suffers
                      from instability in water under operating conditions, the
                      recorded photocurrents are repeatedly misinterpreted as
                      hydrogen evolution evidence. We investigated the
                      photocorrosion behavior of LixCu1−xO cathodes in detail
                      and give the first mechanistic study of the fundamental
                      physical process. The reduced copper oxide species were
                      localized by electron energy loss spectroscopy mapping. Cu2O
                      grows as distinct crystallites on the surface of LixCu1−xO
                      instead of forming a dense layer. Additionally, there is no
                      obvious Cu2O gradient inside the films, as Cu2O seems to
                      form on all LixCu1−xO nanocrystals exposed to water. The
                      application of a thin Ti0.8Nb0.2Ox coating by atomic layer
                      deposition and the deposition of a platinum co-catalyst
                      increased the stability of LixCu1−xO against
                      decomposition. These devices showed a stable hydrogen
                      evolution for 15 minutes.},
      cin          = {IEK-1},
      ddc          = {600},
      cid          = {I:(DE-Juel1)IEK-1-20101013},
      pnm          = {131 - Electrochemical Storage (POF3-131)},
      pid          = {G:(DE-HGF)POF3-131},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {pmid:32215409},
      UT           = {WOS:000529531500029},
      doi          = {10.1039/C9NR10250G},
      url          = {https://juser.fz-juelich.de/record/877280},
}