TY - JOUR
T1 - Modulating Hole Transport in Multilayered Photocathodes with Derivatized p-Type Nickel Oxide and Molecular Assemblies for Solar-Driven Water Splitting
AU - Shan, Bing
AU - Sherman, Benjamin D.
AU - Klug, Christina M.
AU - Nayak, Animesh
AU - Marquard, Seth L.
AU - Liu, Qing
AU - Bullock, R. Morris
AU - Meyer, Thomas J.
N1 - Funding Information:
The research on the photoelectrodes (at UNC Chapel Hill) was supported as part of the UNC EFRC: Center for Solar Fuels, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001011. Synthesis of the catalyst (at PNNL) was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. The scanning electron microscopy experiment was performed at the Chapel Hill Analytical and Nanofabrication Laboratory, CHANL, a member of the North Carolina Research Triangle Nanotechnology Network, RTNN, supported by the National Science Foundation, Grant ECCS-1542015, as part of the National Nanotechnology Coordinated Infrastructure, NNCI.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/9/21
Y1 - 2017/9/21
N2 - For solar water splitting, dye-sensitized NiO photocathodes have been a primary target. Despite marginal improvement in performance, limitations remain arising from the intrinsic disadvantages of NiO and insufficient catalysis. We report here a new approach to modifying NiO photocathodes with doped NiO bilayers and an additional layer of macro-mesoporous ITO. The trilayered electrode is functionalized with a surface-attached ruthenium polypyridyl dye and a covalently bridged nickel-based hydrogen evolution catalyst. The NiO film, containing a 2% K+-doped NiO inner layer and a 2% Cu2+-doped NiO outer layer, provides sufficient driving force for hole transport following hole injection by the molecular assembly. Upon light irradiation, the resulting photocathode generates hydrogen from water sustainably with enhanced photocurrents and a Faradaic efficiency of ∼90%. This approach highlights the value of modifying both the internal and surface structure of NiO and provides insights into a new generation of dye-sensitized photocathodes for solar-driven water splitting cells.
AB - For solar water splitting, dye-sensitized NiO photocathodes have been a primary target. Despite marginal improvement in performance, limitations remain arising from the intrinsic disadvantages of NiO and insufficient catalysis. We report here a new approach to modifying NiO photocathodes with doped NiO bilayers and an additional layer of macro-mesoporous ITO. The trilayered electrode is functionalized with a surface-attached ruthenium polypyridyl dye and a covalently bridged nickel-based hydrogen evolution catalyst. The NiO film, containing a 2% K+-doped NiO inner layer and a 2% Cu2+-doped NiO outer layer, provides sufficient driving force for hole transport following hole injection by the molecular assembly. Upon light irradiation, the resulting photocathode generates hydrogen from water sustainably with enhanced photocurrents and a Faradaic efficiency of ∼90%. This approach highlights the value of modifying both the internal and surface structure of NiO and provides insights into a new generation of dye-sensitized photocathodes for solar-driven water splitting cells.
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U2 - 10.1021/acs.jpclett.7b01911
DO - 10.1021/acs.jpclett.7b01911
M3 - Article
C2 - 28853290
AN - SCOPUS:85029744514
VL - 8
SP - 4374
EP - 4379
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 18
ER -