1. Homogeneous Photocatalytic H2 Production Using a RuII
Bathophenanthroline Metal-to-Ligand Charge-Transfer
Photosensitizer
What was the inspiration for this cover design?
Water splitting photocatalysis is a light-driven process aimed at the
formation of hydrogen and oxygen gas from water. Hydrogen is
a high energy feedstock chemical and it is considered an attractive
form of renewables. This cover highlights the major steps involved
in homogeneous hydrogen production from water, important for
revealing mechanistic details ultimately leading to new and im-
proved photocatalytic materials and systems. For the successful
optimization of this reduction half-reaction, water oxidation was re-
placed using a sacrificial electron donation pathway. The process
initiates with the absorption of photons by a ruthenium(II) tris-
bathophenanthroline photosensitizer forming an excited state
which receives an electron from the N,N-dimethyl-p-toluidine
(DMT) electron donor. Subsequently, the reduced photosensitizer
transfers an electron to a molecular cobalt-based water reduction
catalyst. For each molecule of hydrogen evolved, two electrons
and two aqueous protons are required in the process.
What are the most significant results of this study?
We describe in detail a new &composite for&homogeneous hy-
drogen production. A ruthenium(II) tris-bathophenanthroline pho-
tosensitizer was found to impart greater operational stability with
respect to the prototypical ruthenium(II) tris-bipyridine sensitizer.
In addition, the electron donor (DMT) enhanced the longevity of
the system owing to the lack of formation of high-energy radicals
that typically result from the oxidation of related amines used as
sacrificial electron donors. Moreover, the multi-step electron trans-
fer mechanism was probed by transient absorption and photolumi-
nescence spectroscopy to extract critical kinetic rate parameters.
Our findings can lead to further advancements in the field of water
splitting photocatalysis, particular in the associated measurement
science.
What topics are you working on at the moment?
Prof. Khnayzer: Major research includes the photophysics and pho-
tochemistry of transition-metal complexes for utilization in homo-
geneous and heterogeneous solar hydrogen generation, design of
sensors, and photodynamic therapy of cancer.
Prof. Castellano: Current research focuses on metal–organic chro-
mophore photophysics and energy transfer, photochemical upcon-
version phenomena, solar fuels photocatalysis, energy transduction
at semiconductor/molecular interfaces, transient bond forming
photoreactions, and excited state electron transfer processes.
Acknowledgements
R.S.K. acknowledges funds from the School Research and Develop-
ment Council at LAU (SRDC-t2014-02) and the Lebanese National
Council for Scientific Research (Ref: 05-06-14). F.N.C. acknowledges
support from the National Science Foundation (CHE-1465058).
K.A.E. is a Chemistry Graduate Scholars Research Fellow at NC
State.
Invited for this month’s cover are the research groups of Prof. Rony S. Khnayzer at Lebanese American University and Prof.
Felix (Phil) N. Castellano at North Carolina State University. The cover picture illustrates the absorption of visible light by
a ruthenium bathophenanthroline MLCT chromophore followed by a sequence of electron transfer steps that ultimately
leads to the efficient production of hydrogen gas from water. Read the full text of the article at 10.1002/cplu.201600227.
Babatunde S. Olaiya Felix N. Castellano Karim+A. El Roz Rony S. Khnayzer
ChemPlusChem 2016, 81, 1 – 2 2016 Wiley-VCH Verlag GmbH Co. KGaA, Weinheim1
These are not the final page numbers! ÞÞThese are not the final page numbers! ÞÞ
Cover ProfileDOI: 10.1002/cplu.201600424
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2. COVER PROFILE
R. S. Khnayzer,* B. S. Olaiya, K. A. El Roz,
F. N. Castellano*
–
Homogeneous Photocatalytic H2
Production Using a RuII
Bathophenanthroline Metal-to-Ligand
Charge-Transfer Photosensitizer
“…Our findings can lead to further ad-
vancements in the field of water split-
ting photocatalysis, particular in the as-
sociated measurement science….”
Read more about the story behind the
cover in the Cover Profile and about the
research itself (DOI: 10.1002/
cplu.201600227).
Ru bathophenanthroline #photosensitizer to enhance photocatalytic H2 production by Khnayzer (@LebAmU-
niv), Castellano (@NCState) SPACE RESERVED FOR IMAGE AND LINK
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Please check that the ORCID identifiers listed below are correct. We encourage all authors to provide an ORCID identifier
for each coauthor. ORCID is a registry that provides researchers with a unique digital identifier. Some funding agencies
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agency guidelines for details. Registration is easy and free; for further information, see http://orcid.org/.
Prof. Rony S. Khnayzer http://orcid.org/0000-0001-7775-0027
Babatunde S. Olaiya
Karim A. El Roz
Prof. Felix N. Castellano http://orcid.org/0000-0001-7546-8618
ChemPlusChem 2016, 81, 1 – 2 www.chempluschem.org 2016 Wiley-VCH Verlag GmbH Co. KGaA, Weinheim2
ÝÝ These are not the final page numbers!ÝÝ These are not the final page numbers!
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