ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 2, pp. 283−288. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.V. Vasil’ev, A.A. Lobanovskaya, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 2, pp. 281−286.
Production of Hydrogen in a Ternary Photocatalytic
System Based on Water-Soluble
V. V. Vasil’ev and A. A. Lobanovskaya
Herzen State Pedagogical University of Russia, nab. reki Moiki 48, St. Petersburg, 191186 Russia
Received February 26, 2015
Abstract—A new photocatalyst, water-soluble palladium(II) complex with meso-tetrakis(4-N,N,N-trimethyl-
ammoniophenyl)porphyrin, was suggested as a component of a photocatalytic system for water reduction to
hydrogen. In the ternary system palladium(II) porphyrin–methyl viologen–triethanolamine, the metallopor-
phyrin phosphorescence is quenched only by methyl viologen by the mechanism of oxidative electron transfer.
The reduced form of methyl viologen is accumulated in the solution, and hydrogen is evolved in the presence
of colloidal platinum. The highest quantum yield of the formation of the reduced methyl viologen form and
hydrogen in the system reaches 0.4. After 1-h irradiation of the system, 125 mol of hydrogen is evolved per
mole of metalloporphyrin.
Reduction of fossil fuel resources requires search for
alternative energy sources. It is particularly topical to
use the solar radiation energy in photocatalytic processes
for production of molecular hydrogen, a promising
environmentally clean fuel. Resources of water, the main
source of hydrogen, are practically inexhaustible on the
Various classes of photocatalysts that can be used
in systems for hydrogen production from water have
been studied by now. These include semiconductor
materials  and molecular compounds such as organic
dyes, metal polypyridine complxes, porphyrins, and
Deﬁ nite requirements are imposed upon a molecular
photocatalyst: It should efﬁ ciently absorb light in the
visible range, have a long-lived excited state in which it
should be capable of reversible electron transfer, and be
photochemically stable. Water-soluble metalloporphyrins
meet all these requirements. Complexes of water-soluble
porphyrins with zinc and some p metals are the most
studied as photocatalysts [5–8]. However, of particular
interest are metalloporphyrins with the long-lived triplet
state whose lifetime is sufﬁ cient for the participation of
these compounds in bimolecular photochemical redox
processes. Such compounds include complexes of
water-soluble porphyrins with platinum group metals.
For these compounds, the probability of the population
of the lowest triplet excited state is close to unity .
Bimolecular processes of energy transfer from the triplet
excited state of such compounds to molecular oxygen,
leading to the generation of singlet oxygen, were studied
previously [10, 11].
The aim of this study is to develop a model system for
water reduction, acting in accordance with the scheme