ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 9, pp. 1506−1511. © Pleiades Publishing, Ltd., 2016.
The text was submitted by the authors in English.
Recently, hydrogen has been important energy carrier
because of its advantage of clean and high efﬁ ciency. It will
be signiﬁ cant to energy problem that human have to solve
for sustainable development. Hydrogen generation from
water under solar irradiation has received interest [1–3].
The system of homogeneous photocatalysis contains
catalyst, photosensitizer, and sacriﬁ cial electron donor.
In early time, noble metal complexes (such as ruthenium,
platinum, palladium, and rhodium) as catalyst of hydro-
gen production displayed higher activity [4–8], but noble
metal is so expensive that their application is limited.
Therefore, it is necessary to develop less expensive cata-
lysts, such as nickel, iron, and cobalt complexes.
(pyr)Cl (dmgH = dimethylglyoximate
monoanion), one of cobaloxime complexes, representing
a type of noble-metal-free catalyst system, had exhibited
high activity [9–14]. But, the life of cobalt-oxime com-
plexes catalyst was limited and the hydrogen production
ceased after 6 h of irradiation that demonstrated the fact
of catalyst decomposition [15–17]. Nickel pyridinethiolate
complexes as catalysts for the light-driven production of
hydrogen displayed high efﬁ ciency when the system was
coupled with ﬂ uorescein as the photosensitizer and trieth-
ylamine as the sacriﬁ cial electron donor in EtOH/H
In the paper, cobalt pyridinethiolate complexes were
designed in a sample way. The structure of complexes
was characterized by NMR and MS. The effect of reaction
conditions on catalytic performance was studied and the
optimum reaction conditions were selected.
Reagents and instruments. All reactions were
carried out under N
atmosphere with standard Schlenk
techniques. Solvents were dried with 4Å molecular sieves
and distilled prior to be used according to the standard
methods. Pyridine-2-thiol (pySH), 2,2'-bipyridine, cobalt
nitrate hexahydrate, manganese acetate tetrahydrate,
sodium metal, ﬂ uorescein (Fl), and triethylamine (TEA)
were purchased from Aldrich and used without further
(M) was synthesized
according to the literature reported previously .
Synthesis of Co(bpy)(pyS)
(M). The solution
of 2,2'-bipyridine (1.0 g, 6.4 mmol) in 10 mL of
Cobalt Thiolate Complexes Catalyst in
for Photocatalytic Hydrogen
*, Guangyan Li
, Yuan Yang
, Chuang Zhang
, and Xiaoxin Yang
Guangdong Pharmaceutical University, 280 Wai Huan Dong Road, Guangzhou, 510006 P. R. China
Guangdong Cosmetics Engineering & Technology Research Center,
280 Wai Huan Dong Road, Guangzhou 510006 P. R. China
Received May 24, 2016
Abstract—Thiolate complexes Co(bpy)(pyS)
(M) were synthesized, the effect of reaction conditions (such as
pH values, solvents, electron donor, photosensitizers, catalyst, and concentrations) on catalytic performance of
catalyst M was studied and the optimum reaction conditions were selected. The results of catalytic performance
imply that complexes M showed good catalytic activity when concentration of catalyst M was 2.5 μM, concentra-
tion of ﬂ uorescein was 2.0 mM, pH value was 11.6, electron donor was triethylamine (5%), and the solvent was
O (1 : 1 V/V). The catalysis system presented the best performance and hydrogen production reached
369.2 μmol h
after reacting for 15 h; the life of catalyst M was 41 h investigated under the optimum conditions.