Journal of Photochemistry and Photobiology A: Chemistry 281 (2014) 3539

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Journal of Photochemistry and Photobiology A:
Chemistry
j our nal homepage: www. el sevi er . com/ l ocat e/ j phot ochem
Hydrogen photoproduction from bio-derived alcohols in an optical
ber honeycomb reactor loaded with Au/TiO
2
Elena Taboada
a
, Inma Angurell
b
, Jordi Llorca
a,
a
Institut de Tcniques Energtiques and Centre for Research in NanoEngineering, Universitat Politcnica de Catalunya, Av. Diagonal 647, Ed. ETSEIB, 08028
Barcelona, Spain
b
Departament de Qumica Inorgnica, Universitat de Barcelona, Mart i Franqus 1, 08028 Barcelona, Spain
a r t i c l e i n f o
Article history:
Received 26 December 2013
Received in revised form22 February 2014
Accepted 1 March 2014
Available online 12 March 2014
Keywords:
Bio-ethanol
Bio-glycerol
Titania
Gold
a b s t r a c t
Cordierite honeycombs loaded with 1wt.% Au/TiO
2
have been used in an optical ber photoreactor
illuminated with UV LEDs to produce hydrogen at 298 K from aqueous methanol, ethanol, glycerol,
bio-ethanol, and bio-glycerol in liquid phase. The amount of alcohol has been varied between 1% and
100%. Under the same photoreaction conditions, the amount of hydrogen produced follows the trend:
methanol ethanol glycerol > bio-ethanol bio-glycerol. Hydrogen photogeneration is signicantly
enhanced (45-fold increase) in the optical ber honeycomb photoreactor with respect to a conventional
slurry photoreactor.
2014 Elsevier B.V. All rights reserved.
1. Introduction
In the viewpoint of hydrogen production, alcohols represent
an emerging source since they can be produced renewably from
biomass [1,2]. Among them, bio-ethanol constitutes an important
source that seems to be particularly suitable due to its easy and
broadly implemented production from a variety of plants. Also,
bio-glycerol is the main byproduct of biodiesel obtained via trans-
esterication of vegetable oils. Biodiesel production, as a surrogate
of fossil diesel, could be more economical viable using glycerol
as a value added product. Thus, it could be directly used for pro-
ducing hydrogen. Alcohol catalytic reforming processes aimed to
the production of hydrogen have been widely reported in the lit-
erature [3,4]. More recently, alcohols and renewable bio-alcohols
have been used in photochemical processes [510]. Although
the hydrogen yields reported in catalytic reforming are higher
than those obtained by photocatalytic routes, the later is receiv-
ing particular attention because is based on the Sun, which is
a perpetual source of energy, and it is an environmentally safe
technology operating at ambient conditions without undesirable
byproducts.
Photocatalytic processes are based on electronhole pairs that
are generated in semiconductors upon bandgap excitation by light.
Depending on the excitation lifetime relative to that of charge

Corresponding author. Tel.: +34 93 401 17 08; fax: +34 93 401 71 49.
E-mail address: jordi.llorca@upc.edu (J. Llorca).
recombinationanet fractionof photocharges arepresent, whichare
trapped at defect sites or migrate toward the photocatalyst surface.
These surface electrons and holes can reduce and oxidize sur-
face adsorbed molecules, respectively. TiO
2
-based photocatalysts
are among the most attractive due to their availability, corrosion
resistance, non-toxicity, low price and high photoactivity and sta-
bility. Incorporating organics such as alcohols as sacricial electron
donors into the photocatalytic process increase charge-separation
efciency and give higher H
2
generation rates [610]. The rate of
hydrogen evolution is much higher, compared to that obtained in
the absence of organics in the irradiated photocatalyst, due to the
irreversible oxidationof the organic molecule withphotogenerated
holes and the concomitant suppression of electronhole recombi-
nation and H
2
O
2
back reaction, which are the most important
processes for decreasing the light-to-hydrogen conversion ef-
ciency. The effect of the addition of noble metal nanoparticles
(cocatalyst) to TiO
2
is well known as it considerably increases the
hydrogen production rate [5]. Deposition of Au nanoparticles onto
TiO
2
has beenfoundtoenhancehydrogenproductionbyfacilitating
electron transfer and therefore inhibiting electronhole recombi-
nation as well as by reducing the overpotentials for H
2
generation
[710].
It is important to recall that, whereas photocatalyst develop-
ment constitutes an active area of research, if photons are not
effectively transmitted to the photocatalyst then its full potential
will not be reached and system efciency will be lowered [11].
Slurry photoreactors, which are the most used in photocatalysis
research in liquid phase, facilitate mass transfer, but they are
http://dx.doi.org/10.1016/j.jphotochem.2014.03.004
1010-6030/ 2014 Elsevier B.V. All rights reserved.
36 E. Taboada et al. / Journal of Photochemistry and Photobiology A: Chemistry 281 (2014) 3539
limited by poor light penetration in the suspension. In many pho-
toreactor designs (slurry reactors, annular reactors, spinning disk
reactors, optical tube reactors and immersion reactors) the light
has to travel throughthe uidcontaining reagents andalso through
a transparent wall. In addition, it is very difcult to achieve uniform
irradiance on the entire catalyst surface, which is critical because a
minimumenergylevel is neededtoactivatethephotocatalyst. Once
the photocatalyst is activated, maximized contact between the
photocatalyst and reagents should be achieved, as well as removal
of the reaction products formed. An ideally intensied photoreac-
tor should thus be able to integrate both maximized light efciency
and mass transfer simultaneously. We have recently reported pho-
tocatalytic generation of hydrogen from gaseous waterethanol
mixtures in an optical ber honeycomb reactor, where Au/TiO
2
photocatalysts were immobilized on the monolith walls [12].
With this conguration, high light efciency and availability
combined with optimummass transfer and scale-up potential was
achieved.
In this work, we extend our work on photocatalytic produc-
tion of hydrogen in optical ber honeycomb reactors by studying
their performance inliquid phase witha variety of bio-related alco-
hols. Different mixtures of water and alcohol (methanol, ethanol,
glycerol, bio-ethanol and bio-glycerol) have been tested over
1wt.% Au/TiO
2
. We have used dendrimer-protected pre-formed
Au nanoparticles to ensure a constant Au nanoparticle size and to
prevent Au agglomeration [13,14].
2. Experimental
2.1. Photocatalyst preparation
Cordierite (Al
4
Mg
2
Si
5
O
18
) honeycombs (Rauschert, 100 cells
per square inch, pore volume 21030mm
3
g
1
, average pore
diameter 31.5m) measuring 16mm in diameter and 20mm
length were used. They contained exactly 21 square channels with
2.1mm channel width. The preparation of the Au/TiO
2
photocat-
alytic monoliths involved two steps. First, the honeycombs were
coated with a pure TiO
2
layer by soaking theminto pure titanium
isopropoxide, Ti(OCH(CH
3
)
2
)
4
, driedunder continuous rotationand
calcined at 723K for 4h (10Kmin
1
). Titania mass was monitored
by weight gain and was 305mg, which corresponds to a catalyst
loading of about 0.7mg cm
2
.
Gold nanoparticles were loaded onto the TiO
2
layer by incipient
wetness impregnation from a toluene solution containing pre-
formed Au nanoparticles measuring ca. 2.5nm and capped with
thiol-derived carboxilane dendrons HS(CH
2
)
3
Si((CH
2
)
3
Si(CH
3
)
3
)
3
,
which were prepared as reported previously [13]. The Au load-
ing was 1wt.% with respect to TiO
2
. Honeycombs were nally
calcined at 673K for 2h (2Kmin
1
) to eliminate the carboxi-
lane dendron shell and to assure a tight contact between the
Au nanoparticles and the TiO
2
support. This temperature was
selected following a detailed in situ XPS and HRTEM study
reported in [15]. After calcination the monoliths exhibited
the characteristic purple color of Au/TiO
2
containing small Au
nanoparticles.
2.2. Photocatalyst characterization
Surface area measurements (BET) of the TiO
2
powders were car-
ried out with a Micromeritics ASAP 2000 apparatus after degassing
at 443K. The photocatalytic Au/TiO
2
cordierite honeycombs were
characterized by X-ray diffraction (XRD), high resolution trans-
mission electron microscopy (HRTEM), UV-vis spectroscopy, and
X-ray photoelectron spectroscopy (XPS). XRD patterns were col-
lected between 10

and 90

of 2 with a step width of 0.02

and
Fig. 1. Scheme of the photoreactor used in this work.
a step time of 1s using a Bruker D8 instrument equipped with Cu
K incident radiation and a graphite monochromator. HRTEMwas
carried out with a JEOL J2010F electron microscope equipped with
a eld emission gun operating at an accelerating voltage of 200kV.
Samples were dispersed in alcohol in an ultrasonic bath and a drop
of supernatant suspension was poured onto a holey carbon coated
grid. UVvis reectance spectra were collected with a Shimadzu
UV3600 UV-Vis-NIR spectrometer equipped with an integrating
sphere. XPS was performed on a SPECS systemequipped with an Al
anode XR50 source operating at 150mWand a Phoibos 150 MCD-9
detector. The pass energy of the hemispherical analyzer was set at
25eVandthe energystepwas set at 0.1eV. Charge stabilizationwas
achieved by using a SPECS Flood Gun FG 15/40. The binding energy
(BE) values were referred to the C 1s peak at 284.8eV. Stability of
the optical bers was checked before and after the photocatalytic
tests by scanning electron microscopy (SEM) with a Zeiss NEON40
crossbeaminstrument operating at 5kV.
2.3. Photoreaction experiments
The optical ber catalytic wall reactor used in this work was
described in detail in [12]. The light source consisted on four high
efciency UV LEDs emitting at a wavelength of 3655nm (12W,
0.7A) coupled to a bunch of optical bers (Fig. 1). The optical
bers measured 0.8mm in diameter and were made of PMMA
(poly(methyl methacrylate)). The bers were originally coated to
avoid light losses, so they were treated individually to obtain lat-
eral irradiation exactly where the monoliths were placed. To attain
uniformillumination, the end of the optical bers was capped with
a zinc-based paint to attain back-reection of light. The photore-
actor casing was made of glass and consisted of two pieces sealed
by an O-ring that allowed an easy exchange of the photocatalytic
monoliths. The nominal distance between the surface of the ber
and the honeycomb walls was 0.90.2mm.
Photoreactions were carried out in liquid phase at 298K in
batch mode (20mL). In a typical experiment, the optical bers
were rst inserted into the channels of the photocatalytic monolith
inside the photoreactor. Then, the photoreactor was loaded with
the wateralcohol mixture and the system was purged with Ar
until no air was detected and the experiment started. Agitation was
E. Taboada et al. / Journal of Photochemistry and Photobiology A: Chemistry 281 (2014) 3539 37
providedby bubbling Ar throughthe liquidinside the photoreactor,
which also served as sweep gas. Several alcoholwater mixtures
were tested (100%, 80%, 50%, 30%, 10%, and 1% alcohol on a molar
basis). The alcohols used were methanol (Panreac 99.9%), ethanol
(Panreac 99.9%), glycerol (Panreac 99.5%), bio-ethanol (Deulep
96%), and bio-glycerol (fromsunower, 94%). Slurry reactor opera-
tionwas carriedout strictly under the same conditions by replacing
the photocatalytic monolith with photocatalyst powder. The pho-
toreactor efuent was monitored on-line every 1.5min by gas
chromatography (Agilent 3000 AMicroGC) using MS 5

A, Plot Uand
Stabilwax columns. Light irradiation was measured directly with a
UV-A radiation monitor fromSolar Light Co. before and after each
photocatalytic test. Blank experiments were carried out with the
cordierite monolith support and no photoactivity was measured.
3. Results and discussion
3.1. Photocatalyst characterization
The BET surface area of the TiO
2
support was 416m
2
g
1
. XRD
proles showed the presence of both anatase and rutile with a ratio
of anatase:rutile 93:7, as determined according to the method
described in [16]. The microstructure of the Au/TiO
2
photocatalyst
was studiedbyHRTEMandHAADF. Thephotocatalysts wereconsti-
tuted by anatase and rutile crystallites of about 2050nm and Au
nanoparticles measuring 3.80.5nm in diameter (Fig. 2a and b).
This is slightly larger than the size of Au nanoparticles capped with
carboxilane dendrons in the precursor solution (Fig. 2c) as a result
of the calcination treatment, in accordance to [15]. The homogene-
ity in size and good dispersion of the Au nanoparticles merits to
be highlighted, which are a direct consequence of the preparation
method employed. UVvis reectance spectra showed a localized
surface plasmon resonance (LSPR) of Au nanoparticles supported
on TiO
2
at about 567nm (Fig. 2d), which is fairly similar to values
reported in the literature for Au nanoparticles measuring 35nm
supported on anatase [9]. The Au 4f core-level spectra showed
photoemitted electrons with binding energies at 83.783.9eV (Au
4f
7/2
) and 87.287.4eV (Au 4f
5/2
) eV, indicating that metallic Au
was the only gold species on the near surface region of the photo-
catalysts.
3.2. Photocatalytic tests
Fig. 3 shows the results of a typical experiment over a photocat-
alytic 1wt.% Au/TiO
2
honeycomb. In this case, the alcoholwater
mixture employed was EtOH:H
2
O=1:1 (molar basis). After purging
the system, light was turned on and, immediately, the photopro-
duction of H
2
started and shortly after steady state was reached.
By using a sweep ow gas (Ar) of 10mL min
1
the concentration
of H
2
was about 0.05% and the rate of photoproduced hydrogen
11.8mol H
2
min
1
g
1
. When the sweep gas ow was doubled
(20mL min
1
) the concentration of hydrogen halved, but the
rate of photoproduction of hydrogen was maintained. There-
fore, the sweep gas ow had an effect on the concentration of
hydrogen at the photoreactor outlet but no effect on the rate of
photoproduction of hydrogen (no diffusion limitations). Fromnow
onwards, only the photoproduction rates will be then considered,
which are independent of the sweep gas ow used. At the end
of the experiment the light was turned off and the production of
hydrogen stopped. However, the other products of the photore-
action (mostly acetaldehyde) remained in the outlet streamof the
photoreactor since they were dissolved in the liquid medium. For
that reason, no mass balance calculations were possible since the
product distribution between the liquid and gas phases varied. A
blank experiment with a honeycomb loaded only with TiO
2
did not
Fig. 2. (a) Bright eld TEM and (b) HAADF images of the Au/TiO
2
photocatalyst
calcined at 673K. (c) HRTEM images of the dendrimer-capped pre-formed Au
nanoparticles. (d) UVvis spectrumof the Au/TiO
2
photocatalyst calcined at 673K.
show appreciable hydrogen photoproduction. Also, the Au/TiO
2
photocatalyst was tested under visible light in order to assess if
the Au Plasmon resonance at about 567nm (Fig. 2d) contributed
into the reaction, but no hydrogen was detected.
Fig. 4 compiles the hydrogen photoproduction rates obtained at
steady state using different alcohols and alcoholwater mixtures.
Fig. 3. Hydrogen evolution over 1wt.% Au/TiO
2
( and ) and TiO
2
() honey-
combs with time on streamfroman ethanol:water =1:1 molar liquid mixture using
different sweep gas ows ( and %H
2
, mol H
2
min
1
g
1
).
38 E. Taboada et al. / Journal of Photochemistry and Photobiology A: Chemistry 281 (2014) 3539
Fig. 4. Hydrogen photoproduction rates over 1wt.% Au/TiO
2
honeycombs with dif-
ferent alcoholwater liquid mixtures.
For each alcoholwater mixture ratio tested, the photoproduction
of hydrogen using pure methanol, ethanol and glycerol was always
higher than that obtained with bio-ethanol and bio-glycerol. The
amount of hydrogen photoproduced was virtually indistinguish-
able when comparing methanol and ethanol, and slightly higher
than that obtained with glycerol. Other authors have reported
[17,18] or theoretically predicted [19] higher hydrogen yields with
glycerol with respect to methanol and ethanol, but in any case
they all give good rates. The photoproduction of H
2
from bio-
ethanol was roughly 25% less than that fromthe pure alcohol. The
lowest hydrogen photoproduced rate was obtained when using
bio-glycerol, whichwas about 60%less thanthat frompureglycerol.
Thelower H
2
photoproductionrates obtainedfromthebio-alcohols
with respect to the pure alcohols can be explained by the pres-
ence of impurities such as aldehydes, organic acids and FAMEs.
The strong adsorption of aldehydes on the surface of titania-based
photocatalysts, for instance, has been shown to compete with
the adsorption of alcohol molecules, lowering the overall hydro-
gen photoproduction rate [12,18]. Concerning the effect of the
alcoholwater mixture composition on the photoproduction rate
of H
2
, although the rate behavior as a function of alcohol concen-
tration is shallow, it is observed that the higher the water content
in the mixture the lower the H
2
photoproduction rate. This has
been already reported in the literature [12] and related to a bene-
cial effect of alcohol concentration on hole scavenging on TiO
2
.
Interestingly, whereas the trend between alcohol concentration
and H
2
photoproduction rate was maintained approximately lin-
ear for the pure alcohols, a different behavior was observed for the
bio-alcohols. In this case, the scavenging effect was progressively
suppressed at high water concentrations (110% alcohol) and the
photoproduction of H
2
decreased markedly. Since CO
2
production
was almost inexistent, photo-induced reforming of alcohols was
ruled out.
Fig. 5 shows the hydrogen photoproduced rates at steady state
obtained fromthe different alcohol:water =1:1 molar mixtures by
using the optical ber honeycomb photoreactor and the slurry
photoreactor conguration with the same amount of 1wt.%
Au/TiO
2
photocatalyst. Clearly, in all cases the photocatalytic per-
formance of the honeycomb photoreactor is much better than
that of the conventional slurry reactor conguration (ca. 45-fold
increase). Taking into account that in both cases the light source
was exactly the same (optical bers), either inside the monolith
channels (catalytic wall photoreactor) or without them (slurry
reactor), the better photocatalytic performance of the optical ber
honeycomb photoreactor is ascribed to a better photon delivery.
Fig. 5. Hydrogen photoproduction rates and AQE values over 1wt.% Au/TiO
2
in a
catalytic wall photoreactor (dark gray) or a slurry reactor (light gray) conguration.
Alcohol:water =1:1.
Both the immobilization of the photocatalyst onto the honeycomb
structure and the insertion of optical bers inside the channels
likely result in enhanced photon delivery to the photocatalyst,
which yields a higher H
2
photoproduction rate with respect to
that obtained in the slurry photoreactor conguration, where pho-
ton delivery is less controlled. Assuming optimal light absorption,
operation in a non-diffusion-limited regime, and that two pho-
tons are required for liberation of one hydrogen molecule, the
apparent quantum efciency (AQE) for hydrogen photogenera-
tion was calculated from the ratio of the double amount of H
2
(r
H
2
) and the overall amount of photons irradiated by the optical
Fig. 6. SEMimages of anoptical ber before (a) andafter (b) the photocatalytic tests.
E. Taboada et al. / Journal of Photochemistry and Photobiology A: Chemistry 281 (2014) 3539 39
bers (N

, 2.4mol photons min

1
) using the equation AQE =
(2r
H
2
/N

) 100 [20,21]. The AQE values corresponding to the opti-

cal ber honeycomb and the slurry photoreactors are included in
Fig. 5.
Light irradiation was measured directly on the optical bers
before and after each photocatalytic test and was maintained
constant within 3% error. All the hydrogen photogeneration rates
were normalized to the initial value N

. However, a progressive
decrease of the overall amount of photons irradiated by the optical
bers was observed over all the different experiments (decrease
of ca. 60%). Fig. 6 shows SEM images of a fresh optical ber and
an optical ber at the end of the experiments. It is evident that
the roughness of the optical ber increased markedly at the
end of the experiments (Fig. 6b), which explains the decrease of
photons irradiated. The deterioration of the optical PMMA bers
was mostly due to the adverse effect of aldehydes, as tested in a
separate experiment. Therefore, chemical-resistant optical bers
(i.e. quartz) would be more adequate for longer durability in the
photoproduction of hydrogen from water-alcohol/bio-alcohol
mixtures.
4. Conclusions
Au/TiO
2
photocatalyst (1wt.% Au, 93% anatase, 7% rutile)
preparedfrompre-formedAunanoparticles was testedfor the pho-
toproduction of hydrogen from various alcohols and bio-alcohols.
The photocatalyst was used in powdered form in a slurry reactor,
or was deposited onto catalytic walls (cordierite honeycomb) in an
optical ber photoreactor. The hydrogen photoproduction rate was
higher when pure methanol, ethanol and glycerol were used, fol-
lowed by that of bio-ethanol and bio-glycerol, thus suggesting that
impurities that commonly accompany bio-alcohols are adsorbed
onto the photocatalyst surface and compete with alcohol hole
scavenging capacity. Alcoholwater mixtures were also tested and
the hydrogen photoproduction rate progressively decreased with
water content. Aqueous bio-alcohol showed a stronger decline
of hydrogen photoproduction at increasing water content. The
optical ber honeycomb photoreactor showed better performance
(45-fold enhancement of hydrogen photoproduction rates)
than the conventional slurry reactor under the same operational
conditions, allowing a higher degree of process intensication.
Acknowledgements
This work has been funded through grant MINECO ENE2012-
36368. E.T. acknowledges UPC for a postdoc grant. J.L. is grateful to
ICREA Academia program.
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