Research Article
Chemistry—A European Journal doi.org/10.1002/chem.202302284
Initial Quenching Efficiency Determines Light-Driven H2
Evolution of [Mo3S13]2 in Lipid Bilayers
Amir Abbas,[a] Eva Oswald,[b] Jan Romer,[b] Anja Lenzer,[a] Magdalena Heiland,[a]
Carsten Streb,[a, c] Christine Kranz,[b] and Andrea Pannwitz*[a]
Nature uses reactive components embedded in biological
membranes to perform light-driven photosynthesis. Here, a
model artificial photosynthetic system for light-driven hydrogen
(H2) evolution is reported. The system is based on liposomes
where amphiphilic ruthenium trisbipyridine based photosensi-
tizer (RuC9) and the H2 evolution reaction (HER) catalyst
[Mo3S13]2 are embedded in biomimetic phospholipid mem-
branes. When DMPC was used as the main lipid of these light-
active liposomes, increased catalytic activity (TONCAT ~200) was
observed compared to purely aqueous conditions. Although all
tested lipid matrixes, including DMPC, DOPG, DPPC and DOPG
Introduction
The transition to a sustainable energy economy requires the
development of technology to exploit abundant and renewable
resources that can be used to generate green fuels, such as
hydrogen gas (H2).[1] The most promising process – yet still
challenging – for the H2 production is the light-driven splitting
of water by artificial photosynthesis using bioinspired
systems.[1–3] Typically, these systems are composed of three
components: a sacrificial electron donor as reductant, a photo-
sensitizer (PS) and the H2 evolution reaction (HER) catalyst
(CAT).[4] In natural photosynthesis, light-driven catalysis is
carried out in an aqueous environment, where chromophores
and catalytic units operate within biological membranes.
Specifically, transmembrane protein complexes such as light
[a] A. Abbas, A. Lenzer, Dr. M. Heiland, Prof. Dr. C. Streb, Jun.-
Prof. Dr. Dr. A. Pannwitz
Institute of Inorganic Chemistry I
Ulm University
Albert-Einstein-Allee 11, 89081 Ulm (Germany)
E-mail: andrea.pannwitz@uni-ulm.de
[b] E. Oswald, J. Romer, Prof. Dr. C. Kranz
Institute of Analytical and Bioanalytical Chemistry
Ulm University
Albert-Einstein-Allee 11, 89081 Ulm (Germany)
[c] Prof. Dr. C. Streb
Department of Chemistry
Johannes Gutenberg University Mainz
Duesbergweg 10–14, 55128 Mainz (Germany)
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/chem.202302284
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH
GmbH. This is an open access article under the terms of the Creative
Commons Attribution Non-Commercial NoDerivs License, which permits use
and distribution in any medium, provided the original work is properly cited,
the use is non-commercial and no modifications or adaptations are made.
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liposomes provided similar liposomal structures according to
TEM analysis, only DMPC yielded high H2 amounts. In situ
scanning electrochemical microscopy (SECM) measurements
using Pd microsensors revealed an induction period of around
26 minutes prior to H2 evolution, indicating an activation
mechanism which might be induced by the fluid-gel phase
transition of DMPC at room temperature. Stern-Volmer-type
quenching studies revealed that electron transfer dynamics
from the excited state photosensitizer are most efficient in the
DMPC lipid environment giving insight for design of artificial
photosynthetic systems using lipid bilayer membranes.
harvesting complexes (LHCs), photosystem I and II perform solar
energy absorption and conversion as illustrated in Figure 1. The
self-assembled lipid bilayer promote (supra)molecular organiza-
tion and high local concentration of reactive components to
enhance reactivity and suppress side reactions.[5,6] Vesicles with
lipid bilayer membranes and embedded functional molecules
were reported as model systems to perform light absorption
and light-driven reactions such as H2 generation, CO2 reduction
and water oxidation by embedding the active units at the
membrane, and thereby overcome organic solvent usage and
solubility problems.[7–12]
In this work, the light-driven H2 evolution reaction (HER) at
lipid bilayer membranes of liposomes is reported, using the
amphiphilic photosensitizer bis(2,2’-bipyridine)-(4,4’-dinonyl-
2,2’-bipyridine)-ruthenium(II) (RuC9), and the molybdenum
sulfide cluster [Mo3S13]2 as HER catalyst (see Figure 1).
The amphiphilic photosensitizer RuC9 is known to integrate
at the bilayer-water interface of phospholipid membranes due
to hydrophobic interactions between the alkyl tails and the
hydrophobic core of the membrane, and electrostatic inter-
actions of its [Ru(bpy)3]2 + -type headgroup and the lipid
headgroups.[5,13–15] Upon incorporation into the membrane,
RuC9 retains its photosensitizer activity, as exemplified for light-
driven CO2 reduction.[5,14]
Molecular molybdenum sulfides (thiomolybdates), and
specifically [Mo3S13]2 , are known to be highly active HER
catalysts when dissolved in organic solvent,[16–19] while their HER
reactivity is affected in presence of water.[20,21] However, the
performance of [Mo3S13]2 in heterogenous environments for
light-driven H2 evolution showed promising activity when using
soft polymeric materials such as nanoporous polymeric mem-
branes consisting of amphiphilic block copolymers (e. g. P(S-co-
I)-b-PDMAEMA),[22] polyampholytic graft copolymers as matrix
for TiO2/Eosin Y/[Mo3S13]2 -organic-inorganic hybrid
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Research Article
Chemistry—A European Journal doi.org/10.1002/chem.202302284
Figure 1. A) Light-driven reactions in natural photosynthesis take place in
the thylakoid membrane of chloroplasts, where electrons are donated via
the electron transfer chain to photosystem I (PSI) which subsequently
reduces the NADP + reductase for NADH generation. B) H2 evolution in our
biomimetic system, using liposomes as membrane for assembling the
charged photosensitizer (PS2 +) RuC9 and the HER catalyst (CAT2 ) [Mo3S13]2
along with ascorbic acid as sacrificial electron donor, depicting the electron
transfer steps and reaction pathway. Figure A was adapted from “Light
Dependent Reactions of Photosynthesis”, by BioRender.com (2022), retrieved
from https://app.biorender.com/biorender-templates.
Figure 2. Quantification methods used for light-driven HER in this study: A) Bulk liposome samples and sampling of H2 in the gas phase for quantification via
head space gas chromatography. B) SECM setup for in situ electrochemical determination of H2 using a two-compartment electrochemical cell with a track-
etched membrane for separating the liposome containing solution from the electrodes.
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materials,[23] polymeric carbon nitrides,[24] and polymeric
micelles.[25] Electrostatic attraction between the negatively
charged [Mo3S13]2 and positively charged photosensitizer
molecules such as [Ru(bpy)3]2 + was reported to be beneficial for
immobilization into nanoporous polymeric membranes as well
as charge transfer dynamics in the light-driven HER.[22] Building
on these results, we designed a biomimetic liposome-system
with the positively charged and membrane-bound PS2 + RuC9
that can electrostatically attract the negatively charged HER
catalyst [Mo3S13]2 to perform light-driven H2 evolution. To
investigate the role of the lipid environment, we tested several
lipids with different properties. Besides bulk measurements,
scanning electrochemical microscopy (SECM)[26] was used to
study the onset dynamics upon start of light irradiation and
probe the early phase of the H2 evolution catalysis (methods
see Figure 2).
Results and Discussion
Synthesis and liposomes preparation
The synthesis of the photosensitizer, RuC9,[5,14] and the catalyst,
Na2[Mo3S13] x 5H2O,[21,24,27] was performed as described previ-
ously. Light-active active liposomes were prepared using a
100 : 1 molar ratio of a selected main lipid with various transition
temperatures and charges (see Table 1) and the sterically
stabilizing lipid 1,2-dimyristoyl-sn-glycero-3 phosphoethanol-
amine-N-[methoxy(polyethylene glycol)-2000] (14:0 PEG2000
PE). In a typical experiment, RuC9 and Na2[Mo3S13] x 5H2O were
incorporated into the lipid bilayer in 100 : 1 : 5 : 1 molar ratio of
the (main lipid): (14 : 0 PEG2000 PE) : RuC9 : [Mo3S13]2 via a lipid
film rehydration with phosphate buffer (10 mM) and follow-up
extrusion, as described in previous studies and in the Support-
ing Information in Figure S1.[5,28]
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Research Article
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Table 1. Molecular structures, names and transition temperatures (Tm) of main phospholipids and the sterically stabilizing lipid 14:0 PEG2000 PE.[29]
Phospholipid structure Name Tm Charge of
(°C) the head
group

1,2-dimyristoyl-sn-glycero-3-phosphocholine 14 : 0 PC
1 24 Zwitterionic
(DMPC)

1,2-dioleoyl-sn-glycero-3-phospho-(1’-rac-glycerol)
2 18 Negative
18 : 1 (Δ9-Cis) (DOPG)

1,2-dioleoyl-sn-glycero-3-phosphocholine 18 : 1
3 17 Zwitterionic
(Δ9-Cis) PC (DOPC)

1,2-dipalmitoyl-sn-glycero-3-phosphocholine 16 : 0 PC
4 41 Zwitterionic
(DPPC)

1,2-dimyristoyl-sn-glycero-3 phosphoethanolamine-N-
5 [methoxy(polyethylene glycol)-2000] (14 : 0 PEG2000 n.a. Negative
PE)

Structural properties TEM-analysis confirmed size and structure of the functionalized

The liposomes’ size and morphology were characterized by
dynamic light scattering (DLS) and transmission electron micro-
scopy (TEM). DLS yielded typical hydrodynamic diameters (ZAvg)
of 140–155 nm (Figure S2), which was confirmed by TEM
imaging (see Figure 3). TEM analysis of light-active liposomes
was carried out via a negative staining technique, using uranyl
acetate as contrast agent.[30] Figure 3 A–D show TEM images of
light-active liposomes based on DMPC, DPPC, DOPC and DOPG.
These images show mainly wrinkled spherical structures with
diameters below 200 nm. The wrinkled shapes are typically due
to the vacuum-drying of the samples that is required for TEM
analysis.[31] Furthermore, Figure 3 shows some planar structures
that are also generated from the lipid bilayers during the
temperature and pressure changes in the TEM experiment
leading to structural changes within the vesicles.[32] Overall, the
vesicles.
Light-driven HER
Visible light-driven HER activity was explored by combining the
buffered liposome sample with ascorbic acid as sacrificial
electron donor at pH 6, (pH was adjusted by diluted aqueous
NH4OH solution). The pH was chosen based on efficiency of
electron donating properties of ascorbic acid, which is best in
its deprotonated form (ascorbate), as previously demonstrated
in light-driven H2 evolution reactions of the [Mo3S13]2
catalyst.[16,33] Typical light-driven experiments were performed in
8 mL GC vials under argon atmosphere at room temperature in
a modular 3D printed and fully characterized open-source
photoreactor,[21] using a 460 nm LED light source and a sample
holder for up to 10 GC vials to be irradiated simultaneously

Figure 3. TEM images of negatively stained liposome samples with a composition of 100 : 1 : 5 : 1 of main lipid:(14 : 0 PEG2000 PE) : RuC9:[Mo3S13]2 , prepared
with 10 mM phosphate buffer and the main lipid being A) DMPC, B) DPPC, C) DOPC and D) DOPG.

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under identical irradiation conditions (see Figure S3). The
photon flux of the setup was 1001 nmol s 1 at the outer glass
walls of the GC reaction vessels[21] and the reaction mixtures
were stirred during irradiation. Each experiment was carried out
in triplicate and quantification of H2 was performed by gas
chromatography of samples from the respective head spaces
after 2 h, 4 h, 6 h and 24 h of irradiation (see Figure 4A and
Figure S6 for a typical GC data trace). Additionally, a time-
dependent HER activity of the light-active DMPC vesicles were
performed over 1 h with sampling every 5 minutes (Figure 4B).
The performance of the catalyst was quantified via the turnover
number (TONCAT) which is the amount of H2 produced divided
by the amount of catalyst according to the following equation:
n ðH Þ
TONCAT = nð ½Mo2 S213 �2 Þ . The TONCAT values in this study always
refer to the amount of catalyst which was added during sample
preparation. It is assumed that not all catalyst molecules are
taken up in the membrane or may be lost in the filter
membrane during the extrusion of the liposomes. Therefore,
the real TONCAT may be higher than the herein reported TONCAT.
The performance of the photosensitizer was also quantified via
n ðH Þ
its turnover number (TONPS) with TONPS = 2� nð RuC29 Þ . The factor
of two arises from the fact that two consecutive one-electron
donation steps are necessary from the PS to the catalyst. As the
PS is one-electron donor two turnovers of the PS per molecule
of H2 are required.[10] In previously reported studies, it was
found that only 75 % of RuC9 was taken up in DPPC vesicles
under comparable conditions.[14] Based on these data, it can be
estimated that the real TONPS, in all investigated cases, might be
around 30 % higher than we report here, however it should be
noted that we report catalysis not only in DPPC but also in
other lipid environments, where the real uptake might be
different.
It was found that DMPC based liposomes with a composi-
tion of 100 : 1 : 5 : 1 of DMPC:(14 : 0 PEG2000 PE) : RuC9 : [Mo3S13]2
generated H2 with a TONDMPC = 196 � 7 within 24 h. However,
maximum activity was observed during the first 6 hours after
which only minor amounts of H2 were produced additionally
(see Figure 4A). Such behavior is well known for light-driven
catalysis with [Ru(bpy)3]2 + based photosensitizers and is due to
decomposition of the photosensitizer during prolonged
irradiation.[5,34–37] The stability of RuC9 during catalysis was
evaluated via UV-Vis spectroscopy. It was found that the
characteristic absorption band between 450 and 460 nm almost
disappeared after 24 h of irradiation (Figure S8), indicating that
the RuC9 photosensitizer had been degraded over the course of
the light-driven catalysis. H2 production reached a maximum
after around six hours with an average reaction rate of 111
pmol·s 1 which translates to an average turnover frequency of
DTON
the catalyst of TOFCAT = Dt = 28.5 h 1 over these 6 hours. Under
aerated conditions, the HER activity of light-active DMPC
liposomes dropped significantly, and after 24 h of irradiation, a
TONDMPC,air = 21 � 3 was observed, indicating that oxygen
interferes with the productivity of the system. The absence of
phospholipids reduced the TONCAT significantly to TONCAT = 18 �
3, which is in line with previous reports on degradation
hydrolysis[16] of the [Mo3S13]2 as well as deactivating
aggregation[38] of positively charged PS with negatively charged
catalyst in water. On the other hand, electrostatic interactions
at soft interfaces, such as previously reported POMbranes can
promote effective charge transfer between the PS and the
catalyst and therefore H2 evolution.[22] As mentioned above,
DMPC has zwitterionic head groups, in combination with
around 5 % loading of dicationic RuC9, a net-positive surface
charge was expected and confirmed by a zeta potential of
+ 2.3 � 1 mV according to electrophoretic light scattering
measurements. We therefore anticipate that the positive surface
charge electrostatically attracts the negatively charged
[Mo3S13]2 HER catalyst and promotes charge transfer between
the PS and the catalyst, resulting in H2 evolution. The absence
of PS, catalyst, sacrificial electron donor or light resulted in H2
production below the detection limit, even after 24 hours of
irradiation.

Figure 4. Time-dependent HER activity and TONCAT results of the light-active DMPC vesicles and system where phospholipids were absent, with various
reference experiments A) monitored over 24 h and B) data of the first hour. Experimental conditions: liposome sample with a composition of 100 : 1 : 5 : 1 of
DMPC:(14 : 0 PEG2000 PE) : RuC9 : [Mo3S13]2 , with c(DMPC) = 5 mM, c([Mo3S13]2 ) = 50 μM, pH = 6 and control experiments where phospholipids, ruthenium
photosensitizer, HER catalyst, light source or sacrificial electron donor were absent. All values were acquired in Ar atmosphere and in triplicate with error bars
presenting the standard deviation. Note: The data of the control experiments overlap at 0 μmol and TONCAT = 0 respectively.

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Table 2. Light-driven H2 evolution (460 nm LED, head space GC sampling) after 24 h of liposome samples with various CAT:PS ratios and ascorbic acid
concentrations. Experimental conditions: liposome samples in Ar atmosphere with a composition of 100 : 1:Y : X of DMPC:(14 : 0 PEG2000 PE) : RuC9 : [Mo3S13]2 ,
with c(DMPC) = 5 mM at various loadings of RuC9 and [Mo3S13]2 and various concentrations of ascorbic acid, respectively. CCAT and CPS indicate the bulk
concentrations.
Entry Cascorbic acid[mM] CAT:PS ratio CCAT [μM] CPS [μM] H2 (μmol) TONCAT TONPS

1 100 1:5 50 250 2.50 � 0.04 196 � 7 78 � 1

2 100 1 : 10 25 250 1.53 244 49
3 100 1 : 20 12.5 250 1.77 566 57
4 100 1 : 40 6.25 250 1.34 856 43
5 100 1:1 50 50 0.43 34.4 69
6 150 1:5 50 250 2.44 � 0.09 195 � 7 78 � 3
7 70 1:5 50 250 2.22 � 0.15 177 � 12 71 � 5
8 40 1:5 50 250 1.07 � 0.06 92 � 4 36 � 2
9 10 1:5 50 250 0.68 � 0.08 54 � 7 22 � 3

Varying the ratio between catalyst and photosensitizer by
reducing the amount of catalyst and keeping RuC9 loading
constant reduced the overall H2 evolution (see Table 2) but
increased the catalyst performance documented by an increas-
ing TONCAT at lower catalyst loading. We recorded the highest
TONCAT = 856 at a ratio of 1 : 40 CAT : PS. At the same time, the
TONPS is minimum under these conditions with TONPS = 43 (see
Figure 5 and Figure S4 for time traces). The performance of
photosensitizer was better at lower CAT:PS ratio with the best
TONPS = 78 � 1 at 1 : 5 ratio with a liposome composition of
100 : 1 : 5 : 1 of DMPC:(14 : 0 PEG2000 PE) : RuC9:[Mo3S13]2 . It is to
mention the irregular performance at 1 : 10 ratio, slightly differ-
ent from the general linear trend, we recorded for all the other
case studies. We hypothesize that further increasing of CAT:PS
ratios would yield better performance of the photosensitizer,
which is the only component in the system that contains a
precious element. Unfortunately, increasing catalyst loading
was impeded by its precipitation during sample preparation at
higher concentrations. Therefore, we investigated higher
CAT : PS ratios at constant 1 % catalyst loading while reducing
the photosensitizer loading. As a consequence, we could only
detect H2 production at 1 : 1 ratio at our setup and not with
lower loadings. At 1 : 1 ratio, we observed a TONPS = 69 and
TONCAT = 34.4. Comparing these values with the ones at 1 : 5
ratio at higher loading reveals that the system performs better
with higher local concentrations within the membrane.
The effect of ascorbic acid concentration is depicted in
Figure 6 and Figure S5. We observed the best H2 production
between 70 mM and 150 mM. Reducing electron donor concen-
tration below 70 mM reduces the overall H2 evolution in a close
to linear relationship.
To check the role of electron donor lactic acid at pH 6,
triethylamine at pH 8 or triethanolamine at pH 8 were tested.

Figure 6. Effect of different ascorbic acid concentrations on the H2 evolution

Figure 5. Effect of different CAT:PS ratios on the TONs results under
irradiation with 460 nm LED for 24 h for bulk liposome samples. H2
quantification was performed using head-space GC sampling in the gas
phase. Experimental conditions: liposome samples in Ar atmosphere with a
composition of 100 : 1 : 5 : X of DMPC:(14 : 0 PEG2000 PE):RuC9:[Mo3S13]2 , with
c(DMPC) = 5 mM, X = 1, 0.5, 0.25 or 0.125 and c(ascorbic acid) = 100 mM,
pH = 6.
under irradiation with 460 nm LED for 24 h of bulk liposome samples. H2
quantification was performed using head-space GC sampling in the gas
phase. Experimental conditions: Liposome samples in Ar atmosphere with a
composition of 100 : 1 : 5 : 1 of DMPC:(14 : 0 PEG2000 PE) : RuC9 : [Mo3S13]2 ,
with c(DMPC) = 5 mM, c([Mo3S13]2 ) = 50 μM and c(ascorbic acid) = 150, 100,
70, 40 or 10 mM, pH = 6. All values were acquired in triplicate with error bars
presenting the standard deviation.

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The pH was chosen based on the best electron donating

properties of the respective electron donor.[33] However, only
the beforementioned ascorbate electron donor yielded H2
evolution after 24 hours of irradiation (see Figure S7), which
highlights that ascorbic acid is the best suitable electron donor
for H2 evolution with RuC9 and : [Mo3S13]2 under the inves-
tigated conditions in liposomes.
We also performed in situ microelectrochemical studies to
monitor the H2 evolution using SECM in generation/collection
mode.[39] The advantage of in situ SECM measurements com-
pared to head space GC is the possibility to measure
continuously the H2 evolution without requiring a sampling
step. Hence, these in situ SECM experiments on light-active
DMPC liposomes gave insights about the first 60 minutes of
light-driven H2 evolution. The Pd microsensors[26] were posi-
tioned at a distance of approx. 50 μm to the surface of a track-
etched membrane, which separated the lower compartment
containing either the light-active DMPC-based liposomes or the
catalyst [Mo3S13]2 and RuC9 in solution without lipids. (Exper-
imental details, see Supporting Information). A potential of
600 mV vs. quasi Ag/AgCl reference electrode (QRE) was
applied and the current resulting from the palladium-hydride
(Pd H) formation[26] was recorded to determine the dissolved H2
evolution, diffusing from the lower compartment to the upper
compartment, using Faraday’s law (integration of the current
response). Figure 7A shows exemplary current response curves
with and without illumination. A large capacitive current and
associated long decay times are observed, which are related to
the large electroactive area of the Pd-modified, etched Au Figure 7. A) Amperometric i-t curves, recorded via in situ SECM experiments.
Liposome samples with a composition of 100 : 1 : 5 : 1 of DMPC : (14 : 0
microelectrodes. The immediate increase in anodic current at PEG2000 PE) : RuC9 : [Mo3S13]2 , and samples where phospholipids were
the start of the illumination is related to the photocurrent of absent. Illumination was from the bottom of the transparent electrochemical
RuC9.[40] As shown in Figure 7B, a H2 evolution rate of 3.5 � cell using a 400 μm optical fiber connected to a 21.8 mW blue LED
(λ = 470 nm). Vertical dashed lines indicate the start of illumination. B) Bar
0.31 fmol/s (n = 3) was obtained for the light-active active diagram of H2 evolution reaction rate, obtained from in situ SECM irradiation
DMPC liposomes. In contrast, the SECM measurements with experiments of samples with and without phosopholipids during the first 60
[Mo3S13]2 and RuC9 in the absence of phospholipids in the minutes.
lower compartment resulted in 0.08 � 0.02 fmol/s under the
same experimental conditions. These results show that under
the given experimental conditions, significant H2 evolution peroxide (H2O2) measurements at porcine blood cells using a
activity is only achieved with light-active DMPC based vesicles similar set-up with the two-compartment cell, detection of H2O2
and not from the individual molecular components in aqueous started instantly after adding the porcine blood cells to the
solution. Comparing the SECM results with bulk catalysis lower compartment.[42] Therefore, the delay in H2 evolution
(Figure 2A), it has to be considered that this significant lower observed in our system seems to be related either to some
rate observed in SECM is related to the different experimental delay in the photocatalysis or in low rates in the first minutes of
setup. The solution in the lower compartment was not stirred, irradiation so that the sensitivity of the measurements is not
also, the photon flux, respectively the light intensity is different sufficient to detect this initial low concentrations.[26] Hence, for
for the two approaches, clearly affecting the H2 production rate. the SECM measurements, HER catalysis can be observed after
Moreover, as shown in the setup (Figure 2B), only an area of approx. 26 minutes, with an average reaction rate of 3.5 fmol/s.
approx. 0.004 mm2 and a volume of 0.0002 mm3 is probed. Previous studies on light-driven reactions with liposome
Nonetheless, the continuous measurements allowed us to reported strong effects of the surface charge and the diffusion
monitor the H2 evolution over the first 60 minutes of the mobility within the membrane on the photocatalytic
experiment, and interestingly, the onset for both sets of conversion.[8,14,43,44] We therefore screened various lipid composi-
experiments (with and without liposomes) is delayed by ca. 21 tions to find the optimum composition. As mentioned above,
to 35 minutes with an average delay of approx. 26 min from the DMPC has zwitterionic head groups and a transition temper-
start of irradiation (see Figure 7A for example of amperometric ature at around room temperature. Exchanging the main lipid
i-t curves). In contrast, in other in situ SECM H2 measurements to the zwitterionic fluid phase DOPC, zwitterionic gel phase
with heterogenized cobaloxime catalysts, H2 evolution started DPPC, or negatively charged fluid DOPG reduced the H2
directly upon illumination.[41] Also in SECM-based hydrogen evolution (after 24 h irradiation) to TONDOPC = 9 � 3, TONDPPC =

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11 � 4 and TONDOPG = 10 � 3, which is comparable to the results
in absence of any phospholipid (TONCAT = 18 � 3) (Figure 8).
These results are surprising, as in previous reports with similar
amphiphilic ruthenium-based photosensitizers it was shown
that higher mobility within the lipid bilayer membrane are
advantageous for light-driven reduction reactions as this is
advantageous for intermolecular electron transfer dynamics
within the soft matter matrix.[14,43] The opposite effect was
reported for a different type of photosensitizer based on oleic
acid capped quantum dots, where the advantageous effect of a
rigid lipid bilayer is to protect the photosensitizer and yield
more hydrogen evolution.[14,43,44] In our case, no such trend is
observed and the membrane environments with mobile fluid
aggregation state (DOPC, DOPG) perform equally poor as the
membrane with a rigid gel-phased aggregation state (DPPC).
Only the membrane which operates at the transition temper-
ature, DMPC, yields significant hydrogen production.
Figure 8. Effect of the main phospholipid on the TONCAT results under
irradiation with 460 nm LED for 24 h for bulk liposome samples with H2
quantification in the gas phase. Experimental conditions: Liposome samples
in Ar atmosphere with a composition of 100 : 1 : 5 : 1 of main lipid:(14 : 0
PEG2000 PE) : RuC9 : [Mo3S13]2 , with c(main lipid) = 5 mM, c([Mo3S13]2 ) -
= 50 μM, c(ascorbic acid) = 100 mM (pH 6). All values were acquired in
triplicates with error bars presenting the standard deviation.
Figure 9. A) Normalized emission intensity, B) lifetime measurements and C) Stern-Volmer plot as a function of catalyst concentration from DMPC liposome
samples with a composition of 100 : 1 : 5:X of DMPC:(14 : 0 PEG2000 PE) : RuC9 : [Mo3S13]2; c(main lipid) = 5 mM at various loadings of [Mo3S13]2 prepared with
10 mM phosphate buffer in presence of 100 mM ascorbic acid (pH 6) as sacrificial electron donor.
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Excited state electron transfer dynamics
The effect of the lipid bilayer matrix on excited state electron
transfer dynamics was investigated using steady state and time
resolved emission quenching studies. In principle, it is possible
that upon PS excitation, the initial electron transfer takes place
either i) from the sacrificial electron donor to the excited PS
(reductive quenching), or ii) from the excited PS to the catalyst
(oxidative quenching). In a so called Stern-Volmer experiment,
the excited state reaction dynamics of the photosensitizer were
resolved and the following experiments were conducted: life-
time and emission intensity of i) liposomes with constant
amount of RuC9 PS (no catalyst) and various amounts of
sacrificial electron donor ascorbate, ii) liposomes with constant
amount of RuC9 PS and varying amount of [Mo3S13]2 catalyst in
the membrane, iii) liposomes with constant amount of RuC9 PS
and varying amount of [Mo3S13]2 catalyst in the membrane at a
constant ascorbate donor concentration. A typical dataset is
shown in Figure 9A–B and in the Supporting Information on
page 7–12, respectively. For the Stern-Volmer analysis, the
I t
intensities and lifetimes were then plotted as I0 and t0 vs.
quencher concentration [Q] (quencher = catalyst or electron
donor) where I0 and I are emission intensities in the absence
and presence of quencher; τ0 and τ are excited state lifetimes in
the absence and presence of quencher, respectively.
I0
¼ 1þKsv ½Q�¼ 1þkq t0 ½Q� (1)
I
Applying the Stern-Volmer equation [Equation (1)] as a
linear regression yields the Stern-Volmer constant Ksv and the
quenching constant kq. From the slope of the linear regression
I
of the I0 vs. [Q] plot, Ksv and the quenching constant kq [see
Equation (1)] can be derived.
Experimentally, it was found that the excited state lifetime
τ0 of RuC9 always ranges around 400 ns (see Table 3) and
remained unchanged irrespective of the quencher concentra-
tion. On the other hand, the emission intensity was reduced in
almost all cases, which lead to the conclusion that static
quenching takes place in almost all cases, where quenching
was observed (see Figure 9 for exemplary data set for DMPC
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Research Article
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Table 3. Summary of Stern-Volmer constants, quenching rate constants and lifetime from mechanistic studies. Experimental conditions: DMPC, DPPC, DOPC
and DOPG liposome samples with a composition of 100 : 1 : 5 of main lipid:(14:0 PEG2000 PE):RuC9, and c(main lipid) = 5 mM prepared in 10 mM phosphate
buffer containing sodium ascorbate as sacrificial electron donor; and DMPC, DPPC, DOPC and DOPG liposome samples with a composition of 100 : 1 : 5:X of
DMPC : (14 : 0 PEG2000 PE) : RuC9 : [Mo3S13]2 , with c(main lipid) = 5 mM at various loadings of [Mo3S13]2 , prepared in 10 mM phosphate buffer with or without
100 mM ascorbic acid (pH 6) as sacrificial electron donor. Values are reported as mean values + / standard deviation.
Samples Lipid Ksv (L moL 1) kq (L moL 1
s 1) τ0 (ns) Quenching mechanism
7
Varying donor concentration, no catalyst DMPC 32 � 3 (8 � 2) · 10 390 static
DPPC 23 � 2 (5 � 1) · 107 466 static
7
DOPC 4�1 (1.0 � 0.3) · 10 389 static
DOPG 0.8 � 0.1 (1.7 � 0.3) · 106 455 negligible quenching

Varying catalyst concentration, no donor DMPC (3.6 � 0.3) · 104 (9 � 1) · 1010 383 static
4
DPPC (2.0 � 0.3) · 10 (5 � 1) · 1010 415 static
DOPC (9 � 1) · 103 (1.9 � 0.4) · 1010 486 static
3 9
DOPG (2.9 � 0.6) · 10 (6 � 2) · 10 498 static

Varying catalyst concentration, constant donor concentration DMPC (3.0 � 0.6) · 104 (8 � 2) · 1010 390 static
DPPC (1.5 � 0.2) · 103 (4 � 1) · 109 342 static
3 10
DOPC (5 � 1) · 10 (1.4 � 0.8) · 10 372 static
DOPG (2.0 � 0.3) · 103 (4 � 1) · 109 485 static

and Supporting Information on page 7–10).[45] A static quench-

ing mechanism is typical for excited state charge transfer where
the photosensitizer and the quencher form an encounter
complex prior to photoexcitation. All molecules in the encoun-
ter complex are quenched completely, while the remaining
photosensitizer molecules can luminesce with their normal
luminescence lifetime. In fact, static quenching seems to be the
common mechanism with positively charged amphiphilic
ruthenium trisbipyridine type photosensitizers within a lipid
bilayer membrane and a water soluble, negatively charged
quencher.[5,46] It is therefore concluded that a high local
concentration of ascorbate is attracted to the liposome
membranes loaded with cationic photosensitizer. In fact, the
only case with only negligible emission quenching, hence no Figure 10. Comparison of normalized emission intensities from DMPC lip-
osome samples with c(main lipid) = 5 mM, prepared in 10 mM phosphate
initial light-driven electron transfer, was the negatively charged buffer with or without 50 μM HER catalyst and 100 mM ascorbic acid (pH 6)
lipid bilayer of DOPG in presence of negatively charged as sacrificial electron donor (ED).
ascorbate electron donor (see Supporting Information on
page 7–10), which is due to electrostatic repulsion and is in line
with the poor performance in light-driven hydrogen evolution conclusion that excited state electron transfer takes place via
in DOPG vesicles. Comparing the other lipids with DMPC and both reductive and oxidative quenching with the electron
DOPG, the quenching by ascorbate ions ranges is either one donor and catalyst (steps 2 in Figure 1B).
third less effective (DPPC, gel phase) or approximately factor 10 To analyze the competition of oxidative and reductive
less effective (DOPC, fluid phase) than the best performing host quenching, further Stern-Volmer experiments were performed
lipid DMPC (transition temperature between gel and fluid using different CAT:PS ratios in the presence of a constant
phase). concentration of electron donor. They showed that oxidative
Considering the quenching of excited state photosensitizer quenching by the catalyst still took place with similar KSV and
by the catalyst, the trend is the same: Quenching in DMPC is quenching constants kq compared to conditions where no
more effective than in all other lipid matrices, in the series competing reductive quencher was present (see Table 3),
DMPC > DPPC > DOPC > DOPG. The quenching constant is sig- including the fact that quenching is fastest in DMPC (kq = (8 �
nificantly higher than for quenching by the electron donor. 2) · 1010 L moL 1 s 1).
However, at catalytic conditions the overall quenching by The only exception is the gel-phase lipid DPPC with kq =
ascorbate and catalyst is similar and the combination leads to (4 � 1) · 109 L moL 1 s 1 which showed factor 10 less effective
even stronger quenching (see Figure 10), leading to the quenching by the catalyst in presence of ascorbate compared

Chem. Eur. J. 2023, 29, e202302284 (8 of 11) © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

Research Article
Chemistry—A European Journal doi.org/10.1002/chem.202302284
to DPPC liposomes in absence of the electron donor, making
oxidative quenching in DPPC one order of magnitude slower
compared to DMPC. The fact that the presence of both
quenchers makes the oxidative quenching by the catalyst less
favorable in DPPC, hints towards a competition of catalyst and
electron donor in the gel phase lipid bilayer of DPPC which can
be explained with the low mobility of RuC9 and [Mo3S13]2 at
the membrane-water interface. It also allows to conclude that,
although oxidative and reductive quenching take place at the
same time, oxidative quenching initiates the main productive
reaction pathway through initial electron transfer to the catalyst
in DPPC liposomes.
In summary, DMPC performs best in the catalysis experi-
ments, and the excited state PS is most efficiently quenched by
the CAT and the electron donor, suggesting that initial
quenching efficiency determines the light-driven H2 evolution
of [Mo3S13]2 -CAT in lipid bilayers. DMPC is the lipid which has a
transition temperature at room temperature and therefore a
mix of fluid and gel phase regions (see Figure 11 for visual-
ization) which seems to provide the best local environment for
charge transfer between CAT, PS and electron donor.
Conclusions
The present study demonstrates that material integration of the
molecular photosensitizer RuC9 and the molybdenum sulfide
HER catalyst [Mo3S13]2 into biomimetic lipid bilayers produces
stable vesicle structures and can lead to significant improve-
ments of catalytic performance in water when choosing the
optimum lipid environment. Zwitterionic DMPC lipid bilayers
with a transition temperature at the experimental conditions
provide the optimal environment for this specific photosensi-
tizer-catalyst combination, by promoting effective charge trans-
fer between the PS, the electron donor and the catalyst. Lipids
with higher or lower transition temperatures (DOPC, DPPC,
DOPG) seem to block the activity in light-driven HER and
perform equally poor as the reaction in purely aqueous environ-
ment. These findings were underlined by quenching studies,
revealing that initial photoexcitation of the photosensitizer is
followed by simultaneous reductive and oxidative quenching
which are fastest in DMPC compared to the other lipid
environments. The DMPC membrane is at the transition temper-
ature under experimental conditions and shows preferential
electron transfer dynamics for the excited state PS which might
be due to the presence of a mixture of gel phase and fluid
phase domains. In situ SECM measurements using Pd micro-
Figure 11. Representation of the mix of fluid and gel phase for DMPC,
compared to the pure gel phase (DPPC Tm = 41 °C) and gel phase (DOPG,
DOPC Tm = 18 °C and 17 °C respectively), at the temperature applied
during light-driven catalysis experiments and mechanistic studies.
Chem. Eur. J. 2023, 29, e202302284 (9 of 11)
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sensors allowed us to continuously measure the H2 evolution
over the first 60 minute of irradiation and revealed an onset of
measurable H2 evolution after around 26 min of the DMPC
based photoactive DMPC liposomes, which indicates a relatively
slow activation mechanism, probably due to charge recombina-
tion processes. Future studies on the lipid – molecule
interactions will be performed to fully understand and predict
the performance of any new light-driven system on lipid
bilayers.
Experimental Section
Materials
RuC9 and Na2[Mo3S13] x 5H2O were synthesized as previously
reported in our studies.[1–3,4,5]
Lipids 1,2-dimyristoyl-sn-glycero-3-phosphocholine 14:0 PC (DMPC),
1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine-N-[meth-
oxy(polyethylene glycol)-2000] (14:0 PEG2000 PE), 1,2-dioleoyl-sn-
glycero-3-phosphocholine 18 : 1 (Δ9-Cis) PC (DOPC), 1,2-dioleoyl-sn-
glycero-3-phospho-(1’-rac-glycerol) 18 : 1 (Δ9-Cis) (DOPG) and 1,2-
dipalmitoyl-sn-glycero-3-phosphocholine 16 : 0 PC (DPPC), were
purchased from Avanti Polar Lipids, L-ascorbic Acid 99 % was
purchased from Sigma Aldrich, methanol, acetonitrile, chloroform,
lactic acid 99 %, triethylamine and triethanolamine with analytical
grade of purity were purchased from Sigma Aldrich.
For Pd-microsensor fabrication and experiments di-potassium
hydrogen phosphate were purchased from VWR Chemicals, Darm-
stadt, Germany. 1,1’-ferrocendimethanol (97 %) was purchased from
Acros Organics, Fair Lawn, USA. Potassium tetrachloropalladate(II)
(99.99 %) was purchased from Alfa Aesar, Thermo Fisher GmbH,
Kandel, Germany. Potassium chloride, sodium chloride and potas-
sium dihydrogen phosphate were purchased from Merck KGaA,
Darmstadt, Germany. The SECM studies were performed in a three-
electrode setup with the Pd-modified microelectrode as WE, a Ag/
AgCl quasi reference electrode (QRE) and a Pt wire as CE using a
custom-built SECM two-compartment electrochemical cell. All
experiments were controlled via a CH Instrument potentiostat
(Modell: 760E CH Instruments, Texas, USA). The two compartments
(lower and upper compartment) of the electrochemical cell were
separated by a track-etched polycarbonate membrane with a pore
density of about 4.5 · 1012 pores/m2 and a pore size of 50 nm to
prevent fouling of the Pd-modified microelectrode by the lip-
osomes. Illumination occurred from the bottom of the transparent
electrochemical cell using a 400 μm diameter optical fiber (MT-
28L01, Thorlabs GmbH, Bergkirchen, Germany) connected to a
21.8 mW blue LED (λ = 470 nm, M470F3, Thorlabs GmbH).
TEM analysis were carried out with a Jeol 1400 TEM via negative
staining technique using uranyl acetate as suitable electron-dense
material to provide high contrast.
Particle size measurements were performed with a Zetasizer Pro
from Malvern Panalytical by Dynamic Light Scattering (DLS)-Non
Invasive Back Scatter (NIBS) using 900 μL of sample in a disposable
polystyrene cell (DTS0012) with a measurement angle of 173°, 13°
in a diameter range of 0.3 nm–10 μm at 20 °C. Zeta potential
measurements were performed with a Zetasizer Pro from Malvern
Panalytical by Mixed-Mode Measurement phase analysis light
scattering (M3-PALS) using a disposable folded capillary cell
(DTS1070) in a diameter range of 3.8 nm–100 μm.
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

Research Article
Chemistry—A European Journal doi.org/10.1002/chem.202302284
H2 evolution was quantified using a Bruker Scion SQ GC/MS by
injecting manually 100 μL of the head space. Sample preparation
under inert conditions was performed in an MBRAUN LABSTAR
glovebox and pH values were measured with a Mettler Toledo
FiveGoTM pH meter. Photocatalysis was performed in a 3D printed
photoreactor from project C6 in Catalight network equipped with a
LZ1-00DB00 Dental Blue LED emitter (λ = 460 nm). UV-Vis Absorp-
tion spectroscopy was performed on a V-760 JASCO UV-VIS-NIR
Spectrophotometer. [Gas-tight] Quartz glass cuvettes (d = 10.0 mm)
were used for optical measurements. Emission intensity and lifetime
measurements were performed, respectively, using a Horiba Jobin-
Yvon FluoroMax Plus C automated benchtop spectrofluorometer
equipped with a 150 W Xe arc excitation lamp (horizontal,
continuous wave), a R13456 photon-counting PMT detector (190-
930 nm) and DeltaPro from Horiba Scientific using a 451 nm pulsed
Laser source (Class 3B Laser Product, < 0.5 W peak in pulsed and
CW mode.
Vesicle preparation
Stocks solutions are reported in the Supporting Information.
Vesicles were prepared as previously reported,[5,28] details can be
found in the Supporting Information.
Photocatalysis
Sample preparation was done under Argon atmosphere within a
glovebox (O2 content < 0.5 ppm) using 250 μL of liposomes
solution at 5 mM main lipid concentration and different amounts of
the electron donor solution, to obtain different concentrations (see
Figure S5 and see preparation of stock solutions), which were
combined in an 8 mL WICOM WIC 41600/333 clear glass screw neck
GC vial (ND13). The vial was then sealed, transferred into a 3D
printed photoreactor, and irradiated by LZ1-00DB00 Dental Blue as
LED light source (λ = 460 nm, 800 to 1250 mW) with a current of
0.7 A and voltage of 4 V. Simultaneously, 3 identically prepared
vials were irradiated while stirring for 24 hours, using two ring
holders to improve the alignment. The experiment was performed
at room temperature via a ventilation system in the back of the
reactor. After 2 h, 4 h and 24 h, the evolved H2 was analyzed via
head-space gas chromatography from each reaction vessel.
Turnover numbers data were calculated from the ratio between
moles of H2 produced and moles of Na2[Mo3S13] x 5H2O or bis(2,2’-
bipyridine)-(4,4’-dinonyl-2,2’-bipyridine)-ruthenium(II) (RuC9).
Figures of the photoreactor see Supporting Information.
Acknowledgements
A. P. acknowledges the Vector Stiftung (project number P2019-
0110) for financial support and the authors thank the Deutsche
Forschungsgemeinschaft (DFG, project TRR234 “CataLight”
project number 364549901, projects A5, B8, C4) for financial
support. We thank Renate Kunz and Paul Walther from the
Central Facility for Electron Microscopy, Ulm University, for help
with Transmission Electron Microscopy measurements. Some
figures were created with BioRender.com as indicated in the
figure captions. Open Access funding enabled and organized by
Projekt DEAL.
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Conflict of Interests
There are no conflicts to declare.
Data Availability Statement
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
Keywords: catalysis · electron transfer · hydrogen · liposomes ·
photochemistry
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Manuscript received: July 17, 2023
Accepted manuscript online: September 12, 2023
Version of record online: November 8, 2023
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH