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ChemPhotoChem doi.org/10.1002/cptc.202200044

www.chemphotochem.org

Making Photocatalysis Comparable Using a Modular and

Characterized Open-Source Photoreactor**
Daniel Kowalczyk,[a] Pengcheng Li,[a] Amir Abbas,[b] Jonas Eichhorn,[c] Philipp Buday,[d]
Magdalena Heiland,[b] Andrea Pannwitz,[b] Felix H. Schacher,[c] Wolfgang Weigand,[d]
Carsten Streb,[b, e] and Dirk Ziegenbalg*[a]

Reproducibility and comparability of photocatalytic experi- documentation of the incident photon fluxes in the reaction
ments are still challenging, owing to the large number of vessels for different setups as well as the homogeneity of
experimental parameters and their comprehensive documenta- irradiation in multi-reactor setups. Comprehensive documenta-
tion. To overcome this limitation, a modular, adaptable, and tion minimizes the need for repeated photonic characterization
extensible photoreactor platform is reported, which enables when modifying the setups. Experimental reproducibility within
experiments under well-characterized, reproducible conditions. and across experiments was evaluated with studies of photo-
Comparability is ensured by comprehensive photonic character- catalytic systems for hydrogen evolution, emphasizing the
ization with chemical actinometry, radiometry and open validity of the concept.

Introduction earth (ca. 106 PWh) with the current global annual energy
demand (ca. 17 PWh).[3] However, while the amount of solar
Increasing atmospheric CO2 concentrations and global warming energy is immense, its global harvesting is restricted by
are stark reminders for the need to develop sustainable, geographic issues as well as diurnal and seasonal cycles.[4]
carbon-neutral energy schemes.[1,2] Solar irradiation provides by Conversion of abundant solar energy into storable fuels is
far the most promising sustainable energy source. This is therefore a key challenge for energy technologies. In particular,
evident when comparing the annual solar energy influx on visible light-driven photochemistry is a versatile approach to
store solar energy as fuels; in addition, photochemical concepts
can also be used for organic synthesis, e. g. to access value-
[a] D. Kowalczyk, P. Li, Prof. D. Ziegenbalg added chemicals, such as pharmaceuticals.[5–7] Efforts of storing
Institute of Chemical Engineering
Ulm University solar energy by light-driven chemistry can be traced back to
Albert-Einstein-Allee 11 the 18th century, where solar photochemical experiments were
89081 Ulm (Germany) simply performed by placing the reaction vessel in direct
E-mail: [email protected]
[b] A. Abbas, M. Heiland, Jun.-Prof. A. Pannwitz, Prof. C. Streb sunlight.[8] However, complexity challenges related to photo-
Institute of Inorganic Chemistry chemistry, photophysics and reaction engineering have thus-far
Ulm University limited progress in the field, and particular in the technological
Albert-Einstein-Allee 11
89081 Ulm (Germany) deployment of photochemical conversions in industry. How-
[c] J. Eichhorn, Prof. F. H. Schacher ever, recent progress in irradiation sources (LED technology)
Institute of Organic Chemistry and Macromolecular Chemistry and reaction systems,[9] combined with a raised awareness of
University of Jena
Lessingstr. 8, 07743 Jena (Germany) climate change has led to increasing interest in (sun)light-
[d] P. Buday, Prof. W. Weigand driven chemistry, both in academia and industry.[10] In addition,
Institute for Inorganic and Analytical Chemistry photochemistry is a prime example of green chemistry, adding
University of Jena
Humboldtstr. 8 further environmental interest in this concept.[10]
07743 Jena (Germany) With focus on the use of solar light, photocatalytic water
[e] Prof. C. Streb splitting into hydrogen and oxygen has received widespread
Deapartment of Chemistry
Johannes Gutenberg University Mainz attention.[11–15] This principle opens new pathways to virtually
Duesbergweg 10-14 unlimited amounts of hydrogen as secondary energy carrier
55131 Mainz (Germany) with high gravimetric energy density.[16] However, the reaction
[**] A previous version of this manuscript has been deposited on a preprint
system, including light source, photocatalyst, and photoreactor
server (DOI: 10.5281/zenodo.6085915).
Supporting information for this article is available on the WWW under
type, can be quite different across different research groups,
https://doi.org/10.1002/cptc.202200044 currently limiting a wide-spread application of this promising
© 2022 The Authors. ChemPhotoChem published by Wiley-VCH GmbH. This process.
is an open access article under the terms of the Creative Commons At this point, ensuring reproducibility and comparability of
Attribution Non-Commercial NoDerivs License, which permits use and
distribution in any medium, provided the original work is properly cited, the photocatalytic experiments in general remains a challenge that
use is non-commercial and no modifications or adaptations are made. is not solved yet.[17] Since research on light-driven reactions

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Research Articles
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involves a broad range of experimental parameters that require ing the effect of reaction conditions might only be suitable to a
consideration, an experimental platform that ensures compara- limited extent when applied for the development of new
bility and reproducibility across different laboratories and synthesis routes. Different chemical systems frequently require
chemical systems is required. This contribution aims at filling larger changes to the experimental setup to address the
this gap with a modular, documented and characterized properties of different chemical species.
photoreactor platform presented in this study. Consequently, ensuring comparability across different
chemical systems and experimental platforms is more valuable
in research than sole standardization for certain tasks. Ensuring
Challenges in Achieving Reproducibility and Comparability comparability requires two main steps: first, experimental
conditions must be thoroughly defined prior to conducting the
Reproducibility of experiments from the scientific literature is of experiments. Second, the experimental conditions need to be
fundamental importance in chemistry. However, more often reported in a very comprehensive manner according to the
than desired, many researchers experience difficulties repro- FAIR principles.[24] Only when such comprehensible datasets are
ducing reported results which can even comprise their own freely and easily accessible, experimental results can be
results.[18] The basis for reproducibility is the knowledge of compared or even joined to an even more comprehensive
parameters that influence the performance of a chemical larger dataset that allows global analysis to gain overarching
reaction, including the reaction system, i. e. the sum of all insights.[17]
components in the reaction such as the reactive components, Since for light driven reactions photons must be considered
solvent, concentrations or partial pressures. More technical as a reagent, the challenge for comparability lies in the
aspects such as reaction temperature, continuous or discontin- knowledge of the photon flux available to the photoactive
uous operation mode, morphologies of heterogeneous compo- species. Even more precisely, the photon flux absorbed by the
nents and reactor design are further parameters that can photoactive species should be known.[25] The absorbed photon
significantly influence the observed activity of a chemical flux strongly depends on the technical and molecular parame-
system. For light-driven reactions, guiding light to the photo- ters. Consideration of this aspect requires a comprehensive
chemically active species represents an additional aspect whose photonic characterization of the experimental platforms that
importance cannot be underestimated. The amount of available would pave the way towards comparability of experimental
photons or the photon flux for the reaction within a reaction results. Radiometry and actinometry are the methods of choice
compartment is influenced by various parameters like the in this case.[26,27] Radiometry yields insights into the radiation
properties of the light source, the geometrical arrangement of field mostly outside of the actual reactor but can also be used
light source with respect to the reactor, the reactor material, to calculate the photon fluxes inside reactors. Complementary
etc. (technical parameters).[19] This adds an additional parameter to this, chemical actinometry can be used to measure the
space to the already large list of molecular parameters that photon flux available inside the reactor.[28,29] Characterization of
influence the performance of a photoinduced chemical reac- the experimental platform has to be repeated every time when
tion. Molecular parameters cover e. g. the absorption spectra of components that influence the radiation field are changed, i. e.,
photoactive as well as photoinactive species, scattering coef- light source, reactor, geometric arrangement, etc.
ficients of heterogeneous matter as well as the underlying
reaction network. These molecular photophysical properties are
inherently interlinked with the technical parameters of the Modularity and Photonic Characterization as Key for
reaction setup. It is obvious that the extensive set of relevant Reproducibility and Comparability
parameters raises challenges to comparability.[17] Only if the
influencing factors are known, they can be adjusted purpose- An experimental platform that is standardized in the narrow
fully to ensure comparability. sense of the term is not desirable when aiming for compara-
bility since optimal reaction conditions can only be provided to
some but not for all of the chemical systems under inves-
Commercial and Open Source Photoreactors tigation. Consequently, an experimental platform that offers a
high flexibility to address the different demands of the
To improve comparability of experimental results for light- chemical systems while still ensuring comparability is required.
driven reactions, various experimental platforms have been To meet this demand, modularization together with a compre-
suggested recently.[20–23] To minimize the impact of the hensive photonic characterization were used to develop a new
extensive parameter space, various concepts were reported experimental platform. This way it becomes possible to fulfil
that define the arrangement of the light source and the reactor the demands of different chemical systems. Knowledge of the
through the use of commercially available or Open Source incident photon flux as key parameter governing the activity of
photoreactors. The term “standardization” is frequently related a light-driven system enables comparisons. As third pillar, the
to such experimental platforms but should be interpreted with experimental platform together with the characterization
care. The purpose of such a standardization must be very clear results are published as Open Source and Data.[30] During the
to avoid misguided use of experimental platforms for different development, the following design criteria were considered:
applications. For instance, a standardized platform for screen- 1) easy handling in chemical laboratories

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Research Articles
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2) simple extensibility with new modules also in the future chosen.[31,32] This combination was deliberately chosen despite
3) easy and fast adaptation to changing demands during the relatively high cost compared to e. g. Arduino micro-
everyday lab work, controllers for the two following reasons:
4) cost-effective and simple manufacturing, i) The Raspberry Pi can run independent of other hardware,
5) simple control of the whole platform through a system that either as a desktop computer with monitor, input devices
offers and network connection or headless without additional
a. the possibility to integrate and control active equipment periphery except for the Tinkerforge modules. Compared to
such as pumps and stirrers, the sole use of a microcontroller, individual adaptation of
b. the possibility to integrate sensors and analytics, the controller module can be realized in a more convenient
c. the possibility to further automate the platform e. g., way and often with a higher programming level. This allows
through a software interface, also simple interfacing with machine learning software or
6) applicability for screening purposes and case studies and online data management concepts.
7) comprehensive photonic and reaction engineering charac- ii) The Tinkerforge platform offers a multitude of so called
terization. “Bricks” and “Bricklets” with different functionalities, e. g.,
These design criteria were met by close collaboration with temperature and light intensity sensors, analogue and
experimentalists, the use of 3D-printing for manufacturing,[19] digital in and out hardware, input devices, displays, etc. This
the development of parts that can be widely reused for portfolio allows easy and straightforward extension of the
different purposes, the use of affordable high-level electronic basic functionalities since the extensions can be installed by
components for controlling the equipment and the develop- plug and play on the controller. The wide range of available
ment of the controller software in a high-level programming functionalities also reduces the need to create own
language. Characterization of the platform was conducted in electronic functions. Furthermore, programming can be
parallel and iteratively contributed to the optimization of realized with high-level programming languages such as
individual parts of the platform. Python, LabVIEW or even Matlab. A simple viewer allows
also limited direct control of the Bricks and Bricklets without
additional programming. The Tinkerforge devices can either
Modular Photoreactor Platform be used with a desktop computer and a USB connection or
with a Raspberry Pi HAT (Hardware Attached on Top). The
The development of the photoreactor platform was based on 4 first use case allows convenient programming on a desktop
major categories of modules: i) controller module, ii) corpus computer, while the second use case enables standalone
and holders, iii) irradiation modules and iv) peripheral modules. operation.
A comprehensive documentation can be found on GitHub and The controller module offers several interfaces, i) two HDMI
Zenodo.[30] The 3D-printed parts were manufactured out of ports, ii) four USB ports, iii) a Tinkerforge Hat Brick with 8
commercially available thermoplastic polymers such as poly- interfaces and iv) a network port. Figure 1 gives a schematic
lactic acid (PLA) and acrylonitrile butadiene styrene (ABS). The overview of the controller module and its functionality. The
material PLA is particularly suitable due to its uncomplicated controller interfaces and its electronic setup are depicted in
handling. It can be used without problems with all available 3D Figure 2. Pictures of currently available modules which can be
printers that work according to the principle of fused connected to the controller module are shown in Figure 3.
deposition modelling (FDM). Nonetheless, the use of PLA is not By default, PWM Bricklets are installed on the controller unit
suited for elevated temperatures due to its relatively low glass that are used to control the stirrer and the fan modules (see
transition temperature of 61 °C (Raise 3D Premium). The good below). The controller module also hosts the electronics that
mechanical properties such as high impact resistance, tough- are used to drive the LEDs. The LED drivers are connected to a
ness, and rigidity and its stability at higher temperatures with a PWM channel, enabling operation with constant electric current
glass temperature of 98 °C (Raise 3D Premium) render ABS an (350 mA, 500 mA and 700 mA) as well as pulsed operation with
attractive alternative to PLA to ensure high stability even at frequencies up to 1 kHz and different duty cycles. Furthermore,
elevated reactor temperatures. It should also be noted that the it is possible to directly control a conventional lab power
colour of the printed filament has a significant influence on the supply KORAD Ka3005P as driver for LEDs with high electrical
wavelength-dependent reflectivity of the chamber and should currents or voltages. The lab power supply is therefore
therefore be chosen with care (see SI). connected to the controller by a USB connection.
The software for the controller module was developed in
Python and enables easy extension of the controller module
Controller Module also on the software side. Registration of modules is realized
with simple config files that contain information on the
The control unit is the core module for controlling active installed modules and their standard settings. With this
components, e. g. LEDs or pumps, and logging of sensor data, information, the software automatically generates the graphical
e. g. temperature or pressure. To enable a high flexibility with user interface (GUI) on a touchscreen module that is always
respect to the extension of the reactor platform, a Raspberry Pi installed on the controller. This touchscreen is the main human
computer together with a Tinkerforge microcontroller were interface device to control all connected modules. As indicated

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Figure 1. Schematic overview of the controller and its functionality. PM: peripheral module.

Figure 2. Overview of the modular photoreactor controller.

above, direct control with the Raspberry Pi is also possible but

not considered as main use case.

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Figure 3. Modular photoreactor setup and available modules: a = tempering module, b = modular corpus, c = LED module, d = ambient temperature readout,
e = pressure sensor extension, f = thermocouples, reactor and chamber temperature readout, g = controller, h = master extension (4 ports), i = membrane
pump module, j = stirrer module.

Corpus and Reaction Vessel Holder Modules (see Figure 4-c), which can also be used as a sample holder (see
Figure 5-c). The modular setup of the reactor corpus also
These modules represent the base modules in and at which enables radiometric studies of the reactor, ensuring an easy
other modules can be installed. The corpus itself has a modular assessment of changes in photon fluxes when individual
structure. Figure 4 shows schematically which modules can be reactor components are changed or modified. The design of
used with the different components of the corpus. the corpus enables easy scale-up of the irradiation chamber to
Corpus: This module is the base module that is always either hold more samples for screening or larger lab-scale
required (see Figure 4-c). Its functional principle and setup are reaction vessels within the corpus. Corpuses with the dimen-
depicted in Figure 5. It consists of two walls with slots (see sions of 90 × 90 × 100 mm, 90 × 90 × 140 mm and 130 × 130 ×
Figure 4-e), in which sample holder can be installed (see 130 mm are already in use.
Figure 4-d). Different reactor holders can be installed at a Holders: Depending on the chamber dimensions, a variety
defined (adjustable) distance (see Figure 4-h) and irradiated of holders can be used to place 1 to 18 GC-vials with volumes
from the bottom with an irradiation module (see Figure 6-a). from 5 to 8 mL in the corpus module. Correct positioning of
This modular cassette can be inserted between the side walls the vials can be enforced by using an additional alignment ring
(see Figure 4-c), closing the corpus from below and thus acts as holder. The irradiation module can also be used as a Schlenk
a bottom wall of the corpus. Instead of an irradiation module, tube holder, when installed upside down. The Schlenk tube is
different peripheral modules can be installed in the bottom as then additionally fixed from above with an extension for the
well. The modularity of the reactor also enables the exchange top cover. The reactor holders are shown Figure 5.
of the side walls with LED modules (see Figure 6-b) to enable
irradiation from the sides. A third wall is equipped with an
opening. Here, a fan can be installed to temper the inner Irradiation Modules
volume of the corpus (see Figure 4-f). A fourth wall is used to
close the reactor (see Figure 4-e). It is equipped with an Irradiation modules allow the direct installation of self-made
opening which works as exhaust for the ventilation air, either light sources or the connection of light sources from
for operation with or without the tempering module. The commercial manufacturers to the corpus. Irradiation modules
reactor can be closed from above using a modular top cover are available either for irradiation from the bottom or the sides.

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Figure 4. Schematic overview of the photoreactor corpus and modules and their interplay. a = Functional principle, structure and functionality of the corpus
module. b = Irradiation principle of circular oriented reaction vials with a LED comprising a conical light emission. c = Overview of the corpus module. d = Top
view of the corpus with installed vials. e = Modularity of the side parts of the corpus. f = Photographs of the front ventilation part of the corpus. g = Front and
back view of the fully assembled closed corpus. h = example of vials positioning at different distances relative to the radiation source.

Figure 5. Overview of holder modules and 90 × 90 × 90 mm corpus: a, b) holder and alignment rings for GC vials in 90 × 90 × 140 mm corpus and c) holder for
Schlenk flasks.

For all light sources, possibly required cooling equipment such which consists of four high power LEDs with peak emission
as heat sinks and/or fans are installed outside the corpus to wavelengths of 623 nm (red), 523 nm (green), 460 nm (blue)
avoid any additional heat spreading in the irradiation chamber. and 590 nm (amber) can be used. This enables switching
Currently, the following irradiation modules are available. between desired wavelengths while experiments are running
LED modules: Narrow band high-power LEDs with peak without the need to exchange the modules. The modularity of
emission wavelengths of 365 nm, 385 nm, 405 nm, 450 nm, the corpus not only allows the use of the described LED
530 nm are currently in use. In addition, an RGBA module modules as bottom part of the chamber but enables the use of

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Figure 6. Photographs and CAD models of a) the LED module and b) the corpus with sidewise irradiation.

the side parts as irradiation modules as well which is shown in Ambient-, surface- and reactor temperature modules: The
Figure 6. temperature can be measured at various positions. A typical
Adaptor for Asahi Spectra Max-350: This extension couples setup includes measurements of the ambient, reactor and
the Asahi Spectra Max-350 irradiation source to the corpus chamber temperature. The ambient temperature module does
using an RLQL80-1 collimator lens and an RLQ-BH downward not require any additional thermocouple and is simply placed
illumination unit depicted in Figure 7. The irradiation source at a suited position. Reactor and chamber temperature are
can be used with either bandpass filters or a monochromator, measured with type K thermocouples that can be installed at
enabling studies on the impact of irradiation with different the required positions. Type K thermocouples are available for
wavelengths. various applications so that e. g. surface temperatures or the
Adaptor for Thorlabs LED with collimator: This extension temperature in the reactor can be measured. The latter one can
enables the use of commercially available lamps for irradiation. be used together with a PTFE adapter (1/8” to ND13) to seal
Thorlabs LEDs can be screwed into the collimator and fixed in the reaction vessel.
the adapter using M3 screws as shown in Figure 8. Stirring module: This module can be inserted into the
bottom of the corpus instead of an LED module. It consists of
an electric fan that is equipped with neodymium magnets and
Peripheral Modules is controllable by a PWM signal. The module enables mixing in
the reactors independent of a laboratory magnetic stirrer.
All peripheral modules can be used as standalone modules or Fans: Depending on the tempering requirements, a fan can
together with other modules. To enable reactor tempering, a be installed for constant flow of fresh air into the irradiation
module containing a temperature measurement device must chamber.
be combined with the tempering module and a fan to ensure Tempering module: This module can be installed for
air circulation through the reactor. A schematic overview over tempering the inner volume of the corpus and with this the
the modules and possible new functionalities through a reactor vessels. This module consists of a fan, a thermoelectric
combination of those is shown Figure 9. temperature control unit and a thermal hose. The temperature
control unit can either cool or heat the reactor. The pre-

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Figure 7. a) Ashai downward illumination unit RLQ-BH for collimator lens RLQL80-1 (Asahi Spectra Co., Ltd., Japan), b) 3D-printed holder for RLQ-BH and
c) CAD model illustrating the fixation of the holder to the irradiation module.

Figure 8. a) Side view of the Thorlabs adapter module for the installation of a Thorlabs collimator (b) and a Thorlabs LED (c). d) Top view of the irradiation
module with installed Thorlabs collimator and e) CAD model of the adapter.

tempered air is circulated through the reactor by a fan and is solid-liquid two-phase systems and can be operated with flow
subsequently recycled through the thermal hose. This allows rates of 10 to 110 mL min 1.
efficient temperature control of the system with temperature Master extension module: This module enables the
differences to the room temperature of around 16 K to more installation of up to four additional modules by providing
than + 35 K. Within this temperature range, the controller additional Bricklet ports.
keeps the temperature constant within � 1 K of the set temper-
ature.
Pressure sensor module: This module can be used to Photonic Characterization
record the pressure in the reaction vessel.
Membrane pump: This module operates a KFN FEM 1.09 The experimental platform was photonically characterized by
KP.55RC diaphragm dosing pump for continuous reactor chemical actinometry and multidimensional radiometry.[26–29]
setups. Since all pump components in direct contact with The raw data can be found on Zenodo and evaluated with the
chemicals are made of fluorinated polymers, a high degree of tools published on GitHub.[33,34] Using the ferrioxalate actino-
resistance against various solvents and reactants can be meter and a 365 nm LED (LST1-01G01-UV01-00) at a current of
assured. The pump can handle liquid-liquid, gas-liquid and 500 mA, a mean photon flux per vial of qvial = 89 nmol s 1 was

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Figure 9. Assembly and functionality of the tempered modular photoreactor: a) thermal hose for air recycling, b) tempering module, c) irradiation chamber,
d) variable irradiation module.

determined by recording a time series, when using an 8-vial (see SI) the obtained photon fluxes can also be applied to
holder at a distance of 7 cm from the radiation source chambers printed using white and black PLA. In comparative
(Figure 10). For the experiments with the 365 nm LED all measurements to determine the spatial homogeneity of the
printable components were manufactured using orange PLA irradiation at 120 s and 240 s, mean photon fluxes of 87 �
(Raise 3D premium). Since for the UV region all examined 5 nmol s 1 and 89 � 6 nmol s 1 were recorded, respectively. It
filaments show a relatively low and comparable reflectance should be noted that the outlier at position 7 at 240 s was not

Figure 10. Photon fluxes determined by chemical actinometry, a) comparison for the 1-vial holder, 4-vial holder and 8-vial holder at a distance of 7 cm for a
365 nm LED. The 8-vial holder was used if not indicated otherwise. b) Position dependent photon flux for the 8-vial holder at 120 s and 240 s.

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included in the calculation of the mean photon flux. The lower same setup with a light source of e. g. different wavelength and
conversion of the said outlier in vial 7 resulted from a missing radiant power. The efficiency of irradiation of the reactor ξirr
stirring bar, through which the application limits of the can be determined according to Equation (1):
ferrioxalate actinometer were surpassed. The deviation within a
series of measurements is about 6 %, which is within the qtot
xirr ¼ (1)
expected experimental error. The average photon fluxes of the qemit
measurements for spatial homogeneity also agree very well
with the averaged photon flux of the time series. with the photon flux absorbed under full absorption qtot and
Photon fluxes were also determined by chemical actino- the photon flux emitted by the light source qemit . This efficiency
metry for the 4-sample holder equipped with 4 vials and the 1- can also be calculated for a single vial with the photon flux
sample holder equipped with one vial (s Table 1). An average absorbed in one vial qvial [Eq. (2)]:
photon flux of 157 nmol s 1 per vial could be determined for
the 4-sample holder. For the vial in the 1-sample holder, an qvial
xvial ¼ (2)
average photon flux of 168 nmol s 1 was measured. qemit
Complementary to the actinometric determination of the
photon fluxes, photon fluxes were determined for the 365 nm A similar trend as for the photon flux can also be observed
LED with 2D radiometry following a three-step scheme (see SI) for ξirr as a function of the number of vials. The radiometrically
for the 8-vial holder, positioned at a distance of 7 cm from the determined irradiation efficiencies per vial ξvial, (Figure SI-13
radiation source (Figure 11). The calculation of the photon (left)), are 3.2 %, 5.8 % and 5.9 % for the 8-vial holder, the 4-vial
fluxes is based on the radiometric measurements shown in holder and the 1-vial holder, respectively. The total ξirr,
(Figure 11). A photon flux of qvial = 92 nmol s 1 corresponding to however, is only 5.9 % for the 1-vial holder and increases to
a total absorbed photon flux of qtot = 732 nmol s 1 was 23.4 % and 25.7 % for the 4-vial holder and the 8-vial holder,
determined. The radiometric scans can be converted to maps respectively. This is shown in (Figure SI-13 (right)). Thus, a
of the absorbed fraction of the light (Figure 12), indicating fourfold increase from the 1-vial holder to the 8-vial holder can
efficient light absorption when the vials are filled with highly also be observed for ξirr. Please note that high irradiation
concentrated methyl orange solution. About 31 % of the efficiencies are only of secondary importance for the developed
photons available in the corpus can be absorbed by a fully reactor setup. Knowledge of the photon flux is the key
absorbing solution. information that enables comparison, irrespective of the
Radiometric photon fluxes of qvial = 92 nmol s 1, irradiation efficiency.
1 1
167 nmol s and 168 nmol s were determined for the 8-vial To compare different reaction systems, the absorbed
holder, the 4-vial holder and the 1-vial holder, respectively photon flux should be normalized to the volume. For the three
(Table 1). holder setups introduced above, this is illustrated in Figure SI-
The comparison of the vial holders clearly shows that the 12. This volumetric photon flux qvol will be used for the
horizontal placement of the vial has a significant influence on comparison of the case studies below.
the absorbed photon flux qvial. For the 1-vial holder an about The influence of the vertical distance of the holder to the
83 % higher qvial is calculated compared to the 8-vial holder radiation source dvert for the 8-vial holder is shown in Table 2.
(Figure SI-10 (left)). However, when the total absorbed photon The distance is measured from the holder to the radiation
flux of all vials is compared, (Figure SI-10 (right)), 168 nmol s 1 source. An increasing distance leads to an increasing photon
were measured for the 1-vial holder, 667 nmol s 1 for the 4-vial flux per vial. By increasing the vertical distance from 5 cm to
holder, and 732 nmol s 1 for the 8-vial holder. In total, the 8-vial 9 cm, qvol can be increased from 29 to 34 nmol s 1 mL 1,
holder absorbs a more than 4-fold higher photon flux than the corresponding to ξirr ranging from 24.4 % to 28.4 %, respec-
1-vial holder. Results from chemical actinometry were found to tively.
be in good agreement with radiometry (Table 1). The results of the photonic characterization of the systems
Knowledge on the efficiency of guiding photons to the used for the case studies are summarized in Table 3. In
reaction solution can be used to transfer knowledge of the dependence of the used setup and light source, the volumetric
irradiation field from a setup with a certain light source to the photon flux lies between 32 and 399 nmol s 1 mL 1 resulting in

Table 1. Photon fluxes determined by actinometry and radiometry for different vial holders for a 365 nm LED with 130 ° beam angle operated with a
constant electrical current of 500 mA.
Method Holder qtot ξirr qvial ξvial Vvial qvol
[nmol s 1] [%] [nmol s 1] [%] [mL] [nmol s 1 mL 1]

1 168 5.9 168 5.9 3 56

Radiometry 4 667 23.4 167 5.8 3 56
8 732 25.7 92 3.2 3 31
1 168 5.9 168 5.9 3 56
Actinometry 4 629 22.0 157 5.5 3 52
8 710 24.9 89 3.1 3 30

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Figure 11. Radiometric scans for the setup with an 8-vials holder. The first row always represents the radiometric scan and the second row shows the reactor
setup. A) 365 nm LED module, b) LED module installed in the corpus, c) empty vials installed in the setup, d) vials filled with methyl orange installed in the
setup.

a more than 12-fold difference in the available volumetric Case Studies

photon flux between the setups used for the case studies. It is
obvious that relatively small changes of the used setup like Light-driven hydrogen evolution from water is a promising
changes in the reaction vessels, volume, relative positioning to approach to achieve a renewable and emission-free energy
the radiation source or the use of different radiation sources cycle.[35] Most of the concepts developed for light-driven
can have a large impact on the absorbed volumetric photon hydrogen evolution reaction (HER) are somehow derived from
fluxes. Thus, a valid comparison of different systems is only natural photosynthesis, combining specialized units for light-
possible with a sufficient photonic characterization of the absorption and as catalytic centres.[35,36] While solar simulators
setup. can be used as standardized light sources, the use of other

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Figure 12. Spatial distribution of the absorption fraction for 8 circular arranged 4 mL GC-Vials filled with 3 mL methyl orange solution with a transmission of
a) 75 %, b) 50 % and c) 0 % measured at 450 nm and a pathlength of 1 cm.

light sources such as LEDs offers benefits with respect to deviation of 3–4 % while irradiating at 470 nm in a different
equipment costs, or specific excitation at a certain wavelength. photoreactor setup operating at 40 mW cm 2 irradiance.[40]
Independent of the light source, the use of different reactor Since the irradiated area was not reported, the reported
types with e. g. curved or flat windows results in different irradiance loses its significance and the incident radiant power
photon fluxes incident on the reaction solution. Using well cannot be calculated. The main difference for the different
characterized experimental setups, as the one presented in this TONs might be caused by the different irradiation wavelength
work, will enable objective comparison based on the knowl- at a potentially lower radiant power combined with the
edge of the incident photon flux even for different reactor absorption properties of the photosensitizer.
types. To demonstrate this, the following case studies were Increasing the methanol content to MeOH/H2O 9 : 1, low-
conducted at different locations in Ulm and Jena with ering the pH to 4, and using a 455 nm LED (qvol =
individual setups at each institution. 56 nmol s 1 mL 1, experiments conducted in Jena) as well as
performing the reaction without stirring resulted in an average
TON of around 16,633 with a standard deviation of 2 %
Hydrogen Evolution Reaction with Molecular Molybdenum between trials and of 4 % to 7 % for each trial.
Sulfide Catalysts By changing to a more powerful LED (453 nm, qvol =
399 nmol s 1 mL 1) in this irradiation setup, we increased the
Promising earth abundant HER catalysts are amorphous HER performance in the MeOH/H2O 9 : 1 system by 68 %,
molybdenum sulfides.[37,38] In 2018, the potential of this cluster reaching an average TON of 27,920 with a standard deviation
was investigated in homogeneous light-driven HER catalysis of 4 % over 8 samples (Figure 14 d yellow bar). The more than
and showed promising activity towards hydrogen evolution, 6-fold higher photon flux increased the hydrogen evolution
while mechanistic details of HER were investigated in later activity by merely 21 %, compared to previously published
studies.[37–39] results.[40] This shows that the activity at high intensities is no
We investigated the HER with [Ru(bpy)3](PF6)2 as photo- longer limited by the photon flux. Reproduction of the experi-
sensitizer, ascorbic acid as sacrificial electron donor and ment in Ulm led to very similar results with a mean TON of
Na2[Mo3S13] x 5H2O or (NH4)2[Mo3S13] x 2H2O as catalysts in 27,658 observed for three trials (standard deviations: 7–9 %
different methanol/water mixtures and varying pH according to within trials; 7 % between the trials), corresponding to devia-
a published and adapted procedure (Figure 13).[40] Besides tions of around 1 % between the different locations and
investigating the absolute performance, reproduction of activ- individual setups. Consequently, manufacturing and assembly
ity correlation to the water content reported in the literature of the modules and their components can be neglected as an
was in focus of the work. Depending on solvent mixtures and error source. Interestingly, performing the reaction under
pH, indeed different activities of the systems were observed stirring decreased the activity by 29 % resulting in an average
(see Figure 14, experiments conducted in Ulm). While at pH 6 TON of 19,864 with a standard deviation of 9 % over 8 samples,
in MeOH/H2O 1 : 2 an average turnover number of 1454 with a which may arise from an interference with local mass transfer
standard deviation of 9 % between trials and a standard in the stirred system (Figure 14 d).
deviation of 7 % to 12 % within trials were determined, In summary, variations of reaction conditions at the same
increasing the methanol content to MeOH/H2O 1 : 1 resulted in solvent ratio and pH can induce changes in observed catalysis
an average TON of 5103 with a standard deviation of 3.8 % performance between 21 % to 68 %, which underlines that not
between trials and 3 % to 4 % within trials. In these experiments only irradiation, but interference with local mass transport are
we utilized a 460 nm LED (LZ1-00DB00) in the setup resulting also important for activity. In addition other factors such as
in a qvol of 32 nmol s 1 mL 1 (see Table 3). However, TONs concentrations and (photo)stability of reagents can cap the
obtained are not identical to the published results which report activity in this system,[40,41] emphasizing the need for a
TON = 3950 in the MeOH/H2O 1 : 1 mixture with a standard

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Figure 13. Reaction scheme for the three-component system for the light-induced hydrogen evolution reaction using ascorbic acid (1) as electron donor,
[Mo3S13]2 (2) as catalyst and [Ru(bpy)3]2 + (3) as photosensitizer.

comprehensive documentation of the experimental procedure and co-workers in 2008.[43] Based on this benchmark work, a
along with the need for further investigations. series of multicomponent photocatalytic systems comprising 4,
The standard deviations in trials for water contents � 50 % a photosensitizer and a sacrificial donor were investigated.[44] In
range from 2 % to 9 %. However, operating in a 2 : 1 solvent 2018 Lu et al. combined 4 with the widely used [Ru(bpy)3]2 + (3)
mixture of water/MeOH resulted in larger deviations, caused by as photosensitizer and N,N-Dimethyl-p-toluidine (DMT) (5) as
an increased sensitivity of the photocatalytic system. A higher electron donor to compare different Ru-based light harvesters.
water content accelerates the exchange of terminal disulfide The three-component system (3–5) yielded a turnover number
ligands with water molecules, causing a deactivation of the of 376 after six hours of irradiation with visible light
catalyst.[40] Variations during sample preparation, especially (450 nm).[45] In the present case study, this hybrid system was
dwell times before irradiation can cause increased deviations in used to investigate the reproducibility of the photocatalytic
this chemically more unstable system. Photonic characteriza- results in the modular photoreactor.
tion yielded standard deviations of 6 %. Larger deviations of the For first photocatalytic experiments with eight samples, an
actual catalytic experiments are also linked to the experimental average turnover number of 6.14 was measured with a
analytical method which includes manual injection of a head standard deviation of 3 to 5 % within each trial and a standard
space volume into the GC, as well as manual sample deviation of 5 % between the trials (see Figure 16). Using a
preparation with a pipetting standard error of 0.3 %. 453 nm LED for irradiation, a qvol of 76 nmol s 1 mL 1 was
determined based on radiometric measurements (see Table 3).
For further investigations on the effect of the incident photon
Hydrogen Evolution Reaction with [Co(dmg)2ClPy] flux, two reaction vials were placed oppositely to each other in
a four-sample holder and irradiated for 30 minutes with
The proton reduction electrocatalyst [Co(dmg)2ClPy] (4)[42] (Fig- different intensities (qvol = 120 nmol s 1 mL 1 and
1 1
ure 15) was successfully introduced in the scope of photo- 240 nmol s mL , see Table 3). This procedure was carried out
catalytic proton reduction from aqueous solutions by Eisenberg with two different catalyst stock solutions. The results are

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Figure 14. Results of reproducibility tests for HER with [Mo3S13]2 and [Ru(bpy)3]2 +. c([Mo3]) = 0.3 μM, c([Ru(bpy)3](PF6)2) = 20 μM, c(ascorbic acid) = 0.1 M, 6 h
irradiation time in different solvent mixtures and pH. Left: average results for different trials; right: individual results for different positions in the setup. a:
MeOH/H2O 1 : 2, pH 6, 460 nm; b: MeOH/H2O 1 : 1, pH 6, 460 nm; c: MeOH/H2O 9 : 1, pH 4, 455 nm, no stirring; d: 453 nm LED; yellow bar: trial performed in
Jena, no stirring; blue bars: reproduction trials performed in Ulm, no stirring; grey bar: with stirring.

Figure 15. Reaction scheme for the three-component system for the light-induced hydrogen evolution reaction using [Ru(bpy)3]2 + (3) as photosensitizer,
[Co(dmg)2ClPy] (4) as catalyst and N,N-dimethyl-p-toluidine (5, DMT) as electron donor.

shown in Figure 15. For stock solution 1 (stock solution 2 in turnover numbers of stock solution 2 are about 8 % lower than
brackets) the low photon flux resulted in an average turnover those of stock solution 1.
number of 6.50 � 2 % (6.03 � 0.6 %) between the trials; for the In the case of the four-sample holder, the different photon
high photon flux an average TON of 9.42 � 3 % (8.58 � 1 %) was fluxes (difference of about 100 %) do not lead to a similar
registered. Due to preparation inaccuracies, the averaged increase of the averaged turnover numbers (difference of 42 %
(stock solution 1) and 45 % (stock solution 2)). Furthermore, the

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Figure 16. Top: Results of reproducibility tests for HER with Co(dmg)2ClPy and [Ru(bpy)3]2 + (ILED = 200 mA). Bottom: Results of reproducibility tests for a
constant current of 0.2 A (qvol = 120 nmol s 1 mL 1) and 0.4 A (240 nmol s 1 mL 1); left: average results for different trials; right: individual results for different
positions in the setup.

higher volumetric photon flux available in the four-sample for the reported setup, which is very similar to our setup with
holder compared to the eight-sample holder (about 58 %) is 76 nmol s 1 mL 1. The investigated three-component system (3-
also not reflected by the similar averaged turnover numbers. 5) is found to be poor in the scope of photocatalytic proton
The case study shows a good reproducibility within experi- reduction and also lacks robustness. Despite this, the low
ments conducted in parallel as well as between different trials. activity results in a high sensitivity towards experimental errors,
Despite a low observed turnover number, the hydrogen especially for short experiments. This is an issue that was not
evolution during half-hour irradiation is quite rapid (about observed with the photoreactor platform, emphasizing the
30 μL H2 in 2 mL headspace), thus small random mutations can advantages of a well-defined experimental setup.
easily lead to deviations within and between the measure-
ments. There is a big deviation between literature results and
the present study with respect to the catalytic turnover. After Discussion
half-hour irradiation (450 nm), the reported turnover number
(280) is significantly higher than the one achieved herein The case studies confirm a very good reproducibility of the
(about 6 to 9). However, it is noted that the TONs reported in catalytic experiments, being in good agreement with the
the literature might be miscalculated: our own calculations photonic characterization. The practical need for adaptations of
with experimental data presented by Lu et al.[45] (V = 5 mL, the experimental setup led to changes of the incident photon
ccat = 77.5 μM, nH2 = 9.4 μmol) yielded a TON of about 24. This flux that directly influenced the photocatalytic activity. For
value is in better agreement with our measurements, since the instance, using 8 instead of 1 vials almost halved the photon
reported radiant power reaching the reaction vessel and the flux per vial, variations of the distance between LED and vial
radiant power calculated for one vessel in our setup using the cause differences of more than 10 % and the use of different
8-vial sample holder are in good agreement as well. The types of LEDs resulted in changes of the photon flux by an
reported LED irradiance of 122 mW cm 2 and the irradiated area order of magnitude (see Table 1, Table 2, and Table 3). Thus,
of 0.8 cm 2 indicate a radiant power of 98 mW corresponding parameter studies on non-photonic parameters can be falsified.
to 369 nmol s 1 reaching the reaction vessel. Therefore, a Compared to reactor concepts reported previously, com-
volumetric photon flux of 74 nmol s 1 mL 1 can be calculated prehensive characterization of the modular photoreactor plat-

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Table 2. Photon flux measured by radiometry in dependency of the vertical position relative to the radiation source for the 8-vial holder and a 365 nm LED
with 130 ° beam angle operated with a constant electrical current of 500 mA.
dvert qtot ξirr qvial ξvial [%] Vvial qvol
[ cm] [nmol s 1] [%] [nmol s 1] [mL] [nmol s 1 mL 1]

5 696 24.4 87 3.0 3 29

7 732 25.7 92 3.2 3 31
9 811 28.4 101 3.6 3 34

Table 3. Photonic characterization of the setups used for the case studies with 3 LEDs: 1 (LED Engin, LZ1-00DB00, λP = 460 nm, Θ0.9 = 90°) the case studies
for this LED were performed in 8 mL WICOM WIC 41600/333 clear glass screw neck GC-vials (ND13), 2 (New Energy, LST1-01F06-RYL1-00, λP = 455 nm, Θ0.9 =
120°) and 3 (LED Engin, LZ4-40B208-0000, λP = 453 nm, Θ0.9 = 120°). The case studies for the 453 nm and 455 nm LED were performed in 4 mL LABSOLUTE
7613421 clear glass screw neck vials (ND13) GC-Vials.
LED holder vials dvert I qtot ξirr qvial ξvial Vvial qvol
[cm] [mA] [nmol s 1] [%] [nmol s 1] [%] [mL] [nmol s 1 mL 1]

1 8 8 10 700 1001 31.4 126 3.9 4 32

2 8 8 7 290 891 41.5 111 5.2 2 56
3 8 8 7 960 6380 33.6 797 4.2 2 399
3 8 8 7 200 1820 32.4 227 4.0 3 76
3 4 2 7 200 718 12.8 359 6.4 3 120
3 4 2 7 400 1440 15.1 721 7.6 3 240

form overcomes this issue. Open documentation minimizes the characterization of the studied systems. The photonic charac-
need for repeated actinometric and/or radiometric measure- terization of different systems by using complementary
ments since characteristic figures, e. g. ξvial, allow exchange of methods such as chemical actinometry and radiometry pro-
modules without the need of new measurements. Given that vides highly reliable results for incident and absorbed photon
the new module is sufficiently characterized, e. g. the emitted fluxes. This knowledge allows comparison of experimental
photon flux of a different LED is known, the characteristic results between different setups and a simple transfer in case
figures can be used to consider modifications. Knowledge of of modifications of the setup, minimizing the need for repeated
normalized photon fluxes (qvial or qvol) allows for comparison photonic characterization.
between different setups, as demonstrated for trials with The modular, documented, characterized and Open Source
different positions and vials in the case studies. The modularity photoreactor platform presented in this contribution is an
of the presented photoreactor concept ensures simple extensi- initial step to overcome the experimental challenges of
bility and adaptation to specific demands, e. g. when used for research on light-driven reactions. It is envisioned that a broad
synthetic photochemistry. adaptation will lead to ongoing improvements and the
development of new modules, that will be shared with the
research community together with a comprehensive character-
Conclusions ization in the available repositories.

The highly modular photoreactor was successfully used for

different photocatalytic hydrogen evolution systems, proving Supporting Information
reproducibility and comparability. Compared to standardization
approaches, adaptability and extensibility of the photoreactor Supporting Information available: Description of experimental
enables the use of different reaction vessels, positioning of the procedures and details of photonic characterization.
reaction vessel relative to the radiation source and the use of All CAD drawings of the modular reactor platform, assembly
different radiation sources, while a thorough photonic charac- descriptions and the Python code for the controller are
terization ensures comparability based on the known volumet- available on GitHub https:// github.com/photonZfeed/modular-
ric photon flux even for modified setups. By design an intuitive Photoreactor and as a stable version in the Zenodo repository
use of the platform is given, preventing user errors. Compre- https://doi.org/10.5281/10.5281/zenodo.5615742. Raw data of
hensive and open documentation of the photoreactor con- the characterization can be found on Zenodo https://doi.org/
struction as well as the photonic characterization ensures 10.5281/10.5281/ 10.5281/zenodo.5614942 and evaluated with
reproducibility and lays the foundation for its widespread use the tools published on GitHub.[33]
in photochemical laboratories. The use of relatively inexpensive
and photonically characterized radiation sources such as high-
power LEDs and the use of 3D printing for the fabrication of
most reactor components results in affordable cost.
Reproducibility and comparability of photocatalytic experi-
ments are inherently linked to a comprehensive photonic

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Experimental Section the following concentrations, according to literature:[45] [Co-

(dmg)2ClPy] (78 μM); [Ru(bpy)3]2 + (5 μM); DMT (5.5 mM); H2O
Actinometry (2.2 mM). CH3CN, H2O and DMT were degassed with an N2 or Ar
flow before use. The sealed samples were stored in the dark until
Chemical actinometry was performed using the ferrioxalate actino- they were placed in the reactor and subsequently irradiated for 30
meter based on the method of Hatchard and Parker and following minutes with the 453 nm LED operated with a constant current of
the procedure presented by Wriedt et al.[28,46,47] Actinometric experi- 0.2 A (or 0.4 A) and under vigorous stirring in the 90x90x100 mm
ments were performed in 4 mL GC vials under constant stirring. corpus. The sample holder was placed in position 7 with an
The vials were each filled with 3 mL of a 0.016 M K3Fe(C2O4)3 additional alignment ring holder in position 6. Samples (200 μL) for
solution in 0.05 M H2SO4. A 365 nm LED (LST1-01G01-UV01-00, I = hydrogen quantification were drawn from the headspace and
0.5 A) operated at constant current was used for the actinometric measured by GC-TCD.
experiments (see SI for more details).

Radiometry Acknowledgements
2D radiometry was performed according to the method published
by Sender.[26] Full surface 2D scans were performed for all used This research was funded by the Deutsche Forschungsgemein-
radiation sources. 2D scans of all reactor setups with installed schaft DFG as part of the collaborative research center TRR234
radiation sources were performed using a reduced scan surface “CataLight” (364549901), projects A02, A05, B05, and C06. AP and
adjusted to the radiation field. The obtained incident radiant
AA thank the Vector foundation for financial support through
powers of the different sole radiation sources were calibrated and
this calibration was applied to all other measurements of the project number P2019-0110. Open Access funding enabled and
radiation sources installed in the reactor setup. The absorbed organized by Projekt DEAL.
photon fluxes were determined using a 3-step-procedure (see SI).

Hydrogen evolution reaction with molecular molybdenum

Conflict of Interest
sulfide catalysts
The authors declare no conflict of interest.
Sample preparation was carried out according to a published and
adapted procedure and is further specified in the SI.[40] For each
trial 8 solutions consisting of [Ru(bpy)3](PF6)2 (20 μM), ascorbic acid
(100 mM) and [Mo3S13]2 (0.3 μM) in different mixtures of meth- Data Availability Statement
anol/water were irradiated simultaneously for 6 hours at room
temperature ventilated by a fan. Afterwards, evolved hydrogen was The data that support the findings of this study are openly
quantified using head space gas chromatography analysis. available in Zenodo at https://doi.org/10.5281/zenodo.5614941,
Turnover numbers were calculated from the number of hydrogen reference number 5614941.
molecules produced per molecule [Mo3S13]2 .
Photocatalytic experiments in methanol/water 1 : 1 and 1 : 2 were
carried out in 8 mL WICOM WIC 41600/333 clear glass screw neck
Keywords: actinometry · open source · photocatalysis ·
vials (ND13) GC vials with 4 mL of catalysis solution at pH 6 under photoreactors · radiometry
stirring utilizing Na2[Mo3S13] × 5H2O as catalyst. As LED emitter a
460 nm LED operating at an electrical current of 0.7 A was used as
light source equipped in the 90 × 90 × 140 mm corpus. The sample [1] IEA, World Energy Outlook 2018: Highlights, 2018.
holder was placed in position 10 with an additional alignment ring [2] S. Shafiee, E. Topal, Energy Policy 2009, 37, 181–189.
holder in position 6. [3] N. Abas, A. Kalair, N. Khan, Futures 2015, 69, 31–49.
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