Accepted Article

Title: Reactor technology concepts for flow photochemistry

Authors: Thomas Rehm

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ChemPhotoChem 10.1002/cptc.201900247

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Reactor technology concepts for flow photochemistry

Thomas H. Rehm*[a]

In memory of Prof. Carsten Schmuck (1968-2019)

Accepted Manuscript
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Abstract: Synthetic organic photochemistry has been intensively
carried out in the 20th century and paved the way to complex
organic molecules, which were not yet accessible via thermal
chemistry. Several photochemical synthesis routes have found
their way into industrial applications for the production of everyday
commodities, but photochemistry was still underutilized as a
synthesis method in organic chemistry until recently. With the
advent of novel photocatalytic and photophysical concepts for the
use of high power visible light the research field of synthetic
organic photochemistry has evolved to a vivid and highly
recognized technique in the last years. Fortunately, continuous
flow technology has become a more and more accepted tool as
well and proved to be an excellent key player for the advancement
of photochemistry in academic and industrial research. This
review shall give an overview on the recent developments of
continuous flow photoreactors and their application to
photochemical syntheses under mild and defined process
conditions.
1. Introduction
In the last decade photochemistry experienced a renaissance
with fundamental impact on academic research. Major driving
force for this rapid development was the application of visible light
to photocatalytically active materials like metalorganic complexes
with e.g. Ru or Ir metal centers, metal-free sensitizers (e.g. Rose
Bengal, riboflavin derivatives or perylene diimides) or colored
electron donor-acceptor complexes.[1] Dual catalysis was applied
as well to photochemical reaction pathways enabling precise
control over the reactivity of combined catalyst systems. [2] All
efforts in this field stimulated both the development of novel
(molecular) photocatalysts with specific control of light absorption
properties and redox parameters as well as the understanding of
photophysical processes of catalyst excitation and subsequent
interaction with the substrate.[3] The use of visible light clearly
broadened the application horizon of photochemistry with milder
reaction conditions available via less energetic light. Now
sensitive fine chemicals can be converted by mild visible-light
photocatalysis with high (stereo)selectivity.[4] In contrast, less
reactive aryl carbon-halogen bonds can be selectively cleaved
with consecutively excited photocatalysts, which opens a pathway
to noble metal-free cross coupling reactions.[5] In parallel many
research groups worldwide started to transfer their results in
photocatalysis from batch mode to continuous flow mode in order
to improve light-matter interaction on smaller length scales. And
in fact, the recent years and countless publications clearly prove
that photochemistry benefits from “going to flow”. [6]
[a] Dr. Thomas H. Rehm
Division Energy & Chemical Technology / Flow Chemistry Group
Fraunhofer Institute for Microengineering and Microsystems IMM
Carl-Zeiss-Straße 18-20, 55129 Mainz, Germany
*E-mail: thomas.rehm@imm.fraunhofer.de
Website: https://www.imm.fraunhofer.de
Website: https://www.flowphotochemistry.com
This article is protected by copyright. All rights reserved.
10.1002/cptc.201900247
Continuous flow chemistry is inseparably linked to a higher level
of technology than common batch synthesis on lab scale. The
ongoing transfer from flask, stir bar and oil bath to flow chemistry
equipment leads to the integration of new concepts in mixing or
dosing, heating and processing in general.[7] Other materials than
glass come into focus, e.g. stainless steel or high performance
polymers. This extension in reaction volume determining
materials allows so-called Novel Process Windows with much
broader physical regimes for chemical reactions (e.g. temperature,
pressure, substrate concentration) than possible for common
batch chemistry.[8] In the case of photochemistry the contacting
event between the chemical phases (gas, liquid, solid) and the
physical phase of electromagnetic radiation dominates.[6e, 6f, 9]
Accepted Manuscript
Contrary to batch mode synthesis in static reaction volumes (mL
scale!) flow chemistry can take place on the µL scale, but
continuously. The reduction of the reaction volume to thin films in
open microchannels or fine streams in capillaries is the major
advantage for photochemical applications in flow equipment as it
is prerequisite for defined irradiation time and full transmission of
light through the reaction solution as well as intensive absorption
by molecules in solution or by surfaces with immobilized
catalysts.[6] The regulating variables are in this latter context the
molar extinction coefficient ε and the molar concentration c of the
light absorbing matter. The relevant dependency is expressed in
the Lambert-Beer law with A = log10T = log10(I0/I) = ε × c × d with
A as molar absorption, T as transmission, l0 and I as incident and
transmitted light intensity, and d as light path length through the
reaction volume.[10] The latter variable d lost its significance on the
µ scale whereas the molar concentration c gets more important
due to theoretical and practical reasons: a) The Lambert-Beer law
is only valid for dilute and homogeneous substrate solutions,
which compromises the advantage of continuous flow synthesis
running reactions with high substrate concentrations; b) Too high
concentrations of substrates can result in precipitating
intermediates or products. Under these conditions of solid
formation with concentration gradients in the solution the
Lambert-Beer law is not valid at all.[11] Possibly, clogging of the
flow system might stop any efforts immediately. In our case
results derived from the Lambert-Beer law should be seen as
estimation with a clear view on the physical and chemical
conditions in the irradiated sample volume. Furthermore, an
imprudent concentration increase of e.g. a polyaromatic sensitizer
can lead to soluble aggregates with different photophysical
properties and potentially different catalytic activity. [12] Hence,
new pitfalls clearly follow up to new and enticing possibilities of
novel technology. But, and this is a most fortune coincidence,
photochemistry of the 21st century stimulated not only chemists in
thinking about chemistry in a novel fashion, but also chemical
engineers in performing chemical processes in continuous flow
with the delicate tool of light. [6a,13] It is indeed amazing how
chemistry and technology development go hand in hand in the
recent years for understanding flow photochemistry and
advancing it towards real applications. In parallel, rapid
development of novel light emitting materials boosted the market
of LED technology as adaptable light source for roughly any
photoreactor architecture and photochemistry application.[14]
Finally, continuous flow technology supports the paradigm
ChemPhotoChem 10.1002/cptc.201900247

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change for running chemistry in a sustainable and green
manner.[8b]
General information about photochemistry and the beneficial use
of continuous flow reactors for photochemistry has been
described already before in several reviews and books. [1-6,15]
Hence, the intention of this review is to summarize recent
developments in reactor designs for flow photochemistry. As it is
usually the case for a review on a specific topic, the selected
examples cannot cover the complete field in photochemistry and
flow technology development. From a personal view both
literature survey and content selection was a bottomless pit and
new papers on novel synthesis routes or reactor concepts and
characterizations were published frequently per week. Hence, this
e.g. incident photon flux, medium absorbance and photonic
efficiency.[13] In consequence to the strong interest in
photochemistry (with visible light) and the growing acceptance of
flow chemistry in industry, ready-to-use photoreactors and setups
have become commercially available as well.[18] Such complete
flow chemistry machines allow easy access to flow synthesis and
clearly reduce any fear of contact to this technology. In parallel
photochemistry setups have run into further evolution and
combine multiple application scenarios like high-throughput
screening, preparative-scale batch reactions or continuous
processing with a single source of light. [19] The following chapters
will give an overview about the advancement of already known
reactor types as well as rather novel reactor concepts for more

Accepted Manuscript
vast base of information was used to gather advancements in specified applications in photochemistry.
(micro)reactor design and architecture for flow photochemistry.
The review ends with a rather personal conclusion on this vibrant 2.1. Capillary photoreactors
research field looking at the impact on universities, industry and
funding agencies. 2.1.1 Polymer capillary photoreactor for collimating light
sources

Polymer capillary reactors have become the easiest accessible

Thomas Rehm studied chemistry at the
photoreactor systems for continuous flow applications.
Julius Maximilians University in Würzburg,
Chemically inert (co)polymers like fluorinated ethylene propylene
Germany and finished his PhD thesis in 2008
(FEP) or perfluoroalkoxy alkane (PFA) exhibit a very good light
with Carsten Schmuck focusing on
transmission in the ultraviolet and visible light region and allow
supramolecular polymer chemistry in polar
flexible adaptation of the tubings to various reactor
solutions. Afterwards he joined the group of
architectures.[20] Usually polymer capillaries are wrapped around
Frank Würthner at the same university and
a light-transparent annular support that allows central
worked on perylene diimides for DNA/RNA
incorporation of a light source with radial emission, e.g. mercury
recognition. In 2011 he started a new position
vapor lamps. In most cases heat management and control of
at Fraunhofer IMM in Mainz, Germany
emission wavelength can become rather complicated due to less
working on continuous flow chemistry. His
space between light source and capillary. Hence, Telmesani et al.
research is focused on the use of microreaction technology for
developed a photochemistry platform that allows the straight-
photochemical applications in flow and on the integration of benchtop NMR
forward use of an external Hg-Xe light source emitting a
technology as online analysis tool.
collimated light beam of defined irradiance to a capillary
photoreactor.[21] The commercially available high-power light
source provides a homogenous emission of light for irradiating a
planar target. In order to use the benefits of a capillary reactor the
2. Reactor concepts for flow photochemistry
authors had to design a support for the flexible capillary that
imitates a planar surface in view from the light source. This
The focus of this chapter is on reactor concepts for flow
requirement was made possible by using a cone-shaped
photochemistry that emerged in recent years. The main
stainless-steel support with a helical groove on the outer surface.
application range of these photoreactors is the synthesis of fine
The FEP capillary (o.d. 1.59 mm, i.d. 0.79 mm) is wrapped around
chemicals. Reactor concepts for wastewater purification or
the cone and gets stabilized by the cavities of the groove (Figure
degradation of e.g. pharmaceuticals will be not discussed as well
1). The cone itself is hollow and can be continuously flushed with
as water-splitting for hydrogen production. These topics are
a coolant to maintain the desired temperature inside the capillary.
summarized and highlighted in various reviews. [16,17] In the initial
Heat transfer from the reaction solution to the coolant is even
years of flow photochemistry most of the reactors were custom-
promoted by the ideal contact between the stainless-steel
made with equipment easily available from the lab bench and
grooves and the capillary.
shelf. This straightforward strategy is easy to understand from a
chemist’s point of view with a sole focus on running chemical
reactions in flow. But from an engineering point of view this
approach is less reasonable since the physical conditions in
“hand-made” reactors are not as reproducible as necessary for
comparing reactors and processes or for scale-up. Fortunately,
there are meanwhile many activities concerning the investigation
of flow photoreactor equipment on the engineering level, which
make the process parameters easier to understand and deploy,

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ChemPhotoChem
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Figure 1. A) Continuous flow photochemistry platform with directional irradiation
by an external light source; B) photoreactor with cone-shaped heat exchanger
as stabilizing element for the capillary. Adapted with permission from ref. [21]
copyright 2015 Wiley-VCH.
Telmesani et al. applied this photoreactor system to the [2+2]
photocycloaddition of methyl cinnamate 1 (0.8 M in acetonitrile) to
methyl truxinate 2. Unfortunately, neither reactor volume nor flow
rates were given in this work, but variations in temperature,
electrical light source power and emission cut-off are described.
A maximum conversion of 29% were obtained for 2 (d.r. = 1:1) at
0 °C, 500 W power and with an irradiation greater 305 nm. Batch
tests resulted in a low conversion of 14%. A strong increase in
conversion and diastereoselectivity towards the δ-truxinate 2 was
achieved by the use of a thiourea organocatalyst 3 (10 mol%).
Pre-coordination via strong hydrogen-bonding boosted the
conversion to 76% with a diastereomeric ratio of 3:1 in favour of
δ-truxinate (Figure 2).
Just recently Telmesani et al. could improve this process by
switching to a biphasic liquid-liquid process with ethyl acetate and
water as solvent system (1:10).[22,23] The conventional capillary
photoreactor was used with an inner volume of 11 mL at a net
flow rate of 100 µL min-1 (τres = 110 min). The resulting water slugs
inside the organic phase led to a better circulation thus mixing of
the organic reaction solution. Furthermore, thin film formation
around the water slugs resulted in an improved interaction with
UV light. Both advantages resulted in a maximum conversion of
87% for methyl truxinate 2 with a diastereomeric ratio of 3:1 (δ:β).
Without slug flow recirculation was necessary for 8 hours to reach
a yield of 75%.
Figure 2. Synthesis of methyl δ-truxinate 2 via [2+2] photocycloaddition of
methyl cinnamate 1 using thiourea organocatalyst 3.
2.1.2 Triphasic micro-batch reactors in flow
Slug flow conditions can be also extended to a triphasic system
as demonstrated by Pieper et al. for the incorporation of a solid
This article is protected by copyright. All rights reserved.
10.1002/cptc.201900247
photocatalyst into a regular gas-liquid flow inside a capillary
reactor.[24] The basic idea of this approach is the formation of so-
called serial micro-batch reactors (SMBRs), which are simply
well-ordered liquid phase segments alternating with inert gas
segments inside the capillary reactor. This classical slug flow
regime allows efficient mixing inside the liquid segments and
excellent gas mass transfer at the gas-liquid interface.
Furthermore strong interfacial forces between the gas and the
liquid phase are the prerequisite for constant and efficient
transport of solid material inside the capillary. Nevertheless, the
incorporation of equal amounts of solid catalyst into SMBRs is
mandatory for enabling equal reaction conditions inside each
micro-batch reactor. Pieper et al. solved this problem by the
Accepted Manuscript
preparation of a photocatalyst suspension in a viscous solvent,
e.g. an ionic liquid like [Bmim]BF4. Sedimentation of solids is
strongly hindered in such a solvent and can be even more
reduced to a negligible rate by active mixing with a magnetic stir
bar inside the dosing syringe. The authors exemplified their
approach for the heterogeneously catalyzed decarboxylative
fluorination of phenoxy acetic acid 4 using CMB-C3N4 as
photocatalyst derived from cyanuric acid, melamine and barbituric
acid (Figure 3).
Figure 3. Continuous flow synthesis of (fluoromethoxy)benzene 5 with carbon
nitride as solid photocatalyst in a triphasic slug flow system.
The preparation of the triphasic system was done by mixing at first
the liquid phase (acetonitrile-water, 1:1, fl = 0.5 mL min-1)
containing 4 (0.2 mol L-1) and SelectFluor® (3 eq) with nitrogen
gas (fg = 0.3 mL min-1) via Y-shaped mixer into a FEP capillary
(i.d.: 1.6 mm). The stabilized slug flow was then contacted with
the solid catalyst in a T-piece connected to a syringe filled with
the photocatalyst suspension of 85 mg CMB-C3N4 in 4.2 mL
[Bmim]BF4 with 0.8 mL H2O (Figure 4). A flow rate of fsus = 50 µL
min-1 was applied here and led to the generation of the triphasic
mixture, which was finally transferred into the capillary
photoreactor (FEP, τres = 14 min, 17 mL) and irradiated with an
LED array at 420 nm (12 W). Under these conditions the
decarboxylative fluorination proceeded smoothly with full
conversion and 94% NMR yield. Importantly, any CO2 generated
during the reaction can easily diffuse out of the liquid slugs without
disturbing the stability of the solid-liquid SMBRs by extended gas
slugs. Finally, a first approach for the scale-up of this process was
done as well. The authors integrated a second suspension dosing
device prior to the photoreactor, which allowed the on-the-fly
exchange of empty syringes for the CMB-C3N4 suspension. Within
an overall run time of 390 min approx. 1.6 g of 5 was produced.
This work by Pieper et al. clearly sets the stage for future
applications of many solid reagents and catalysts to be used in
continuous flow reactors. Gas-liquid and liquid-solid phase
ChemPhotoChem
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separation can be easily done by filtration of the solid content form
the reaction stream. Depending on the character of the solid
material a re-use may be possible as well, which is beneficial for
the overall (cost) efficiency of the process.
Figure 4. A) Suspension dosing device for triphasic mixing (inset: schematic
representation of gas-liquid-solid contacting); B) Resulting slug flow with solid
photocatalyst in the liquid phase; C) FEP capillary reactor with SMBRs under
steady state conditions. Adapted with permission from ref. [24] copyright 2018
Wiley-VCH.
2.1.3 Multilayer capillary photoreactor
The next step in the evolution of capillary photoreactors goes
ahead to multilayer capillary designs. In general, this approach is
attractive due to two reasons: a) Residual photons, which were
not absorbed in the first layer can be further used in a second or
third layer; b) Any additional capillary layer can be used either for
increasing the residence time or for running different or cascade
reactions in one reactor. In 2014 Elliott et al. published a work
about the question which process mode is more productive for
photochemistry: batch or continuous flow. [25] The authors
performed and compared several photochemical reactions under
This article is protected by copyright. All rights reserved.
10.1002/cptc.201900247
the same process conditions (photolysate concentration, UV lamp
power, emission wavelength) either in batch mode or in capillary
photoreactors with one or three layers. Based on this work the
authors revealed three very interesting trends for synthetic
photochemistry processes: a) At full conversion the yields are
basically the same in batch and continuous flow mode; b) FEP
photoreactors with three capillary layers have on average a 20%
higher productivity compared to the same batch end point; c) In
reverse one-layer FEP photoreactors have on average a 20%
lower productivity compared to the same batch end point. The
authors state that the lower productivity of the one-layer
photoreactor can be attributed to the shorter light path length of
2.7 mm in the capillary against 8.7 mm in the batch vessel. In
Accepted Manuscript
reverse, the three-layer photoreactor offers superior productivity
due to a strongly increased residence time over three capillary
lengths and the possibility to absorb remaining photons in the
second and third capillary layer after passing the first layer. But
finally Elliott et al. also conclude that the superiority of the FEP
capillary photoreactor technology is not yet fully understood.
Parameters like gradients in concentration and light absorption
throughout the complete capillary system must be investigated as
well as light scattering and refraction effects.
Just recently, Wriedt at al. published their work on the
experimental determination of photon fluxes in multilayer capillary
photoreactors.[13g] The authors applied the photochemical
decomposition of [FeIII(C2O4)3]3- to [FeII(C2O4)2]2-, carbon dioxide
and oxalate (ferrioxalate actinometer) to a three-layer FEP
photoreactor with a medium pressure Hg lamp (150 W) as central
light source (Figure 5).
Figure 5. A) Self-made three-layer FEP capillary photoreactor used for the
experimental determination of photon fluxes in separate capillaries; B)
schematic representation of the capillaries wrapped around the central Hg lamp.
Adapted with permission from ref. [13g] copyright 2018 Wiley-VCH.
Interestingly, Wriedt et al. could show that the on average external
photonic efficiency as ratio between the absorbed and available
photons is 11% for the inner layer, 3% for the middle layer and
finally 1% for the outer layer. The data obtained in this work show
an exponential decay of the amount of absorbed photons with
ChemPhotoChem
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increasing number of capillary layers, which is in accordance with
the Lambert-Beer law. This behavior points to the fact that each
additional capillary layer acts with its cross section as extended
optical path length for any photons that were able to pass the
foregoing layer by scattering or refraction.
From a technological point of view our group started to set up
capillary photoreactors with permanently integrated and water-
chilled LED light sources and FEP capillaries wrapped around a
quartz glass cylinder.[26] While working with this first version of the
photoreactor it became obvious that a separate temperature
management for capillaries and LED arrays is necessary as well
as an useful opportunity to switch to defined wavelengths
depending on the reaction to be performed. Hence, the revised
version is a two-layer capillary photoreactor (0.8 or 1.6 mm i.d.
with 2 × 15 mL or 2 × 30 mL inner volume) with exclusive cooling
for the capillaries in a double cylinder chamber (Figure 6). The
LED arrays are exchangeable and are placed on a separately
chilled cooling finger in the center of the reactor assembly.
Emission wavelengths can be chosen from the UV to visible light
region (six LED emitters per circuit board fixed on a hexagonal
aluminum support). A maximum of 110 W electrical power is
applicable to such an LED array with 36 emitters. Thanks to the
rapidly developing LED market high power LEDs with an emission
wavelength below 340 nm will hopefully become available in near
future. With this device our current research is focused on the
areas of dye-sensitized singlet oxygen formation, cyanation
reactions, diazonium salt chemistry and photochemical
nanoparticle formation.
Figure 6. A) Compact two-layer capillary photoreactor with exchangeable LED
arrays and separate capillary and LED cooling; B) Assembled photoreactor with
LED array for green light emission at 520 nm; C) Holder for LED arrays
facilitating an easy switch to other emission wavelengths. Copyright 2018
Fraunhofer IMM.
2.1.4 Photonic crystal fibers as ultra-low volume
photoreactors
The last example in this chapter deals with the use of photonic
crystal fibers (PCFs) as an advanced version of conventional solid
optical fibers and hollow capillaries. [27] The latter ones can be
already used as light-guiding capillaries loaded with a chemical
sample for intense interaction with the injected light. Unfortunately,
the interaction length is most often restricted to some centimeters
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10.1002/cptc.201900247
since light leaks pretty easily out of the waveguide. To overcome
this problem photonic crystal fibers have been developed, which
consist of a waveguide core surrounded by a periodic array of
holes ranging over the complete length of the fiber. [28,29] This
architecture acts as a trap for the light inside the central hollow
core with a highly reflective cladding structure. One example is
the so-called kagomé hollow core PCF whose name originates
from the specific arrangement of triangles and hexagons around
the central hollow core (Figure 7A and B). This architecture allows
a broadband spectral transmission through the liquid filled fiber
for sensing or photochemical experiments with sub-µL samples
(Figure 7C).
Accepted Manuscript
Figure 7. A) Schematic representation of a kagomé hollow core PCF with a core
diameter of 20 µm; B) SEM image of a kagomé hollow core PCF; C) Schematic
representation of continuous flow setup with a PCF as microreactor on the µL
scale. Adapted with permission from ref. [27] copyright 2013 Wiley-VCH and ref.
[28] copyright 2013 Royal Society of Chemistry.
Of course, PCFs used as “capillary” photoreactors cannot be
compared with their larger FEP relatives, but they offer several
very interesting properties, which complement the application
portfolio of common photoreactors: a) The optofluidic channels of
PCFs exhibit an extremely reduced sample volume; b) Low
transmission losses inside PCFs allow the detection of extremely
low concentrated analytes within a light path length of up to
several meters; c) Low quantum yield photochemical processes
can be measured and analyzed due to the strongly enhanced
light-matter interaction inside the PCF core. [28] Despite these
obvious advantages PCF-based flow set-ups can be also
combined with classical analytical tools of mass spectrometry or
in situ spectroscopy. Finally, the inner surface of PCFs can be
chemically modified and used as support for e.g. catalytically
active particles.[30]
ChemPhotoChem
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2.1.5 Polymer-based waveguides as photoreactors
Optofluidic PCF microreactors are limited to either liquid or
gaseous phase inside the hollow fiber. Bubble formation in the
liquid stream or even gas-liquid slug flow destroys the light
guidance inside the fiber and hinders efficient light-matter
interaction.[31] Solvents with good gas solubility can be
presaturated with the appropriate gas and pumped into the PCF,
but continuous dosing of gas into the reaction solution is not
possible as well. To circumvent this problem Ponce et al. used an
amorphous fluoropolymer (Teflon® AF-2400), which allows gas
permeation through chemically inert polymer membrane. Most
importantly this fluoropolymer has a very low refractive index
<1.30.[32] Capillaries made of this material can be filled with a
solvent (e.g. water) and used as liquid core waveguide membrane
(LCWM) due to total internal reflection. In analogy to the setup
depicted in Figure 7C Ponce et al. used this concept to design a
continuous flow photoreactor system with water as solvent.[31] The
authors could show that in the visible light region optical losses
are fairly low at wavelengths <575 nm (1.67 ± 0.70 dB m -1). At
longer wavelengths the optical loss increases due to the stronger
absorption of light by the solvent water (Figure 8A). The UV-Vis
spectroscopy performance of the system was then evaluated by
comparing absorption spectra of dye solutions containing Azure
A (AA) or Acid Orange (AO) with those obtained in standard
cuvettes. As depicted in Figure 8B an excellent accordance is
obtained with the reference measured in the cuvette.
Figure 8. A) Optical losses in the visible light region as measured in Teflon® AF
2400 tube filled with bi-distilled water; B) Absorption spectra of Azure A (AA)
and Acid Orange (AO) obtained from the tube system (LCWM) or from a
standard cuvette. Adapted with permission from ref. [31] copyright 2018 Wiley-
VCH.
The polymer waveguide was supplied with air by placing it into a
pressurized steel tube. Bubble formation inside the polymer
capillary (i.d. 1.0 mm, o.d. 1.6 mm, length: 52 cm) was
investigated for a gas pressure range of 0.5 to 8 bar while the
liquid pressure inside the capillary was maintained at 2.8 bar.
Short residence times <5 s allow a high gas pressure of up to 8
bar, whereas a more reasonable residence time >20 s requires a
lower gas pressure of approx. 4 bar to avoid oversaturation and
bubble formation inside the capillary. The system was finally used
to perform a continuous flow methylene blue photocatalyzed
oxidation of D-glucose.
2.2 Glass (tube) photoreactors
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10.1002/cptc.201900247
Coiled quartz glass tubes exhibit an excellent transmission even
in the deep UV light region. Hence, they have been used as
integral part of continuous flow photoreactors, but they never
gained so much attention compared to their relatives made of
flexible polymer materials, although such solid glass coils are
commercially available and can be implemented in complete
photoreactor systems.[33] On the contrary, straight quartz glass
tubes have meanwhile made their way into several technological
applications for photochemical processes. Recent examples will
be summarized in this chapter, whereby conventional glass chip
reactors with chemically etched or mechanically machined
microchannels will not be discussed here. These rather small
versions of glass reactors have been already described in detail
Accepted Manuscript
as well as their applications in photochemistry. [34]
2.2.1 Quartz glass photoreactor for UV-C photochemistry
In the first example DeLaney et al. describe an annular continuous
flow reactor combined with a set of excimer lamp light sources for
the irradiation with defined wavelengths (KrCl: 222 nm; XeBr: 282
nm; XeCl: 308).[35] The reactor itself consists of a stainless steel
cooling finger (o.d. 12 mm), which is placed inside a quartz glass
tube (o.d. 15.6 mm). The outlet of a 1/16” stainless steel capillary
leaves the cooling finger at its end inside the quartz tube and is
used as supply for the reaction solution, which flows back as thin
film of approx. 120 µm thickness between the inner glass wall and
the outer cooling finger wall (Figure 9). The assembled reactor is
then placed in the excimer lamp housing with an overall irradiation
volume of 1.37 mL.
Figure 9. Schematic representation of the continuous flow device to be placed
inside an excimer lamp housing. Adapted with permission from ref. [35]
copyright 2016 Royal Society of Chemistry.
The photoreactor set-up was used for the photodecarboxylative
cyclisation of phthalimid 6 in a 1:1 water-acetone solvent mixture
(Figure 10). The best yield for cyclized 7 was obtained with an
irradiation at 308 nm and a substrate concentration of 0.1 M. With
a flow rate of fl = 0.2 mL min-1 nearly 100% yield could be obtained
corresponding to a space time yield (STY) of 0.88 mmol h -1 mL-
1 [36]
. A maximum STY of 2.99 mmol h-1 mL-1 was obtained by
increasing the flow rate to fl = 1.0 mL min-1, which, in reverse,
resulted in a lower yield of 68%. Irradiation at 222 nm led under
ChemPhotoChem 10.1002/cptc.201900247

REVIEW
the same reaction conditions to 37% yield. This low value results
from the smaller number of emitted photons at 222 nm compared
to the irradiance with the XeCl lamp (308 nm) at the same
electrical power level. Finally, the authors summarize that in view
of green chemical reaction technology excimer lamps are favored
against Hg lamps due fewer safety issues. And especially for this
novel reactor concept less stray light is produced by the lamps as
well as less ozone due to the straight fit of the reactor inside the
lamp housing.

Accepted Manuscript
Figure 10. Photodecarboxylative cyclisation of potassium N-phthalimido-
butanoate 6 with UV light in continuous flow.

2.2.2 Gas-liquid mixing via vortex formation
A second reactor concept is based on the generation of Taylor
vortices by a rapidly rotating stainless steel cylinder inside of a
transparent Pyrex® jacketed tube with a sealed bottom.[37] Based
on already existing design studies of such a vortex reactor Lee et
al. developed an advanced version for reactions with oxygen gas
in combination with high power LED technology.[38] Intense mixing
of gas and liquids is made possible in the annular gap between
the rotating cylinder and the inner glass tube (approx. 1 mm;
reactor volume: 8 mL). The reactant solution is pumped via the
rotating cylinder to the bottom of the glass tube whereas the
oxygen-containing gas phase is directly drawn from the
surrounding atmosphere without the necessity of pressurizing it
(Figure 11). The glass tube itself can be cooled with a standard
cryostat as well as the three LED arrays located in close proximity
to the glass tube (distance: 5 mm). In total, the arrays provide a
luminous flux of 21,000 lm (3 × 5 × 1400 lm, 5,000 K), which is
directed on the glass tube photoreactor. Polished aluminum
blocks located in between the LED arrays are used for reflecting
any residual light scattered or refracted from the inside of the
reactor assembly. CFD studies have been performed with water
as solvent in order to visualize the vortex flow structure in the
annular gap. Already a rotational speed of approx. 955 rpm gave
a Taylor number of about 100,000, which is far above the critical
value of 1,700 for vortices formation. The reactor setup allows a
freely selectable rotational speed up to 4,000 rpm thereby offering
a broad regime for efficient gas-liquid contacting.
Figure 11. A) Disassembled vortex reactor with LED arrays, motor and control
box; B) LED arrays and mirror blocks assembled around the glass tube; C)
Schematic representation of the vortex reactor showing delivery and removal of
reaction solution and gas intake; D) and E) Vortices formation as modelled via
CFD and in live operation. Adapted with permission from ref. [37] copyright 2017
American Chemical Society.
Lee et al. performed several photooxygenation reactions, which
showed the general trend of higher conversion rates at increased
rotational speed. Finally, the authors applied their reactor concept
to the three-step synthesis of artemisinin 11 from
dihydroartemisinic acid 8 (Figure 12). Variation of the solvent,
type of sensitizer and temperature resulted at 25 °C in 50% yield
at full conversion with acidified meso-tetraphenylporphyrin (TPP)
as dye sensitizer for 1O2 generation. The reaction solution (0.05
M 8 acid in toluene) was pumped through the reactor with a flow
rate of fl = 0.5 mL min-1, the cylinder was rotated with maximum
speed of 4,000 rpm. Variation in the amount of trifluoroacetic acid
(TFA) between 0.1 and 1 eq gave identical conversion and yield
as for 0.5 eq. This result indicates excellent mixing properties in
the reactor for catalytic applications.

This article is protected by copyright. All rights reserved.

ChemPhotoChem
REVIEW
Figure 12. Schematic overview on the three-step synthesis of artemisinin 11
with air as oxygen source: photooxigenation with 1O2; acid-catalyzed Hock
cleavage (TFA = trifluoroacetic acid) and rearrangement; oxidation with 3O2
(other hydroperoxides and tautomers are omitted for clarity).
2.2.3 Aerosol droplet formation for gas-liquid mixing
In the previous example the liquid phase was in high excess
compared to the gas phase take in by the rapidly rotating steel
cylinder. In the following example the ratio of liquid to gas is
reversed with a larger amount of gas being used to nebulize the
liquid reaction solution for efficient gas-liquid mixing in a confined
space. Ioannou et al. use a rather large Pyrex® glass cylinder
(length: 370 mm, diameter: 65 mm) with a front inlet for the
pneumatic nebulizer and a rear outlet for product solution.[39] Air
or oxygen gas can be introduced with a flow rate of fg = 0.7-1.1 L
min-1 in a pressure range of 2.76-4.14 bar. For the liquid phase a
flow rate of fl = 0.5-1.0 mL min-1 is recommended. White light
producing LED stripes (3,800-4,200 K) are wrapped around the
reactor chamber with a distance of 10 mm to the glass wall in
order to prevent heat transfer from the LEDs to the reactor (Figure
13).
Figure 13. A) Schematic representation of the nebulizer photoreactor; B) Fully
operating nebulizer photoreactor assembled in a standard fume hood.
Reproduced with permission from ref. [39] copyright 2017 Wiley-VCH.
The pneumatic nebulizer, the core element of the reactor, was
originally designed as part of trace-level analysis equipment for
ICP-MS or ICP-OES analysis of aqueous samples. This device
allows the production of droplets with a diameter of approx. 6 µm
when operated with argon gas and water-based solutions.[40] In
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10.1002/cptc.201900247
the present case Ioannou et al. use air or oxygen gas as reactive
carrier phase and methanol as solvent. In consequence to these
different conditions and variation in flow rates the authors also
assume a larger droplet size of up to 60 µm in diameter. However,
this still conservative value for the droplet size implies an
exceedingly high surface to volume ratio of 100,000 m 2 m-3, which
is the base for a very efficient gas-liquid mass transfer made
available by the nebulizer reactor. Ioannou et al. applied their
photoreactor setup to the continuous flow synthesis of ascaridol
13 (Figure 14). A solution of α-terpinene 12 (1.0 M in MeOH) and
Rose Bengal (0.8 mol%) was transferred to the nebulizer with a
flow rate fl = 0.8 mL min-1 and sprayed with pure oxygen gas into
the glass chamber (pgas = 4.14 bar). Under these conditions nearly
Accepted Manuscript
full conversion was possible with a productivity of 8 g h -1. A
maximum productivity of 14.2 g h-1 was achieved with higher
substrate concentration (2.0 M 12) and slightly lower liquid flow
rate of fl = 0.75 mL min-1. Interestingly, the exchange of oxygen
gas with air resulted under the same process conditions in still a
high productivity of 12.0 g h-1.
Figure 14. Ascaridol synthesis with Rose Bengal as dye sensitizer for 1O2
formation in the aerosol.
2.2.4 Gas-liquid mixing under high pressure
The reactor concept comprises an upright standing high pressure
resistant sapphire glass tube (o.d. 10 mm, length: 120 mm, wall
thickness: 1 mm), which was filled with glass beads having a
diameter of 6 mm.[41] The incorporation of the spheres results in
better mixing of the gas-liquid mixture and a reduced light path d
between the inner wall of the glass tube and the bead surface (1
mm < d < 8 mm). Three high power LED arrays were applied for
irradiation with white light (5,000 K). A back pressure regulator
was installed to maintain the system pressure between 1-20 bar.
Penders et al. used their reactor concept for the dye sensitized
hydroxylation of arylboronic acid 14 in an aqueous ethanol
solution with high excess of air compared to the substrate solution
(Figure 15). The phases were combined in a micromixer and the
dispersion was transferred into the glass tube photoreactor. At
atmospheric pressure a conversion rate of 67% was achieved
with a 0.05 M solution of 14 in H2O-EtOH (1:1), Rose Bengal as
sensitizer (2 mol%) and Hünig’s base as reductive quencher (2
eq). The liquid flow rate was set to fl = 0.8 mL min-1 with a
corresponding gas flow rate of fg = 53.6 mL min-1 (fl : fg = 1 : 67).
Conversion was increased to nearly 100% by increasing the
system pressure to 20 bar while maintaining the liquid and gas
flow rate at the same level.
ChemPhotoChem
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Figure 15. Hydroxylation of arylboronic acid 14 with Rose Bengal as dye
sensitizer for 1O2 formation and Hünig’s base as reductive quencher using a
high pressure resistant glass tube photoreactor with glass beads. Adapted with
permission from ref. [41] copyright 2015 Royal Society of Chemistry.
2.2.5 Gas-liquid mixing via rotating liquid thin film
In the last example, a semi continuously working photoreactor is
described for gas-liquid reactions. Clark et al. modified a lab rotary
evaporator for the generation of a liquid thin film in rotating glass
flasks of various volumes (Figure 16).[42] The substrate solution
and the reactive gas were fed into the glass flask with separate
peristaltic pumps. Two LED arrays were located in close proximity
to the flask (approx. 20 mm) providing white light with a luminous
flux of either 1,000 lm or 8,000 lm. The authors used this simple
and versatile photoreactor as well for the synthesis of ascaridol
13 in a 1,000 mL flask (Figure 14). α-Terpinene 12 (0.1 M in EtOH,
5.0 mL) and Rose Bengal (1.0 mol%) were transferred into the
flask and oxygen gas was bubbled through the solution. A
custom-made UV-Vis spectrometer was used to analyze the film
thickness of the solution inside the rotating flask. With a rotation
speed of 175 rpm a film thickness of approx. 260  40 µm was
obtained. The reaction solution was irradiated for 10 s with the
high power LEDs at 8,000 lm resulting in 72% yield, which
corresponds to a productivity of 22.2 g h -1. With this high value,
the rotary evaporator photoreactor outperforms the already pretty
productive nebulizer photoreactor described above.
This article is protected by copyright. All rights reserved.
10.1002/cptc.201900247
Figure 16. Schematic representation and assembled reactor setup of a modified
lab rotary evaporator as photoreactor for thin liquid film formation in the turning
flask. Adapted with permission from ref. [42] copyright 2016 American Chemical
Society.
2.3 Microchannels in light-converting media
2.3.1 Luminescent solar concentrators with fixed emission
wavelength
Luminescent solar concentrators (LSC) are optical devices for
light harvesting and transportation.[43] Usually they exhibit a large
area for illumination with solar light and are made of glass or
Accepted Manuscript
polymeric material. The rather thin devices are doped with
fluorescent materials like dyes or quantum dots. [43b,44] The energy
of incident light with appropriate wavelength is absorbed by the
luminophores and is ideally emitted at longer wavelength again.
By total internal reflection the emitted light is waveguided inside
the device to its thin edges, which leads to bright and
concentrated refulgence. Based on this effect LSCs have been
utilized e.g. as solar light harvesting devices optically coupled to
small-area photovoltaic cells or as switchable windows in the case
of chemical host-guest systems composed of liquid crystals and
dyes.[45,46] Recently Cambié et al. applied the concept of LSCs for
harvesting and concentrating (diffuse solar) light at the walls of
microchannels, which were integrated into the LSC device.[47] The
emitted light of the dopant luminophore can then be absorbed by
a sensitizer dissolved in the reaction solution and fed into the
microchannels. In order to yield a perfect match between
fluorescence emission of the LSC and absorption capability of the
sensitizer the authors selected a commercially available perylene
diimide dye (Lumogen F red 305) as dopant for the LSC and
methylene blue as sensitizer for the photochemical process.
Perylene dyes exhibit a broad absorption spectrum in the visible
region between 400 and 600 nm and offer a strong emission
between 600 and 700 nm, which fits perfectly to the absorption
band of methylene blue (Figure 17A). Prior to the fabrication of
the photomicroreactor Cambié et al. performed in silico
optimization of the channel dimension and architecture using
Monte-Carlo ray-tracing simulations. The optimal conditions were
found with a 50 × 50 × 3 mm3 device containing six microchannels
of 500 µm width and 1 mm height (Figure 17B).
Polydimethylsiloxane (PDMS) was selected as LSC microreactor
material due to its chemical stability, high transparency and
moderate refractive index of n = 1.41, which is enough for total
internal reflection and minimized reflection on the outer surface. [45]
Various PDMS-dye mixtures were prepared with a dopant share
of 10-200 ppm. The reactor body was fabricated by casting the
dye-doped PDMS in 3D-printed mold with the positive relief of the
intended channel design. A plane dye-doped PDMS slab was
prepared as lid for the microchannel structures. Both slabs were
cured at 60 °C for 2 h and bonded via oxygen plasma treatment.
Residual PDMS was cut off and 1/16” PFA capillaries were press
fit into inlet and outlet of the LSC microreactor (Figure 17B). Now
photons can be collected inside the microchannels directly from
the incident light and by light-guided photons from the LSC reactor
body.
ChemPhotoChem
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Figure 17. A) Absorption (red) and emission (green) bands from the perylene
dye as well as the absorption band of methylene blue (blue); B) final LSC
microreactor filled with methylene blue solution; C) Conversion rates by solely
waveguided photons with light blocked microchannel; D) Conversion rates of
fully irradiated LSC microreactor. Adapted with permission from ref. [47]
copyright 2017 Wiley-VCH.
Cambié et al. characterized the novel photoreactor by applying it
to the [4+2] cycloaddition of 9,10-diphenylanthracene 16 and in
situ-generated singlet oxygen with a solar simulator as light
source (Figure 18). The substrate solution (0.1 mM in acetonitrile)
was mixed with the sensitizer solution (methylene blue, 0.2 mM in
oxygen saturated acetonitrile) prior to the inlet of the LSC
microreactor. The impact of waveguided photons has been
analyzed by blocking direct irradiation of the microchannels with
a black card board (Figure 17C). For the non-doped LSC a
minimum conversion of approx. 9% was obtained with a residence
time of τres = 90 s. The 200 ppm-doped LSC reactor achieved 54%
conversion, which is an increase by a factor of 6 solely due to
waveguided photons, which were harvested and concentrated in
the non-blocked part of the reactor. The fully irradiated LSC
reactor with 200 ppm dopant achieves a conversion as high as
90% with a residence time of τres = 90 s (Figure 17D). The non-
doped version converts approx. 40% of the substrate at the same
time. These results clearly show the high potential of harvesting
and concentrating solar light for photochemical reactions in LSC
devices.
This article is protected by copyright. All rights reserved.
10.1002/cptc.201900247
Figure 18. [4+2] Cycloaddition of 9,10-diphenylanthracene 16 with in situ-
generated singlet oxygen.
Based on this first conceptual paper several other papers were
Accepted Manuscript
published in the following time by the same work group. A
theoretical study was performed by Cambié et al., which
investigates the possible pathways of photons into and inside
microstructured LSC devices: a) top reflection, b) transmission
through the device, c) emission due to insufficient total reflection
inside the device (escape cone), d) emission via the edges of the
device, e) general losses by e.g. matrix absorption, and most
important f) absorption by the reaction media directly from incident
light or from waveguided light.[48] The authors also investigated
the impact of the device size, channel height and channel pattern
as well as the impact of the photon path length across the LSC
material to the microchannel. This detailed theoretical study was
done with a Monte-Carlo ray-tracing algorithm designed to model
LSCs.[49] The results gave important hints for the fabrication of
future LSC reactors. Large area LSC devices (1 m2) exhibit fewer
losses via edge emission than small devices (25 cm 2). The same
trend is seen for devices with larger channel heights and a greater
number of integrated channels, ideally as grid with a small gap
between the channels. Especially the latter parameter is
important as it directly correlates with the possibility of photon
reabsorption by the luminophore in bulk LSC material. For the
best theoretical device (1 m2 area, grid, 2.5 cm channel distance)
the following numbers were obtained for the photon balance: 4%
direct reflection, 44% transmission, 4% non-radiative losses, 16%
escape cone, <1% edge emission, 28% absorption of waveguided
photons in microchannel, and 3% direct absorption of photons in
microchannel.
Another project was dedicated to a scale-up approach of LSC
photoreactors via a numbering-up strategy.[50] Zhao et al.
investigated the impact of different zones in the microreactor
structure: inlet, distributor, reaction zone, collector and outlet. 3D-
printed molds were easily available for rapid prototyping of several
LSC reactor devices. As already mentioned in the foregoing
theoretical paper the interchannel distance is an important
parameter, which now has been evaluated in this practical work
in greater detail for the [4+2] cycloaddition of 16 with 1O2. An
increase in interchannel distance (1.5  2.5  5 mm) results in
a significant increase in conversion (43%  59%  72%;
residence time for all experiments: τres = 12.5 s). A further increase
to 10 or even 20 mm is less effective for the conversion ( 80%
 95%). Both trends lead to the assumption that with increasing
interchannel distance a greater number of photons is harvested
and concentrated at the microchannels. In contrast to this positive
trend any further increase of bulk LSC material between the
ChemPhotoChem
REVIEW
channels also leads to reabsorption of waveguided photons and
to a higher degree of non-radiative losses. In consequence the
process gets less efficient with a lower rise in conversion. Zhao et
al. could also show that a symmetrical bifurcated distributor leads
to an excellent flow distribution over up to 32 channels, whereas
a simple collection chamber overcomes high pressure drops in
the complete reactor.
Furthermore, Zhao et al. developed a real-time reaction control
system for their original LSC microreactor, which allows a more
or less constant photochemical process under fluctuating solar
daylight.[51] The idea behind this approach is the adjustment of the
residence time in the reactor to the incident solar light. In order to
get a measure of incident light on the reactor surface the authors
integrated a light sensor at the edge of the LSC device, which
detects the photon flux emitted there. This readout value is
proportional to the incident light and can be finally linked by
electronics to the piston pumps for varying the reaction solution’s
flow rate and residence time in the microreactor (Figure 19A).
Figure 19. A) Schematic representation of the setup used; B) Conversion as
measure of process stability with reaction control system (red) and without
(green). Adapted with permission from ref. [51] copyright 2018 Royal Society of
Chemistry.
The set-up was applied to the well-known benchmark reaction of
[4+2] cycloaddition of 16 with 1O2. Strong fluctuations in
conversion are observed for the non-controlled process with an
amplitude between 55% to 97% (green line in Figure 19B). In the
case of the controlled process a significantly more constant
conversion rate can be achieved with small fluctuations between
86% and 93% (red line in Figure 19B).
Just recently, the 1st generation of LSC devices has been
improved according to stability and light emission. [52] In order to
achieve greater chemical stability Cambié et al. replaced the
reactangular microchannels in the PDMS light guide by PFA
capillaries, and self-made PDMS light guiding material was
substituted with commercially available PMMA light guiding
devices (Figure 20). PMMA offers a higher refraction index (n =
1.49 vs. n = 1.41 for PDMS), which results in consequence in an
improved photon directing ability inside the light guiding device. In
addition, PMMA is more compatible to other classes of
luminophores and offers a lower dye degradation over time
compared to PDMS. Based on these new PMMA devices blue
(430 nm) and green (510 nm) light emitting LSCs are available
now besides the original red one (640 nm). In the case of the blue
LSC device, photochemistry with common Ru-based dyes
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10.1002/cptc.201900247
became possible (e.g. aryl amination with NiCl2∙glyme), as well as
the application of Eosin Y or Rose Bengal with the green LSC
photomicroreactor for benzylamine oxidation or ascaridol
synthesis.
Accepted Manuscript
Figure 20. Advanced LSC photomicroreactors for a broader application range
of light and catalyst classes. Adapted with permission from [52] copyright 2019
Wiley-VCH.
2.3.2 Fluorescent fluids for photoreactors with variable
emission wavelength
Contrary to the LSC devices with fixed emission wavelengths
Zhang et al. designed a 3D-printable, two-channel reactor
concept, which allows a specific emission wavelength by using
different fluorescent fluids.[53] These luminophore-containing
solutions are placed in the so-called light channel, which enfolds
the reaction channel. The physical principle is the same as for
LSC devices. Diffuse light is harvested by the dissolved
luminophores in the light channel, and emitted as fluorescent light
of specific wavelength to the reaction channel. In order to analyze
and optimize the light illuminance distribution and uniformity on
the reactor channel, the authors performed Monte-Carlo ray-
tracing simulations of several light channel architectures, e.g.
helical, linear or cylindrical (Figure 21 A). As supposed a full
enclosure of the reaction channel by a cylindrical light channel
results in the best illuminance distribution and uniformity. In the
case of optimizing the reaction channel architecture, numerical
simulation analysis was done with the finite element method. Here,
optimal mixing and diffusion was found for a 12-fold helical
channel architecture being superior over a 6-fold helix and linear
arrangement (Figure 21 B). Based on these results an appropriate
photomicroreactor was designed via computer-aided design and
transferred to a commercially available stereolithographic 3D-
printer (Figure 21 C and D).
ChemPhotoChem
REVIEW
Figure 21. A) Different light channel architectures enfolding a linear reaction
channel. Illuminance distribution is given for the central cross-section (1 mm2)
of the reaction channel; B) Mixing efficiency of linear, 6-fold and 12-fold helical
reaction channels; C) Final photomicroreactor with cylindrical light channel and
helical reaction channel under UV irradiation; D) Fabrication process of 3D-
printed two-channel photomicroreactors as exemplified with a linear reaction
channel surrounded by a helical light channel. Adapted with permission from
[53] copyright 2019 Wiley-VCH.
Zhang et al. used their reactor concept for the [4+2] cycloaddition
of in situ-generated singlet oxygen to 9,10-diphenylanthracene
(16). With Luminogen F Red 305 as luminophore in the light
channel and methylene blue as sensitizer in the reaction channel
the same couple was used as in the work of Campié et al. (Figure
18 and ref. [47]). As light source either a custom-made cylindrical
LED array was used for blue light irradiation at 440 nm, or a solar
simulator (1 sun). The 12-fold helical reaction channel has an
internal volume of 1.23 mL and was fed with 16 (0.1 mM in
acetonitrile) and methylene blue (0.2 mM in oxygen-saturated
acetonitrile) at equal flow rates. At a maximum luminophore
concentration of 400 ppm in the light channel a maximum
conversion of 70 % was obtained within a residence time of τres =
85 s. By using a solar simulator as light source a conversion of
approx. 60 % could be achieved within a residence time of τres =
15 s, again with a maximum luminophore concentration of 400
ppm. The standard setup of Cambié et al. gives approx. 40%
conversion, but already at the half of luminophore concentration
(200 ppm; Figure 17D). Zhang et al. also performed the same
reaction with other dyes as luminophores in the light channel. In
the case of Eosin Y and Rhodamin 6G light harvesting and photon
transmission is only half as efficient as for Luminogen F Red 305.
Finally, fluorescein isothiocyanate was tested as well, but this dye
did not achieve any increase in conversion compared to a non-
doped solution in the light channel. Both results are in line with
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10.1002/cptc.201900247
the decreasing overlap between luminophore emission band and
sensitizer absorption band.
2.4 Falling film microreactor
Many examples discussed in the previous chapters are based on
tubular architectures for the transportation of gas and liquid
phases. The diameter of these closed capillaries is usually in the
range of several hundred µm to mm scale. Another concept is the
use of small-sized open microchannels with free access to the gas
phase throughout the complete channel length. [54] These open
microchannels are available in different architectures, e.g. as
array of 32 parallel channels with a width of 600 µm and a depth
Accepted Manuscript
of 200 µm wet-chemically etched into a stainless steel reaction
plate with 89 mm in length and 46 mm in width (Figure 22A).
These devices are usually operated in a tilt or even completely
upright manner. Hence, the liquid phase can flow down inside the
open microchannels by gravitational forces. In addition, capillary
forces result in the formation of a very thin liquid film, which lines
the wall of the microchannels (Figure 22B). Depending on the flow
rate and the viscosity of the liquid phase a film thickness below
50 µm is easily possible offering an excellent gas mass transfer
into the liquid phase with surface to volume ratio up to 20,000 m 2
m-3.[55] With these advantages combined a so-called falling film
microreactor (FFMR) was developed with a reaction plate as core
element in vertical position. This reactor concept was primarily
used for highly exothermic reactions (e.g. hydrogenation of nitro
groups) or as solvent evaporator due to its integrated heat
exchanger (Figure 22C). [54,55]
The falling film approach has been also used for photochemical
applications, as exemplified at first by Griesbeck et al. using a
XeCl excimer lamp (3 kW, length: 60 cm) as central light source
inside a water-cooled glass barrel.[56] The reaction solution was
pumped from a reservoir to the top of the falling film glass barrel,
from where it rinsed down along the barrel surface as thin film with
intensive contact to the outer gas phase and with strong
irradiation from the central excimer lamp. In the case of the FFMR
any light must be incorporated through the inspection window at
the front of the microreactor. Apart from the possible use of
classical light sources, e.g. Xe arc lamps or compact fluorescence
lamps,[57] modern high power LED technology allows the
wavelength-specific irradiation of the reactor chamber without
complex filter equipment and less safety or heat management
issues (Figure 22C). The small emitters can be arranged in arrays
and easily adopted to the appropriate reactor design. [58]
ChemPhotoChem
REVIEW
Figure 22. A) Stainless steel FFMR reaction plate with 32 microchannels (width:
600 µm, depth: 200 µm). Copyright Fraunhofer IMM; B) Schematic
representation of the falling film approach for microchannels: (S) stainless steel
microchannel reaction plate, (L) liquid film, (G) gas chamber, (W) microchannel
width and (H) height, (δl) liquid film height and (δg) gas chamber height. Adapted
with permission from ref. [55] copyright 2012 Elsevier; C) FFMR with LED arrays
magnetically fixed at the front plate (inset). Copyright Fraunhofer IMM.
Meanwhile the FFMR technology has been used for several
different photochemical reactions: a) photochlorination of toluene-
2,4-diioscyanate, b) photooxygenation of cyclopentadiene, and c)
the synthesis of juglone and ascaridole. [57,59] The aforementioned
reactions are gas-liquid reactions with e.g. homogeneously
dissolved sensitizers for the in situ generation of 1O2. The
application of a heterogeneous photocatalyst with the FFMR has
been demonstrated recently by our group for the blue-light
mediated C-H arylation of heteroarenes with various diazonium
salts as substrates (Figure 23).[60] As solid catalyst material TiO2
(anatase phase) was used and immobilized as thin catalyst layer
on the microchannel walls of the FFMR reaction plate.
Figure 23. Blue-light mediated C-H arylation of pyridine with TiO2 as
photocatalyst immobilized onto the FFMR microchannel walls.
The diazonium salt substrates (0.05 M) were dissolved in a 1:1
mixture of ethanol with furan, thiophene or pyridine. The reaction
solution was fed into the FFMR with a flow rate of fl = 0.5 mL min-
1
while maintaining the temperature inside the reactor at 20 °C.
The LED array was switched on providing light with an emission
wavelength of 455 nm (Pele  2.4 W). Under these conditions good
to excellent yields were obtained for e.g. 4-
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10.1002/cptc.201900247
chlorobenzenediazonium tetrafluoroborate 18 with furan (79%),
thiophene (72%) and pyridine (99%) in a single run with a very
short residence time of approx. τres = 9 s. Compared to the batch
tests with a reaction time of several hours a strong process
intensification has been achieved with the FFMR due to its
efficient irradiation of the liquid phase as thin film on the TiO 2
photocatalyst layer.
2.5 Dedicated reactor concepts for scale-up
2.5.1 Gas-liquid flow uniformity during numbring-up
The examples of this chapter focus on the developments of
Accepted Manuscript
continuous flow photoreactor concepts for larger scales
compared to the smaller lab devices presented before. The first
reactor system is based on a numbering-up strategy for gas-liquid
reactions in capillary photoreactors. Su et al. investigated a scale-
up methodology for parallelized 2-, 4- and 8-capillary photoreactor
systems applied to the dye sensitized aerobic oxidation of
thiophenol 20 (0.5 M in ethanol) to diphenyl disulfide 21 as test
reaction. Rose Bengal was used as sensitizer (1 mol%) with 1 eq
TMEDA as reductive quencher (Figure 24).[61]
Figure 24. Dye sensitized oxidation of thiophenol to diphenyl disulphide
(TMEDA = tetramethylethylenediamine).
Actually, the focus of this work is on the assessment of the flow
non-uniformity in parallel channels used for the necessary gas-
liquid two-phase flow splitting in up to eight photoreactors (Figure
25A, B). The 2n-capillary photoreactor systems (n = 1, 2, 3) were
built from standard equipment with PFA capillaries for the
connections (i.d. 750 µm) and the reactors (i.d. 500 µm, 2.15 m
length, 0.95 mL) as well as T-micromixers (1/16”, PEEK). The
pressure drop in the distributer system was adjusted by PFA
capillaries with smaller diameter (i.d. 250 µm) and backpressure
regulators, respectively. White light-emitting LEDs are placed in
the capillary photoreactors, while pressurized air is used to
maintain the reactor temperature at approx. 22 °C. The ratio of
the gas to liquid flow rate was set to 3:1. The authors define a
standard deviation (SD) between the actual mass flow rate in
each capillary reactor and the average total mass flow rate for all
capillaries. The SD is used to compare the various 2n-reactor
systems in dependence to the average liquid flow rate. In the case
of the non-photocatalytical assessment no oxygen gas is
consumed. For all 2n-capillary reactor systems a very low SD <5%
was achieved at average liquid flow rates of fl = 0.4-0.7 mL min-1
per capillary. These results are a very good improvement
compared to the literature with values >10%.[62] The authors state
that pressure drop management inside the distributer part was
very important to achieve a stable and uniformly distributed gas-
liquid flow. In the case of the 4-capillary reactor system a
ChemPhotoChem
REVIEW
backpressure regulator was necessary and set to Δp = 0.34 bar.
In the case of the 8-capillary reactor system the intrinsic pressure
drop of the capillaries and the T-micromixers was high enough to
generate a uniform gas-liquid distribution throughout the complete
system without backpressure regulation. Based on these results
the planned photocatalytic gas-liquid reaction was investigated
with oxygen gas being consumed during the process. The real
process conditions gave a higher SD, but still under 10%. This
result is the consequence of the quick oxygen gas consumption
and accompanying changes in the hydrodynamic behavior of the
gas-liquid flow. As seen in Figure 25C and D liquid flow rate and
yield differ for each of the eight capillary reactors, but the relative
deviations are smaller than 4%, which can be also assumed for
consecutive runs of a single photocapillary reactor. Hence, the
work of Su et al. is an impressive example for the scale-up of
photocatalytic gas-liquid processes via the numbering-up strategy
with stable gas-liquid flow distribution over several photoreactors.
Figure 25. Schematic representation (A) and photograph (B) of the 8-capillary
photoreactor system used for the investigation of flow non-uniformity of gas-
liquid mixed phases in parallel channels. Relative deviation of flow rate (C) and
This article is protected by copyright. All rights reserved.
10.1002/cptc.201900247
yield (D) per single capillary. Adapted with permission from ref. [61] copyright
2016 Royal Society of Chemistry.
2.5.2 Low power light for scale-up
In the second example Gonçalves et al. describe the multigram
synthesis of hypericin 23, a natural product rarely available by
direct extraction from St. John’s Wort as main herbal source. [63]
The photocyclisation of protohypericin 22 is the final step in the
synthesis of 23 yielding a compound with strong light absorption
in the orange region at λmax = 596 nm (Figure 26). In previous
synthesis routes high power light sources with multiband
Accepted Manuscript
emissions have been used, which always show a strong overlap
with the absorption band of hypericin. Gonçalves et al. suggest
that detrimental photobleaching of hypericin is the reason for the
moderate to bad productivity of the processes reported so far.
Figure 26. Efficient photocyclisation of protohypericin to hypericin with low-
power red light.
Kinetic studies with small batch samples of 22 (2 µL, c = 1.6 × 10-
5
mol L-1) performed with a high power Hg lamp (400 W) resulted
in 79% yield for 23 after seven minutes, whereas after a prolonged
irradiation time of 35 min only 4% yield was remaining. By
switching from multiband light emission to single band emission
with LED arrays the yield for 23 increased dramatically. In the
case of blue light with λem = 463 nm and a low power of 10.2 mW
cm-2 23 was obtained in 97% yield after 20 min, which decreased
to 89% yield after a prolonged irradiation time of 800 min. Finally
the use of lowest power LED arrays for red light (λem = 629 nm,
0.6 mW cm-2) gave quantitative yield after 74 min. This excellent
result can be attributed to the sufficient overlap of red light
emission with the spectral absorption of 22 and a negligible
overlap with the spectral absorption of 23 (Figure 27A). Based on
these findings Gonçalves et al. designed a glass capillary
photoreactor module with a Pyrex® tube in zigzag-format (i.d. 3
mm, length 180 cm) sandwiched in between two glass slabs.
Each side of this flow device was equipped with three LED arrays
carrying 108 diodes for an emission wavelength of 629 nm. In total
four photoreactor modules of this type were stacked above each
other and used in series (Figure 27B). Starting material 22 (5.0 g)
was dissolved in three liters of acetone (c = 3.3 × 10-3 mol L-1) and
fed into the reactor modules with a very high flow rate of approx.
fl = 1.8 L min-1. The light dose was set to 4.0 mW cm-2. Within an
overall reaction time of 13.6 min the reaction solution was
circulated eight times for full conversion and 97% yield after
ChemPhotoChem
REVIEW
recrystallization (4.85 g of 23). The authors could show that a
defined control of irradiation wavelength and power can have a
tremendous effect on the productivity of a photochemical reaction.
This is especially important for the scale-up of expensive natural
products with costs of approx. 300 € mg-1 (95% purity by
extraction from St. John’s Wort / hypericum perforatum).[64]
Figure 27. A) Visible light spectral changes upon 8-times cycling of the reaction
solution through the photoreactor modules (left), and spectral overlap between
red LED light emission and absorption spectra of 22 (right); B) Schematic
representation of the glass capillary photoreactor setup for the red-light
mediated photocyclisation of protohypericin to hypericin. Adapted with
permission from ref. [63] copyright 2017 American Chemical Society.
2.5.3 Scale-up for kg production
Capillary photoreactors have been intensively used in the last
years and promoted the field of flow photochemistry especially on
the academic level. Scale-up approaches resulted in multi-
capillary systems, which still have the problems related to the
polymeric material FEP during long-term use: a) FEP is not fully
UV transparent and can degrade upon strong UV irradiation; b)
mechanical stress like abrasion or kinks can result in weak spots
or even rupture of the tubing and complete replacement. In order
to circumvent particularly the UV degradation problem Elliott et al.
designed a novel high capacity photoreactor based on quartz
glass tubes.[65] The new concept was planned for a higher
This article is protected by copyright. All rights reserved.
10.1002/cptc.201900247
productivity 1 kg per day and a safe containment of a standard
UV light source with an energy consumption of 1-5 kW. With these
specifications at hand Elliott et al. constructed the so-called Firefly
reactor.[66] In sum 2 × 12 glass tubes are arranged in two circles
around the central light source and are contained in between two
glass cylinders (Figure 28). The resulting annular cavity formed
by the cylinders can be flooded with coolant to maintain the
desired temperature in the reaction tubes. The top and bottom
plate of the reactor exhibit channels, which interconnect the glass
tubes in a serial manner resulting in an overall reactor volume of
120 mL. The central light source can be easily exchanged and
adapted to the photochemical process. A fan is installed at one
plate of the reactor and is used to remove the hot air and ozone
Accepted Manuscript
from the gap between light source and interior glass cylinder.
Finally, the complete outer glass cylinder is surrounded by a
polished and earthed metal tube, which reflects any residual UV
light back into the reactor and serves as protection of the
experimenter against the intense UV radiation. As planned the
fully assembled Firefly reactor is compact and can be easily used
in a standard fume hood.
Figure 28. A) Schematic representation and photograph of the Firefly
photoreactor as scale-up approach to classical FEP capillary photoreactors.
Adapted with permission from ref. [65] copyright 2016 American Chemical
Society; B) exploded view of the reactor as described in the corresponding
patent application. Adapted from patent application WO2018011550A1, ref. [66].
Elliott et al. applied their novel reactor to several photochemical
processes and compared the productivity with classical FEP
capillary reactors and literature data. The intramolecular [2+2]
photocycloaddition of tricyclic dione 24 has been efficiently
produced with a capillary photoreactor yielding 6.13 g h-1 of
“Cookson’s Dione” 25 based on a 0.1 M substrate solution (Figure
29).[25] In the case of the Firefly reactor a 0.5 M solution was
irradiated in a single run of 140 min at 1.5 kW light source power
and resulted in 167 g h-1 of product. By doubling both the
substrate concentration to 1.0 M and the light source power to 3
kW a doubled productivity of 331 g h-1 was achieved. A kilogram-
scale run was made possible under these optimized conditions
within an overall process time of approx. 3.5 h yielding 1,165 g of
product, which crystallized in the receiving flask. Just recently,
Clark et al. also performed this reaction with their modified lab
rotary evaporator photoreactor in batch mode (introduced in
Figure 16) and achieved a productivity of 210.6 g h-1.[67]
ChemPhotoChem 10.1002/cptc.201900247

REVIEW
processes. During visits at industrial fairs one can realize the
interest of the chemical industry in novel technology for a
sustainable production. But novel production technology and
synthesis concepts need new hardware and well-trained and
educated people to set-up and run such new plants. Hence,
academic training at universities must also reflect the new needs
in industry to prepare future employees for new challenges in a
Figure 29. Photochemical synthesis of “Cookson’s Dione” 25 via [2+2]
changing industrial market. Students must be educated in flow
photocycloaddition.
(photo)chemistry to get to know the benefits of this technology
and for being able to discover the potential of “old” batch
processes to be translated to flow mode. [68]
Another kilogram-scale process was presented for the cyclisation
The research in visible-light photocatalysis has contributed a lot
of phthalimid 6 exemplified before by Griesbeck and DeLaney,
in translating classic chemical concepts with e.g. costly noble
respectively (introduced in Figure 10).[56,35] Griesbeck et al.

Accepted Manuscript
metal catalyst systems and rather harsh reaction conditions to
reported a productivity of 7 g h-1 for their falling film reactor,
more green processes with higher selectivity. The last ten years
whereas DeLaney et al. achieved 0.78 g h-1 with their glass tube
proved that photons can be used as a delicate energy source or
photoreactor. Elliott et al. outperformed these values by far with a
“traceless” reagents in synthetic organic chemistry. The on-going
productivity of 57.9 g h-1 (0.2 M, 30 mL min-1, 3 kW). Interestingly,
rapid development of novel synthesis routes and
the authors used acetonitrile instead of acetone as co-solvent to
photocatalytically active materials opens the door for replacing
water, pointing out that acetone is not necessary as triplet
well-known chemistry with new reactivity concepts in bond
sensitizer for this photodecarboxylative cyclisation. These two
activation and formation via direct or sensitized interaction with
examples clearly show the great potential of the Firefly reactor
light. Based on these achievements photochemistry got more and
concept. The authors conclude that the Hg lamp is not an integral
more into the focus of larger public funded programs, especially
of the reactor. It can be replaced either by future high power UV
with the prominent idea of using solar light to run chemical
LEDs or other LEDs to match especially the strongly increasing
reactions.[69] National programs combine photocatalysis with e.g.
number of sensitized photoreactions utilizing visible light.
activation of atmospheric/anthropogenic CO2 and its conversion
to energy carriers or bulk chemicals. [70] International programs
and cooperations foster academic research between countries,
4. Conclusion and perspective whose technology and geographical location can provide
synergies for solar photochemistry. In addition several European
As mentioned already at the beginning of this manuscript
programs clearly call up industrial participation to advance the use
continuous flow photochemistry has run through a major evolution
of solar energy for industrial processes.[71] At this stage a multi-
in the last decade. The selected examples depict an amazing
disciplinary approach is necessary, which combines and aligns
increase in reactor concepts, which have been designed from
the expertise of chemistry, physics, biology, material development
scratch or advanced from already existing architectures. The
and engineering. Finally, scientific long-term programs have been
important fact about this development is clearly the acceptance of
rated just recently as a most important chance to solve global
continuous flow technology and its advantages for
problems of energy consumption and climate change on an
photochemistry. Research groups worldwide are no longer afraid
international level.[72] Solar light and photochemistry play pivotal
to use technology for photochemical synthesis and become
roles in the projected concepts. Therefore, we can all hope that
convinced by the results and advantages of these flow devices.
photochemistry and its adjunct technologies will keep track on
Solid catalysts can be applied meanwhile without immobilization
their way to a conceptual chemical technology with disruptive
as well as challenging reactions with e.g. singlet oxygen can be
impact on sustainable production of energy carriers, everyday
performed under strictly controlled conditions. In parallel
commodities and specialty chemicals.
photoreactors became characterized not only at the chemical
level by running and comparing benchmark reactions. Detailed
investigations were done on the engineering level to understand
the way and flux of light interacting with gas, liquid and solid Acknowledgements
phases inside defined reactor architectures. These results can
help to utilize incident (solar) light even more efficiently inside flow The author would like to thank MSc Christoph Deckers, Dr.
photoreactors and reduce energy costs. Finally, flow Gabriele Menges-Flanagan and Dr. Stefan Kiesewalter (all
photoreactors have also entered the commercial market as Fraunhofer IMM) for proofreading. The author would also like to
optional part of already existing continuous flow “machines” for thank Lisa Pokropp (Fraunhofer IMM) for creating the frontispiece.
thermal chemistry. Hence, it is consequential, that photoreactors This work has been additionally supported by the German Federal
become re-designed to larger scales in order to be promoted for Ministry of Education and Research (BMBF) under the program
industrial applications. Especially any future integration into CO2Plus (Project CarbonCat; grant number: 033RC009A).
chemical industry will stimulate the adaptation of flow
photoreactors to worldwide standardized plant components with Keywords: photocatalysis • continuous flow • microreactor •
an increased compatibility and comparability of photochemical intensification • mixing

This article is protected by copyright. All rights reserved.

ChemPhotoChem
REVIEW
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ChemPhotoChem 10.1002/cptc.201900247

REVIEW

REVIEW
Photon2Flow: In the last decade Thomas H. Rehm*
photochemistry experienced a
renaissance with fundamental impact Page No. – Page No.
on academic research. In conjunction,
Reactor technology concepts for flow
the growing acceptance of continuous
photochemistry
flow technology in the chemical
community resulted in a most fruitful
alliance up to date and revolutionized
“thinking and doing chemistry” with

Accepted Manuscript
light as delicate energy source.

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