Fluorescent Sulphur- and Nitrogen-Containing Porous Polymers with Tuneable Donor–Acceptor Domains for Light-Driven Hydrogen Evolution

Article abstract of DOI:10.1002/chem.201802902

Light-driven water splitting is a potential source of abundant, clean energy, yet efficient charge-separation and size and position of the bandgap in heterogeneous photocatalysts are challenging to predict and design. Synthetic attempts to tune the bandgap of polymer photocatalysts classically rely on variations of the sizes of their π-conjugated domains. However, only donor–acceptor dyads hold the key to prevent undesired electron-hole recombination within the catalyst via efficient charge separation. Building on our previous success in incorporating electron-donating, sulphur-containing linkers and electron-withdrawing, triazine (C₃N₃) units into porous polymers, we report the synthesis of six visible-light-active, triazine-based polymers with a high heteroatom-content of S and N that photocatalytically generate H₂ from water: up to 915 μmol h^?1 g^?1 with Pt co-catalyst, and—as one of the highest to-date reported values ?200 μmol h^?1 g^?1 without. The highly modular Sonogashira–Hagihara cross-coupling reaction we employ, enables a systematic study of mixed (S, N, C) and (N, C)-only polymer systems. Our results highlight that photocatalytic water-splitting does not only require an ideal optical bandgap of ≈2.2 eV, but that the choice of donor–acceptor motifs profoundly impacts charge-transfer and catalytic activity.

Full text of DOI:10.1002/chem.201802902

A Journal of
Accepted Article
Title: Fluorescent sulphur and nitrogen containing porous polymers
with tuneable donor-acceptor domains for light-driven hydrogen
evolution
Authors: Dana Schwarz, Amitava Acharjya, Arun Ichangi, Pengbo Lyu,
Maksym V. Opanasenko, Fabian R. Goßler, Tobias F. König,
Jiří Čejka, Petr Nachtigall, Arne Thomas, and Michael Janus
Bojdys
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201802902
Link to VoR: http://dx.doi.org/10.1002/chem.201802902
Supported by

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COMMUNICATION
Fluorescent sulphur and nitrogen containing porous polymers
with tuneable donor-acceptor domains for light-driven hydrogen
evolution
Dana Schwarz,[a,b] Amitava Acharja, Arun Ichangi, Pengbo Lyu, Maksym V. Opanasenko, Fabian
[c]
[c]
[d]
[d]
[
b]
[b]
[d]
[d]
[c]
[c,e]
R. Goßler, Tobias A. F. König, Jiří Čejka, Petr Nachtigall, Arne Thomas, Michael J. Bojdys*
Dedication ((optional))
Abstract: Light-driven water splitting is a potential source of abundant, Polymeric semiconductor photocatalysts for hydrogen evolution
clean energy, yet efficient charge-separation and size and position of
the bandgap in heterogeneous photocatalysts are challenging to
predict and design. Synthetic attempts to tune the bandgap of polymer
photocatalysts classically rely on variations of the sizes of their π-
conjugated domains. However, only donor-acceptor dyads hold the
key to prevent undesired electron-hole recombination within the
catalyst via efficient charge separation. Building on our previous
success in incorporating electron-donating, sulphur-containing linkers
from water are an intriguing material class, since they can be
produced from a continuous spectrum of variable monomers. This
sets them apart from crystalline inorganic semiconductors that
rely on very discrete compositions for bonding or catalytic activity
to occur.[1] For example, conjugated microporous polymers
(CMPs) can be prepared from statistical co-polymerisation of
polycyclic, aromatic sub-units of varying sizes that enable pore-
size tuning,[ a continuous spectrum of bandgaps, and as a
result also varying degrees of photocatalytic activity.[ The
chemical make-up of the overwhelming majority of CMPs is
carbon-only. As a consequence, charge-transfer is insufficient to
prevent spontaneous recombination of photo-induced electron-
hole pairs,[5] and efficient photocatalysis using CMPs strictly relies
on electron migration to a noble-metal co-catalyst, usually
platinum (Pt). In practice, nearly all photocatalytic water splitting
studies explore one half-reaction – proton reduction – in a set-up
that provides a sacrificial electron donor, such as triethanolamine
(TEOA) and Pt as a co-catalyst. Cooper et al. pointed out that to
make use of the full benefit of polymeric photocatalysts, the
addition of Pt as a co-catalyst should not be essential.[
2]
[3]
4]
and electron-withdrawing, triazine (C
3 3
N ) units into porous polymers,
we report the synthesis of six visible-light active, triazine-based
polymers with
a
high heteroatom-content of
S
and
N
that
with
-
1
-1
photocatalytically generate H
2
from water: up to 915 µmol h
g
Pt co-catalyst, and – as one of the highest to-date reported values –
-
1
-1
2
00 µmol h g without. The highly modular Sonogashira-Hagihara
cross-coupling reaction we employ, enables a systematic study of
mixed (S, N, C) and (N, C)-only polymer systems. Our results highlight
that photocatalytic water-splitting does not only require an ideal optical
bandgap of ~2.2 eV, but that the choice of donor-acceptor motifs
profoundly impacts charge-transfer and catalytic activity.
4b]
Conversely, polymeric carbon nitride has
a
very high
stoichiometric ratio of carbon-to-nitrogen of 6-to-9. Although this
polymer shows some, low activity in noble metal free
photocatalysis, again only the addition of a Pt co-catalyst makes
this process efficient.[6] Substantially higher hydrogen evolution
[
[
[
a]
b]
c]
Dr., D, Schwarz, A. Ichangi
Department of Organic Chemistry
Charles University
Hlavova 8, 128 43 Prague 2, Czech Republic
Dr., D, Schwarz, F. R. Goßler, T. A. F. König
Leibniz-Institut fuer Polymerforschung Dresden e.V.,
Institute of Physical Chemistry and Polymer Physics,
Hohe Str. 6, 01069 Dresden, Germany
A. Acharjya, Prof. Dr. Arne Thomas
Institute of Chemistry
Technische Universität Berlin
Hardenbergstraße 40, 10623 Berlin, Germany
A. Ichangi, Dr. M. J. Bojdys
Institute of Organic Chemistry and Biochemistry of the CAS,
Flemingovo nám. 2, 166 10 Prague 6, Czech Republic
Dr. M. V. Opanasenko, Prof. Dr. J. Čejka, P. Lyu, Prof. Dr. P.
Nachtigall
rates are achieved predominantly via post-synthetic modifications
of polymeric carbon nitrides by templating or by further
[
7]
heteroatom-doping. In summary, it seems that introduction of
distinct domains or point-defects increases the likelihood of
electron-hole separation and thus of enhanced photocatalytic
activity; a finding that was confirmed for azine covalent organic
frameworks.[ It is worth to note, that claims of no addition of a
metal co-catalyst do not necessarily equate to a truly "metal-free”
catalysis. Oftentimes, heavy metal ions and other elements (e.g.
Pd, Cu, P) remain in the polymer matrix as residue from the linking
8]
[
[
c]
d]
Faculty of Science, Department of Physical and Macromolecular
Chemistry
Charles University
Hlavova 8, 128 43 Prague 2, Czech Republic
Dr. M. J. Bojdys
reaction and have to be taken into account when comparing
photocatalytic activity.[9]
There are ways of tuning surface polarity, pore structure,
and catalytic properties of conjugate polymer frameworks for
[
e]
Humboldt-Universität zu Berlin
Department of Chemistry
Brook-Taylor-Str. 2, 12489 Berlin, Germany
E-mail: m.j.bojdys.02@cantab.net
example by incorporation of the triazine (C
electron-withdrawing and spatially co-planar,
N
) group – an
symmetric
3
3
C
3
building block.[10] We explored further modifications in a series of
sulfur- and nitrogen-containing porous polymers (SNPs) that
exploit donor-acceptor interactions for bandgap-tuning and
charge separation for photocatalysis,[11] and one of these
networks shows the highest reported hydrogen evolution rate
Supporting information for this article is given via a link at the end of
the document.
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under visible light irradiation for an as-received polymer
polarisation
magnetic-angle
spinning
(CP/MAS)
NMR
[
12]
photocatalyst to-date. Inspired by the lead that incorporation of
donor-acceptor domains holds the key to enhanced photocatalytic
activity, here, we explore six covalent triazine-based porous
polymer frameworks with subtle variation of their heteroatom
content.
Two principle groups of (S, N, C)- and (N, C)-containing
porous polymers have been achieved referred to as SNPs and
NPs, respectively. The network-forming reaction is the palladium-
spectroscopy, X-ray photoelectron spectroscopy (XPS), and
combustion elemental analysis (EA) to confirm the structure and
possible impurities from the synthesis (see Supporting
Information). In 13C CP/MAS NMR spectroscopy all materials
show a peak at 172 ppm ascribed to the C
3
N
3
ring (Figure 1).
2
Peaks between 142 and 124 ppm are assigned to the sp
hybridised carbons (C–C and C–H) and carbons within the
sulphur- and nitrogen-containing heterocycles. Quaternary
catalysed Sonogashira-Hagihara cross-coupling protocol.[13] Note, carbons are visible around 124 ppm. Peaks at approx. 99 and
that the polymers contain a very low residual of Pd from the cross-
coupling of 0.04 to 0.13 wt% (see below and in the Supporting
Information). Hence, it is unlikely that the Pd contributes
significantly to the observed hydrogen evolution rates in the
presence of co-catalyst. After purification, the products NP-3
88 ppm are sp hybridised –C≡C– sites. All networks show two sp-
hybridised –C≡C– environments due to asymmetric substitution
across this bridge. IR spectra of all six polymers are shown in
Figure S10 and reveal miniscule peaks at 3300 cm-1 that
correspond to the unreacted –C≡C–H bond vibrations. The –
C≡C– bond formed during the polymerisation shows as a peak at
(
based on anthracene linkers), NP-4, NP-5, NP-6 (based on
-1 [14]
asymmetric N-heterocycles), SNP-3, and SNP-4 (based on
sulphur- and nitrogen-containing tectons) were obtained as yellow
around 2200 cm .
EA, EDX, and TGA confirm the yields of
around 100% with almost no residual elements from the coupling
reaction (e.g. residual Pd content varies between 0.04 to 0.13
wt%) (Table S4, S5, S6 and Figure S5). Similar Sonogashira and
also Suzuki coupling reactions often lead to higher concentrations
of residual catalyst.[13, 15]
(
NP-4, NP-5, and NP-6), orange (SNP-4) and brown (NP-3 and
SNP-3) powders with yields above ~90% (see Scheme 1 and
Figure S2). Experimental details are given in the supporting
information.
The polymers were characterised by infrared (IR)
13
spectroscopy, thermogravimetric analysis (TGA), C cross-
Scheme 1. Synthetic route to NPs and SNPs. C
dibromoanthracene to yield NP-3, 2,5-Dibromopyridine to yield NP-4, 2,5-dibromopyrimidine to yield NP-5, 3,6-dibromopyridazine to yield NP-6, 4,7-dibromobenzo-
c]-1,2,5thiadiazole to yield SNP-3, and 5,5’-dibromo-2,2’-bithiazole to yield SNP-4.
3 2
-symmetric 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine is coupled with a C -symmetric bridge such as: 9,10-
[
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The pore systems of the polymers were investigated by
nitrogen sorption measurements at 77 K (Figure 2a). All polymers
feature micro- and mesopores with a visible hysteresis. The
accessible surface areas calculated by Brunauer-Emmett-Teller
All networks have an intergrown, particle-like morphology.
Remarkably, samples NP-3, NP5, NP-6 and SNP-4 feature
pronounced Moiré fringes in their TEM images and/or electron
diffraction spots indicative of some degree of internal order.
Nonetheless, powder X-ray diffraction (PXRD) patterns reveal
that the bulk of the samples is predominantly glassy and
amorphous (Figure S6). Interlayer stacking peaks around 25° 2θ
are observed and are comparable to other layered, aromatic
systems such as CMPs and covalent organic frameworks
(COFs).[18]
2
-1
(
BET) equation are between 210 and 600 m g (Table 1) which
is in the range of similar, carbon-only CMPs (e.g. CMP-3 with
2
-1 [13]
5
22 m g ). In general, surface areas of previously reported S-
and N-containing polymers are on average lower with values
2
-1 [14-15, 16]
between 12 and 250 m g .
CO uptake values are within the range of nitrogen-
2
containing CMPs and show a dependence on overall nitrogen
content and surface area.[2, 17] NP-5 and NP-6 have the highest
amount of nitrogen and feature the highest CO
2
uptake with
uptake with
-1
around 1.9 mmol g . SNP-4 has the lowest CO
2
-1
1
.30 mmol g (similar to NP-3) due to the comparably low guest-
accessible surface area. CO sorption isotherms are shown in
2
Figure 2b and show a linear uptake with no discernible hysteresis
which is typical for microporous polymers.
2
Figure 2. a) Nitrogen adsorption/desorption isotherms and b) CO sorption
isotherms measured at 273K for NP-3 (in black), NP-4 (in red), NP-5 (in blue),
NP-6 (in magenta), SNP-3 (in green), SNP-4 (in orange). Data points in the
adsorption and desorption branch of the isotherms are indicated by filled and
empty circles, respectively
Table 1. Gas sorption data of all 6 polymers, including pore sizes and CO
2
uptake calculated from sorption isotherm.
Sample
NP-3
S
BET (m2 g-1)[a]
468
PV (cm3 g )
-1 [b]
CO
2
uptake (mmol/g)
0.643
1.32
1.65
1.89
1.96
1.71
1.30
NP-4
600
0.193
NP-5
590
0.223
NP-6
545
0.376
Figure 1. 13C CP-MAS ssNMR spectra of NPs and SNPs from top to bottom
SNP-4 (in orange), SNP-3 (in green), NP-6 (in magenta), NP-5 (in blue), NP-4
SNP-3
SNP-4
445
0.382
(in red), and NP-3 (in black). Spectra were recorded at a MAS rate of 12.0 kHz
210
0.159
featuring triazine, phenyl and ethylene groups from left to right-hand-side,
asterisks denote spinning sidebands.
[
a]Surface area calculated from N
2
adsorption isotherm using the BET
uptake for pore-sizes
equation. [b]Pore volume (PV) calculated from N
2
between 1.7 and 300 nm. Pore volume calculated via the Barrett-Joyner-
Halenda (BJH) method.
Figure
3 shows scanning and transmission electron
microscopy (SEM and TEM) images together with the
corresponding selected area electron diffraction patterns (SAED).
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Figure 3. Electron microscopic investigation of SNPs. SEM (top), TEM (centre), and SAED (bottom) images for: a-c) NP-3, d-f) NP-4, g-i) NP-5, j-l) NP-6, m-o) SNP-
, and p-r) SNP-4. b, h and n) Networks NP-3, and NP-6 show Moiré fringes in TEM images indicative of overlapping, ordered layers. c, i, o and r) show concentric
3
rings in the electron diffraction that are indicative of polycrystalline domains.
Solid-state UV/Vis spectra of the polymers were recorded at
room temperature and are displayed in Figure S9. The direct band
gaps were calculated using the Kubelka-Munk method
containing domains, the triazine-based ethynyl-phenyl linker
features intrinsic donor-acceptor properties that can facilitate
intramolecular charge transfer and, hence, exciton migration on a
more local scale. As a result, all polymers with high nitrogen
content (i.e. all NPs) can retain the excited state for a longer time.
Indeed calculations suggest that the triazine ring has a larger
hyperpolarisability and more electron-withdrawing character than
the analogous carbon-only benzene core.[21]
All samples were investigated in photocatalytic hydrogen
evolution from water using platinum (Pt) co-catalyst and
triethanolamine (TEOA) as sacrificial agent under visible light
(395 nm cut-off filter). Control reactions in the dark were
performed prior to each test run to verify photocatalytic action.
Figure 5 summarises the hydrogen evolution rates (HERs) for all
samples with and without platinum as a co-catalyst in dependence
of the calculated, direct optical band gap. NP-5 has the highest
(
Figure S10) and vary between 1.9 and 2.52 eV and are in broad
agreement with the calculated band structures (at
PBE/DZP/GD2/5x5x16k-points level) of periodic, single layer
structures of the corresponding materials (Figure S12).
Photoluminescence emission (PLE) measurements show
emission maxima in the range of 550 to 610 nm upon excitation
at 405 nm (Figure 4b) as a result of the extended conjugation in
the polymer network. Furthermore, the red shift implies the degree
of near-perfect polymerisation which is in agreement with the low
residual halogen content in the polymers (see ICP-analysis,
SI).[19] NP-3 is the structure without heteroatoms except for the
triazine bridge acceptor and features the highest red shift followed
by SNP-3, SNP-4, and NP-6. Time-correlated fluorescence
spectra were performed at 400 nm for NPs and SNPs in the solid
state to investigate the dynamics of the excited-state (Figure 4c).
The average fluorescence lifetimes are 1.49 (NP-3), 1.72 (NP-4),
HER with Pt at 915±10 µmol h g-1 (9.15±0.1 µmol h ) and
-
1
-1
-1
-1
-1
200±10 µmol h g (2.00±0.1 µmol h ) without additional co-
catalyst; one of the highest HER values for a noble metal free
1.69 (NP-5), 1.48 (NP-6), 1.29 (SNP-3), and 1.17 ns (SNP-4), and
photocatalyst
to-date.
Common
benchmark
polymeric
they were estimated by a double-exponential fitting. Excitons in
NP-4 and NP-5 have the longest lifetime, and they are shortest in
SNPs. Electron donation from sulphur heteroatoms may result in
faster fluorescence quenching. An increase in N-content from
pyridine- (NP-4) or pyrimidine-linkers (NP-5) leads to an increase
in exciton lifetimes due to stronger C-H∙∙∙N hydrogen bonds
between adjacent layers. We have seen previously that it is not
only the size of the π-conjugated organic tecton that determines
the band gap of the resulting polymer but also the strength of
donor-acceptor interactions within the network.[3, 20] In addition to
charge-delocalisation between far-apart sulphur- and nitrogen-
photocatalysts based on organic nitrogen rich moieties are
heptazine based polymers such as pure g-CN [23], CNC30 (with
[22]
cytosine) [23], B-modified g-CN [24], poly(triazine imide)
[25]
and
azine-based COFs [26]. At first glance, we see a similar trend to
previous publications that an ideal optical band gap for efficient
photocatalysis is situated around 2.2 eV,[4b, 11] and that band gaps
below 2.0 eV fail to catalyse the reaction presumably because
they are too narrow to straddle the potential between proton
reduction and oxidation of the sacrificial agent. However, we also
observe a (weak) correlation of HER and guest-accessible
surface area with more accessible pore structures achieving
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higher efficiencies (Figure S28). The highest HER values with
platinum as co-catalyst were obtained for pyridine (NP-4) and
pyrimidine (NP-5) as a tecton. However, within the group of NPs
the pyridazine tecton (NP-6) has a low HER. Overall, the absolute
heteroatom content did not show any correlation with
electron-hole separation needs to be promoted by the addition of
Pt or Pd co-catalysts (Figure S30). Thus, we achieve hydrogen
evolution rates of up to 200±10 µmol h-1 g-1 without co-catalyst
which is one of the highest values reported to date. This is a
significant finding and we believe that it highlights the importance
of tuneable donor-acceptor domains in the development of a truly
noble metal free photocatalyst in the future.
Figure 4. a) Absorbance, b) fluorescence spectra, and c) time-correlated
fluorescence spectroscopy for SNPs and NPs with SNP-4 (in orange), SNP-3
(in green), NP-6 (in magenta), NP-5 (in blue), NP-4 (in red), and NP-3 (in black).
Figure 5. Hydrogen evolution rates of NP-3, NNPs, and SNPs (10 mg) under
visible light (395 nm cut-off filter) correlated with the direct optical band gap in
-
1
-1
-1
HER (Figure S29), and hence, we assume that it is the
µmol h g (above) and µmol h (below). Each measurement was performed
position of heteroatoms in the frameworks (rather than their sheer
amount) that has the most impact on donor-acceptor interactions,
charge-delocalisation and photocatalytic activity. In the light of the
PLE study, we observe the trend that long exciton life-times in
NPs are a good indicator for efficient photocatalysis, most likely,
because photoexcited electrons and holes do not spontaneously
recombine so readily in these materials.
in a water:acetonitrile (1:1) mixture using triethanolamine (TEOA) as sacrificial
agent with 3 wt% platinum (Pt) (filled symbols) and without Pt co-catalyst (empty
symbols). Corresponding solid-state UV/Vis diffuse-reflectance spectra are
shown in Figure S9.
Acknowledgements
We thank Dr. Nikolai Makukhin for discussions, Šárka Pšondrová
is acknowledged for IR, Dr. Simona Hybelbauerova and Martin
Dracinsky for their support and access in solid-state NMR, Dr. Jiri
Rybacek and Dr. Martin Racek for their support in SEM and EDX,
Stanislava Matejkova.is acknowledged for ICP-OES, Jaroslava
Hnilickova is acknowledged for EA and Christina Eichenauer is
acknowledged for BET. M.J.B. thanks the European Research
Council (ERC) for funding under the Starting Grant scheme
In conclusion, we have expanded the family of sulphur- and
nitrogen-containing porous polymers – a class of photoactive,
heterogeneous catalysts – by six further members with mixed (S,
N, C) and (N, C)-only heteroatoms in their backbones. Intrinsic
donor-acceptor interactions within these networks allow fine-
tuning of the optical bandgap between 1.90 and 2.57 eV.
Surprisingly, we find that efficient photocatalytic hydrogen
evolution from water does not only depend on the optimal size of
the bandgap (~ 2.2 eV) – as suggested in previous reports. We
find that materials that effectively extend the life-time of the
photoexcited electron-hole pair – for example via effective charge
(
BEGMAT – 678462). M.J.B., J.C. and P.N. further acknowledge
the Charles University Centre of Advanced Materials (CUCAM)
OP VVV Excellent Research Teams, project number
CZ.02.1.01/0.0/0.0/15_003/0000417).
(
separation
– can achieve high hydrogen evolution rates
irrespective at sub-optimal bandgap values. In conventional
systems that do not feature intrinsic donor-acceptor dyads, this
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Nachtigall, A. Thomas, J. Tarábek, M. J. Bojdys, Chemistry – A
European Journal 2017, 23, 13023-13027.
Keywords: conjugated microporous polymers • donor-acceptor
dyads • triazine • photocatalysis
[
12] K. Yaroslav S., S. Dana, A. Amitava, I. Arun, K. Ranjit, E. Pavla, V.
Jaroslav, S. Johannes, T. Arne, B. Michael J., Exploring the “Goldilocks
Zone” of Semiconducting Polymer Photocatalysts via Donor-Acceptor
Interactions, 2018.
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Donor-acceptor domains in sulphur
and nitrogen containing porous
Dana Schwarz, Amitava Acharja, Arun
Ichangi, Pengbo Lyu, Maksym V.
polymers enable effective charge
separation and bandgap tuning, and
hence, photocatalytic water splitting.
Opanasenko, Fabian R. Goßler, Tobias
A. F. König, Jiří Čejka, Petr Nachtigall,
Arne Thomas, Michael J. Bojdys*
Page No. – Page No.
Fluorescent sulphur and nitrogen
containing porous polymers with
tuneable donor-acceptor domains for
light-driven hydrogen evolution
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