A multifunctional triazine-based nanoporous polymer as a versatile organocatalyst for CO2 utilization and C-C bond formation

Article abstract of DOI:10.1039/c9cc04975d

A triazine-based nanoporous multifunctional polymer with a SA_BET of 304 m² g^-1 has shown versatile catalytic activity in the conversion of CO₂ to cyclic carbonates at 4 bar with almost 100% yield and selectivity, and in the conversion of CO₂ to methanol and methane electrochemically. Additionally, it also catalyzes C-C bond formation via the Knoevenagel reaction.

Full text of DOI:10.1039/c9cc04975d

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S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
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DOI: 10.1039/C9CC04975D
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Multifunctional triazine-based nanoporous polymer as versatile
organocatalyst for CO2 utilization and C-C bond formation
Ruchi Sharma,1 Ankushi Bansal,1 C. N. Ramachandran2 and Paritosh Mohanty1*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Triazine-based nanoprous multifunctional polymer with SABET of development of methodologies to synthesize various organic
304 m2 g-1 has shown versatile catalytic activity in CO2 conversion to polymeric as well as inorganic-organic hybrid materials with
cyclic carbonates at 4 bar with almost 100% yield and selectivity, high specific surface area led to their use in the utilization of
and CO2 to methanol and methane electrochemically. Additionally, CO2. Recently, both theoretical investigations and experimental
it also catalyzes the C-C bond formation via the Knoevenagel evidences suggest superiority of the catalytic activity due to the
reaction.
presence of heteroatoms such as N, O, B, and P.5a,6
Among different approaches of CO2 utilization, synthesis of
cyclic carbonates and electrochemical reduction of CO2 to
methanol and methane have dominated the research area.1b,6
Porous materials such as metal organic frameworks,
microporous organic polymer, imidazolium and triazine-based
porous organic polymers, triphenylphosphine-based porous
polymer and porous organic polymers have been reported for
the synthesis of cyclic carbonates.6,7 However, reports on
developing efficient metal-free functional materials for CO2
electroreduction to methanol is rare,8 although, very few
reports are available on the synthesis of CO or formic acid from
CO2 using nitrogen enriched carbonaceous catalysts.1,8,9
Moreover, presence of multifunctionality such as hydroxyl or
carboxyl group along with the Lewis basic amine functionality in
the catalyst play significant role in the activation of epoxides
through the hydrogen-bonding and activation the CO2 molecule
for cycloaddition, respectively.5a,6
Carbon dioxide (CO2) capture, sequestration and utilization
(CCSU) is considered as the potential solution to address the
global warming while fulfilling the energy need.1 Even after a lot
of efforts use of non-conventional and renewable energy could
not even reach up to 20%.2 Hence, to satisfy the extraordinary
increase in demand of energy has left with only one choice to
use the fossil-based energy sources. The proper utilization of
CO2 to produce useful chemicals of industrial importance or
fuels such as methane, methanol and ethanol could
fundamentally address the issues towards sustainability.1b,c,d
This could change the image of CO2 from anthropogenic to
naturogenic. However, the non-polar nature, chemically
inertness and high thermodynamic stability (–∆Hf = 394
kJ/mol) of CO2 makes its chemical conversion to targeted
chemicals tedious. To facilitate the activation of CO2 various
catalysts have been used in different processes such as
thermochemical reduction, biochemical transformation,
photochemical reduction and electrochemical reduction.3
Environmental concerns related to metal leaching and cost
of the metal based catalysts have led to the growing interest
towards the development of metal-free organocatalysts.4
Conventionally, small organic molecules such as ionic liquids,
quaternary ammonium salts, imidazolium salts, organic amines,
and phosphonium salts have been used for CO2 utilization,
however, their separation and reusability has forced to think
about their heterogeneous counterpart.1b,5 The recent
Considering the contribution of heteroatoms along with
multiple functionality in the framework on the catalytic activity,
multifunctional nitrogen-enriched nanoporous polymer
(MNENP) with amine and hydroxyl functionalities has been
synthesized
by
condensation
of
2-hydroxy-1,3,5-
benzenetricarbaldehyde (compound-I) and melamine as shown
in Fig. 1a. The formation of the MNENP as per the proposed
structure in Fig. 1a was confirmed by FT-IR and 13C CP-MAS NMR
spectroscopy. The absence of strong bands at 1686 and 1665
cm−1 attributed to the C=O stretching of the –CHO group in
compound-I and the appearance of the bands from the triazine
ring at 1548 and 1477 cm−1 along with the broad bands at 3445
cm−1 due to the N-H and O-H stretching vibrations (instead of a
doublet for the –NH2 in this region) confirms the complete
condensation of the precursors to form the product.10
Moreover, the C–H stretching vibrations below 2923 cm-1 and
absence of imine band at 1620 cm-1 further confirms the
formation of aminal linkage (Table S1).10a The 13C CP-MAS NMR
1Functional Materials Laboratory, Department of Chemistry, IIT Roorkee, Roorkee-
247667, Uttarakhand, India
2Theoretical and Computational Chemistry Laboratory, Department of Chemistry,
IIT Roorkee, Uttarakhand-247667, India
E-mail: pmfcy@iitr.ac.in, paritosh75@gmail.com
†Electronic Supplementary Information (ESI) available: [Experimental details,
characterization of precursor and catalyst and catalysed products i.e. cyclic
carbonates, methanol and Knoevenagel products]. See DOI: 10.1039/x0xx00000x
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spectrum in Fig. 1c further corroborates the observation of FT- pressure (P/P0 < 0.01) confirms the microporous nature of
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IR analysis and strongly support the proposed structure. The specimen. Significant multilayer adsorptiDoOnIi:n10in.1t0e3r9m/Ce9dCiCa0te49a7n5Dd
resonance signals at 166, 157, 135, 128, 122 and 57 ppm are high-pressure region could also be seen along with a small
assigned to different carbons (inset of Fig. 1c) of MNENP (inset hysteresis extends from low to high pressure range.12 All these
of Figure 1c and ESI).10b,c The elemental composition of MNENP observations indicate the presence of some amount of
estimated from the CHNS analysis reveals high nitrogen content mesopores as well. The pore size distribution (PSD) estimated
of 32.6 wt%. The XPS analysis further provides insightful by DFT model (inset of Fig. 1e) confirmed the presence of
information regarding the structure of the MNENP. The survey majority of micropores along with some mesopores. The
scan in Fig. 1d shows the peaks from C1s, O1s and N1s. The high combination of all these make the MNENP as a hierarchical
resolution C1s spectrum in Fig. S3a has shown five different nanoporous material. The specific surface area estimated using
types of carbon corroborates the observation of 13C CP-MAS BET (SABET) model was 304 m2 g−1 with the total pore volume of
NMR spectrum. Similarly, the high resolution N1s XPS (Fig. S3b) 0.95 cm3 g−1. The SABET of MNENP is comparable to some of the
spectrum shows two peaks at 399.6 and 400.1 eV attributed to recently reported nitrogen enriched polytriazine and triazine
the −C=N− and −NH− functionalities, respectively.10b,11 The O1s based polymers (Table S2).
(Fig. S3c) spectrum has maxima at 531.5 eV due to −OH
attached to the aromatic ring. A minor peak at 532.6 eV could
be attributed to the −S=O from trapped DMSO.10b,c
N
(a)
N
N
N
N
OH
NH2
N
NH OH NH
N
N
N
OHC
CHO
DMSO, 170 o
24 h
C
HN
N
N
N
N
N
Fig. 2. (a) FE-SEM, (b) TEM and (c) HRTEM images of MNENP. The SAED pattern is
N
H
+
given in the inset of (b).
N
H2N
N
NH2
N
HN HN
N
N
CHO
N
In an attempt to further improve the textural properties,
additional specimens were made by varying the temperature or
time keeping other parameters same. The specimens made at
150 and 180 C keeping other parameters identical have SABET
of 77 and 242 m2 g-1, respectively (Fig. S7a). These values are
less than the SABET of MNENP (304 m2 g−1) made at 170 C.
Further, neither an increased reaction time of 48 h (SABET = 135
m2 g-1) nor a decreased reaction time of 12 h (SABET = 105 m2 g-
1) could help in improving the SABET (Fig. S7b). Thus, the reaction
carried out at 170 C for 24 h yield the product with best
possible textural properties. The CO2 capture capacity of 8.9 and
6.2 wt% was estimated for the MNENP measured at 0 and 25
C, respectively, at 1 bar (Fig. S7c). The isotherms didn’t close at
the low pressure range indicates a stronger interaction of the
CO2 with the framework of MNENP.
N
Compound-I
Melamine
MNENP
(c)
1
(b)
Melamine
1
N
N
N
NH OH NH
2
3
N
4
6
H
6
5
Compound-I
MNENP
HN HN
#
2
3
# DMSO
5
* rotational side band
6
4
*
*
250
200
150
100
50
0
4000
3500
3000
2500
2000
1500
)
1000
500
-1
Chemical Shift (ppm)
Wavenumber (cm
O1s
(d)
(e)
200
150
100
50
C1s
N1s
OKLL
0.4
0.3
0.2
0.1
Presence of the different basic sites and their distribution
was investigated by CO2-TPD (Fig. S8). The TPD profile of the
depicted three CO2 desorption peaks at about 100, 400 and 530
C attributed to weak basic sites due to –OH, medium basic sites
due to –NH and strong basic sites due to aromatic nitrogen of
the triazine ring present in the MNENP framework,
respectively.13 The total basic sites calculated from the area
under the peak from CO2-TPD is about 2.91 mmol g−1.
The presence of heteroatoms with multiple functionality
have shown superior catalytic activity.5a,6 Hence, the presence
of -OH and –NH- groups in the MNENP framework along with
the high SABET and hierarchical pore structure have encouraged
us to investigate the catalytic behaviour. Especially, the
utilization of CO2 to produce materials of industrial importance
and energy materials have been the major objectives. For this
purpose, the MNENP was explored as heterogeneous catalyst
for the cycloaddition of CO2 to epoxides for the formation of
cyclic carbonates as well as electrochemical conversion of CO2
to methanol and methane by using MNENP as the active
0.0
Adsorption
Desorption
0
5
10
15
Pore Width(nm)
20
25
0
0.0
0.2
0.4
0.6
0.8
1.0
1000
800
600
200
0
Binding ener4g0y0(eV)
Relative pressure (P/P0)
Fig. 1. (a) Synthesis scheme, (b) FT-IR, (c) 13C CP-MAS Spectra, (d) Survey scan and
(e) Nitrogen sorption isotherm of MNENP. The PSD has been given in the inset of
(e).
The TGA/DTG thermograms show multistep mass loss (Fig.
S5) due to the removal of trapped solvent/moisture up to 200
C.10b The successive mass losses could be attributed different
processes such as condensation, carbonization and
decomposition of the of the framework at higher temperatures.
The FE-SEM image (Fig. 2a) shows almost spherical
agglomerated nanoparticles with size of 30-70 nm. A similar
information could be derived from the TEM image (Fig. 2b). The
HRTEM image in Fig. 2c shows the porous nature of the
specimen. No ring or spot pattern could be seen in the SAED
shown in the inset of Fig. 2b indicates the amorphous nature of
the specimen, which was further confirmed from XRD (Fig. S6).
The textural property of MNENP was investigated by N2
sorption (Fig. 1e). A type-I isotherm with steep N2 uptake at low
2 | J. Name., 2012, 00, 1-3
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electrode material. The MNENP further catalyse C-C bond molecules, density functional theoretical calculations were also
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formation via Knoevenagel condensation.
carried out (please see ESI, Fig. S22).15 ThDeOsIt:u1d0.i1e0s3r9e/Cv9eCaCle0d49t7h5aDt
Epichlorohydrin was selected as a model substrate to carry the interaction energy of epoxide with the hydroxylated
out the cycloaddition reaction at 100 °C under 4 bar pressure of framework (MNENP) is ~4 kcal/mol more than that for the
CO2 in a high-pressure reactor. The obtained product was framework without the hydroxyl group which activate the
purified by column chromatography and analysed by NMR (Fig. reaction for the formation of the desired product.
S9) and GC-MS (Fig. S10). In 13C NMR spectrum the observation
Table 1 Catalytic conversion of epoxides into carbonates by metal-free catalyst MNENP.
of signal around 154 ppm attributed to the incorporation of CO2
into epoxide ring and confirms the conversion of epoxides into
cyclic carbonates.5a,6b,c Moreover, the single product with 100%
selectivity and 100% conversion was determined from GC-MS
investigation (Fig. S10). Further, the kinetic study revealed a
complete conversion of reactants into product after 20 h at 100
C (Fig. S11).
The cycloaddition of CO2 with different epoxide substrates
such as epibromohydrin, 1,2-epoxy hexane, styrene oxide and
glycidyl phenyl ether were also investigated, the results are
shown in Table 1. It has been found that epichlorohydrin
showed highest conversion, followed by glycidyl phenyl ether
and epibromohydrin. Although, lower conversion of phenyl
glycidyl ether into cyclic carbonate could be expected owing to
the steric hindrance of the substrates,14 but to our surprise an
unusually high yield of 96 % was realized (Table 1, entry 5).
Identical reaction in the absence of catalyst (blank reaction) has
yielded no product. All these products were similarly purified
and characterized by NMR and GC-MS (Fig. S12-19).
After the completion of reaction, catalyst was separated by
centrifugation and washed several times with ethyl acetate and
dried at 100 °C, and its recyclability was investigated. The
catalyst showed good recyclability. Even after fifth cycle,
retention of 79% of its activity was observed, when the
reactions were repeated under identical conditions (Fig. S20).
The higher activity of the MNENP can be attributed to
multiple factors such as SABET, hierarchical pore structure, large
and uniform distribution of task-specific functionality. The large
SABET yielded large number of accessible active sites where as
the hierarchical pore structure accelerates mass transfer of
substrates and products. The presence of –OH and –NH
functionalities play their respective roles by interacting with the
epoxide and CO2 molecules via H-bonding and Lewis acid-Lewis
base interactions, respectively. The ability to reversibly adsorb
CO2 by MNENP owing to the presence of large number of amine
groups and triazine moieties has a combined effect of activation
of CO2 as well as increase in the concentration of CO2 around
the catalytically active centers. The plausible mechanism for the
formation of cyclic carbonates via cycloaddition of epoxides and
CO2 is shown in Fig. S21. The cycloaddition occurs by the
adsorption and activation of CO2 on the Lewis basic sites (-NH-)
of MNENP to afford the formation of carbonate anion, followed
by the subsequent nucleophilic attack to the less sterically
hindered carbon of the epoxide leading to the ring opening.5a
This was facilitated due to the C-O bond activation through
hydrogen bonding in the epoxides. the nucleophilic attack of the
epoxide oxygen on carbonyl carbon led to the ring closure
forming a five membered cyclic carbonate.5a
S.No.
1.
Epoxide
Product
Conv. (%)*
Selec. (%)#
100
O
O
O
O
Cl
Cl
O
100
92
O
O
O
2.
3.
4.
5.
Br
Br
100
O
O
O
O
O
58
100
O
O
Ph
Ph
O
85
100
O
O
O
O
O
O
96
100
Reaction conditions: Catalyst =10 mg; epoxide = 0.25 ml; Pressure of CO2 is 4 bar;
Time = 20 h, Temperature=100 °C. (*based on reactant and #based on product)
Electrocatalytic reduction of CO2 by MNENP was evaluated
in a two-compartment cell using 0.1M KHCO3 as an electrolyte
in the potential range 0 to −2 V. As expected, the current density
in the electrolyte solution saturated with argon could be
attributed to the hydrogen evolution reaction (Fig. 4a), while, in
case of CO2 saturated solution the observed higher current
density could be attributed to the joint contribution of CO2
reduction and H2 evolution. This confirms that the MNENP is
electrocatalytically active for CO2 reduction reaction. The liquid
1
product obtained after electrolysis was analysed by H NMR.
The signal at 3.21 ppm in the H NMR spectrum confirms the
1
reduction of CO2 to methanol, which was further compared
1
with the H NMR of methanol (Fig. S23).16 The stronger Lewis
base-Lewis acid interaction of the nitrogen in MNENP with the
CO2 helps in increasing the rate of reduction of the CO2 by
stabilizing intermediate products formed during the conversion.
The chronoamperometric analysis of MNENP was carried
out at a constant potential of −1.0 V vs Ag/AgCl for 14,400 s as
shown in Fig. 4b. Initially, a decrease in the current density,
followed by a steady state response is observed in accordance
with the reported literatures.17 In order to understand if any
gaseous product formed during the electrocatalysis, the gases
product was analysed by GC (Fig. S24), which indicate the
formation of methane during the electrocatalytic reduction of
CO2. Thus, the active catalyst MNENP is capable of reducing CO2
through electrocatalysis forming both methanol and methane
as main products as per scheme-S4, which was supported by the
adequate literatures.18 To study the role of the MNENP catalyst
for the electroreduction of CO2, an identical experiment was
performed by taking only graphite sheet as the electrode. No
1
liquid product was formed as depicted from the H NMR (Fig.
S25) further strongly support our claim.
To prove the versatility nature of the catalyst MNENP, a
popular base catalyzed reaction, Knoevenagel condensation,19
for the C-C bond formation was explored. In this reaction, ten
To get more insight on the role of –OH group in the
interaction between the MNENP moiety and epoxide
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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L. Rotundo, C. Garino, E. Priola, D. Sassone, H. RVaieow, ABr.ticMleaO,nMline.
different aromatic aldehydes reacted with malononitrile in
presence of MNENP as catalyst (ESI, Table S3) and products
were analysed by 1H and 13C NMR (ESI, Fig. S26-35). It is
important to note that the catalyst has shown a very good
activity with the maximum yield reaches up to 95 % in 4h.
Robert, J. Fiedler, R. Gobetto and C. Nervi, Organometallics,
DOI: 10.1039/C9CC04975D
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4
5
0.0
(b)
(a)
0.000
-0.5
-1.0
-0.004
-1.5
-0.008
-2.0
in Argon
in CO2 (bare Graphite sheet)
-2.5
-3.0
bare graphite sheet
with MNENP
-0.012
in CO2 (MNENP)
0
5000
Time (sec)
10000
15000
-2.0
-1.5
-1.0
-0.5
0.0
Potential (V)
Fig. 4. (a) CV curves of MNENP electrode and bare graphite sheet @ 5 mV s−1 in Ar
and CO2 saturated 0.1M KHCO3 aqueous solution, (b) Chronoamperogram
(absolute current density vs time) @ −1.0 V vs. Ag/AgCl in tested duration of 4 h.
6
7
In summary, multifunctional nitrogen-enriched nanoporous
polymer (MNENP) synthesized by the condensation of
compound-I with melamine has high SABET of 304 m2 g-1 with
hierarchical pore structure. The multifunctional MNENP has
catalysed multiple reactions for the utilization of CO2 as well as
for the C-C bond formation through Knoevenagel reaction. The
formation different cyclic carbonates with 100% selectivity and
almost 100% yield make it an important family in the metal-free
organocatalyst. Moreover, the electroreduction of CO2 to
methanol and methane by MNENP is a rare example where an
organic polymeric material was used for this purpose,
otherwise, the field is mostly dominated by metal based
catalysts. Formation of ten different Knoevenagel products by
reacting different aromatic aldehydes with malononitrile with
high yield that reaches as high as 95% has made MNENP as a
multipurpose versatile catalyst. Hence, development such
metal-free catalysts that could show the potential for multiple
organic conversions is beneficial from both energy and
environmental perspective while keeping cost of the catalyst
minimum due to the use of inexpensive precursors.
8
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This research was financially supported by DST, Govt. of
India with Grant No. DST/TDT/TDP-03/2017(G).
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Conflicts of interest
There are no conflicts to declare.
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4 | J. Name., 2012, 00, 1-3
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