Samples for adsorption studies were first degassed in vacuum, then saturated with CO2 at 20 °C, heated to 100 °C under N2 (Pre-heating) and cooled down under CO2
prior to measurements (Pre-cooling, Figure 36). Then two cycles of heating (1st and 2nd) without CO2 purge and cooling under CO2 purge were conducted.
Figure 36 TG gas adsorption-desorption sequence and the mass changes of PGEMA 28.
The adsorption data for the studied samples are shown in Table 6. N2 adsorption was negligible in all samples. However, with CO2, there were significant differences between the samples. Adsorption of CO2 to the salt form PAEMA and PEO-PAEMA was minimal and most of the adsorption is most likely physical adsorption into the polymer matrix (Figure 37A and 38A). This is supported by the relatively low release temperatures of CO2 below 60 °C for both polymers (Figure 37B and 38B). When the polymers were regenerated into their free base forms, an impressive increase in CO2 adsorption capacity is observed. PAEMA REG has a capacity of over 1.7 mmol/g (200 % increase) and PEO-PAEMA REG over 0.5 mmol/g (50 %). These can be attributed to the higher amount of available amine groups for CO2 binding. 121
CO2adsorption and desorption data.
a Values are not exactly 0, but very small and can be considered negligible.
bCalculated values based on theoretical 100% NH2content.
The increased interactions between the polymers and CO2are also suggested by the increase in heat of desorption in DSC measurements (Figure 37D and 38D), namely, the heat of desorption of CO2is 110 J/g for PAEMA REG and 54 J/g for PEO-PAEMA REG compared to 2 J/g of PAEMA and ~0 J/g for PEO-PAEMA. The temperatures of the onset of desorption of CO2from TG are also increased due to the stronger interaction between the gas and the material (Figure 37B and 38B).
When PAEMA and PEO-PAEMA are modified, the more basic guanidine increases the capacity up to a maximum of 2.4 mmol/g with 7 % modification, a 35 % increase compared to PAEMA REG. The capacity of PEO-PGEMA goes up to 1.8 mmol/g with 22 % guanidinylation degree, a 260 % increase compared to PEO-PAEMA REG. The theoretical maximum amine efficiency of dry adsorption CO2for
For the polymers in this study, the efficiencies are 0.29 for PAEMA REG and 0.10 for PEO-PAEMA REG with increasing efficiency when modified (Table 6). This suggests that not all functional groups participate in the adsorption process. The morphology of materials also has an effect on the available sites for adsorption.
According to SEM, homopolymers PAEMA, PAEMA REG and PGEMA 7 formed microspheres of size 1-5 μm, while irregular granular morphology was observed in PEO-PAEMA, PEO-PAEMA REG and PEO-PGEMA 22. The amine efficiency values combined with SEM indicate that the morphology of the samples affect the amine distribution and induce steric hindrance for adsorption. 123,152 The differences between the homopolymer and block copolymer could be related to the crystalline nature of the PEO-block affecting the morphology of the copolymer samples and lowering the adsorption performance. 159
Figure 38 TG data of the PEO-PAEMA copolymers visualized, CO2 capacity (A), Desorption temperature (B), Kinetics of desorption (C), Heat of desorption (D), 10 min capacity (E) and recyclability during one cycle (F).
NMR measurements showed that guanidine functions assist in CO2 binding more strongly to adjacent amines than to plain amines in an aqueous environment.
While this is not directly relatable to the dry adsorbtion testing conditions, it reveals differences in CO2 interactions between the two polymers. When the amount of modified side groups is increased considerably, the total adsorption capacity decreases accompanied by lowering of desorption onsets and the heats of desorption. According to NMR-studies, residual CO2 is present in the modified PGEMA solutions after heating (Figure 34 and 35). Residual carbamate is also observed after synthesis. Carbamate binds active amines and decreases potential adsorbtion locations. However, heating should decompose carbamate and other
This suggests that during desorption, not all of the adsorbed CO2 is released from the guanidine polymers, manifested as lower overall capacity when measured from mass changes.
As more guanidine is introduced, more CO2 remains adsorbed in the polymer as carbamate, lowering the observed capacity in TG-measurements further. Wang et al. observed a slight increase in carbamate concentration in the first 30 min when desorption was conducted via heating, suggesting that the desorption time of 15 min at 100 °C used in our experiments could be too short to completely regenerate our samples. 169 Also, guanidines have been shown to form stable carbamates with amines, having higher sorption at temperatures over 50 °C suggesting even further that, in our experiments, the adsorption/desorption conditions for guanidinylated polymers are not optimal. 153
Yet, other factors may explain the results as well. Steric restrictions may play a part due to the bulky guanidine preventing access to some side groups and affecting adsorption. 149,166,167 Another aspect is that guanidinylation may cause morphological changes in the material, such as crosslinking, that has been shown to decrease adsorption via fewer amines available, simultaneously increasing desorption performance due to increased physical adsorption and less stable carbamates. 166,170,171
All samples reached over 80 % of their adsorption capacity in under 10 minutes, indicating overall fast CO2 scavenging potential (Figure 37C and 38C). The adsorbance-desorbance recyclability was assessed by comparing the adsorbance between two heating cycles (Figure 37E and 38E). Recyclability improved overall in both PGEMA and PEO-PGEMA when guanidine was introduced. Regarding the energy consumption, desorption temperatures and heats of desorption also decreased with guanidinylation. Introducing PEO resulted in lower desorption temperatures and heats and improved recyclability but lower capacity and slower adsorption and desorption.
5 CONCLUSIONS
Colloidally stable dispersions of negatively charged nanodiamonds (ND) combined with amphiphilic poly(ethyleneoxide)-block-poly(dimethylaminoethyl methacrylate)-block-dodecyl (PEO-PDMAEMA-C12) copolymers were prepared and studied. The binding interactions between the ND surface and polymer were studied with NMR spectroscopy and showed dependence on the PEO length.
Nanodiamond-polyelectrolyte complex dispersions with large positive zeta potential, neutral pH, improved colloidal stability and particle sizes below 200 nm were obtained.
A series of cross-linked, ND containing polyelectrolyte copolymer films based on poly(butylacrylate) (PBA) and PDMAEMA were prepared by photopolymerization and their mechanical-, swelling- and stimuli-responsive properties were investigated. Addition of plain NDs only slightly changed the mechanical properties of the films due to aggregation and sedimentation of the NDs. When NDs complexed with PEO-PDMAEMA-C12 were used, improved dispersion and interaction of NDs with the P(BA-DMAEMA) matrix resulted in stiffer materials that had over a ~161%
increase in modulus and ~118% increase in stress at break. These films showed a reversible thermal phase-transition in basic environments.
Poly(aminoethyl methacrylate) (PAEMA) and poly(ethylene oxide-block-aminoethyl methacrylate) (PEO-PAEMA) were synthesized via RAFT and modified with guanidine (PGEMA and PEO-PGEMA). NMR studies under CO2 revealed a stronger affinity of the guanidinylated polymers towards CO2. The polymers with free base amines and guanidinylation had high CO2 adsorption capacities, lower desorption onset temperatures and recyclability. A raw unprocessed material with 2.4 mmol/g capacity, over 90% of capacity reached in 10 min and desorption temperature under 80 °C is certainly very promising for future applications in CO2
adsorbents.
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