Green Polyelectrolyte-Functionalization of Carbonaceous

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Green polyelectrolyte-functionalization of carbonaceous nanospheres and its application in ion chromatography Qiming Zhao, Shuchao Wu, Peimin Zhang, and Yan Zhu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b00802 • Publication Date (Web): 28 Nov 2016 Downloaded from http://pubs.acs.org on November 29, 2016

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ACS Sustainable Chemistry & Engineering

Green polyelectrolyte-functionalization of carbonaceous nanospheres and its application in ion chromatography Qiming Zhaoa, Shuchao Wub, Peiming Zhanga, Yan Zhua* a

Department of Chemistry, Xixi Campus, Zhejiang University, 148 Tianmu Road, West Lake District, Hangzhou 310028, Zhejiang, P. R.China

b

Zhejiang Institute of geology and mineral resources, 508 Stadium Road, West Lake District, Hangzhou 310007, Zhejiang, P. R.China

Abstract: Carbonaceous nanospheres (CNSs) synthesized from hydrothermal carbonization of glucose were facilely modified with quaternary ammonium polyelectrolytes (QAPs) through a green and high-efficient strategy, and successfully applied in anion-exchange chromatography (AEC). Methylamine and 1,4-butanediol diglycidyl ether were utilized as monomers to start the polymerization for constructing QAPs. All the synthesis was achieved in water without damage to the monodispersity of CNSs. The water-dispersibility of CNSs was significantly increased after QAP-modification. The QAP-grafted CNSs (QAP-CNSs) were characterized by FTIR, XPS, SEM, TGA, and zeta potential measurement. The functionalization

methodology

was

further

extended

to

produce

octadecylamine-modified CNSs, which demonstrated its versatility in preparation of functional carbons. For application in AEC, the QAP-CNSs were adhered on sulfonated poly (styrene-divinylbenzene) (PS-DVB) microspheres by electrostatic interaction. Using the PS-DVB/QAP-CNS composite as anion-exchange phase and potassium hydroxide solution as eluent, seven common anions were efficiently separated with superior stability. Keywords: hydrothermal carbonization; carbon materials; polyelectrolyte; surface modification; ion chromatography ______________________________ *Corresponding author. Tel.: +86-571-88273637; E-mail address: [email protected]

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Introduction The hydrothermal carbonization (HTC) of biomass to fabricate carbon spheres (CSs) has captured broad attention owing to its sustainability, economy and high-efficiency.1-6 The hydrothermal CSs have presented tempting application in multiple areas, such as catalysis,7,8 lithium-ion battery,9-11 and adsorbents12,13. To achieve desired properties for a specific use, chemical functionization of CSs was usually inevitable. There were two basic approaches: one-pot synthesis and post-synthesis modification.8 The synthesis of CSs with nitrogen-containing groups was achieved through one-pot hydrothermal method using nitrogen-rich reagents, such as ammonia,15-17 glucosamine18,19 and ammonium sulfate20

as initiative

products. Titirici and coworkers successfully incorporated water soluble monomers in CSs during the HTC of glucose to obtain carboxylated CSs21 and imidazole functionalized CSs.22 Similar strategy was also employed to prepare sulfur-containing CSs via introducing L-cysteine or S-(2-thienyl)-L-cysteine into the glucose HTC,23,24 and

CSs

with

phosphorus-containing

groups

using

phosphoric

acid

or

tetraphenylphosphonium bromide as hydrothermal reactant.25,26 Compared with in situ functionalization, post-modification of the formed CSs provided a milder and controllable functionalization process, where the functionality of added molecule could be preserved. By post treatment of CSs with amine,27 cysteine,28 4-amino benzamide29 or urea,30 nitrogen-bearing CSs were facilely fabricated. The CSs grafted with salicylidene imine and 5-azacytosine were also prepared and showed excellent selective absorption towards uranium (VI) from aqueous solution.31,32 Liu et al. introduced functional double bonds onto the CSs’ surface via post-modification to improve CSs' dispersibility and compatibility in polymer matrix.33 The surface Diels-Alder reaction was also developed as a facile and effective methodology to synthesize CSs with functional groups.34,35 However, the traditional

post-modification

was

usually

performed

in

ungreen

organic

solvent.22,30,34-36 Furthermore, the reported functionization methods often had potential damage to the structure of CSs, which led to the formation of irregular and


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crosslinked carbonaceous clusters.20,23,24,37 For all we know, grafting polyelectrolytes onto HTC material surfaces has seldom been researched. Poly (diallyl dimethyl ammonium chloride) was bonded as polyelectrolyte brushes on the surface of hydrothermal CSs to enhance their dispersibility in water.37 However, the approach utilized anhydrous toluene as solvent and required the addition of prepared 4,4’-azobis (4-cyanovaleric acylchloride) as initiators and triethylamine as catalyst, which was tedious and environmentally unfriendly. Furthermore, the amount of bonded polyelectrolyte was limited by the surface hydroxyl groups of hydrothermal CSs. Herein, we reported a green, high-efficient and tunable surface modification of HTC-derived carbonaceous nanospheres (CNSs) with quaternary ammonium polyelectrolytes (QAPs), and the successful application of QAP-grafted CNSs (QAP-CNSs) in anion-exchange chromatography (AEC). The functionization was conducted in water at 333 K without any initiator or catalyst, using methylamine and 1,4-butanediol diglycidyl ether (BDDGE) as reagents to activate the fasculation and epoxy-amine reactions. Based on the existing epoxy groups of QAP-CNSs, octadecylamine-functionalized CNSs were also facilely produced through the simple ring-opening addition. Thus, this modification of HTC carbon via the use of methylamine, BDDGE and subsequent functionalization reactions could be further extended as an attractive methodology to produce more novel carbon-based materials.

Experimental Instruments The Fourier transform infrared (FTIR) characterization was achieved by a Bruker Vector 22 spectrometer (Bruker, German). The elemental and thermogravimetric analysis (TGA) were performed with a Flash EA 1112 elemental analyzer (Thermo Fisher Scientific, USA) and SDT-Q600 analyzer (TA, USA), respectively. The samples’ morphologies were observed using a HITACHI SU-8010 field emission scanning electron microscope (SEM). The nitrogen adsorption analysis was conducted



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with a Micromeritics ASAP 2020 at 77 K. The X-ray photoelectron spectra (XPS) information was obtained by an ESCALAB_250Xi device with a Mg anode (1.2536 keV) as X-ray source. All chromatographic experiments were fulfilled through ICS-2000 system (Thermo Fisher Scientific, USA). Materials Poly (styrene-divinylbenzene) (PS-DVB) microspheres were fabricated based on our previous literature.38 The monodisperse CNSs were produced via HTC of glucose.39 Methylamine (40 vol%) and BDDGE (60 vol%) were bought from Shanghai Aladdin Chemical Co., Ltd.. Glucose (99.0%), acetic acid (99.7%), sulfuric acids (98%) and dichloromethane (99.5%) were supported by Hangzhou Huipu Chemical Reagent Co., Ltd.. Deionized water was generated by a GenPure ProUV/UF purifier (Thermo Fisher Scientific, USA). Synthesis of QAP-CNSs The QAP-CNSs were prepared via a multi-step condensation as displayed in Figure 1. Specifically, 0.4 gram of CNSs was added to 50 mL water solution of methylamine (4 vol%) and BDDGE (7.5 vol%) under magnetic stirring, and the mixture was treated with water bath at 333 K for one hour. Surface carbonyl groups of hydrothermal CNSs could be reacted with BDDGE and methylamine to form the tertiary amine groups through ring cleavage reaction of BDDGE (Figure 1A).40 Thereafter, 50 mL methylamine (4 vol%) was added to the above CNSs and treated with water bath at 333 K for one hour, and then 50 ml BDDGE (10 vol%) was added to the obtained products and treated at 333 K for one hour. In this process, the epoxy-amine addition reaction resulted in generating one QAP layer on CNSs’ surface (Figure 1B, C), and the terminal amines of QAP functioned as active sites for next epoxy-amine reaction (Figure 1C, D).38 Therefore, the CNSs modified with more QAP layers could be facilely gained by repeating the last epoxy-amine additions. The products in all above procedures should be filtered and washed by deionized water after reaction.


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Figure 1. Illustration of CNSs functionization strategy

Preparation of PS-DVB/QAP-CNS anion exchangers The sulfonation of PS-DVB microspheres was carried out based on reported work.[36] Then, 20 mL of QAP-CNSs colloidal solution was added into the water suspension of sulfonated PS-DVB microspheres and stirred for four hours. QAP-CNSs were electrostatically coated onto the surface of PS-DVB microspheres. After that, the yellowish solid could be observed at the bottom of flask. The formed PS-DVB/QAP-CNS compound was applied as stationary phases for AEC. Procedure of column packing Slurry of 2.7 gram of PS-DVB/QAP-CNSs powders in 45 mL deionized water was sonicated for five minutes, and packed into the stainless steel column (150×4.6 mm i.d.). 0.5 L of deionized water was used to press above slurry into the column at



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40 MPa. The prepared column was washed with 0.01 mol L-1 KOH at 0.2 mL min-1 for 40 h, and then connected to AEC for the following study.

Results and discussion The characterizations of CNSs and QAP-CNSs The CNSs functionalized with varied QAP layers were synthesized through a simple reaction strategy as illustrated in Figure 1. Figure 2a reflected that the hydrothermal CNSs were monodisperse with mean diameter of 330 nm. The CNSs bonded with ten QAP layers were still monodisperse without crosslinked carbonaceous clusters, and the particle size was significantly increased compared by that of raw CNSs (Fig. 2b, c). The brown CNSs powder turned light yellow after QAP-functionalization (Figure 2d). The N2 adsorption measurements showed the surface areas of CNSs and QAP-CNS with ten layers were less than 5 m2 g-1, which indicated that the produced CNSs and QAP-CNSs had poor porosity. These facts illustrate that our modification strategy has little effect on the morphology and monodispersity of CNSs.


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Figure 2. SEM images of raw CNSs (a), CNSs modified with ten QAP layers (b) (c), and their different macroscopic morphologies (d).

Figure 3. FTIR spectrums of CNSs and CNSs with five QAP layers

Figure 4. XPS analysis of QAP-CNSs with five layers



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The FTIR and XPS spectra of CNSs and QAP-CNSs are exhibited in Figure 3 and Figure 4, respectively. The characteristic peak at 3470 cm-1 resulted from the O-H stretching vibration (Figure 3), which was indicative of the existence of rich hydroxyl groups on both CNSs and QAP-CNSs. The two peaks at 2920 cm-1 and 2840 cm-1 were designated to the non-aromatic C-H stretch. The absorption peaks between 1750 cm-1 and 1550 cm-1 could be ascribed to the C=O and C=C stretching vibrations. However, it should be noted that the absorption strength of carbon hydrogen bonds in QAP-CNSs spectrum was markedly heightened, while the carbonyl bond stretch was significantly weakened in contrast to that of CNSs. Meanwhile, a distinctly different and sharp peak at 1116 cm-1 appeared in FTIR spectrum of QAP-CNSs, which was linked to C-N stretch on QAPs. To further confirm the formation of QAPs, XPS was also carried out to characterize the nitrogen-containing groups of QAP-CNSs (Figure 4). Figure 4 manifests the existence of two kinds: quaternary-N denoted by the peak of 402.1 eV, and secondary-N denoted by the peak of 399.2 eV. The quaternary-N amount was much more than that of secondary-N. These facts indicate that carbonyl groups are reacted with methylamine and BDDGE to form QAPs, which contain rich quaternary ammonium groups and methylene groups. Owing to the weak thermo stability of most functionalized polymers on carbon materials, the TGA analysis could provide valuable information about polyelectrolytes bonded on CNSs. The TGA results of CNSs and CNSs with three layers and ten layers of QAPs are displayed in Figure 5. The experiments were conducted under nitrogen atmosphere with temperature increasing speed of 10 K min-1 and the same amount of samples (10 mg). CNSs sample began to lose weight at about 563 K due to the decomposition of surface oxygen-containing groups such as –COOR and –OH (Figure 5a), and remained 66 wt% of the total until 773 K. As revealed in Figure 5b and c, the quite distinct curves from that of CNSs were received for QAP-CNSs, the lower weight-loss temperature (463 K) was attributed to the easier decomposition of QAPs. Apparently, QAP-CNSs with ten layers lost considerably more weight than that with three layers during the TGA investigation. Above facts imply that our


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functionalization strategy can effectively graft QAPs on CNSs, and the QAP mass is augmented with grafted layer counts.

Figure 5. TGA results of raw CNSs (a), CNSs with three QAP layers (b), and ten QAP layers (c).

The polyelectrolytes grafted on CNSs’ surface are nitrogenous while raw CNSs do not have nitrogen at all. Therefore, the percentage of nitrogen in QAP-CNSs reflects the amount of QAPs grafted on CNSs. Elemental analysis presented that the N-content was 0.27%, 0.63%, 0.98%, 1.56% and 1.84% for QAP-CNSs with 1, 3, 5, 10 and 15 layers, respectively. The N-content in QAP-CNSs was scaled up with QAP layer counts, whereas the increment speed was inferior to that of exponential increase as theory predicted. That could originate from high stereo-hindrance effect of ideal reactions in Figure 1. The results proved that the QAP-modification of CNSs was successfully performed and could be simply tuned by our strategy. Comparation of water-dispersibilities of QAP-CNSs and CNSs The

valid

QAP-modification

was

also

illustrated

by

the

different

water-dispersibilities of CNSs and QAP-CNSs. This parameter was investigated by treating same amount (2.5 g L-1 herein) of CNSs and QAP-CNSs with three layers in pure water for fifteen minutes and comparing with the sedimentation of CNSs and QAP-CNSs after seven days. Figure 6 demonstrats the different dispersedness of



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CNSs and QAP-CNSs water-based suspension after ultrasonication and seven-day standing. The CNSs could be well dispersed like QAP-CNSs at first, owing to the surface hydrophilic –OH and –COOH groups (Figure 6a). However, observation of QAP-CNSs slurry with naked eyes only exhibited little solid deposit after one week, whereas the CNSs were totally precipitated (Figure 6b). The results indicate that QAP-CNSs have much better dispersing performance in water-based system than CNSs.

Figure 6. Water dispersions of CNSs and QAP-CNSs after ultrasonication (a) and seven days’ standing (b).

Figure 7. Zeta potentials of CNSs with different QAP layers in water


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The different stabilities of QAP-CNSs and CNSs suspensions are related to their surface potentials. Figure 7 presents the zeta potentials of CNSs modified with different QAP layers and CNSs in deionized water. The raw CNSs were negatively charged with the zeta potential of -15.1 eV, which could be attributed to the partial ionization of surface carboxyl groups. After the QAP-functionalizaion, obtained QAP-CNSs possessed positive charges accordingly, and their zeta potentials obviously increased with bonded layer counts, which contributed to their excellent water-dispersibility. The zeta potential reached 58.8 mV when three polyelectrolyte layers were grafted onto the surface of CNSs, which was much larger than that of raw CNSs thus resulted in better dispersion in water. These facts reveal that CNSs with tunable amounts of positive charges can be facilely produced and their dispersibility in water could be greatly improved through our modification methodology. Potential of the modification strategy in preparation of functional carbons Owing to the high reactivity of epoxy groups (or amine groups) at the terminal of QAP molecular, established QAP-CNSs could be further modified as required under mild conditions. To prove that, octadecylamine (ODA) was used as the substrate for the ring-opening addition (Figure S1). The elemental analysis (Table S1), FTIR spectrum

(Figure

S2)

and

toluene

dispersibility

(Figure

S3)

of

the

ODA-functionalized CNSs (ODA-CNSs) compared to those of QAP-CNSs or CNSs demonstrated the successful modification. After modified with octadecylamine, the CNSs had much better dispersity in toluene, and the C-H stretching vibration in FTIR spectrum was significantly enhanced due to the rich methylene and methyl groups in octadecylamine. Meanwhile, the increase of C% and H% observed from ODA-CNSs supported

the

successful

ring-opening

addition.

These

confirm

that

our

functionalization strategy can be expanded as a universal approach to sustainably prepare novel functional carbon materials. Application of QAP-CNSs in AEC QAP-CNSs have abundant quaternary ammonium groups, which can function as anion-exchange positions and be applied in AEC. However, nanosized QAP-CNSs are



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too small to be chromatographic packing materials, thus sulfonated PS-DVB microspheres are chosen for the basements to establish PS-DVB/QAP-CNS composites. As manifested in Figure 8, the composite fabrication depends on the classic electrostatic attraction-triggered agglomeration between positive QAP-CNSs and negative PS-DVB basements. The coverage of five-layer QAP-CNSs on PS-DVB could be observed by SEM images (Figure 9). Prepared PS-DVB microspheres are almost monodisperse with an average size of 7.5 ߤm, and the surface is smooth with only few attached small particles (Figure 9a). By contrast, Figure 9b manifests that PS-DVB/QAP-CNS materials have an obvious pellicular structure, and QAP-CNSs are tightly agglomerated on the surface of sulfonated PS-DVB basements.

Figure 8. The formation process of the PS-DVB/QAP-CNSs composites.

Figure 9. The SEM characterizations of PS-DVB basements (a) and PS-DVB/QAP-CNSs composites (b).


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Figure 10. The separation of seven common anions on the PS-DVB/QAP-CNSs phase. Eluent: 0.01 mol L-1 KOH; flow rate: 1.0 ml min-1; injection volume: 25 µl; conductivity detector.

The obtained PS-DVB/QAP-CNS compound has a similar structure as the commercial agglomerated anion exchange phase.41 The PS-DVB basements are the core and QAP-CNSs with five layers are served as the agglomerated ion-exchange layer. To evaluate the chromatographic performance of PS-DVB/QAP-CNS stationary phases, a mixed solution of seven common anions including fluoride, formate, chloride, nitrite, bromide, nitrate and sulfate was tested with 0.01 mol L-1 hydroxide as eluent. Figure 10 reflects the chromatographic separation of these anions on a PS-DVB/QAP-CNS column. All the anions were separated by baseline in 13 minutes. The chromatographic peaks were highly symmetrical without tailing appearance, the reason could be attributed to the highly hydrophilic surface of QAP-CNSs with little nonspecific absorbance. The anion-exchange capacity was measured to be 0.049 mequiv./column based on the breakthrough curve of nitrite.38 The obtained column presented outstanding stability to hydroxide eluents, and the RSD of retention times was < 0.45% after flushed with eluent of 2.5 × 104 column volumes. The efficiencies of seven anions were in the range of 6800 to 15500 N/m (Table S2), which could be



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improved by decreasing the diameter of QAP-CNSs and strengthening the uniformity of agglomeration. These results reveal that the QAP-CNSs are promising packing materials for AEC owing to their green preparation and good separation performance.

Conclusions This work proposed a green and simple methodology to functionalize HTC-derived CNSs with required QAP layers, and first applied the QAP-CNSs in AEC. The functionalization was facilely achieved in water at 333 K based on the fasculation of methylamine and BDDGE. Modified CNSs remained to be monodisperse with enhanced water-dispersion stability. The synthesis of ODA-CNSs further supported the potential of our strategy in preparing novel carbon-based materials. Moreover, via the electrostatic agglomeration of QAP-CNSs on negative PS-DVB basements, the PS-DVB/QAP-CNS composites were fabricated to investigate the application of QAP-CNSs in AEC. Seven common anions could be baseline separated on PS-DVB/QAP-CNS stationary phase with nice stability. On account of the superior water-dispersibility, tunable charge amount, easiness for further functionalization and monodispersity with small particle size, it is believed that QAP-CNSs also have potential applications in biomaterials, drug delivery and catalyst support, etc.

Supporting Information Preparation scheme of ODA-CNSs, dispersion of CNSs and ODA-CNSs in toluene, FTIR spectrum and element analysis of CNSs, QAP-CNSs and ODA-CNSs, and column efficiencies of above anions were supplied in supporting information section.

Acknowledgments This research was supported by National Important Project on Science Instrument (No. 2012YQ09022903), Zhejiang Provincial Natural Science Foundation of China (Nos.


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LY12B05003, LQ13B050001, Y4110532), National Natural Science Foundation of China (No.21405141) and Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province (Nos. 2014006, 2014007).

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For Table of Contents Use Only

Green polyelectrolyte-functionalization of hydrothermal carbon nanospheres and its application in anion-exchange chromatography Qiming Zhao, Shuchao Wu, Peiming Zhang, Yan Zhu*

A green and low-cost polyelectrolyte-modification strategy was proposed for sustainable production of novel functional carbons and chromatographic stationary phases.


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Green Polyelectrolyte-Functionalization of Carbonaceous

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