Selective Low-Energy Carbon Dioxide Adsorption Using

Dec 7, 2017 - ... the melamine polymer-coated particles (1) were carbonized in a furnace under nitrogen atmosphere at 550 °C. As expected from the si...
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Selective Low-energy Carbon Dioxide Adsorption using Monodisperse Nitrogen-rich Hollow Carbon Submicron Spheres Aditya Farhan Arif, Yuma Kobayashi, Elia Michael Schneider, Samuel C Hess, Ratna Balgis, Takafumi Izawa, Hideharu Iwasaki, Shuto Taniguchi, Takashi Ogi, Kikuo Okuyama, and Wendelin J. Stark Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b01353 • Publication Date (Web): 07 Dec 2017 Downloaded from http://pubs.acs.org on December 8, 2017

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Selective Low-energy Carbon Dioxide Adsorption

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using Monodisperse Nitrogen-rich Hollow Carbon

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Submicron Spheres

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Aditya F. Arif1, Yuma Kobayashi1, Elia M. Schneider2, Samuel C. Hess2, Ratna Balgis1,

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Takafumi Izawa3, Hideharu Iwasaki3, Shuto Taniguchi1, Takashi Ogi1,*, Kikuo Okuyama1, and

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Wendelin J. Stark2

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Japan

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Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University,

Institute for Chemical and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich,

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Switzerland

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Sakazu, Kurashiki, Okayama 710-0801, Japan

Battery Materials Research Laboratory, Kurashiki Research Center, Kuraray Co., Ltd., 2045-1,

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ABSTRACT

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Monodisperse, nitrogen-doped hollow carbon spheres of submicron size were synthesized using

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hexamethoxymethyl melamine as both a carbon and nitrogen source in a short (1 h) microwave-

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assisted synthesis. After carbonization at 550 °C, porous carbon spheres with a remarkably high

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nitrogen content of 37.1% were obtained, consisting mainly of highly basic pyridinic moieties.

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The synthesized hollow spheres exhibited high selectivity for carbon dioxide (CO2) over nitrogen

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and oxygen gases, with a capture capacity up to 1.56 mmol CO2 g−1. The low adsorption

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enthalpy of the synthesized hollow carbon spheres permits good adsorbent regeneration.

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Evaluation on the feasibility for scaling-up shows their potential for large-scale applications.

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KEYWORDS microwave, polystyrene latex, pyridinic nitrogen, Van der Waals, physisorption

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Introduction

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Hollow nanostructures1 have attracted an enormous amount of attention lately because of

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their tunable and often remarkable properties (e.g., ultrahigh surface area, shell permeability to

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allow improved internal access, high surface-to-volume ratio, and low density). Such

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nanostructures are appealing for various applications, such as drug delivery,2 catalysis,3 and

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energy conversion.4 Carbon-based materials have been viewed as promising inexpensive sources

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as the scaffold for hollow nanostructures, mainly because they exhibit the well-known features of

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carbon; namely, high chemical stability and electrical conductivity. Combining the

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aforementioned properties of carbon-based materials with hollow spherical structures has led to a

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novel kind of material known as hollow carbon spheres (HCS). Various synthetic pathways to

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obtain HCS that exploit either a soft or hard templating approach have been investigated.5 The

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former method involves the self-assembly of carbon precursors using a variety of different

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surfactants or organic additives,6,

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nanoparticles,9, 10, 11 polystyrene spheres,12, 13, 14, 15 or nanoparticles with a metal core.16, 17 HCS

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have been applied in catalysis, carriers, and drug delivery.18 However, the intrinsic chemical

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inertness of pure carbon structures renders them ineffective for numerous interesting applications

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like CO2 adsorption.

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while the latter uses hard templates such as silica

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Among the current commercial CO2 capture technologies, such as chemical absorption by

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monoethanolamine (MEA) or monodiethanolamine (MDEA), physical absorption by Selexol,

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and chemical adsorption, adsorption by carbon generally has the lowest CO2 capture ability.

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However, carbon exhibits interesting advantages in CO2 adsorption, including low desorption

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energy because of its weak adsorption interaction, easy adsorbent regeneration, and low cost.19, 20

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Unlike most absorption chemicals, carbon is non-corrosive. Thus, the need for corrosion

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inhibitors and corrosion-resistant alloys for the construction materials is suppressed or even

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eliminated in CO2 adsorption by carbon. The low CO2 uptake can be overcome through

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functionalization to create basic sites,21, 22 primarily through functionalization with nitrogen. A

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general way to dope HCS with nitrogen is by polymerization of nitrogen-containing monomers

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and subsequent carbonization. Usually, 3-aminophenol or aniline is used as the nitrogen donor.23

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It was recently shown that using a melamine resin as the N-dopant increased the nitrogen-doping

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content of carbon.24 However, this synthesis was conducted using ultrasonic spray pyrolysis,

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which gave a low yield of polydisperse particles.25 A general, scalable process for the large-scale

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production of N-doped HCS is needed. There are several reports of hydrothermal syntheses of N-

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doped HCS with high monodispersity, but the synthesis time is generally long (up to 24 h).26, 27,

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Herein, we report the synthesis of monodisperse N-doped HCS of submicron size via a short

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(1 h) microwave-assisted synthesis and subsequent carbonization. Because of the high content of

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nitrogen atoms in the aromatic rings of hexamethoxymethylmelamine (HMMM), which is used

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as a nitrogen source, HCS with nitrogen contents as high as 37.1% after carbonization at 550 °C

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are achieved. A preliminary evaluation of CO2 adsorption ability is also conducted at ambient

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temperature and pressure. We evaluate feasibility of scaling up this process from the standpoints

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of energy consumption and equipment size through comparison with a state-of-the-art

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commercial CO2 removal process.

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2.

Experimental

2.1. Synthesis of HCS

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In a standard procedure, positively charged PSL particles with a diameter of 220 nm (ζ-

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potential = 46 mV, 0.9 mL, 1.1 wt%) were diluted in ultrapure water (125 mL). HMMM (1 g,

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2.56 mmol) was added and then the solution was stirred for 1 hat ambient temperature. AIBA

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radical starter solution (15 mL, 0.01 g mL−1, 0.55 mmol) was added to the nanoparticle

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dispersion, which was subsequently heated using a microwave-assisted organic initiator

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(Biotage, Uppsala, Sweden) for 1 h at 90 °C. The obtained particles were washed with water

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twice using centrifugation at 10000 rpm and then dried at 40 °C in a vacuum oven over night.

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The particles (~0.1 g) were heated in an electric ceramic furnace at 550 °C under nitrogen

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atmosphere (0.5 L min−1) for 4 h for carbonization, yielding the HCS product (0.03 g).

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2.2. Physical Characterization

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The ζ-potential of the PSL particles was measured using a zetasizer (Zetasizer Nano ZSP,

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Malvern Instruments Ltd., Malvern, UK). The morphology of the synthesized HCS was observed

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using field-emission SEM (S-5000, 20 kV, Hitachi High-Tech., Tokyo, Japan) and TEM (JEM-

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2010, 200 kV, JEOL Ltd., Tokyo, Japan). Fourier transform infrared (FT-IR) spectroscopy was

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used to investigate the chemical reactions that occurred during the microwave irradiation process

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(Spectrum One, Perkin Elmer Inc., Waltham, MA, USA). Elemental analysis was carried out

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using XPS (PHI Quantera II, Physical Electronics, Chanhassen, MN, USA). The thermal

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behavior of the materials before and after carbonization was investigated using TGA (TGA-

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50/51 Shimadzu, Kyoto, Japan). The nitrogen adsorption–desorption properties of the HCS were

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evaluated using gas adsorption measurement equipment (BELSORP-max, MicrotracBEL, Osaka,

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Japan), and their surface area was calculated using the BET method based on N2 isotherm

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curves. CO2 adsorption measurements were conducted using the same equipment as the BET

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analysis. Prior to the adsorption analysis, each sample was degassed at 300 °C for 3 h. CO2

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capture experiments were performed at 25 °C in a thermostatic bath.

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Results and discussion

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To obtain monodisperse hollow carbon spheres with a high nitrogen content, the following

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two-step synthesis pathway was pursued (Scheme 1). In the first step, HMMM was cross-linked

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and condensed as both a carbon and nitrogen source onto monodisperse polystyrene latex (PSL)

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nanoparticles via microwave-assisted polymerization at 90 °C for 1 h.

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Scheme 1. Illustration of the microwave-assisted process used to synthesize HCS.

HMMM is usually used as a thermally activated curing agent for polymers bearing hydroxyl

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groups.29,

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dinonylnaphthalene disulfonic acid as a catalyst at high temperatures (>150 °C).31 However in

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this case, the use of this kind of acid catalyst did not result in efficient crosslinking. Therefore,

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the ability of other reactants to crosslink HMMM and PSL was examined. Surprisingly, the

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crosslinking worked well in the presence of 2,2′-azobis(2-methylpropionamidine) (AIBA), a

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common water-soluble radical initiator. A plausible explanation for this finding is the radical-

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induced oxidation of polystyrene by an AIBA/H2O/O2 system,32,

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binding sites (i.e., hydroxyl and carboxyl groups) for the covalent attachment of HMMM via

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ether bond formation (Fig. 1). Formation of the ether bond is confirmed by the peak at 1150 cm-1

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in the FT-IR spectrum of the polycondensated HMMM (Fig. S1 of supplementary information).34

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This novel reaction is currently the subject of further investigation in our laboratory. An

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important factor for the successful synthesis of monodisperse polymer-coated nanoparticles was

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the amount of HMMM used. We found that 0.7 wt% of HMMM was the ideal amount; higher

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and lower amounts resulted in agglomerated particles that were not monodisperse (Fig. S2). In

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the second step, the melamine-polymer coated particles (1) were carbonized in a furnace under

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nitrogen atmosphere at 550 °C. As expected from the size distribution before carbonization, only

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the sample synthesized using 0.7 wt% melamine had spherical geometry and a monodisperse size

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distribution (Fig. S3).

For example, HMMM and substituted phenols were condensed using

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thus generating possible

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Figure 1. Oxidation of polystyrene nanoparticles and subsequent polycondensation of HMMM

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as a possible reaction pathway to obtain HCS.

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To investigate the effect of the template size on the HCS formed, two different sizes of

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PSL nanoparticles (120 and 220 nm) were coated with polymer and subsequently calcined (Fig.

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2). The larger PSL template resulted in monodisperse, N-doped HCS 2, while with the smaller

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template gave a mixture of hollow and dense particles. A possible explanation for this

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phenomenon is the intrinsic shrinking of the polymer shell by 50% to 60% depending on the PSL

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size,12 which occurs when the PSL template is thermally removed at high temperature during

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carbonization.

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Figure 2. Figure 2. (a, b) SEM images of polymer-coated PSL particles and (c, d) TEM images

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of HCS. (a) and (c) were synthesized from a PSL diameter of 120 nm while (b) and (d) were

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prepared from a PSL diameter of 220 nm. TEM image of polymer-coated PSL particles and SEM

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image of HCS are provided in the supplementary information.

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The shrinkage factor should be considered when choosing the size of the template

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nanoparticles to obtain optimal results. Therefore, the PSL template with a diameter of 220 nm

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was used in the following experiments. The thickness of the resulting carbon shell was ~49 nm.

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It should be noted that the diameters of the core (110.3±3.6 nm according to the TEM image in

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Fig. 2) and shell (207.8±3.9 nm) are quite uniform; i.e., they exhibit quite small standard

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deviations. Other TEM images of the HSC showed similar distributions, thus we can consider the

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HCS monodisperse.

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Like the previously reported carbonization of melamine resin,24 thermogravimetric

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analysis (TGA) of 1 in N2 showed four carbonization stages (Fig. 3(a)). We therefore expect that

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these materials possess a similar carbonization mechanism. Similar with the previous research on

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the melamine resin, the first heating stage may be assigned to water evaporation.24 Cleavage of

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hydrocarbon and nitrogen bonds occurs up to 400 °C (stage II), while the considerable weight

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loss in stage III is caused by thermal decomposition of PSL.12, 24, 35 Decomposition of PSL led to

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the formation of hollow structure inside the particles, while the gas released by PSL

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decomposition promoted the formation of micro- and mesopores within the shell. Weight loss in

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stage IV is consistent with continuous carbonization.12 Meanwhile, 2 was stable in air after

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carbonization at temperatures up to 440 °C (Fig. 3(b)), indicating these HCS should tolerate gas

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adsorption/desorption cycles. Melamine@PSL in N2

80 60 40 I

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II

III

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(b) 100 Remaining weight (%)

(a) 100 Remaining weight (%)

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HCS in air

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400 600 Temperature (ºC)

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400 600 Temperature (ºC)

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Figure 3. TGA of sample (a) 1 in N2 and (b) 2 in air at a heating rate of 5 °C min−1.

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An important feature of this synthesis using HMMM as a nitrogen source (HMMM has a

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nitrogen content of 21.5%) is the resulting amount of nitrogen in the final HCS 2, which can be

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as high as 37.1% (Table S1). In a similar approach to synthesize HCS using 3-aminophenol as a

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nitrogen source, a nitrogen content of 15.6% was obtained;12 this value is high compared to that

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reported in other literature,36, 37 but lower than that achieved with this protocol. A high nitrogen

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content is important for substantial CO2 adsorption, because it increases the number of basic sites

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on the carbon surface, thus promoting the adsorption of acidic CO2.38, 39 Additionally, the nature

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of the nitrogen incorporated in the HCS is important. Therefore, in-depth X-ray photoelectron

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spectroscopy (XPS) analysis of HCS 1 was performed (Fig. S6). The nature of nitrogen species

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present in 2 was determined to be 60.1% pyridinic nitrogen moieties, 31.9% pyrrolic and amino

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nitrogen, and only 7.9% graphitic nitrogen species. Pyridinic moieties on graphene exhibit a

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positive pKa of around 5, so are highly basic compared with graphitic nitrogen (pkA = −29).40 It

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is assumed that a high content of pyridinic nitrogen in HCS will translate to a high CO2 uptake.

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However, another factor influencing CO2 adsorption is porosity; i.e., accessible surface area.

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Brunauer–Emmett–Teller (BET) measurements revealed that 2 possessed a specific surface area

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of 323 m2 g−1.

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The N2 adsorption–desorption isotherms of 2 were measured (Fig. 4a) to further

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investigate the nature of its porosity. A substantial monolayer and micropore adsorption occurred

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below p/po = 0.05, followed by a linear type-II isotherm between p/po = 0.05–1. The hysteresis

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loop can be described as H4-type hysteresis, with a clear drop around p/po = 0.5. The observed

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isotherms are typical for a hollow structure with a mesoporous shell.23 The pore size distribution

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is multimodal in the micro- and mesoporous domains (Fig. 4b). Based on the N2 adsorption

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analysis, most pores have a diameter of less than 2 nm, which implies they are in the micropore

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range. However, it was difficult to precisely estimate the micropore size of 2 based on its N2

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adsorption data because of the large molecule size. Therefore, another non-linear density

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functional theory (NLDFT) analysis based on CO2 adsorption was performed, which gave a

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micropore size of 1.9 nm (Fig. S8).

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(b)

500

Incremental volume (cm3 g -1)

(a) Adsorbed value (cm3 g -1)

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Pore diameter [nm]

Figure 4. a) N2 sorption isotherms of HCS 2 and b) NLDFT pore size distribution of HCS 2.

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It was recently shown that the performance of a material in CO2 capture strongly depends

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on its micropore content.41 Micropores with diameters of less than 1 nm are particularly desired

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for CO2 adsorption at ambient temperature and pressure.42 Thus, the CO2 capture capacity of the

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HCS was measured at room temperature (Fig. 5). Through a preliminary evaluation, a CO2

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capture capacity up to 1.56 mmol g−1 at room temperature and 1 bar was obtained. This is subpar

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when compared with recent literature This is subpar when compared with recent literature

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although this material contains a significant amount of nitrogen.27, 36 It is important to note that

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the depth of XPS analysis is 4 nm from the outer surface of the particles, hence the XPS results

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cannot reflect the accessibility of the nitrogen sites. We therefore analyzed the surface acidity of

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2 by measuring the ζ-potential. The average ζ-potential of 2 was -33.7 mV, indicating the

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presence of surface functional groups containing free electrons to be donated to acidic carbon

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atoms of CO2 molecules. However, the adsorption enthalpy of CO2 on HCS was calculated to be

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31.5 kJ mol−1 based on the adsorption kinetics, indicating that CO2 and 2 displayed van der

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Waals interactions (see the Supporting Information). This is a typical value for the physisorption

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of CO2, which also implies that the CO2 is dominantly physisorbed on the carbon instead of

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chemisorbed on the nitrogen sites, i.e. the accessibility of nitrogen sites should be improved. In

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addition, the presence of the highly electronegative C=O, shown by the strong peak at 1670 cm-1

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in the FT-IR spectrum of 2 (Figure S1), potentially weakens the attractiveness of N to C from

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CO2.43 While these issues give good insight for the future development of this material, it is

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noteworthy that the current CO2 uptake was achieved in a structure without micropores of