Mesoporous Carbon

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Article
Mesoporous Carbon Stabilized MgO Nanoparticles Synthesized by Pyrolysis
of MgCl2 Preloaded Waste Biomass for Highly Efficient CO2 Capture
Wu-Jun Liu, Hong Jiang, Ke Tian, Yanwei Ding, and Han-Qing Yu
Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/es401286p • Publication Date (Web): 29 Jul 2013
Downloaded from http://pubs.acs.org on August 8, 2013
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Page 1 of 27 Environmental Science & Technology
Mesoporous Carbon Stabilized MgO Nanoparticles Synthesized by Pyrolysis of
MgCl2 Preloaded Waste Biomass for Highly Efficient CO2 Capture
Wu-Jun Liu,† Hong Jiang,†,* Ke Tian,† Yan-Wei Ding,‡ Han-Qing Yu†
†
Department of Chemistry, University of Science and Technology of China, Hefei
230026, China
‡
Hefei National Laboratory for Physical Sciences at Microscale, University of Science
and Technology of China, Hefei 230026, China
Corresponding author:
Dr. Hong Jiang, Fax: +86-551-63607482; E-mail: jhong@ustc.edu.cn
ACS Paragon Plus Environment

Environmental Science & Technology Page 2 of 27
1 ABSTRACT
3 Anthropogenic CO2 emission makes significant contribution to global climate change
4 and CO2 capture and storage is a currently preferred technology to change the
5 trajectory toward irreversible global warming. In this work, we reported a new
6 strategy that the inexhaustible MgCl2 in seawater and the abundantly available
7 biomass waste can be utilized to prepare mesoporous carbon stabilized MgO
8 nanoparticles (mPC-MgO) for CO2 capture. The mPC-MgO showed excellent
9 performance in the CO2 capture process with the maximum capacity of 5.45 mol kg-1,
10 much higher than many other MgO based CO2 trappers. The CO2 capture capacity of
11 the mPC-MgO material kept almost unchanged in 19-run cyclic reuse, and can be
12 regenerated at low temperature. The mechanism for the CO2 capture by the
13 mPC-MgO was investigated by FTIR and XPS, and the results indicated that the high
14 CO2 capture capacity and the favorable selectivity of the as-prepared materials were
15 mainly attributed to their special structure (i.e., surface area, functional groups, and
16 the MgO NPs). This work would open up a new pathway to slow down the global
17 warming as well as resolve the pollution of waste biomass.
18
19
20
21
22
23
24
25

26
27 TOC Art
MgCl2
adsorption
Fast pyrolysis
Bio-oil
Seawater
Mg loaded Biomass
Biomass
Mesoporous carbon
stabilized MgO NPs
CO2 capture
28

29 INTRODUCTION
30
31 The ever-increasing CO2 concentration in the atmosphere has posed a serious threat to
32 global climate balance.1 The global CO2 emissions from fossil fuel burning and other
33 industrial processes have risen by more than 3% annually since 2000,2 totalling 33
34 billion tons in 2010.3 The growing CO2 emissions put the Earth on a trajectory toward
35 irreversible global warming, which is dangerous to the global eco-systems.4 An
36 overwhelming technique for the CO2 capture is adsorption with solid regenerable
37 sorbents,5 including carbonaceous materials,6 solid amine-based materials,7 and
38 alkaline earth metal oxides.5 Among them, the alkaline earth metal oxides, mainly
39 CaO-based materials, are the most widely used CO2 trappers through a CaO looping
40 process (Fig. 1a) at about 873 K and a regeneration reaction at a temperature higher
41 than 1073 K for further cyclic use.8 However, due to the high thermal stability of the
42 CaCO3, the regeneration of CaO from CaCO3 usually requires a high energy
43 consumption, which may cause additional CO2 release. In addition, the regeneration at
44 high temperatures is always accompanied by a sintering process, which can
45 significantly decrease their CO2 capture capacity.
46 Compared to the CaO-based materials, MgO can capture CO2 at temperature
47 lower than 473 K, and be regenerate at low temperatures (e.g., 573-773 K), which can
48 well avoid the sintering process and greatly decrease the energy requirement for the
49 regeneration.9 Furthermore, if MgCl2, an inexhaustible salt in naturally abundant
50 seawater, could be cost-effectively and massively converted to MgO, it would be a
51 great advance for CO2 capture. However, the CO2 capture capacity of the
52 commercially available MgO is fairly small (0.5 mol/kg).10 The CO2 capture sites of
53 the MgO are mainly the basic O2- in the O2--Mg2+ bonds, and the basic strength of the

54 O2- depends on its coordination. The O2- located at edges and corners of the crystal
55 surfaces often have stronger basicity than those in the planes.11 Thus, many efforts
56 have been made to develop MgO-based materials with high basic O2- contents.
57 The MgO nanoparticles (NPs), due to their small size, have more edges and
58 corners per weight, and thus possess more basic O2-. Therefore, compared to the bulk
59 MgO materials, the MgO NPs have more active sites for CO2 capture, allowing
60 efficient utilization of MgO.12 Notably, the MgO NPs can capture a large amount of
61 CO2 at a relatively low temperature (<373 K) because of their high basicity.5 To avoid
62 agglomeration, the NPs are usually synthesized on solid supports, among which the
63 carbonaceous materials are widely used because of their well-defined porosities and
64 high surface areas.13
65 On our continuing efforts toward environmentally friendly biomass disposal and
66 resource recovery,14-17 we proposed a facile and sustainable approach to synthesize
67 mesoporous carbon stabilized MgO NPs through fast pyrolysis of the MgCl2-loaded
68 waste biomass. The MgCl2 is available in naturally abundant seawater with a high
69 concentration (average 0.45%),18 and the MgCl2-loaded biomass can be easily
70 obtained by adsorption of MgCl2 from seawater using biomass as sorbents. In the fast
71 pyrolysis process, the MgCl2 is hydrolyzed and decomposed to form MgO NPs, while
72 the biomass is decomposed and carbonized to form mesoporous carbon, which can
73 serve as a support to stabilize the MgO NPs. Furthermore, in addition to the
74 mesoporous carbon stabilized MgO NPs, bio-oil, a renewable liquid which can be
75 used as fuel or source of chemicals, is also yielded. In the entire process, no extra
76 energy is needed. More importantly, the used MgO NPs can be stored directly without
77 regeneration.
78

79
80 EXPERIMENTAL SECTION
81 Preparation of the Mesoporous Carbon Stabilized MgO NPs. The
82 mesoporous carbon stabilized MgO NPs was synthesized by fast pyrolysis of the
83 MgCl2 loaded biomass. The pyrolysis experiments were performed in a vertical drop
84 fixed bed reactor described in our previous work. 16 The detailed pyrolysis experiment
85 were described in supporting information (SI). After the fast pyrolysis process
86 accomplished, the temperature of the heating zone kept unchanged for another 3 hours
87 to further carbonize the remained solid residue. Finally the reactor was moved out of
88 the heating zone and cooled in the nitrogen flow to room temperatures, and the
89 mesoporous carbon stabilized MgO NPs (mPC-MgO) were obtained. The materials
90 used in the experiments and detailed characterization of the mesoporous carbon
91 stabilized MgO NPs are given in supporting information (SI).
92 CO2 Capture Performance Test. The CO2 capture capacities of the mPC-MgO
93 were measured using a thermogravimetric analyzer (DTG-60H/DSC-60, Shimadzu,
94 Co., Japan). First, a certain amount (~10 mg) of mPC-MgO was placed in an alumina
95 pan and degassed under N2 (99.99% purity) flow of 100 mL min-1 at 573 K for 30 min.
96 Then the temperature was lowered to desired values, and the gas flow was switched to
97 CO2 (99.99% purity) to investigate the CO2 capture capacities of the mPC-MgO. For
98 the investigation of the temperature influence, the temperature increased from 323 to
99 573 K with a heating rate of 5 K/min under a CO2 flow of 100 mL min-1, and the
100 weight variation of mPC-MgO with temperature was recorded. For the kinetic
101 analysis, the temperature was fixed at 353 K under a CO2 flow of 100 mL/min for 90
102 min, and the weight variation of mPC-MgO with time was recorded. For capture
103 selectivity toward N2 and O2, the temperature was fixed at 353 K under a N2 (99.99%

104 purity) or O2 (99.99% purity) flow of 100 mL min-1 for 60 and the weight variation of
105 mPC-MgO with time was recorded. For the cycle experiments, the sample was first
106 exposed to a CO2 flow (100 mL/min) at 353 K for 90 min to adsorb CO2, then the gas
107 was switched to N2 (100 mL/min) and the temperature increased to 773 K for 30 min
108 to desorb the CO2. The adsorption-desorption cycle was repeated several times and
109 the weight variation of mPC-MgO with time was recorded. The CO2 capture capacity
110 of the mPC-MgO was calculated as follows (eq 1):
( mt − mi )
111 CO2 capture( mol kg −1 ) = (1)
mi M w
112 where mi and mt (kg) are the weights of the mPC-MgO at initial time and time t, and
113 Mw (0.044 kg/mol) is the molecular weight of CO2. For comparison, the CO2 capture
114 performance of the mPC-773 and commercially available MgO NPs (99.99% metal
115 basis, 50 nm) were also determined under the same conditions and the results are
116 shown in Figs. S6 and S9, respectively.
117
118
119 RESULTS AND DISCUSSION
120
121 The Strategy for the Synthesis of mPC-MgO. A schematic illustration of the
122 synthetic pathway for the mesoporous carbon stabilized MgO NPs (mPC-MgO) is
123 shown in Fig. 1b. Firstly, the MgCl2 in seawater was loaded on the biomass waste.
124 Secondly, the MgCl2 preloaded biomass was subjected to a fast pyrolysis process to
125 convert into carbonaceous materials. In the fast pyrolysis process, the temperature of
126 the biomass increased from room temperature to the reactor temperature in its falling
127 process within about 1-2 s at a heating rate over 300 K/s. At such a high heating rate,
128 the components of biomass (e.g., lignin, cellulose, and hemicelluloses) were quickly
7

129 decomposed to volatile matters and condensed to form bio-oil (Fig. 1c), a liquid with
130 a great potential use as fuel or chemical feedstocks.19-21 Meanwhile, the MgCl2●6H2O
131 was dehydrated and decomposed to MgO at high temperatures (eqs 2-4).22
132 MgCl2●6H2O→MgCl2●2H2O+4 H2O↑ (2)
133 MgCl2●2H2O→Mg(OH)Cl+H2O↑+HCl↑ (3)
134 Mg(OH)Cl→MgO+HCl↑ (4)
135 Though there are many other abundant compounds (e.g., NaCl, CaCl2, KCl) in
136 seawater, they can neither be hydrolyzed nor decomposed under pyrolysis conditions
137 due to their high stability, thus exerting little influence on the formation of MgO.
138 Thirdly, the mPC-MgO was used to capture CO2 from flue gas emitted from fossil
139 fuel combustion. Finally, the used mPC-MgO can be easily regenerated at low
140 temperature. In this integrated system, the CO2 emitted from fossil fuel combustion
141 and in atmospheres could be gathered and stored.
142 Composition and Structure of the mPC-MgO.The elemental compositions and
143 textural properties of the mPC-MgO materials prepared at different temperatures are
144 listed in Table S1. The Mg contents continuously decreased with an increase in
145 temperature, implying that there was a certain amount of Mg species volatilized in the
146 pyrolysis process, which is very different from the behaviors of other metal species
147 (e.g., Pb(NO3)2 and CuCl2) under the same conditions.14,23 This unusual phenomenon
148 can be explained as follows: under the pyrolysis conditions (e.g., high heating rate),
149 some of the MgCl2●6H2O may undergo a drastic dehydration process to form
150 MgCl2,22 which is volatile at high temperatures (melting point ~973 K); both of
151 Pb(NO3)2 and CuCl2 are prone to be hydrolyzed and decomposed, forming PbO and
152 CuO with little volatility even at high temperatures.
153 The XRD patterns of the mPC-MgO prepared at different temperatures are shown

154 in Figure 2a. The patterns show five diffraction peaks at 2θ of 37.1°, 43.1°, 62.5°,
155 74.7°, and 78.6°, which can be attributed to the (111), (200), (220), (311), and (222)
156 lattice plane of MgO (JCPDS, 65-0476), respectively, indicating the formation of
157 MgO crystallite in the fast pyrolysis process. With an increase in temperature from
158 773 to 973 K, both the peak intensity and diffraction angle of the MgO lattice planes
159 exhibit no significant changes, suggesting the thermal stability of the mPC-MgO. The
160 crystalline size of MgO was calculated from the (200) diffraction peak using the
161 Scherrer equation (Eq 5):
Kλ
d=
162 B cos θ (5)
163 where d (nm) is the crystalline size of MgO, K is a dimensionless constant depending
164 on the specific geometry of the scattering objects (K=0.94 for MgO), λ is the
165 wavelength of the X-ray (λ =0.154056 nm), θ (rad) and B (rad) are the angles between
166 the incident and diffracted beams and the full width at half maximum, respectively.
167 The sizes of MgO crystals were calculated as 17.1, 18.6, and 17.8 nm for the
168 mPC-MgO-773, 873, and 973, respectively (Table S1). The sizes of MgO crystals are
169 smaller than those of the MgO NPs observed in the TEM images (Fig. 3), indicating
170 that the each MgO nanoparticle comprised of more than one MgO crystal. The
171 thermal stability of the mPC-MgO was also analyzed by TGA (Fig. S2). The weight
172 loss of all the three mPC-MgO materials is less than 3 wt.%, further confirming the
173 thermal stability of the mPC-MgO.
174 The texture features (e.g., surface area and pore structure) of the mPC-MgO were
175 analyzed by nitrogen adsorption-desorption methods. As shown in Fig. 2b, the
176 nitrogen sorption isotherms of all the mPC-MgO materials exhibited typical type IV
177 patterns according to IUPAC classification,24 which correspond to the mesoporous
178 materials. The hysteresis loops are type H3 at high relative pressures, suggesting the
9

179 presence of slit-shaped pores with non-uniform size and shape.25 According to the
180 nitrogen quantity adsorbed at different relative pressures, the surface areas and pore
181 volumes of the mPC-MgO materials were calculated and are shown in Table S1. The
182 mPC-MgO-873 exhibited the best textural properties, i.e., the highest surface area and
183 pore volume, among the three mesoporous carbon stabilized MgO NPs (Fig. S2).
184 Compared to the mesoporous carbon prepared by the pyrolysis of the biomass without
185 MgCl2 (mPC-773, with surface area and pore volume of only 14.0 m2 g-1 and 0.067
186 cm3 g-1, respectively, Table S1 and Fig. S1), the textural properties of the mPC-MgO
187 were greatly improved, implying that the presence of MgCl2 could catalyze the
188 formation of porous structure in the carbonization of biomass.
189 The surface morphology of the mPC-MgO was characterized by scanning
190 electron microscope (SEM) and transmission electron microscope (TEM) (Fig. 3 and
191 Fig. S3). The SEM images show that all the mPC-MgO materials possess porous
192 morphology, comprised of rough carbon sheet, while the TEM images indicate that
193 the MgO NPs are evenly distributed on the carbon sheet. The particle size
194 distributions of the MgO NPs in the mPC-MgO-773 and mPC-MgO-873 are similar,
195 both of which were dominating in 35-69 nm, while for the mPC-MgO-973, the
196 particle size of MgO NPs was mainly in a range of 24-39 nm, much smaller than those
197 of mPC-MgO-773 and mPC-MgO-873, indicating that higher temperature is favorable
198 for the formation of MgO NPs with a smaller particle size.
199 CO2 Capture Performance of the mPC-MgO. Figure 4a shows the CO2
200 capture capacity of the mPC-MgO-873 at different temperatures (323-573 K). Its CO2
201 capture capacity sharply increased from 2.7 to 5.2 mol/kg when the temperature was
202 increased from 323 to 353 K, and had a peak value at 353 K. With a further increase
203 in temperature to 573 K, the CO2 capture capacity continuously decreased from 5.2 to
10

204 1.3 mol/kg. This phenomenon may be explained by the fact that the physical and
205 chemical interactions are the main attributions to the CO2 capture by the mPC-MgO.
206 For the physical interaction, it decreased with an increase in temperature,26 while for
207 the chemical interaction, the capacity increased with an increase in temperature in a
208 low temperature range, but decreased with a further increase in temperature.7,27 The
209 synergetic effects of physical and chemical interactions made the CO2 capture
210 capacity of the mPC-MgO show a peak value with an increase in temperature.
211 Figure 4b shows the CO2 capture capacities of the mPC-MgO as a function of
212 time. The CO2 capture is a two-stage process: once the mPC-MgO was exposed to the
213 CO2 stream, a sharp weight increase occurred at the first stage, which was completed
214 in less than 20 min, then the weight increase slowed down and even reached a steady
215 state after 30 min. Similar two-stage CO2 capture kinetics have also been observed for
216 other MgO-based CO2 trappers.27,28 The CO2 capture kinetics by the mPC-MgO in the
217 first stage (30 min) can be described by a first-order reaction kinetics model (eq 6)
qt
218 ln(1 − ) = − kt (6)
qe
219 where k (min-1) is the rate constant, qt and qe (mol/kg) are the CO2 capture capacities
220 at time t (min) and equilibrium, respectively.
221 The CO2 capture kinetics by different mPC-MgO materials were compared in
222 terms of the rate constant (k) as shown in Fig. 4b insert. The values of k obtained from
223 the slope of the linear fit for the mPC-MgO-773, 873 and 973 are 0.099, 0.115, and
224 0.102 min-1, respectively, with the correlation coefficients (R2) of 0.995, 0.999, and
225 0.995, respectively, confirming the validity of the first-order reaction model and thus
226 that the chemical sorption is the rate-limiting step of CO2 capture process.
227 For potential practical applications of the mPC-MgO, in addition to high CO2
228 capture capacity and rapid capture rate, long-term stability and regenerability are also
11

229 the key issues. Meanwhile, a short cycle time and a low regeneration temperature are
230 generally preferred.29 For this purpose, the CO2 capture capacity were used to
231 evaluate the regenerability and stability of the mPC-MgO-873 in the cyclic CO2
232 capture. As shown in Fig. 4c, the captured CO2 could be quickly desorbed from the
233 mPC-MgO-873 in less than 10 min after the gas stream was switched from CO2 to N2.
234 This adsorption–desorption cycle was repeated for 19 times and the CO2 capture
235 capacity of the material showed an increase in the initial 9 cycles. Such an increase
236 might be attributed to the activation of the mPC-MgO materials by the captured CO2.
237 With a further increase in the cycles reused, the capture capacity only slightly
238 decreased, suggesting a favorable long-term stability of the mPC-MgO. The stability
239 was also confirmed by the XPS survey spectra of the mPC-MgO before and after CO2
240 capture (Fig. S4 and Table S2). Both the chemical state and elemental compositions of
241 the mPC-MgO kept almost unchanged in the CO2 capture process. Furthermore, the
242 maximum CO2 capture capacity of the mPC-MgO was 5.45 mol/kg, much higher than
243 those of many other MgO-based CO2 trappers, even comparable to those of some
244 CaO- and amine-based trappers (Table S3).
245 Selectivity is another important factor for the potential practical applications of
246 the CO2 trappers, which is often normalized to the capture capacity between CO2 and
247 N2 or O2, the most common gas coexisted with CO2 in the capture process (eq 7).30-32
248 Selectivity factor =(CO2 capture capacity)/(N2 or O2 capture capacity) (6)
249 As shown in Fig. 4d, the mPC-MgO materials could capture very little amount of
250 N2 (0.045 mol/kg) and O2 (0.47 mol/kg), much lower than those of CO2 (5.22 mol/kg).
251 The mPC-MgO materials presented a favorable selectivity toward N2 and O2 with the
252 factors of 112 and 11, respectively. This indicates that the CO2 and N2 can be
253 effectively separated in the CO2 capture process, which is highly advantageous for
12

254 practical applications.
255 The Mechanism for the CO2 Capture by mPC-MgO. We have demonstrated
256 the high CO2 capture capacity of the as-prepared mPC-MgO. Its excellent CO2
257 capture capacity is closely related to its porous structure. The formation of the porous
258 structure is mainly because the dehydration and decomposition of MgCl2●6H2O
259 enhanced the release of volatile matter in the biomass pyrolysis process (e.g., HCl and
260 H2O, Eqs. 2-4), which generally results in an increase in surface area and pore volume.
261 Meanwhile, just akin to the ZnCl2, the MgCl2 has strong dehydration ability toward
262 carbohydrate polymers (e.g., cellulose and hemicellulose) at high temperatures. This
263 can change the decomposition pathway of lignocellulosic biomass and prevent the
264 formation of heavy tars, which may block the pore structure, thus being favorable to
265 the formation of open pores in the carbon matrix.33 Furthermore, the newly formed
266 Mg species, e.g., MgO, might act as an in situ template in the pyrolysis process for the
267 generation of porous structure.34 Similar phenomena have also been observed in the
268 pyrolysis of magnesium acetate (Mg(CH3COO)2) and magnesium citrate
269 (Mg3(C6H5O7)2) loaded carbon precursors.35,36
270 The high CO2 capture capacity of the mPC-MgO (5.45 mol/kg) cannot be solely
271 attributed to its surface area, the special functional groups on the surface of
272 mPC-MgO formed in the thermodecomposition of biomass also play an important role.
273 According to the analysis of FTIR spectra (Fig. 5a and Table S4) of mPC-MgO before
274 and after CO2 capture, the changes of function groups in the CO2 capture process are
275 listed in the inserted Table. In the wavenumber lower than 1600 cm-1, both spectra
276 show three different peaks, which can be attributed to the C-O stretching, CH2
277 bending, and OH bending, respectively.37 Among these, the wavenumber of OH
278 bending significantly red-shifted from 1592 to 1550 cm-1, indicating that the OH was
13

279 one of the functional groups involved in the CO2 capture. Because of the large
280 electronegativity differences between the oxygen (3.5) and hydrogen (2.1) atoms, the
281 hydrogen atoms in the OH groups show strong electropositivity, and can interact with
282 the oxygen atoms, which show a significant electronegativity in the CO2 molecule
283 (O–H…O=C=O) (Fig. 5d). Xing and co-workers have found that the hydrogen
284 bonding formed between OH groups and CO2 molecule, despite relatively weak, can
285 significantly increase the CO2 capture capacity.38 Meanwhile, this weak hydrogen
286 bonding may be damaged at a high temperature, causing the decrease in CO2 capture
287 capacity.
288 In the wavenumber higher than 1600 cm-1, there were two new peaks found in the
289 spectrum after CO2 capture. The peak at 1631 cm-1 can be attributed to the stretching
290 of C=O (in the carboxyl or carbonate groups), while the peak at 2317 cm-1 was
291 assigned to the CO2 molecule stretching.39 These two new peaks provided direct
292 evidences that both chemical reaction (CO2+MgO→MgCO3, the peak at 1631 cm-1)
293 and physical adsorption (the peak at 2317 cm-1) happened in the CO2 capture by the
294 mPC-MgO.
295 The CO2 capture is also related closely to the surface chemical properties of the
296 trappers,40 especially the carbonaceous based trappers. The XPS spectrum of the O 1s
297 before CO2 capture (Fig. 5b) comprised three peaks with differentiated binding energy
298 values, which can be assigned to the O-C or O-H groups (531.4 eV),41 O2- in the
299 planes of MgO crystals (530.1 eV), and O2- at the edges and corners of the MgO
300 crystal (528.9 eV),42 respectively. The O2- at edges and corners of the MgO crystal has
301 stronger basicity than that in the planes, and thus is easier to react with the acidic CO2
302 molecule at a relatively low temperature.43,44 In the XPS spectrum of the O 1s after
303 CO2 capture, the peak at binding energy of 528.9 eV disappeared, instead of another
14

304 peak located at 532.8 eV, which could be attributed to the oxygen atom in the
305 carbonate, confirming that the O2- at edges and corners of the MgO crystal is the main
306 active site for CO2 capture. This mechanism can also explain why the mesoporous
307 carbon stabilized MgO nanoparticles show a high CO2 capture capacity than many
308 other bulk MgO-based trappers (e.g., mesoporous MgO, MgO/K2CO3 composites,
309 Table S3). Thus, for the MgO NPs, due to the extremely small size, they often have a
310 higher ratio of edges to corners in the crystals, and possess more basic O2- compared
311 to the bulk MgO, thus ensuring a higher CO2 capture capacity.
312 The C 1s spectra of the mPC-MgO before and after CO2 capture are shown in Fig.
313 5c. In its spectrum after CO2 capture, in addition to the peaks of C-C and C-O,39
314 another new peak was found in binding energy of 290.6 eV, which could be attributed
315 to the carbon atoms in the forms of CO32-,45 further confirming the formation of
316 carbonate (MgCO3) after CO2 capture.
317 In summary, we have developed a facile and sustainable method for the synthesis
318 of mesoporous carbon stabilized MgO nanoparticles (mPC-MgO). The mPC-MgO
319 showed excellent performance for CO2 capture with a maximum capacity of 5.45 mol
320 kg-1, which kept almost unchanged in 19-run cyclic reuse. The high CO2 capture
321 capacity and favorable selectivity of mPC-MgO were mainly attributed to its special
322 physicochemical structure.
323 Environmental Implications. It is very attractive both in environmental and
324 economical aspects to use the mPC-MgO synthesized by fast pyrolysis of waste
325 biomass pre-loaded with seawater-derived-MgCl2 for the reduction of CO2 emission.
326 Taking China as an example, as a country with more than 18,000 km-long coastline,
327 China has abundant resource of seawater, which contains large amount of easily
328 available MgCl2; meanwhile, it is estimated that approximately 220 million tons of
15

329 dry biomass waste was produced in the coastal areas of China annually, which could
330 be used to extract MgCl2 from seawater and then pyrolyzed to produce 77 million tons
331 of mPC-MgO, which can be used to capture about 17.7 million tons of CO2 (Fig. S10).
332 The sequestrated carbon, including both fixed biomass carbon and captured carbon, is
333 estimated to be about 177.8 million tons of CO2, amounting to about 17.3% of local
334 total CO2 emission. Thus this technology will greatly contributes to the reduction of
335 CO2 emission in China.
336
337
338 ASSOCIATED CONTENTS
339
340 Supporting Information Available. Remark S1, Tables S1-S4; references S1-S10,
341 and Figures S1-S10. These materials are available free of charge via the Internet at
342 http://pubs.acs.org.
343
344 ACKNOWLEDGMENTS
345 The authors gratefully acknowledge financial support from National 863 Program
346 (2012AA063608-01), the Key Special Program on the S&T for the Pollution Control
347 and Treatment of Water Bodies (No.2012ZX07103-001), and the Program for
348 Changjiang Scholars and Innovative Research Team in University, China.
349
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480
21

481 Figure Captions

482
483
484 Fig. 1. (a) Schematic illustration of the conventional CaO looping method for CO2
485 capture; (b) schematic illustration of the synthesis of mesoporous carbon stabilized
486 MgO NPs for CO2 capture; and (c) mechanism illustration of the decomposition of
487 biomass and formation of the mesoporous carbon stabilized MgO NPs in the fast
488 pyrolysis process.
489
490 Fig. 2. (a) XRD patterns of the mesoporous carbon stabilized MgO NPs prepared at
491 different temperatures; (b) N2 adsorpotion-desorpotion isotherms of the carbon
492 stabilized MgO NPs prepared at different temperatures.
493
494 Fig. 3. SEM (upper), TEM (below) images, and particle size distribution (inset) of the
495 carbon stabilized MgO NPs prepared at different temperatures.
496
497 Fig. 4. (a) Effect of the temperature on the CO2 capture by the mPC-MgO-873; (b)
498 CO2 capture kinetics of the mPC-MgO materials prepared at different temperatures; (c)
499 CO2 cyclic adsorption–desorption by the mPC-MgO-873; and (d) comparsion
500 (selectivity) of the capture of CO2, N2, and O2 by the mPC-MgO NPs
501
502 Fig. 5. (a) FTIR spectra of the mPC-MgO-873 before and after CO2 capture; (b) XPS
503 O 1s spectra of the mPC-MgO-873 before and after CO2 capture; (c) XPS C 1s spectra
504 of the mPC-MgO-873 before and after CO2 capture; and (d) mechanism illustration of
505 CO2 capture by the mPC-MgO-873.
22

Conventional CaO looping technology for CO2 capture

a CO2 emission
Natural CO2 capture

Decompose
limeston CaO CaCO3
e d
Recycle
(CaCO3)
Energy input
Energy
CO2 emission input
CO2 storage
Fossil fuel
Fossil fuel
combustion
combustion
CO2 emission
CO2 capture by the mesoporous carbon stabilized MgO NPs

b
Sea water
MgCl2 Energy output
(4500 ppm)
Bio-oil
Mg loaded Pyrolysis
Biomass biomass
MgCl2 loading Carbon
stabilized
MgO NPs
CO2
absorption Fossil fuel
combustion CO2 emission
CO2 capture
Photosynthesis
Energy output CO2 storage

506
c
507
508
509 Fig. 1
510
511
23

512
513
514
515
516 Fig. 2
517
518
519
520
521
522
523
524
525
526
527
528
529
530
531
532
24

533
534
535
MgO MgO
MgO
536
537
538 Fig. 3
539
540
541
542
543
544
545
546
547
548
549
550
551
552
553
554
555
556
557
558
559
560
25

561
562
563
564 Fig. 4
565
566
567
568
569
570
571
572
573
574
575
576
577
578
579
580
581
582
583
584
26

585
586
587
588
589 Fig. 5
27

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Mesoporous Carbon Stabilized MgO Nanoparticles Synthesized by Pyrolysis of

MgCl2 Preloaded Waste Biomass for Highly Efficient CO2 Capture

Wu-Jun Liu,† Hong Jiang,†,* Ke Tian,† Yan-Wei Ding,‡ Han-Qing Yu†

and Technology of China, Hefei 230026, China

Dr. Hong Jiang, Fax: +86-551-63607482; E-mail: jhong@ustc.edu.cn

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3 Anthropogenic CO2 emission makes significant contribution to global climate change

5 trajectory toward irreversible global warming. In this work, we reported a new

7 biomass waste can be utilized to prepare mesoporous carbon stabilized MgO

8 nanoparticles (mPC-MgO) for CO2 capture. The mPC-MgO showed excellent

17 warming as well as resolve the pollution of waste biomass.

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35 irreversible global warming, which is dangerous to the global eco-systems.4 An

37 sorbents,5 including carbonaceous materials,6 solid amine-based materials,7 and

44 high temperatures is always accompanied by a sintering process, which can

45 significantly decrease their CO2 capture capacity.

46 Compared to the CaO-based materials, MgO can capture CO2 at temperature

49 regeneration.9 Furthermore, if MgCl2, an inexhaustible salt in naturally abundant

50 seawater, could be cost-effectively and massively converted to MgO, it would be a

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64 high surface areas.13

65 On our continuing efforts toward environmentally friendly biomass disposal and

66 resource recovery,14-17 we proposed a facile and sustainable approach to synthesize

69 concentration (average 0.45%),18 and the MgCl2-loaded biomass can be easily

73 serve as a support to stabilize the MgO NPs. Furthermore, in addition to the

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81 Preparation of the Mesoporous Carbon Stabilized MgO NPs. The

90 used in the experiments and detailed characterization of the mesoporous carbon

91 stabilized MgO NPs are given in supporting information (SI).

93 were measured using a thermogravimetric analyzer (DTG-60H/DSC-60, Shimadzu,

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110 of the mPC-MgO was calculated as follows (eq 1):

116 shown in Figs. S6 and S9, respectively.

119 RESULTS AND DISCUSSION

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132 MgCl2●6H2O→MgCl2●2H2O+4 H2O↑ (2)

133 MgCl2●2H2O→Mg(OH)Cl+H2O↑+HCl↑ (3)

134 Mg(OH)Cl→MgO+HCl↑ (4)

141 and in atmospheres could be gathered and stored.

142 Composition and Structure of the mPC-MgO.The elemental compositions and

152 CuO with little volatility even at high temperatures.

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161 Scherrer equation (Eq 5):

173 thermal stability of the mPC-MgO.

175 analyzed by nitrogen adsorption-desorption methods. As shown in Fig. 2b, the

177 patterns according to IUPAC classification,24 which correspond to the mesoporous

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188 formation of porous structure in the carbonization of biomass.

189 The surface morphology of the mPC-MgO was characterized by scanning

197 of mPC-MgO-773 and mPC-MgO-873, indicating that higher temperature is favorable

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220 at time t (min) and equilibrium, respectively.

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244 CaO- and amine-based trappers (Table S3).

248 Selectivity factor =(CO2 capture capacity)/(N2 or O2 capture capacity) (6)

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254 practical applications.

258 structure is mainly because the dehydration and decomposition of MgCl2●6H2O

268 pyrolysis of magnesium acetate (Mg(CH3COO)2) and magnesium citrate

269 (Mg3(C6H5O7)2) loaded carbon precursors.35,36

277 bending, and OH bending, respectively.37 Among these, the wavenumber of OH