Accepted Manuscript

A novel pyro-hydrochar via sequential carbonization of biomass waste: Preparation,

characterization and adsorption capacity

Yuyan Liu, Shaoqiang Ma, Jiawei Chen

PII: S0959-6526(17)33040-8
DOI: 10.1016/j.jclepro.2017.12.090
Reference: JCLP 11485

To appear in: Journal of Cleaner Production

Received Date: 22 July 2017

Revised Date: 7 December 2017
Accepted Date: 11 December 2017

Please cite this article as: Liu Y, Ma S, Chen J, A novel pyro-hydrochar via sequential carbonization of
biomass waste: Preparation, characterization and adsorption capacity, Journal of Cleaner Production
(2018), doi: 10.1016/j.jclepro.2017.12.090.

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 ACCEPTED MANUSCRIPT

GRAPHICAL ABSTRACT

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1 This whole manuscript contains 5560 words, 6 figures and 2 tables. The separate

2 ‘Supplementary Information’ file contains 1320 words, 4 figures and 1 table.

4 A novel pyro-hydrochar via sequential carbonization of biomass

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5 waste: Preparation, characterization and adsorption capacity

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6

7 Yuyan Liu a, b, Shaoqiang Ma a, b, Jiawei Chen a, b *

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a
8 State Key Laboratory of Biogeology and Environmental Geology, China University

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9 of Geosciences, Beijing 100083, PR China
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10 b
School of Earth Sciences and Resources, China University of Geosciences, Beijing

11 100083, P. R. China
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14 Corresponding Author

15 Email: chenjiawei@cugb.edu.cn
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16 Phone: 86-10-82321380
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17 Submission: July 22, 2017

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18 Second revision submission: December 6th, 2017

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23 Abstract

24 Comprehensive utilization of agricultural biomass waste, such as biochar, is a hot

25 spot in recent years. In order to keep high chemical stability, large specific surface

26 area, and rich oxygenated functional groups of carbonized product, a novel

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27 rich-carbon material ‘pyro-hydrochar’ was proposed firstly via sequential

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28 carbonization of biomass wastes. In the present study, the pyro-hydrochar was derived

29 from the corn straw and corncob by consecutive hydrothermal carbonization under

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30 200 and then pyrolysis at the temperatures of 350~650 . The physicochemical

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31 properties of biochar, hydrochar and pyro-hydrochar were compared by multi-analysis
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32 including the characterization by elemental composition, BET, FTIR, XPS, SEM,

33 chemical oxidation method by K2Cr2O7 and H2O2. The results showed the
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34 pyro-hydrochar is a newly developed rich carbon material with large specific surface
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35 area, rich functional groups, high aromatization degree and strong chemical oxidation
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36 stability. Specifically, the stable carbon-rich pyro-hydrochar indicates the strong

37 capacity of potential carbon sequestration. Additionally, the biochar, hydrochar and

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38 pyro-hydrochar could show different adsorption performance on the representative

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39 contaminants like atrazine, Cd2+ and Cr(VI). It suggested the pyro-hydrochar with
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40 rich oxygenated functional groups and large specific surface area could be a new

41 candidate of economic adsorbent, and it also indicated the important practical value

42 for further modification and development of pyro-hydrochar derived from biomass

43 wastes.

44 Key words: Pyro-hydrochar; sequential carbonization; chemical oxidation stability;

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45 functional groups; adsorption capacity

46 1. Introduction

47 Comprehensive utilization of agricultural biomass waste has been an important

48 issue for environmental protection and ecological sustainability. In recent years, the

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49 research and application of biochar have received the global widespread attention

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50 (Lehmann et al., 2011). Biochar is a kind of charcoal of high-carbon, fine-grained

51 residue, which is often produced through pyrolysis in the absence of oxygen (Das et

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52 al., 2016).

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53 Since the rich-carbon biochar has strong chemical stability, it can be regarded as
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54 a way of stable carbon sequestration and effective mitigation of the greenhouse gases

55 emissions (Lehmann, 2007). Biochar can be also used as a soil amendment to promote
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56 agricultural productivity (Marris et al., 2006). In addition, due to plenty of surface

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57 functional groups, rich-pore structure and large specific surface area, biochar and its
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58 derivatives can be served as low-cost adsorbent for water or soil remediation (Beesley

59 et al., 2011).
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60 Besides the particle size and specific surface area (Han et al., 2016), the surface
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61 functional groups of biochar play an important role in adsorption capacity of

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62 inorganic heavy metals (Uchimiya et al., 2010), organic pollutants (Chen and Chen,

63 2009), etc. The specific surface area of biochar increased with pyrolysis temperature

64 but the oxygenated functional groups would be easily destroyed (Angın, 2013).

65 In contrast to pyrolysis at high temperature (300~700 ) for biochar, hydrochar

66 is prepared in a closed water mixtures under low temperature (<300 ) (Cao et al.,

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67 2013). The liquid phase in hydrothermal carbonization system provides hydrochar

68 with abundant surface functional groups and forms rich pore structure, which

69 effectively remove contaminants (Liu and Zhang, 2009; Liu et al., 2016). However,

70 there are still questions on hydrochar with low carbonization degree and low

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71 aromatization degree (Fornes et al., 2015), indicating the potentially weak stability of

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72 hydrochar. The property of chemical stability is critical to rich-carbon materials,

73 because the strong oxidation resistance of carbon materials not only determines the

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74 carbon sequestration potential (Woolf et al., 2010), but also impacts the use time on

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75 high adsorption capacity.
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76 In order to keep high chemical stability, large specific surface area, and rich

77 oxygenated functional groups of carbonized product, we proposed a feasible approach

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78 to a novel rich-carbon material, called ‘pyro-hydrochar’, via sequential carbonization

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79 of biomass wastes. That is, after preparation of hydrochar derived from biomass
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80 precursor under hydrothermal carbonization wet system, as-prepared hydrochar was

81 then pyrolyzed under high temperature. This kind of product ‘pyro-hydrochar’ would
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82 combine the characteristics of hydrochar with rich functional groups and biochar with
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83 stable carbon and rich-pore structure, resulting in good adsorption performance.

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84 The contaminants of cadmium (Cd2+) and hexavalent chromium (Cr(VI)) are

85 often found in polluted water or soil (Han et al., 2016; Cui et al., 2016). Atrazine is

86 widely used as a common herbicide in agriculture (Liu et al., 2015), and it has a

87 potential toxic to human beings due to its overuse and high mobility (Lasserre et al.,

88 2012). The economic carbon materials need to develop for removal of these

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89 representative contaminants in the environments.

90 The aim of the work focuses on: (1) Preparing pyro-hydrochar derived from the

91 corn straw and corncob by consecutive hydrothermal carbonization under 200 and

92 then pyrolysis under high temperatures of 350~650 ; (2) Comparing the

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93 physicochemical properties of biochar, hydrochar and pyro-hydrochar, specially on

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94 specific surface area, porosity, chemical oxidation stability and surface functional

95 groups; (3) Exploring the adsorption capacity of biochar, hydrochar and

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96 pyro-hydrochar for representative contaminants like Cr(VI), Cd2+, atrazine. By this,

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97 the present study would enlighten a new candidate rich-carbon of pyro-hydrochar for
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98 the development of bio-waste utilization.

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100 2. Materials and methods

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101 2.1 Chemicals

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102 Atrazine (Dr. Ehrenstorfer GmbH, Augsburg, Germany) and methanol

103 (chromatographic purity) was supplied from ANPEL Laboratory Technologies Inc.
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104 Shanghai, China. Cd(NO3)2·4H2O, NaNO3, H2SO4, HNO3, K2Cr2O7, CaCl2, H2O2,
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105 acetone, and 1,5-diphenylcarbazide were analytical reagent from Beijing Sinopharm
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106 Group Chemical Reagent Co., Ltd. All of the chemicals were used as received without

107 further purification. The deionized water (18.3 MΩ•cm) was used for all the

108 experiments.

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110 2.2 Preparation of biochar, hydrochar and pyro-hydrochar

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111 The biomass wastes of corn straw and corncob were used as carbonaceous

112 material precursors, collected from the suburb near Beijing. All the biomass was

113 washed by deionized water, dried in the oven at 60 for 12 h and then milled by the

114 crusher. The biochars derived from corn straw and corncob were pyrolyzed at 350,

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115 500, 650 , as described in our previous study (Han et al., 2016).

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116 For hydrochar preparation, the hydrothermal process were conducted in a 250

117 mL stainless steel autoclave, in which about 15 g of dried biomass particles was

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118 loaded with 150 mL deionized water. In each run, the autoclave was put in the

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119 chamber and the peak temperature was controlled at 200 with a heating rate of
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120 5 ·min-1. After 5 h heating, the autoclave was naturally cooled to the room

121 temperature. The solid residues was washed three times by deionized water, separated
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122 by vacuum filtration, and dried at 105 in the oven for 12 h. As-prepared hydrochar
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123 was kept in a dry container.

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124 For pyro-hydrochar preparation, we used the above production of hydrochar as a

125 precursor instead of the raw biomass and then similarly pyrolyzed at the desired peak
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126 temperatures of 350, 500, 650 for 2 h. The solids were washed, dried, and then
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127 placed these pyro-hydrochars in a dry container for experiments.

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128 By this we got biochar (BC), hydrochar (HC) and pyro-hydrochar (PHC) derived

129 from the two types of biomass of corn straw (CS) and corncob (CC). We labeled a

130 series of samples as HC-CS, BC-CS350, BC-CS500, BC-CS650, PHC-CS350, PHC-CS500,

131 PHC-CS650 denoting corn straw derived hydrochar at 200 , corn straw derived

132 biochar and pyro-hydrochar at 350, 500, 650 . Also, the corncob derived carbon

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133 materials were designated as HC-CC, BC-CC350, BC-CC500, BC-CC650, PHC-CC350,

134 PHC-CC500, PHC-CC650.

135

136 2.3 Characterization of biochar, hydrochar and pyro-hydrochar

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137 The bulk C, H, N and S contents of biochar, hydrochar and pyro-hydrochar were

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138 characterized by an elemental analyzer (EL cube CHNSO). The ash contents were

139 calculated by the mass difference before and after heating samples at 750 for 4 h

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140 and the bulk content of O was estimated after deduction of ash in samples. The

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141 functional groups of these carbon samples were confirmed from the records in the
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142 region of 4000 ~ 400 cm-1 by Fourier Transform Infrared Spectroscopy (FTIR,

143 Nicolet iS10, Thermo Fisher Scientific, USA). The functional groups were also
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144 determined by X-ray photoelectron spectra (XPS) (ESCALAB 250Xi Thermo Fisher,
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145 USA). The specific surface area was quantified by BET method based on N2
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146 adsorption using a Quadrasorb Station 1 analyzer (Quantachrome Instruments,

147 Boynton Beach, USA). The pore size distribution was measured by the BJH method.
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148 The crystallographic structures of carbon materials were examined by X-ray

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149 diffraction (XRD) using a D/Max 2500 (Rigaku, Japan) with a Cu Kα radiation in the
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150 range of 10-90° (2θ). The surface morphology of samples were obtained from

151 scanning electron microscope (SEM, Zeiss Supra 55-VP).

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153 2.4 Chemical oxidation stability of biochar, hydrochar and pyro-hydrochar

154 The amount of labile fraction of carbon could be used to evaluate the chemical

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155 oxidation stability of carbon materials, and the K2Cr2O7 and H2SO4 method (Chen et

156 al., 2016) was employed to measure the stability of biochar, hydrochar and

157 pyro-hydrochar. In addition, the oxidation treatment by H2O2 was usually employed to

158 assess the ageing stability of biochars (Cross and Sohi, 2013). These methods were

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159 described in details in S1, S2 (Supplementary Information, SI).

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160

161 2.5 Adsorption of atrazine, Cr(VI) and Cd2+ on biochar, hydrochar and

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162 pyro-hydrochar

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163 The carbon materials with particle size of 0.05 ~ 0.15 mm were sieved by 300
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164 mesh and 100 mesh, and used for all the sorption experiments. The batch experiments

165 were conducted for adsorption kinetics and capacities of representative contaminants
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166 of atrazine, Cr(VI) and Cd2+ on biochar, hydrochar and pyro-hydrochar. The detailed
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167 procedures were described in S3, S4 (SI).

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168

169 3. Results and discussion

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170 3.1 Specific surface area, pore structure and XRD pattern of carbonized products
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171 The specific surface area (SSA) and pore structure of carbon materials were
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172 under the influence of the carbonization methods, biomass characteristics and

173 charring temperatures. The surface morphology of biochar, hydrochar and

174 pyro-hydrochar were observed under scanning electron microscope and the SEM

175 images (Figure S1 in SI) clearly demonstrated the porous, rough appearance on these

176 rich-carbon materials. As showed in Table 1, the samples of pyro-hydrochar derived

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177 corncob had the higher specific surface area (SSA) and total pore volume than the BC

178 which is prepared at same temperature. PHC-CS500 and PHC-CS650 also has higher

179 SSA than BC prepared at same temperature. It showed that sequential carbonization

180 could remarkably increase the SSA and porosity of carbonized products, resulting

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181 from the breaking of the hydrogen bonds or phase change which broke up the raw

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182 materials’ fibrous structure. With the pyrolysis temperature, the total pore volume and

183 SSA of biochar and pyro-hydrochar were increase. The SSA of the corncob derived

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184 product was less than the corn straw because the content of volatile matter is less in

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185 corn straw and the volatile devolatilization is beneficial to the formation of porous
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186 structure (Bruun, et al., 2012).The crystallographic structures of carbon materials was

187 confirmed by XRD pattern as illustrated in (Figure S2 in SI). The diffraction peak at
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188 2Ɵ=16° and 22° is corresponding to cellulose structure (Zhang et al., 2015). Under
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189 the protection of the lignin, cellulose would start to decompose at 220 . When the
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190 temperature reaches above 260 , the cellulose would be completely decomposed

191 (Falco et al., 2011). In the present study, the hydrothermal temperature for hydrochar
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192 preparation was only controlled at 200 and the cellulose could be preserved and the
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193 crystalline peaks was clearly observed (Figure S2 in SI). Whereas, XRD showed no
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194 crystalline peaks for biochar and pyro-hydrochar in that the pyrolysis temperature

195 (higher than 500 ) could decompose cellulose completely. Additionally, the

196 diffraction peak around 26.5° corresponds to the characteristics of graphite structure

197 and pi-pi* bond (Navarro-Suárez et al., 2014). Interestingly, the carbonized materials

198 derived from the corn straw showed obvious these diffraction peaks and indicated the

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199 formation of graphite structure. In other study (Donar et al., 2016), olive residue

200 hydrochar prepared at 220 also showed graphite structure, but it didn’t appear in

201 hazelnut shell hydrochar. This indicates the formation of graphite structure should be

202 related to different raw materials feedstock.

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203 Table 1 Specific surface area, porous structure and yield of carbonized products.

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Surface area Vmic a Vtotal b Dave Yield
Sample
(m2·g-1) (cm3·g-1) (cm3·g-1) (nm) %

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HC-CS 6.374 0.001 0.0359 22.55 53.33

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BC-CS350 7.415 0.001 0.0176 9.475 35.33
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BC-CS500 2.676 0.002 0.0153 22.91 31.60
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BC-CS650 327.7 0.059 0.2817 3.438 29.55

PHC-CS350 5.857 0.001 0.0334 22.83 28.31

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PHC-CS500 86.83 0.011 0.1023 4.713 21.93

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PHC-CS650 367.3 0.120 0.2176 2.370 17.87

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HC-CC 5.812 0.000 0.0408 28.10 53.89

BC-CC350 1.021 0.002 0.0088 34.33 34.35

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BC-CC500 2.777 0.001 0.0082 11.78 29.35

BC-CC650 17.26 0.000 0.0251 5.813 27.63

PHC-CC350 7.448 0.001 0.0584 31.34 26.15

PHC-CC500 33.77 0.000 0.0775 9.177 12.30

PHC-CC650 142.6 0.000 0.1823 5.115 11.51

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204 a Vmic: micropore volume.

205 b Vtotal: total pore volume.

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207 3.2 Elemental composition of carbonized products

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208 The elemental analysis of C, H, O, N, S for carbonized products was determined

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209 as showed in Fig. 1(a) and Table S1 (SI). Obviously, pyro-hydrochar has abundant

210 carbon and the C content of PHC-CS500 (65.44%) is relatively higher than HC-CS

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211 (51.46%) and BC-CS500 (65.02%). The C contents of HC-CC, BC-CC500 and

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212 PHC-CC500 were 61.73, 82.29, 84.62%, respectively. The previous hydrothermal
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213 activation promoted the carbonization rates and with the increase of the peak

214 pyrolysis temperature (350 to 650 ), the C content of pyro-hydrochar derived from
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215 corn straw increased (62.81 to 75.02%), similarly for the corncob pyro-hydrochar
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216 (73.85 to 89.59%), indicating an increasing degree of carbonization and carbon

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217 sequestration. Different kinds of raw feedstock have a significant influence on

218 elemental composition of carbonized products. Compared with corn stalk, the C
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219 content in corncob derived products were higher due to more hemicellulose.
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220 The characteristics of the ratios H/C and O/C is often used to describe the
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221 internal chemical transformations that occur during the carbonization process of input

222 materials (Sevilla and Fuertes, 2009). The decrease of H/C and O/C indicates the

223 elimination of -CH3 and -CO2 respectively and the high O/C signifies a low

224 carbonization degree and the existed polar functional groups (Wiedner et al., 2013).

225 From the data in Fig.1 (a), H/C and O/C ratios of carbonized products were calculated

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226 in the Fig. 1(b). With the increase of the peak pyrolysis temperature, the H/C and O/C

227 ratios of both biochars and pyro-hydrochars decrease, indicating a loss in oxygenated

228 functional groups and increases in aromaticity gradually. The O/C ratios of hydrochar

229 HC-CS (0.51) and HC-CC (0.38) is higher than biochars (0.09~0.28) and

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230 pyro-hydrochars (0.04~0.29), indicating hydrochar has a lower carbonization rate and

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231 richer polar functional groups.

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232 Fig. 1. Element analysis of carbonized products for (a) elemental composition and (b)
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atomic H/C-O/C ratios.

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233

234
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235 The solid product yields were listed in Table 1 and it showed the low yield is

236 corresponding to the high carbonization degree, indicating the pyro-hydrochar was
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237 sufficiently pyrolyzed while the carbon might be more stable in the environment.

238 According to the production yields of PHC-CS500 (21.93%), BC-CS500 (31.60%) and

239 HC-CS (53.33%), the yield of pyro-hydrochar is relatively lower compared with

240 biochar and hydrochar in that pyro-hydrochar was derived from the precursor of

241 rich-pore structure hydrochar and heated further by subsequent pyrolysis at higher

242 temperature. Also, the yields of PHC-CC500, BC-CC500 and HC-CC were 12.30, 29.35,
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243 53.89%, respectively. The solid production of corn straw derived pyro-hydrochar

244 decreased (28.31 to 17.87%) and biochar (35.33 to 29.55%) with the increase of the

245 peak pyrolysis temperature (350 to 650 ), similarly for the corncob pyro-hydrochar

246 (26.15 to 11.51%) and biochar (34.35 to 27.63%). In contrast to corn straw, the

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247 carbonized production of corncob at the same production condition showed lower

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248 solid yield, due to the different property of the raw biomass and the higher

249 hemicellulose content in corncob.

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250

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251 3.3 Chemical oxidation stability of carbonized products
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252 The Edinburgh stability tool is a feasible way to estimate the proportion of stable

253 carbon in biochars (Klasson, 2017). According to the O/C molar ratio of carbon
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254 material, the chemical stability of biochar can be predicted by the following robust
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255 correlation (Crombie et al., 2013):

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256 Stable C mass fraction = 1.00-2.24×O/C (1)

257 Carbon stability was calculated in Table S1 (SI). It showed that stable C mass
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258 fraction in biochar and pyro-hydrochar increases with the pyrolysis temperature. Most
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259 pyro-hydrochar has more stable carbon content than biochar at the same pyrolysis
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260 temperature, e.g. PHC-CS650 (0.8069) > BC-CS650 (0.5900). Interestingly, the stable C

261 calculated for hydrochar, HC-CS (-0.1467) and HC-CC (0.1462), indicating the lower

262 stability.

263 In order to directly measure the chemical stability of carbonized products, two

264 oxidation agents were employed in the present study, i.e. K2Cr2O7 (Chen et al., 2016)

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265 and H2O2 (Cross and Sohi, 2013). The amount of oxidized carbon by K2Cr2O7 method

266 with respect to the total carbon of the samples was showed in Fig. 2. The carbon loss

267 of biochar (20.22~4.931%) and pyro-hydrochar (12.90~0.2661%) decreases with the

268 pyrolysis temperature (350~650 ). The proportion of carbon loss for PHC-CS500,

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269 BC-CS500, HC-CS was 12.18, 12.45, 51.71%, respectively. Similarly, the labile carbon

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270 loss of PHC-CC500 (5.22%), BC-CC500 (9.58%) and HC-CC (51.39%) also showed

271 the strong chemical oxidation stability of pyro-hydrochar. Different from strong

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272 oxidation using K2Cr2O7, the mild H2O2 method was always used to simulate natural

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273 aging effect for biochar (Cross and Sohi, 2013). As showed in Figure S3 (SI), the
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274 carbon loss for PHC-CS500 (12.08%), BC-CS500 (12.34%), HC-CS (15.13%), and

275 PHC-CC500 (7.29%), BC-CC500 (7.39%), HC-CC (13.79%), indicate the perfect
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276 chemical oxidation stability of pyro-hydrochar against ageing effect in application.

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277 The stable carbon-rich pyro-hydrochar with high aromatization degree and strong
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278 chemical oxidation stability indicates the strong capacity of potential carbon

279 sequestration.
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280 Fig. 2. K2Cr2O7 method for chemical stability of carbonized products derived from (a)

281 the corn straw and (b) corncob.

282
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283 3.4 Functional groups analysis by FTIR and XPS

284 The surface functional groups of carbonized materials play a critical role in

285 adsorption performance. As showed in Fig. 3(a), FTIR analysis were recorded for the

286 samples of raw biomass, biochar, hydrochar and pyro-hydrochar derived from corn

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287 straw and corncob. The absorbance peaks appearing at 3402 cm-1, 1709 cm-1,

1000~1460 cm-1 were assigned to stretching vibration of O-H, C=O and C-O,

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288

289 respectively. The decrease of these bond probably means dehydration during the

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290 carbonization process (Zhang et al., 2015). The absorbance at 1610 cm-1 is ascribed to

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291 the stretching vibrations of aromatic C=C and C=O, and the peaks at 875~750 cm-1
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292 are ascribed to C=C in aromatic ring carbon, out-of-plane bending of aromatic C-H

293 (Chen et al., 2008). The increase of these peaks mean occurring aromatization during
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294 the carbonization. The spectrum of oxygenated functional groups on the surface, such
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295 as O-H, C=O and C-O, were not obviously observed in biochar and pyro-hydrochar,
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296 while the pyro-hydrochar and biochar have sharper absorbance peaks at C=C than

297 hydrochar. It reveals a lower aromatization degree of hydrochar in comparison to

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298 biochar and pyro-hydrochar. Specifically, the absorption peaks of O-H and aromatic
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299 functional groups in PHC500 are sharper than BC, which suggested pyro-hydrochar
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300 has more O-H and higher degree of aromatization. The FTIR spectrum for the

301 pyro-hydrochars at different peak pyrolysis temperature were illustrated in Fig. 3(b).

302 With increased temperature, the characteristic peaks of O-H, C=O and C-O became

303 weak down and the spectrum of aromatic functional groups increased. It indicated that

304 high and prolonged pyrolysis destroyed the oxygenated functional groups and formed

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305 aromatic carbon, which was consist with the atomic H/C - O/C ratios (Table S1 in SI).

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306 Fig. 3. FTIR analysis of (a) carbonized products and (b) pyro-hydrochars.

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307

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308 Besides FTIR analysis, the surface functional groups could be
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309 semi-quantitatively determined using X-ray photoelectron spectroscopy (XPS) (Donar

310 et al., 2016). XPS spectra C1s core level for the samples of biochar, hydrochar and
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311 pyro-hydrochar were recorded in Fig. 4, and the corresponding quantitative analysis
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312 of the surface chemical composition extracted from the C1s spectra were illustrated in
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313 Figure S4 (SI). The surface functional groups of carbon groups (C=C, CHx, C-C) that

314 generated from aromatization were determined at 284.7± 0.2 eV. Hydroxyl groups or
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315 ethers (-C-OR) from dehydration reaction were determined at 285.5 ± 0.2 eV and
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316 285.1± 0.2 eV. Carbonyl / carbonate groups (C=O) from condensation reaction were
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317 determined at 287.3 ± 0.2 eV and 286.5 ± 0.2 eV. Carboxyls, carboxylic anhydrides,

318 and esters (=COOR) from esterification reaction were determined at 289.1 ± 0.2 eV

319 and 288.2± 0.2 eV. The (Pi-Pi*) transitions formed from condensate aromatic

320 structure were determined at 291.1 ± 0.2 eV (Sevilla and Fuertes, 2009; Kundu et al.,

321 2008; Gong et al., 2014). The functional groups (C=C, CHx, C-C) and (Pi-Pi*) exhibit

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322 forming aromatic structure. Large peak fit areas of (C=C, CHx, C-C) and (Pi-Pi*)

323 were the evidence of high degree of aromatization. Specifically, these groups in

324 pyro-hydrochar suggested the higher aromatization degree of pyro-hydrochar. The fit

325 areas of overall oxygenated functional groups (including C-OR, C=O and =COOR

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326 groups) in PHC-CS500 is higher than BC-CS500, while these in PHC-CC500 is higher

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327 than BC-CC500. Specifically, compared with biochar, pyro-hydrochar has more C=O

328 and -C-OR groups and less =COOR groups. Although the maximum fit areas of

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329 overall oxygenated functional groups were obtained in hydrochars, the groups of

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330 (C=C, CHx, C-C) and (Pi-Pi*) were less, showing the overall low degree of
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331 aromaticity in hydrochar, which was due to preparation at lower temperature. It was

332 consistent with the previous FTIR analysis.

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333 Fig. 4. XPS analysis of carbonized products. (a) HC-CS, (b) HC-CC, (c) BC-CS500, (d)

334 BC-CC500, (e) PHC-CS500, (f) PHC-CC500.

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335

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336 3.5 Adsorption kinetics of atrazine, Cr(VI) and Cd2+ on carbonized products
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337 The samples of PHC-CS500, BC-CS500, HC-CS showed different adsorption

338 capacity due to the intrinsic properties of contaminants and carbon materials. The
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339 adsorption kinetics and fitting models for atrazine, Cr(VI) and Cd2+ on HC-CS,
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340 BC-CS500, and PHC-CS500 were illustrated in Fig. 5 and listed in Table 2. The pseudo
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341 first-order and pseudo second-order kinetic models, the following equations (2) and

342 (3), were typically used to investigate the sorption kinetics.

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343 (
qt = qe 1 − e − k1t ) (2)
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344 ( )
t / qt = 1 / k 2 qe2 + (1 / qe )t (3)
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345 Where qt (mg·g-1) is the contaminant concentration at time t (h), qe (mg·g-1) is the

346 maximal adsorption capacity; k1 (h-1) and k2 (g ·mg-1· h-1) are the pseudo first-order

347 and pseudo second-order sorption rate constants, respectively.

348 The sorption of atrazine was fast in the initial 4 h and then reached equilibrium

349 within 137 h. The pseudo second-order kinetic model showed better fitting from the

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350 high correlation coefficient R2. The rate constant (k2) of atrazine on PHC-CS500 (0.158)

351 and HC-CS (0.227) was largely higher than BC-CS500 (0.0629). The adsorption

352 capacity of PHC-CS500, BC-CS500 and HC-CS was 3.20 mg·g-1, 1.95 mg·g-1, 1.29

353 mg·g-1, respectively. Carbon materials with high aromaticity favored pi-pi electron

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354 interactions and atrazine acted as a pi-electron donor while aromatic carbon served as

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355 an electron acceptor. The polar functional groups and specific surface area also played

356 a role in the removal of atrazine (Liu et al., 2015). PHC-CS500 has plenty of

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357 oxygenated functional groups, rich porosity and high aromaticity. For this, PHC-CS500

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358 normally exhibited a stronger ability to adsorb atrazine, compared with BC-CS500 and
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359 HC-CS.

360 The oxygenated functional groups played a positive role in Cr(VI) removal
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361 (Shen et al., 2012). In the present study, the sorption of Cr(VI) reached equilibrium
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362 within 100 h and the adsorption capacity of PHC-CS500, BC-CS500 and HC-CS to
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363 Cr(VI) was 2.55 mg·g-1, 1.03 mg·g-1, 4.19 mg·g-1, respectively. HC-CS performed

364 better to adsorb Cr (VI), followed by PHC-CS500, which was accordance to the
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365 number of oxygenated functional groups on hydrochar and pyro-hydrochar.

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366 The pseudo second-order kinetic model was fit for the adsorption Cd2+ on
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367 PHC-CS500, BC-CS500 and HC-CS and the adsorption capacity was 7.34 mg·g-1, 15.61

368 mg·g-1, 1.04 mg·g-1, respectively. And the sorption of Cd2+ reached equilibrium within

369 34 h. The ash content or minerals in BC-CS500 could contribute the stronger

370 adsorption ability. For the removal of Cd2+ by biochar, the process contained the

371 cation exchange, surface precipitation and surface complexation with

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372 oxygen-containing functional groups (Sun et al., 2014).

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373 Fig. 5. Sorption kinetics of atrazine, Cr(VI), Cd2+ on HC-CS, BC-CS500, PHC-CS500.
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374 The pseudo first-order kinetic model for fitting sorption data (a) atrazine, (c) Cr(VI)

375 and (e) Cd2+; the pseudo second-order kinetic model for fitting sorption data (b)

376 atrazine, (d) Cr(VI), and (f) Cd2+.

377

378 Table 2. Fitting parameters of sorption kinetic models for atrazine, Cr(VI), Cd2+ on

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379 samples of HC-CS, BC-CS500, PHC-CS500.

Pseudo first order kinetics Pseudo second order kinetics

Carbon Equilibrium
Contaminant qe k1 qe k2
2
materials concentration R R2
(mg·g-1) (h-1) (mg·g-1) (g ·mg-1·h-1)

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PHC-CS500 3.20 3.09 0.408 0.687 3.20 0.158 0.999

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atrazine BC-CS500 1.95 1.62 0.296 0.106 1.99 0.0629 0.991

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HC-CS 1.29 1.18 0.659 0.722 1.30 0.227 0.998

PHC-CS500 2.55 2.59 0.0307 0.984 3.66 0.00583 0.894

Cr(VI) BC-CS500 1.03

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1.00 0.0541 0.950 1.21 0.0359 0.975
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HC-CS 4.19 4.07 0.215 0.767 4.34 0.0458 0.997
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PHC-CS500 7.34 6.64 0.508 0.532 7.35 0.085 0.996

Cd2+
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BC-CS500 15.61 13.03 0.461 0.788 16.23 0.0301 0.997

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HC-CS 1.04 1.04 0.434 0.867 1.19 0.544 0.949

380
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381 3.6 Adsorption performance and implication

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382 The adsorption performance of carbonized products was positively influenced by

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383 the factors of rich-pore structure, large specific surface area and abundant surface

384 functional groups. By this, the representative contaminants of atrazine, Cr(VI) and

385 Cd2+ were selected for the comparison of adsorption capacity of biochar, hydrochar

386 and pyro-hydrochar in Fig. 6.

387 With the increase of pyrolysis temperature, the adsorption capacities of atrazine,

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388 Cr(VI) and Cd2+ on pyro-hydrochar from corn straw and corncob were different. The

389 adsorption capacity of BC-CS500 is higher than BC-CC500, mostly resulted from the

390 total pore volume (Vtotal) in materials. For instance, the Vtotal of BC-CS (0.0153

391 cm3·g-1) is two times higher than BC-CC (0.0082 cm3·g-1).

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392 The pore structure and specific surface area of pyro-hydrochar increased, while

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393 the contents of surface functional groups decreased as the pyrolysis temperature

394 raised. The adsorption capacity of atrazine and Cd2+ on PHC-CS500 performed the best

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395 among pyro-hydrochars of PHC-CS, due to the overall better pore structure, specific

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396 surface area and surface functional groups on PHC-CS500. With increasing pyrolysis
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397 temperature, the adsorption capacity PHC-CC for atrazine and Cd2+ decreased,

398 indicating for the corncob pyro-hydrochar, surface functional groups played a more
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399 important role in removal of atrazine and Cd2+. Hydrochar has more oxygenated
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400 functional groups, showing the maximal adsorption capacity for Cr(VI). Whereas, the
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401 oxygenated functional groups of pyro-hydrochar would lost with the increase of

402 pyrolysis temperature, and the adsorption capacity decreased.

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403 In a word, the pyro-hydrochar could be used as a new candidate of rich-carbon

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404 adsorbent for the development of bio-waste utilization.

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405 Fig. 6. Adsorption capacity of (a) atrazine, (b) Cr(VI), (c) Cd2+ on different

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406 carbonized materials.

407

408 4. Conclusion

409 A novel pyro-hydrochar with large specific surface area, high aromatization

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410 degree and strong chemical oxidation stability was prepared via a feasible sequential

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411 carbonization of biomass waste. The stable carbon-rich pyro-hydrochar shows strong

412 capacity of potential carbon sequestration. During the consecutive carbonization, the

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413 key process for pyro-hydrochar preparation is the biomass firstly treated using

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414 hydrothermal method to get the rich-pore hydrochar, which is the precursor for next
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415 pyrolysis process under oxygen-free atmosphere.

416 With different physicochemical properties, biochar, hydrochar and

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417 pyro-hydrochar could show different adsorption performance on the representative

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418 contaminants like atrazine, Cd2+ and Cr(VI), which provides a basis for the selection
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419 of proper carbonized materials for the removal of pollutants in aqueous solution.

420 Specially, pyro-hydrochar with high aromatization degree and strong chemical
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421 oxidation stability indicated the potentially durable in application. The

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422 physicochemical properties of pyro-hydrochar were impacted by different pyrolysis

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423 temperatures. The properties of the pyro-hydrochar obtained in the present study have

424 important practical value for further development and utilization of biomass wastes.

425

426 Acknowledgement

427 This study was supported by National Nature Science Foundation of China

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428 (41272061, 41472232), Fundamental Research Funds for the Central Universities

429 (2652015113, 2652017234), and the project (DD20160312) from the China

430 Geological Survey. We are grateful to the editor and two anonymous reviewers whose

431 comments improved the quality of the manuscript.

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432

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433

434

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HIGHLIGHTS

A novel carbon-rich pyro-hydrochar was firstly prepared by sequential

carbonization of biomass waste.

Pyro-hydrochar has large specific surface area, rich functional groups, high

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aromatization degree and strong chemical oxidation stability.

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The stable carbon-rich pyro-hydrochar indicates the strong capacity of potential

carbon sequestration.

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Biochar, hydrochar and pyro-hydrochar show different adsorption performance

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on contaminants of Cr(VI), Cd2+ and atrazine.
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