1 Rice Husk Silica Derived Nanomaterials for Sustainable Applications

2 Yafei Shen 1,2 *

3 Jiangsu Engineering and Technology Research Center of Environmental Cleaning Materials (ECM),
4 Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC),
5 Collaborative Innovation Center of Atmospheric Environment and Equipment Technology (AEET),
6 School of Environmental Science and Engineering, Nanjing University of Information Science &
7 Technology, Nanjing 210044, China
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26 ABSTRACT

© 2017. This manuscript version is made available under the Elsevier user license
http://www.elsevier.com/open-access/userlicense/1.0/
 1 27 Rice husk (RH) is an abundant and sustainable waste biomass. Silica-rich RH can be converted to
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28 biofuels (e.g., bio-oil, vapors) and biochars simultaneously via thermochemical processes such as
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6 29 pyrolysis, gasification. Bio-oil can be further upgraded into renewable biofuels (e.g., biodiesel) by
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9 30 using the RH-derived catalysts. Meanwhile, vapors from organic matters decomposition can be
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12 31 converted to value-added syngas for energy purpose or chemical synthesis by using the RH silica
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32 materials, which are used for gas cleaning or catalytic reforming. In general, the applications of
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17 33 RH-derived biochars mainly include soil remediation, pollutants removal, silicon battery materials,
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20 34 and so on. This paper reviewed recent progresses in the syntheses of RH silica materials and their
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23 35 sustainable applications, especially in energy and environment functional materials. As for the
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36 environmental issues, the RH-silica materials can remove heavy metals and organic contaminants
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28 37 in soil amendment, wastewater treatment, and gas purification by means of adsorption, catalysis
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31 38 and integrated processes. In summary, biomass with high content of silica can become a potential
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34 39 resource of low cost precursors for the production of high value-added silica/silicon materials for
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40 practical applications.
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39 41
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41 42 KEYWORDS: rice husk (RH); biogenic silica; catalysis; Si battery anode; functional materials
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60 51 1. INTRODUCTION
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 1 52 1.1. Biogenic Silica
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53 Silicon (Si), which is a ubiquitous and quantitatively the second most prominent element in the
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6 54 earth crust after oxygen (O) [1], is released in soil by means of biological or chemical processes
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9 55 [2-5]. Plants contribute significantly to the biogeochemical cycle of silicon in chemosphere [4, 5].
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12 56 They take up silicon from soil water in the form of water-soluble silicic acid (H4SiO4) [6], which is
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57 polymerized and precipitated as amorphous silica (SiO2), frequently in close proximity to the
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17 58 transpiration conduit. After plant death, SiO2 returns back to the soil and then the plant-decay
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20 59 generates humic acid, which increases the weathering activity in soils. Bio-cycling of SiO2 in soil
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23 60 also occurs via microbial activities that involve fungi, bacteria, and actinomycetes [7]. Therefore,
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61 plants and microbes, through their intricate interplay with soil minerals, contribute appreciably
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28 62 to the global silicon cycle [3-8].
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30 63
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32 64 Silicon is accumulated mainly in the form of phytoliths in plants [9], which consist primarily
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35 65 of the amorphous hydrated silica (SiO2 with 5-15% H2O). Phytoliths-containing plants include
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38 66 dicots (e.g., Myrtaceae, Casuarinaceae, Proteaceae, Xanthorrhoeaceae, Mimosaceae),
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41 67 monocots (e.g., Cyperaceae, Gramineae, Palmae), conifers (e.g., Pinaceae, Taxodiaceae), and
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43 68 sphenophytes/scouring rushes (e.g., Equisetaceae) [10]. The ash content of Equisetaceae
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46 69 and Gramineae/Poaceae may consist of 50-70% silica [11]. Some polyamines, carbohydrates,
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49 70 proteins, and glycoproteins from diatoms and sponges are capable of polymerizing silicic
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52 71 acid at neutral to acidic pH [12-14]. Some plant carbohydrates and proteins would play a key
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54 72 role in biogenic silica polymerization [15-18]. In the biosphere, silica is usually accumulated
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57 73 predominantly in the form of amorphous silica (opal or silica gel) [9].
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60 74 1.2. Rice Husk (RH) Silica
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 1 75 Rice (Oryza sativa), a member of the family Gramineae, typically constitutes 20-22% of its total
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76 produce in the form of RH, and a great deal of RH is presently disposed by rice mill industry as a
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6 77 waste. Interestingly, the highest SiO2 content in rice is observed in its husk, which varies from 8.7%
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9 78 to 12.1%, averaging close to 10.6% [19]. However, SiO2 present in RH is in a hydrated amorphous
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12 79 form similar to that present in most of the other entities in the biosphere [20]. The biological
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80 formation of inorganic materials (e.g., silica materials) with complex forms (i.e. biominerals) is a
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17 81 widespread phenomenon in nature [21]. This paper reviewed recent progresses in syntheses of
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20 82 RH-derived silica materials and their sustainable applications especially in catalysis, energy and
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23 83 environment functional materials.
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25 84
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27 85 2. SILICA/SILICON MATERIALS
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30 86 Silica is considered as an extremely important inorganic material and is extensively used for a
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32 87 wide range of commercial applications such as molecular sieves, catalysts, and in biomedical and
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35 88 electrical applications [22-28]. In general, porous inorganic microstructures are of interest as low
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38 89 density and thermally stable particles, and as mechanically resistant encapsulation structures.
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41 90 The chemical syntheses of silica materials are not only relatively expensive and eco-hazardous,
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43 91 but also require strict synthesis conditions. In contrast, biosilicification by living organisms such
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46 92 as cyanobacteria, diatoms, sponges, and plants proceeds under mild physiological conditions and
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49 93 results in a diversity of complex and hierarchical biogenic silica nanostructural frameworks [9].
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51 94
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53 95 Silica-rich rice husk ash (RHA) can be achieved by thermal treatment at elevated temperatures or
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56 96 it can be extracted from RH in the form of sodium silicate by a solvent extraction method. In most
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59 97 applications, RHA is more favorable compared to RH. RHA is a general term describing all forms of
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 1 98 the ash produced from RH. In practice, the form of RHA obtained varies considerably according to
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99 the temperature. Silica in the RHA undergoes structural transformations based on the conditions
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6 100 (time, temperature, etc.) of combustion. Amorphous silica is formed at 550-800 oC and crystalline
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9 101 silica occurs at temperatures greater than this [29]. These types of silica have different properties
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12 102 and it is significant to produce RH silica of the correct specification for the particular end use [30].
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103 In general, the structure and properties of RH silica are sensitive to the methods. The forms of RH
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17 104 silica are different from amorphous to distinct crystal phases depending on the temperature or
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20 105 chemical treatments [31]. Fig. 1 summarizes the common procedures for producing silica from
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23 106 RH, including impurities removal before and after thermal processes. Of the different synthesis
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107 methods, the chemical method consisting of simple acid leaching and post annealing is of the
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28 108 most simple and successful techniques to synthesize the ultrafine SiO2 nanoparticles from RHA.
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30 109
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32 110 Leaching of RH with a solution of HCl, H2SO4, H3PO4, HNO3, NH4OH and NaOH before thermal
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35 111 treatment at different ranges of temperature and time can be so effective in accelerating the
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38 112 hydrolysis of cellulose and hemicelluloses in RH and removing most of the metallic impurities.
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41 113 This allows producing white-color silica completely, with high specific surface area [32-37]. Apart
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43 114 from the synthesis conditions, the types of biosilica precursors can also influence the properties
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46 115 of silica materials. Sankar et al. [38] synthesized the biogenic silica nanopowders from different
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49 116 types of RH sources (as shown in Fig. 2). The obtained silica nanoparticles had a uniform surface
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52 117 morphology with respect to the particle size distribution, and the sizes of silica nanoparticles
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54 118 decreased from 50 nm (sticky RHA) to 10 nm (brown RHA). The mesoporous silica nanopowder
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57 119 synthesized from brown RHA had the lowest particle size distribution and the highest surface
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60 120 area. In addition, various sizes ranging from nanometer to micrometer of amorphous spherical
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 1 121 silica particles could be controllably synthesized from RH used for different applications [38].
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3 122
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5 123 RH can be converted into bio-oil and syngas for energy applications through the pyrolysis process.
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8 124 Combined with the chemical extraction, the high-yield amorphous silica can be recovered from
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10 125 pyrolysis char. More significantly, the activated carbon with high specific surface area can also be
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13 126 produced by using physical or chemical activation (as illustrated in Fig. 3) [39]. Co-production of
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16 127 silica with other valuable products mainly including activated carbon, biofuels and lignocellulosic
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19 128 components would become the most promising way for RH valorization [39-43].
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21 129
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23 130 Rice grows by taking in silicic acid as well as CO2, water and various minerals [43]. As illustrated in
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131 Fig. 4, rice deposits amorphous silica on their cell walls, forming silica-cuticle and silica-cellulose
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28 132 double layers on the surface of leaves, stems and husks [44, 45]. Therefore, amorphous silica on
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31 133 the cell walls of RH can play as a role of the natural template for the formation of porous carbon
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34 134 (PC), as well as silica recycling. Tabata et al. [46] developed an environmentally friendly process
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135 for synthesis of value-added hierarchical porous carbon (HPC) material, comprising micro-, meso-
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39 136 and macro-pores by using unique structural cell assemblies of RH. Noteworthy, steam activation
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42 137 of PC contributed to the deepening of the meso- and micro-pores with respect to the formation
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45 138 of HPC with low-toxicity and superior in vivo properties. In addition, it can be applied to many
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139 significant applications not only in the electronic and industrial fields but also in the medical field
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50 140 for use as adsorbents, drug delivery and bio-interface materials, and scaffolds for cell incubation
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53 141 [46].
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56 142
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59 143 In addition, RH silica materials with specific morphologies and structures can be synthesized for
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 1 144 several particular applications [47-49]. Wang et al. [47] explored the intrinsic morphology and
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145 microstructure of the biosilica in RH by controlling the pretreatment and reaction conditions to
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6 146 maintain their original structure. Here, porous silica nanoparticles with narrow size distribution
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9 147 and high surface area were initially prepared from the HCl-treated RH by means of controlled
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12 148 pyrolysis. Subsequently, the semi-crystalline porous silica frameworks with tunable pore sizes
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149 were formed by doping the silica nanoparticles with K+ cations and tailoring pyrolysis conditions
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17 150 (as illustrated in Fig. 5). Compared with amorphous porous silica, the synthesized porous silica
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20 151 frameworks have wide applications and exhibit superior performance because of the increased
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23 152 crystallinity and structural integrity [47]. In general, RHA has wide range of applications, including
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153 the production of silica gels, silicon chip, activated carbon and silica, construction materials,
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28 154 catalysts, zeolites, battery materials, graphene, energy storage/capacitor, carbon capture, and in
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31 155 drug delivery vehicles [50].
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33 156
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35 157 2.1. Catalysts for Bio-oil and Vapors Upgrading
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38 158 Biomass has been increasingly targeted as a renewable feedstock for the production of biofuels
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41 159 [51-53] and platform chemicals [54-56]. The cost of the catalyst in a given process is potentially
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43 160 one of the most significant expenses, particularly in a process using waste biomasses as starting
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46 161 materials [57]. Using waste materials to generate the catalysts in addition to the target product
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49 162 makes the system more cost effective and environmentally friendly [58]. In recent decades, the
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52 163 preparation of heterogeneous catalysts from waste biomass has been attracted more attentions.
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54 164 The nature of the waste source affects the properties of the resulting catalyst, and therefore
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57 165 catalysts for a given application are often made from similar groups of materials. The bio-waste
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60 166 of RH can be converted into bio-oil, vapors and the by-product of biochar via thermochemical
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 1 167 process including pyrolysis, gasification [59-63]. The obtained bio-oil and vapors can be further
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168 upgraded for biofuel applications, while the biochar is used for carbon and silica-based materials
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6 169 production [22].
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8 170
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10 171 Silica-rich RHA can be directly modified as catalysts or supports for bio-oil and vapor upgrading
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13 172 [64-69]. Some researchers studied the RHA as a solid acid catalyst used for biodiesel production
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16 173 [64-66]. In common, biodiesel production via low temperature esterification of free fatty acids
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19 174 (FFAs) or transesterification of triacyl glycerides (TAGs) (as illustrated in Fig. 6), is considered as
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21 175 the most popular process for which waste-derived catalysts have been used; solid acid catalysts
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24 176 have been prepared from diverse waste streams including plant matter, algae, eggshell, animal
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27 177 bone, clay, ash and other wastes. In general, solid acid catalysts have been used for esterification
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30 178 based upon activated carbons produced by pyrolysis/carbonization and subsequent sulfonation.
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32 179 Solid base catalysts for transesterification principally comprise calcium oxides (CaO), typically
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35 180 from shells. Waste-derived solid acid catalysts for biodiesel production has been widely reported
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38 181 [70-74]. Heterogeneous solid bases provide significantly higher rates of TAGs transesterification
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41 182 than their solid acid counterparts. CaO as the transesterification catalysts has been applied, due
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43 183 to the wide range of calcium-rich waste materials available. The manufacture of catalysts from
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46 184 waste following bio-oil extraction could enhance the cost-effectiveness of the overall biodiesel
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49 185 production process [58]. Waste shells can be used as a catalyst and source of CaO, which adds
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52 186 value to the generated waste. CaO is a promising basic heterogeneous catalyst for synthesizing
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54 187 biodiesel at mild temperatures (below the boiling point of methanol) and atmospheric pressure
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57 188 [75], but it is rapidly hydrated and carbonated upon contact with room temperature air. Chen et
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60 189 al. [76] synthesized the RHA-derived Li2SiO3 catalyst for biodiesel production using Li2CO3 as an
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 1 190 activating agent through a solid state reaction. Hindryawati et al. [77] synthesized alkali metal
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191 silicates (Li2SiO3, Na2SiO3, and K2SiO3) by the impregnation of alkali hydroxide on RH silica for
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6 192 methyl esters production. Zeng et al. [64] used RHA as a starting material to prepare silica-based
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9 193 solid acid catalyst by acid activation for biodiesel production from soybean oil and methanol.
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12 194 More recently, Chen et al. [65] developed highly efficient catalysts from two waste materials of
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195 eggshell and RHA for the transesterification of palm oil. Here, RHA was served as the support for
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17 196 loading calcined eggshell to prepare solid base catalyst.
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19 197
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21 198 Tar in vapors derived from biomass thermal conversion including pyrolysis, gasification should be
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24 199 removed before the syngas applied for power generation or chemical synthesis. In our previous
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27 200 studies, RHA-based catalysts were synthesized for tar conversion and vapor upgrading during the
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30 201 pyrolysis of RH [67-69]. RHA exhibited fair catalytic performance on tar conversion attributed to
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32 202 the presence of minerals. Furthermore, transition metals such as nickel, iron and copper can be
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35 203 loaded on the silica supports enhancing their catalytic activities [78-80]. The integrated strategy
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38 204 of catalytic biomass pyrolysis or gasification includes different key reaction steps as illustrated in
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41 205 Fig. 7, consisting of (step 1) metal precursors (e.g., Ni2+) insertion into biomass, (step 2) catalytic
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43 206 pyrolysis of biomass, (step 3) the catalytic active nanoparticles (e.g., Ni°) in situ generated and
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46 207 highly dispersed in the biochar matrix, (step 4) catalytic conversion of primary tars by the formed
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49 208 nanocomposites, (step 5) catalytic gasification of the biochar, and (step 6) recycling and reuse of
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52 209 silica-based metal nanoparticles (e.g., Ni/SiO2). Each reaction step needs a thorough fundamental
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54 210 understanding to develop a green high-efficiency biomass pyrolysis or gasification at nanoscales.
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57 211 Therefore, it is critical to develop breakthrough conversion technologies followed by the design
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60 212 of the intensified gasification processes [81, 82]. Among the steps of integrated strategy, it is a
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 1 213 sustainable way to recycle and reuse of metal nanoparticles in the ash. More recently, Braga et al.
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214 [83] synthesized WO3 supported on RHA and RHA-MCM-41 for catalytic upgrading of Elephant
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6 215 grass pyrolysis vapor. In addition, RHA-derived silica catalysts can be used for chemical syntheses
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9 216 [84-87]. These research works proved that RHA derived catalysts have a high potential to be used
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12 217 for bio-oils and vapors upgrading in biomass thermochemical valorization.
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14 218
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16 219 2.2. Battery Materials
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19 220 Silicon with high-purity and crystalline structures is often required for the preparation of battery
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21 221 materials. The conventional process of producing silicon is relatively expensive [88]. Thus, many
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24 222 efforts are being directed to develop a low-cost, high-volume and commercially feasible process
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27 223 for producing high purity silicon in electrical applications [89-91]. One such process involves RHA
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30 224 reduction to silicon. Several approaches have been developed to produce silicon from RH. For
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32 225 instance, amorphous silica can be reduced to silicon via carbothermal reduction at relatively high
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35 226 temperatures [92, 93]. Marchal et al. [93] synthesized the solar grade silicon (≈99.9999% pure)
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38 227 from RHA as a biogenic silica source. RHA is initially purified using acid milling/boiling water wash
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41 228 purification steps and pelletization followed by carbothermal reduction using an experimental 50
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43 229 kW electric arc furnace (EAF) operated at 1700-2100 oC in batch mode. In addition, reduction of
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46 230 amorphous silica to silicon by metallic metals has been studied extensively. The metallic elements
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49 231 of Mg, Ca, Al and Ti can reduce SiO2 at comparatively lower temperature and forms mixtures of
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52 232 condensed phase products [94-97]. The overall reactions with corresponding free energy change
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54 233 and adiabatic temperature rise per mole of silicon are shown in Table 1.
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57 234
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60 235 Thermic reduction of SiO2 can be accomplished via the above-mentioned mechanisms including
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 1 236 carbothermal, magnesiothermic, aluminothermic, and calciothermic reduction. Carbothermal
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237 reduction often utilizes EAF operating at 2000 oC and is the primary mode for metallurgical silicon
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6 238 production [98]. However, this process is generally very energy intensive and liquefies the silicon,
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9 239 thus destroying any original morphology of SiO2. Recently, magnesiothermic reduction has gained
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12 240 much attention due to its lower operating temperatures (650 oC). Typically, Mg powder is placed
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241 adjacent to SiO2 powder and the furnace is heated until Mg vaporizes. However, this reduction
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17 242 scheme produces zonal variations in composition with Mg2Si forming near the Mg powder, Si in
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20 243 the middle, and unreacted SiO2 furthest from the Mg [99]. Luo et al. [100] proved the addition of
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23 244 NaCl to the reduction process aids in scavenging the large amount of heat generated during this
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245 highly exothermic reaction. NaCl effectively halts the reaction temperature rise at 801 oC during
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28 246 fusion, preventing the reaction from surpassing the melting point of silicon and thus aiding in
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31 247 preserving the original SiO2 morphology. Favors et al. [101] synthesized the porous nano-silicon
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34 248 via a scalable heat scavenger-assisted magnesiothermic reduction of sand (as illustrated in Fig. 8).
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249 The addition of NaCl, as an effective heat scavenger for the highly exothermic magnesiothermic
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39 250 reduction process, promotes the formation of an interconnected 3D network of nano-silicon with
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42 251 a thickness of 8-10 nm. Here, carbon coated nano-silicon electrodes could achieve remarkable
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45 252 electrochemical performance with a capacity of 1024 mAhg at 2 Ag after 1000 cycles. This
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253 environmentally benign, abundant, and low cost SiO2 source allows for production of nano-silicon
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50 254 with excellent electrochemical performance as an anode material for Li-ion batteries [101].
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52 255
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54 256 Mishra et al. [91] investigated the purification of silicon through calcium reduction of RHA. They
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57 257 mixed RHA obtained at 500 oC and calcium thoroughly in stoichiometric proportions. Then the
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60 258 mixture was reduced at 720 oC. The reduced product leached with HNO3 and HF to achieve high
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 1 259 purity of 99.9% silicon. Obtaining silicon of (99.9999%) purity by reducing RHA with magnesium
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260 at temperature of 800 oC was followed by several successive acid (mixtures of HF, H2SO4 and HCl)
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6 261 leaching treatments. With acid treatment, it is possible to remove MgO, Mg2Si and unreacted Mg
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9 262 as by-products. Larbi [94] reported that by utilization of pellet of RHA with Mg content 5 wt.% in
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12 263 excess of stoichiometry requirement and heating at 900 oC under the flowing argon, a maximum
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264 silicon yield can be achieved. The fine silicon nanocrystals was also formed via magnesiothermic
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17 265 reaction. The reduction of SiO2 to form Si has obtained popularity since the three-dimensionally
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20 266 structured Si replicas could be produced from parent SiO2 diatom by magnesiothermic reduction
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23 267 [95]. Magnesiothermic reduction of various types of silica/carbon (SiO2/C) composites has been
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268 frequently used to synthesize silicon/carbon (Si/C) composites and silicon carbide (SiC) materials,
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28 269 which are of great interest in the applications of lithium-ion batteries (LIBs) and nonmetal oxide
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31 270 ceramics, respectively [96]. Mg2Si has been considered as intermediates of Si in magnesiothermic
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34 271 reduction of SiO2 [102, 103]. On the basis of these facts, the kinetic product of Si can be formed if
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272 conversion from SiO2 to Si is completed before the silicon intermediates reach carbon. In other
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39 273 words, Si can be synthesized if insufficient diffusion of Si intermediates to carbon is prompted (as
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42 274 illustrated in Fig. 9).
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44 275
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46 276 Based on the methods discussed above, unique nanostructures of amorphous silica derived from
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49 277 abundant biogenic silica sources (e.g., RH) can be reduced to silicon or silicon-carbon composites
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52 278 in high-value LIBs applications [104-110]. Table 2 shows the reported works on RH-derived silicon
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54 279 materials in LIBs applications. Generally, silicon materials have relatively high potential to be used
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57 280 as the LIBs anodes compared with silica composites. Jung et al. [104] synthesized nanostructured
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60 281 Si from RH via magnesiothermic reduction process. After that, 3D porous Si was obtained after an
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 1 282 additional two-stage acid etching process (as illustrated in Fig. 10). This work demonstrated that
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283 RH can be employed to produce Si with an ideal porous nanostructure for use in high-capacity LIB
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6 284 anodes. Its interconnected nanoporous structure, developed via years of natural evolution for
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9 285 efficient cultivation of rice, can resolve important issues in Si anode operation, enabling excellent
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12 286 cycling and power performance.
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14 287
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16 288 Liu et al. [107] proposed an integrated magnesiothermic reduction process for producing nano-Si
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19 289 from RH. As shown in Fig. 11c-g, RH were first converted to nano-SiO2 by thermal decomposition,
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21 290 followed by magnesiothermic reduction to produce nano-Si (Fig. 11a). This innovative method
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24 291 has several advantages: (i) the recovered silicon inherits the intrinsic and unique nanostructure of
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27 292 the RH silica, allowing for excellent battery performance by mitigating pulverization; (ii) RH is an
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30 293 abundant and sustainable silica source; (iii) the whole process is facile, energy-efficient, and easy
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32 294 to scale-up; and (iv) the overall process does not use expensive silica precursors or reagents. And
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35 295 Mg is produced by electrolytic process with a relatively low cost. Mg can be regenerated from the
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38 296 electrolysis of MgCl2 (Fig. 11c). Therefore, this green process only consumes HCl and converts it
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41 297 to Cl2 after the electrolysis.
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43 298
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45 299 In addition, Wong et al. [109] synthesized the silicon nanoparticles from RH-derived silica via the
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300 magnesiothermic reduction process. Subsequently, silicon nanoparticles were used to prepare a
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50 301 binder-free composite of Si-graphene as an anode material for LIBs (as illustrated in Fig. 12). The
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53 302 Si-graphene composite yielded an initial capacity of 1000 mA h/g at high applied current density
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56 303 of 1000 mA/g. In summary, all these studies open up the use of waste materials especially for
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59 304 agricultural wastes (e.g., RH) as a sustainable source in advanced technology applications.
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 305
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2 306 Praneetha et al. [110] proposed a rapid microwave assisted approach to extract SiO2 from various
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5 307 agricultural residues such as bamboo culm (BC), rice husk (RH), and sugarcane bagasse (SB)
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8 308 followed by magnesiothermic reduction of SiO2 into Si within 30 min at temperatures <650 oC
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10 309 without requiring any reducing gas atmosphere. This “metallurgy in a Swagelok” reactor inside
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13 310 the microwave muffle furnace can be provided by the SiC passive heating element (PHE) plates by
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16 311 absorbing microwave radiation and subsequent transfer of heat to the reactants with increase in
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19 312 reaction kinetics during the raw material (SB, BC, and RH) ashing and magnesiothermic reduction
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21 313 processes (Fig. 13A). Furthermore, Si-based nanohybrids were produced by using a microwave
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24 314 assisted solvothermal (MW-ST) process that offer a uniform heating of polar solvent by absorbing
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27 315 microwave energy followed by heating (Fig. 13B). The pristine RH Si and their nanohybrids with
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30 316 carbon, multiwall carbon nanotubes (MWCNT), and graphene had been demonstrated as a high
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32 317 capacity anode for LIBs for energy storage applications [110].
33
34
318
35
36
37 319 3. ENVIRONMENTAL IMPLICATIONS
38
39 320 The application of RH has been limited because of their tough nature, low nutritional value, and
40
41
42 321 great bulk. Currently, the two most common disposal methods include open field burning and
43
44
45 322 land filling, which often result in energy waste, greenhouse gas emission, air pollution, and huge
46
47
48
323 landfill space occupancy due to their low bulk density. To address those issues, researchers have
49
50 324 been exploring more economical ways to make full use of RH. Conventional applications of RH
51
52
53 325 mainly include producing agriculture compost, making construction materials (e.g., cements,
54
55
56 326 bricks, insulation fillers), and generating electricity (controlled burning). In addition, methods to
57
58
59 327 derive higher values from RH have been explored, such as various silicon based materials, which
60
61 14
62
63
64
65
 1 328 have attracted high attention in the past decades. Harvesting silica or silicon from agricultural
2
3
329 wastes including RH can not only take full advantage of their highest potential value, but also
4
5
6 330 minimize the related environmental issues from the valorization of RH [111]. Thermochemical
7
8
9 331 treatment such as pyrolysis, gasification is considered as the most promising approach that can
10
11
12 332 converted RH to biofuels (e.g., bio-oil, syngas) and biochars simultaneously [112]. Subsequently,
13
14
333 bio-oil can be converted to renewable biofuels (e.g., biodiesel) by using the RH-derived catalysts.
15
16
17 334 Vapors from organic matters decomposition can be upgraded to value-added syngas for energy
18
19
20 335 application or chemical synthesis by using the RH silica materials, which are used for gas cleaning
21
22
23 336 [113, 114], catalytic reforming [80, 81]. In general, the applications of RH-derived biochars mainly
24
25
337 include soil remediation, pollutants removal, silicon materials, and so on (Fig. 14).
26
27
28 338
29
30 339 Biochar amendment of soil is viewed as a new opportunity for mitigating global warming and as a
31
32 340 strategy to improve soil health and productivity. Biochars can improve the soil cation exchange
33
34
35 341 capacity (CEC), adjust pH, retain water and fertilizer, reduce greenhouse gas emissions, increase
36
37
38 342 carbon stability in soil, and enhance the sorption capacity for organic pollutants and heavy metals.
39
40
41 343 Therefore, biochar is thought to be an environmentally friendly and cheap remediation agent for
42
43 344 soil pollution and carbon sequestration. One of the interesting properties of biochar that makes it
44
45
46 345 attractive as a soil amendment is its porous structure, which is believed responsible for improved
47
48
49 346 water retention and increased soil surface area. Furthermore, the addition of biochar to soil has
50
51
52 347 been associated with an increase of nutrient use efficiency, either via nutrients existing in biochar
53
54 348 or via physicochemical processes that allow better utilization of soil-inherent or fertilizer-derived
55
56
57 349 nutrients. Additionally, a key property of biochar is its apparent biochemical stability. Studies of
58
59
60 350 charcoal from natural fire and ancient anthropogenic activity indicate millennial-scale stability,
61 15
62
63
64
65
 1 351 allowing biochar to act as a carbon sink. The conversion of biomass to stable soil carbon species
2
3
352 can result in a long-term carbon sink, as biomass removes atmospheric CO2 via photosynthesis.
4
5
6 353 Furthermore, the use of biochar implies a net removal of carbon from the atmosphere. In general,
7
8
9 354 three complementary goals could be achieved by using biochars for environmental management:
10
11
12 355 (1) soil amendment (from both productivity and pollution views), (2) waste biomass valorization,
13
14
356 and (3) energy production (if energy is captured in the biochar production process). In light of this,
15
16
17 357 the production of biochar from agricultural residues is a promising alternative to integrate carbon
18
19
20 358 sequestration and renewable energy generation into conventional agricultural production [112].
21
22 359
23
24 360 Chen and his colleagues [115, 116] studied the transformation, morphology, and dissolution of
25
26
27 361 silicon and carbon in silica-rich biochars by pyrolysis. As illustrated in Fig. 15, with the increase of
28
29
30 362 temperature, silicon accumulated and changed from amorphous to crystalline matter, while the
31
32 363 organic matter evolved from aliphatic to aromatic. Bio-wastes derived from rice plants contains
33
34
35 364 amorphous carbon and amorphous silicon. Dehydration (<250 oC) can make silicic acid polymerize,
36
37
38 365 resulting in a closer integration of carbon and silicon. At medium temperatures (250-350 oC), an
39
40
41 366 intense cracking of carbon components occurred, and the silicon located in the inside tissue was
42
43 367 exposed. At high temperatures (500-700 oC), the biochar condensed due to the aromatization of
44
45
46 368 carbon and crystallization of silicon. Thereby, the carbon release in water significantly decreased,
47
48
49 369 while the silicon release decreased and sharply increased with temperature [115]. Furthermore,
50
51
52 370 it was found that the stability of biochars is not only determined by aromatic structures but also
53
54 371 influenced by silicon protection and particle size [117]. The interaction between Si and C provides
55
56
57 372 a new perspective for assessing the stability of biochar with its soil carbon storage potential and
58
59
60 373 fill a gap in understanding the stability associated with the morphologies of carbon and silica. This
61 16
62
63
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65
 1 374 silica-carbon structure can protect the biochar against physicochemical oxidation and presumably
2
3
375 lead to a longer turnover time in soils and thus a greater potential for carbon sequestration [116].
4
5
6 376 The silicon dissolution kinetics suggests that Si-rich biochars could serve as a novel slow release
7
8
9 377 source of biologically available Si in low Si agricultural soils [115]. In addition, RH-derived biochars
10
11
12 378 containing N, P, and K could be used as nutrient sources [118, 119] impacting the biogeochemical
13
14
379 cycling of C, N, and P. As for the environmental issues, RH-derived biochars or silica materials can
15
16
17 380 remove heavy metals, and organic contaminants in soil amendment, wastewater treatment, and
18
19
20 381 gas cleaning by adsorption [120-125], catalysis [126-128] and integrated processes [129, 130].
21
22 382
23
24 383 4. CONCLUSIONS AND PERSPECTIVE
25
26
27 384 Waste to energy or material is becoming increasingly important. In this context, waste biomass of
28
29
30 385 RH is being considered as a sustainable and renewable energy resource and has high potential as
31
32 386 low cost precursors for the production of value added materials. Harvesting silica or silicon from
33
34
35 387 RH can not only take full advantage of its highest potential value, but also minimize the related
36
37
38 388 environmental issues from the valorization of RH. Thermochemical processes such as pyrolysis,
39
40
41 389 gasification is considered as the most promising approach that can converted RH to biofuels (e.g.,
42
43 390 bio-oil, vapors) and biochars simultaneously. Bio-oil can be upgraded to renewable biofuels (e.g.,
44
45
46 391 biodiesel) by using the RH-derived catalysts. Meanwhile, vapors can be converted to value-added
47
48
49 392 syngas for energy purpose or chemical synthesis by using the RH silica materials, which are used
50
51
52 393 for gas cleaning, catalytic reforming. In general, the applications of RH-derived biochars mainly
53
54 394 include soil amendment, pollutants (e.g., heavy metals, organics) removal, as well as silicon used
55
56
57 395 as battery materials. RH-derived silicon materials could become standard ingredients for LIBs. A
58
59
60 396 cheap resource of porous silica could be useful for the drug delivery system. The RH silica may be
61 17
62
63
64
65
 1 397 utilized in future applications such as surface functionalized mesoporous silica, development of
2
3
398 hybrid mesoporous silica, synthesis of fluorescent silica particles, antireflective optical coatings,
4
5
6 399 addition of carbon nanotubes to mesoporous silica, and nanoparticles supported on silica. RH
7
8
9 400 amorphous silica could also be synthesized to crystal silicon for battery materials (e.g., LIBs) via
10
11
12 401 carbothermal reduction or magnesiothermic reduction, which is performed at a relatively lower
13
14
402 temperature. In summary, the amorphous silica-rich RH could become a potential resource of low
15
16
17 403 cost precursors for the production of high value-added silica/silicon based materials for practical
18
19
20 404 applications.
21
22 405
23
24 406 AUTHOR INFORMATION
25
26
27 407 Corresponding Author
28
29 408 *E-mail: [email protected]
30
31 409 Notes
32
33 410 The authors declare no competing financial interest.
34
411
35
36
37 412 ACKNOWLEDGEMENTS
38
39 413 This work is financially supported by the Startup Fund for Introducing Talent at NUIST (grants no.
40
41
42 414 2243141501046), and the National Science Foundation of China (grant no. 91544220, 21607079).
43
44
45 415
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1 746 Figure 1 Different methods for producing different structural silica from RH
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747 Figure 2 Digital and SEM images of rice plant, rice, RH, RHA and synthesized silica nanoparticles.
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748 Figure 3 Production of both amorphous silica and activated carbon from RH.
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8 749 Figure 4 Schematic illustration of the porous carbon (PC) synthesis from RH and SEM images of
9 750 silica-carbon (SiO2-C) composites (a-c) and PC (d-f).
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11 751 Figure 5 Synthesis of silica nanoparticles from RH and formation of porous silica framework.
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13 752 Figure 6 Schematic of bio-oil transesterification with solid acid catalysts
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15 753 Figure 7 Integrated strategy of bio-wastes catalytic pyrolysis/gasification with the RHA catalysts.
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17 754 Figure 8 (a) Conventional synthesis routes of nano-Si, including the introduction of our synthesis
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19 755 route from beach sand. Optical images of (b) unpurified sand, (c) purified sand, and (d) (from left
20 756 to right) vials of unpurified sand, purified sand, and nano-Si. (e) Schematic diagram of the heat
21 757 scavenger-assisted Mg reduction process.
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23 758 Figure 9 Mechanism illustration of Si and SiC formation by magnesiothermic reduction of SiO2/C
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25 759 composite.
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27 760 Figure 10 Generation of 3D nanoporous Si from RH. (A) Photographs of rice plant. (B) Photograph
28 761 of RH after milling. (Upper Inset) Optical micrograph showing the morphological characteristic of
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30 762 outer/inner surfaces of RH. (Lower Inset) Circular chart indicating the main composition of RH. (C)
31 763 Optical micrograph of a RH shell magnified from the black box in B. (Inset) Si-mapped SEM-EDS
32 764 image suggesting that silica exists mostly along the outer rugged surface of RH. (D) The overall
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34 765 procedure of synthesizing the nanostructured Si from RH. (Left to Right) Pretreated RH by an
35 766 acid-leaching process, RH silica by a thermal decomposition process, a Si/MgO mixture formed
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767 after a magnesiothermic reduction process, and the 3D porous Si obtained after an additional
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38 768 two-stage acid etching process.
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40 769 Figure 11 A large scale production of nano-Si from RH. (a) Comparison of carbothermal reduction
41 770 and magnesiothermic reduction for producing nano-Si. Si(OR)4 denotes silicon alkoxide. (b) A
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43 771 panicle of ripe rice at a rice farm. (c) Flow chart of the process for recovering Si nanoparticles
44 772 from RH. (d-g) Optical images of the intermediate substances. The inset of (f) shows an optical
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773 microscopy image (0.9 mm 3 0.6 mm) of one piece of thermal treated RH.
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774 Figure 12 Synthesis of a binder-free composite of Si-graphene as an anode material for LIBs.
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50 775 Figure 13 (A) A rapid microwave assisted method to extract SiO2 from agricultural residues such
51 776 as BC, RH, and SB followed by the magnesiothermic reduction of SiO2 to Si; (B) Si nanohybrids
52 777 production by using a MW-ST process.
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54 778 Figure 14 Integrated strategy of agricultural wastes (e.g., RH) valorization for the production of
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56 779 biofuels, carbon and silica/silicon materials
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58 780 Figure 15 Schematic of transformation, morphology, and dissolution of silicon and carbon in the
59 781 biochars derived from rice wastes pyrolysis.
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39 892 to right) vials of unpurified sand, purified sand, and nano-Si. (e) Schematic diagram of the heat
40 893 scavenger-assisted Mg reduction process. Copyright with the permission from ref. [101]
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29 902 Figure 9 Mechanism illustration of Si and SiC formation by magnesiothermic reduction of SiO2/C
30 903 composite. Copyright with the permission from ref. [96]
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19 916 Figure 10 Generation of 3D nanoporous Si from RH. (A) Photographs of rice plant. (B) Photograph
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21 917 of RH after milling. (Upper Inset) Optical micrograph showing the morphological characteristic of
22 918 outer/inner surfaces of RH. (Lower Inset) Circular chart indicating the main composition of RH. (C)
23 919 Optical micrograph of a RH shell magnified from the black box in B. (Inset) Si-mapped SEM-EDS
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25 920 image suggesting that silica exists mostly along the outer rugged surface of RH. (D) The overall
26 921 procedure of synthesizing the nanostructured Si from RH. (Left to Right) Pretreated RH by an
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28 922 acid-leaching process, RH silica by a thermal decomposition process, a Si/MgO mixture formed
29 923 after a magnesiothermic reduction process, and the 3D porous Si obtained after an additional
30 924 two-stage acid etching process. Copyright with the permission from ref. [104]
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25 937 Figure 11 A large scale production of nano-Si from RH. (a) Comparison of carbothermal reduction
26 938 and magnesiothermic reduction for producing nano-Si. Si(OR)4 denotes silicon alkoxide. (b) A
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28 939 panicle of ripe rice at a rice farm. (c) Flow chart of the process for recovering Si nanoparticles
29 940 from RH. (d-g) Optical images of the intermediate substances. The inset of (f) shows an optical
30 941 microscopy image (0.9 mm 3 0.6 mm) of one piece of thermal treated RH. Copyright with the
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32 942 permission from ref. [107]
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18 954 Figure 12 Synthesis of a binder-free composite of Si-graphene as an anode material for LIBs.
19 955 Copyright with the permission from ref. [109]
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40 972 Figure 13 (A) A rapid microwave assisted method to extract SiO2 from agricultural residues such
41 973 as BC, RH, and SB followed by the magnesiothermic reduction of SiO2 to Si; (B) Si nanohybrids
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43 974 production by using a MW-ST process. Copyright with the permission from ref. [110].
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22 980 Figure 14 Integrated strategy of agricultural wastes (e.g., RH) valorization for the production of
23 981 biofuels, carbon and silica/silicon materials
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26 996 Figure 15 Schematic of transformation, morphology, and dissolution of silicon and carbon in the
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28 997 biochars derived from rice wastes pyrolysis. Copyright with the permission from ref. [115]
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30 998
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 1010 Table Captions
1
2 1011 Table 1 Silica-metal reaction thermodynamic data
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4 1012 Table 2. Comparison of RH-derived Si materials in LIBs applications
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6 1013
7
8 1014 Table 1 Silica-metal reaction thermodynamic data [94]
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10 Reaction Temperature ∆H (kJ/mol) ∆Go (kJ/mol) Adiabatic
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12 (oC) Temperature (oC)
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14 SiO2 + 2Ca = Si + 2CaO 650 -363 -333 2348
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16 SiO2 + 2Mg = Si + 2MgO 650 -312 -261 1906
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18 SiO2 + 4/3Al = Si + 2/3Al2O3 650 -210 -180 1477
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20 SiO2 + Ti = Si + TiO2 650 -34 -33 407
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23 1015
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26 1016
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28 1017 Table 2. Comparison of RH-derived Si materials in LIBs applications
29
Si Materials Properties Capacity (mAh/g) Life Cycle Ref.
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31
32 Si nanoparticles 10-40 nm 2790 86% (300 cycles) [107]
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34 Nanoporous Si 40-60 nm 1554 100% (200 cycles) [104]
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36 Mesoporous Si 150.1 m2/g 1220.2 1000 mAh/g (100 cycles) [105]
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38 Carbon-SiO2 composite 500 100% (40 cycles) [106]
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40 Si-graphene composite 1000 100% (300 cycles) [109]
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42 1018
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