Biomass-Derived Carbonaceous Materials: Recent Progress in

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Biomass-derived carbonaceous materials: Recent progress in synthetic approaches, advantages and applications Da-Peng Yang, Zibiao Li, Minghuan Liu, Xiaoyan Zhang, Yisong Chen, Hun Xue, Enyi Ye, and Rafael Luque ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b06030 • Publication Date (Web): 24 Jan 2019 Downloaded from http://pubs.acs.org on January 26, 2019

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ACS Sustainable Chemistry & Engineering

Biomass-derived carbonaceous materials: recent progress in synthetic approaches, advantages and applications Da-Peng Yang, ‡a Zibiao Li, ‡b Minghuan Liu,a Xiaoyan Zhang,a Yisong Chen,a Hun Xue,*c Enyi Ye,*b Rafael Luque,d,e a

College of Chemical Engineering & Materials Science, Quanzhou Normal University,

Quanzhou, China b

Institute of Materials Research and Engineering, 2 Fusionopolis Way, Innovis, #8-03,

Singapore 138634, Singapore c

Fujian Key Laboratory of Pollution Control & Rescource Reuse, Fujian Normal University,

Fuzhou, China d

Departamento de Quimica Organica, Universidad de Cordoba, Campus de Rabanales,

Edificio Marie Curie (C-3), Ctra Nnal IV-A, Km. 396 E-14014, Cordoba (Spain) ePeoples

Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya str.,

117198, Moscow, Russia ‡Both

authors contributed equally.

ACS Paragon Plus Environment

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Corresponding Authors: Hun Xue, Email: [email protected]; Enyi Ye, Email: [email protected]; Rafael Luque, Email: [email protected]. KEYWORDS: Biomass, Pyrolysis Carbonization, Hydrothermal Carbonization, Ionothermal Carbonization.

ABSTRACT

Current energy shortages and environmental crisis have compelled researchers to look for inexpensive and sustainable resources that can be obtained via environmentally friendly routes to produce novel functional materials. Biomass has been identified as one of the promising candidates given its availability in large quantities and renewable nature. Amongst the various feasible synthetic strategies, hydrothermal carbonization (HTC) has been admired for its energy efficiency and ability to synthesize carbonaceous materials for use in a wide range of applications. In this review, the different types of biomass and strategies available for the synthesis of carbon-based materials will be discussed. Furthermore, factors influencing the efficiency of each strategy will be analyzed and evaluated. Subsequently, the utilization of carbonaceous materials in environmental, catalytic, electrical and biological applications will be reviewed to further demonstrate their functionalities across different fields.


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Introduction Energy is an inevitable topic of discussion in our society given our heavy reliance on it for development and advancements in technology in order to meet the demands of a growing population for a better life quality. Unfortunately, majority of our current power supplies are derived from the burning of fossil fuels which is taking its toll on the environment with its emission of greenhouse gases, resulting in grave consequences like global warming and climate change. Moreover, with its rising costs and finite quantity, there is an urgent need to explore green, economical and inexhaustible alternatives capable of generating equivalent or greater energy outputs so as to substitute and shift away from fossil fuels. Energy conversion systems and storage technologies like the solar cells1, fuel cells2 and lithium-ion batteries3 are some examples of the more receptive and promising replacements which exploit energy sources like solar, geothermal and biomass4. Intensive research in functional materials for such purposes has been carried out in the past decades5-9. Among them, biomass has received considerable attention lately for its sustainability and potential to be converted into functional carbonaceous materials via pyrolysis, hydrothermal carbonization10 together with various activation methods followed by different applications, as illustrated in Figure 1. Biomass are generally referred as the organic plant-based matter which are synthesized via photosynthesis, a process that involves CO2 and water, under sunlight to produce carbohydrates, which are the building blocks of biomass11-12. Apart from the living organisms, biomass can also refer to animal excrement, industrial wastes, agricultural wastes and sewage sludge13. Much of these wastes were disposed away due to the failure to


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recognize its ability to be transformed into useful carbon materials upon combustion. Unlike the combustion of fossil fuels which generates additional CO2, the burning of biomass is considered as a carbon neutral process as CO2 released originates from the CO2 that has been absorbed initially by the plant during photosynthesis and as such, no new CO2 has been produced. In addition, it contains fewer quantities of S and N, implying a lower SOx and NOx emission as compared to fossil fuels14.

Figure 1. Schematic illustration of biomass-based materials synthetic strategies and their applications. The actual composition of plant-based biomass typically varies with the type of feedstock used. However, they are generally composed of lignin, hemicellulose and cellulose, with contents ranging between 10–25%, 20–40% and 40–60% respectively15. Depending on the biomass composition, different techniques can be employed to synthesize carbonaceous materials with maximum efficiency. The most conventional method for biochar synthesis is pyrolysis, a process that involves the thermal decomposition of biomass under inert


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atmosphere at elevated temperatures, between 300–950 C16, producing unique structures with specific surface area and high porosity. Pyrolysis is a highly desirable technique for biomass with low moisture content thereby producing high product yields. For biomass with higher moisture content, hydrothermal carbonization (HTC) would be a more preferred technique. HTC involves a thermochemical decomposition where biomass and water react in a reactor at lower temperatures ranging between 150–350 C17, producing hydrochar and gases18. Another alternative methodology is ionothermal carbonization (ITC), which employs ionic liquids for the preparation of carbon materials19. Certainly, a range of process conditions including the types of feedstock, temperature, residence time, heating rate and pressure would affect the properties of the resulting carbonaceous materials; whereby different combinations would result in a multitude of characteristics e.g. surface area, surface functional groups, porosity and hydrophobicity etc. Thus, a deeper understanding of such combinations would be essential for different applications of the carbonaceous materials derived from plant-based biomass. Herein, this review aims to discuss the present techniques available to synthesize biomassderived carbonaceous materials, with special focus on hydrothermal carbonization, as well as considerations of the parameters governing each technique, which influences the properties of the resultant carbonaceous materials. With the different properties, they can be used for environmental, catalytic and electrical applications.


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Types and Properties of Plant-based Biomass Biomass is abundantly available around the world and has been utilized in many roles for sustainable development. The sources of biomass include woods, agricultural wastes, and energy crops20-21. In recent years, conversion of biomass to carbonaceous materials has received increasing attention because it can serve as a replacement for fossil fuel and is also considered as an alternative to solid waste management17. In the following section, the types of biomass that can be utilized for the synthesis of carbonaceous material will be introduced.

Saccharides Saccharides are abundant in biomass as they are produced during photosynthesis. The majority of the saccharides found in most plants are based on sucrose, composed of glucose and fructose22. Sucrose is also the main compound that is being transported from the source to the sink tissues22-25. Major production of sucrose is from sugar beet and sugarcane22, 25, which are widely available. Hence, the use of saccharides to produce carbonaceous materials can be considered as it is economically viable.

Cellulose Cellulose is the most abundant polymer that can be found in nature as it constituted approximately 40% of the cell wall of plants26. It is formed by connecting linear chains of glucose units linked through 1,4-β-glycosidic bonds27. These chains can be aligned in parallel to form fibrillar structures which make up the fibrous network28 through hydrogen bonding.


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The basic unit, known as the elementary fibril, was reported with 100 nm in length and 1.5– 3.5 nm in diameter, as shown in Figure 2. The elementary fibrils are further assembled into microfibril and microfibril bundles that are >200 nm in length with diameters ranging between 5–15 nm. This hierarchical structure results in the formation of mesopores within the fibers, which is crucial for ion transportation29. The fibrils of cellulose contain amorphous and crystalline regions and proportions vary between different plants. Extraction of cellulose from plants generally yields two classes of nanomaterials. The first class is cellulose nanocrystals (CNCs), which are obtained by subjecting plants to acid hydrolysis. The amorphous regions are being removed by hydrolysis while the crystalline regions remain intact due to higher resistance, leading to rod-like nanocrystals in which the dimensions depend on the plant source26,

30-31.

The second class is cellulose nanofibrils

(CNFs) or microfibrils, depending on their size32. CNFs are obtained by applying mechanical shear force to the plants, resulting in the disintegration of the fibers to their substructural fibrils26, 30-31. Besides plants, cellulose can also be generated from certain bacteria33. Cellulose generated by bacteria is known as bacterial cellulose (BC) and is obtained by fermentation of bacteria either through the pentose-phosphate or Krebs cycle. The mechanism pathway taken is determined by the physiological state of the cell34. Although BC has the same molecular formula as plant cellulose, microfibrils of BC are 100 times smaller, making them highly porous35. BC has a higher chemical purity compared to plant cellulose as they do not contain hemicellulose or lignin36. As such, bacterial cellulose possesses a higher crystallinity. BC also provides other advantages such as high degree of polymerization, mechanical


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stability, water holding capacity, biodegradability and biocompatibility35, 37-40. The presence of hydroxyl groups in cellulose allows for further modification, enhancing the properties of the precursor. An example is the modification with urea to produce nitrogen-doped precursors and eventually carbonaceous materials with nitrogen content39.

Figure 2. (a) Hierarchical structure of cellulose from wood. (b) SEM of microfibrils on fiber surface (c) SEM of spruce fiber’s cross-section. Adapted with permission from ref29. Copyright (2014) Royal Society of Chemistry.

Lignin Lignin as the most abundant natural biopolymer just behind cellulose, is typically found to cement cellulose fibers in plants40-41. The main sources of lignin are generally from industrial wastes of paper mills and wood fibres, where the global production was amounting to an


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estimate of 50 million tons per year42. As such, it was seen as a viable opportunity to develop new applications from lignin so as to exploit its large quantities and low cost. Lignin is a phenolic polymer resulting from the polymerization of the precursors p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol which synthesizes to form 3 main monomers of lignin: p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S)43-44. The macromolecules are further cross-linked, forming a complex network structure. However, it is noteworthy that the proportion of the monomers and lignin content varies according to the plant species. In general, a lower lignin content is found in herbaceous plants while a higher lignin content is observed in softwoods45. Herbaceous lignin is composed of all three basic units whereas softwood lignin consists of mainly coniferyl alcohol units while hardwood lignin has both coniferyl and sinapyl units. The difference in monomer and lignin content and subsequent extraction methods can eventually affect the properties of the products. Lignin can be classified based on its extraction methods including: kraft lignin45-46, soda lignin47, sulfite lignin48 and organosolv lignin49. Kraft lignin contained more phenolic –OH groups and a more condensed C–C structure. Soda lignin is with increased solubility and generally sulfurfree. Sulfite lignin is water soluble due to the addition of sulfonated groups. Organosolv lignin owns a higher phenolic hydroxyl content and lower carboxyl group than soda lignin50.

Lignocellulosic Biomass Lignocellulosic biomass mainly comprises lignin, cellulose and hemicellulose with compositions between 10–25%, 35–50% and 20–35% respectively. The difference in


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composition is attributed to the type of biomass, with softwood having the highest lignin content among all biomass, as shown in Table 151-52. Hemicellulose contains several heteropolymers such as xylans, mannans, xyloglucans and glucomannans which varies in composition with different species. This results in different hemicellulose structure, and are usually random and amorphous53. For example, softwood hemicellulose is mostly comprised of glucomannans while hardwood hemicellulose contains mostly of xylan54-55. Hemicellulose plays an important role in providing structural strength to the biomass due to its connection with cellulose along with cross-linking to lignin through ester and ether bonds, as shown in Figure 356. As a result of the crystallinity of cellulose, high degree of aromaticity of lignin and encapsulation of cellulose by the hemicellulose-lignin matrix contributes to the recalcitrant nature of lignocellulosic biomass57-58.


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Figure 3. The main components and structure of lignocellulosic biomass. Adapted with permission from ref51. Copyright (2015) Royal Society of Chemistry.


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Table 1. Chemical compositions of various lignocellulosic biomass. Adapted with permission from ref51. Copyright (2015) Royal Society of Chemistry. Lignocellulosic

Cellulose (%)

Hemicellulose (%)

Lignin (%)

Biomass Hardwood

Softwood

Agricultural

Poplar

50.8–53.3

26.2–28.7

15.5–16.3

Oak

40.4

35.9

24.1

Eucalyptus

54.1

18.4

21.5

Pine

42.0–50.0

24.0–27.0

20

Douglas fir

44

11

27

Spruce

45.5

22.9

27.9

Wheat Straw

35.0–39.0

23.0–30.0

12.0–16.0

Barley Hull

34

36

13.8–19.0

Barley Straw

36.0–43.0

24.0–33.0

6.3–9.8

Rice Straw

29.2–34.7

23.0–25.9

17.0–19.0

Rice Husks

28.7–35.6

12.0–29.3

15.4–20.0

Oat Straw

31.0–35.0

20.0–26.0

10.0–15.0

Ray Straw

36.2–47.0

19.0–24.5

9.9–24.0

Corn Cobs

33.7–41.2

31.9–36.0

6.1–15.9

waste

Synthetic strategies of biomass based carbonaceous materials The conversion of biomass to char can be achieved by several methods, which are mainly classified into biological, chemical and thermochemical processes. Among them, thermochemical processes are preferred due to their shorter processing time that leads to higher product yields59. In addition, thermochemical processes allow the utilization of the


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whole biomass to produce value-added materials unlike biochemical processes, which requires specific feedstock20. Hence, various thermochemical processes will be discussed in the following sections, aiming to provide an overview of their reaction mechanism and influencing factors on products distribution (Table 2).

Pyrolysis Pyrolysis has been traditionally used to produce charcoal and tar-like substances, as well as oil and gases60. It is a thermochemical process to degrade organic compounds in the absence of oxygen, which ensures that combustion does not occur13. Pyrolysis can be divided into two stages, primary and secondary pyrolysis. In the primary pyrolysis, the volatile components are cleaved off by dehydration, decarboxylation and/or dehydrogenation, which produce bio-oil when it condenses. Following the primary stage, the secondary pyrolysis represents the main process, where cracking of heavyweight hydrocarbons takes place and converts into char or gases. The char produced is a carbonaceous compound that has proven its potential use in soil amendment and adsorbents61-62. Figure 4 is a representation of possible products obtained resulting from different pyrolysis pathways due to different operating conditions63.


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Table 2. Comparison in conditions and characteristics of different synthetic approaches of biomass-derived carbonaceous materials Synthetic Approaches Pyrolysis

Comparison in Conditions and Characteristics Temperature (C)  300 – 950 C  Increase of surface area with increasing temperature  increase of temperature decreases yield of product

Hydrothermal  150 – 350 C Carbonization  Key factor (HTC) influencing HTC

process and characteristics of hydrochar  Higher temperature lead to higher surface area and N2 adsorption but low yield Ionothermal  General gentle Carbonization heating or atmospheric (ITC) conditions would lead to biomass dissolution and porous carbon

Residence Time/Heating rate

 Longer residence time would result in higher char yield  Increase in heating rate generally increases the specific surface area and pore volume  Residence time ranges between several hours to days  Longer residence time at lower temperatures has a more significant effect

 Residence time ranges from 1 to several hours  Heating rate is not a typical parameter in this method

Molten Salt  100 – over 1000 C  30 min to a few hours Carbonization depending on the at designed temperature (MSC) types of salts ramp process

 Heating rate is not a typical parameter in this

Process/Product Feature

 Surface area ~ 180 m2/g  Pore volumes of chars ~ 10 nm to 100 µm  Product yield affected by particle size  Producing hydrochar, bio-oil, and gases at varied conditions  Presence of lignin increases hydrochar yield  Carbon distribution of hydrochar influenced by residence time  Ionic liquid is utilized instead of water  Bigger anion such as Tf2N- resulted in a more porous carbon  Super high surface area up to 2780 m2/g can be achieved  Low cost  Catalytic effect in cracking the large molecules  Good dissolution

Ref

Pros and Cons  Most conventional method for char synthesis  High porosity  High product yield  Biomass with low moisture content required  Mild processing conditions  Slow process  Low surface area and porosity  Biomass mixed with water required  Suitable for wet agriculture residues  Lower energy consumption  Post-treatment required (Physical and chemical activation, hard and soft templating)  Use ionic liquids to fabricate carbon materials  Enables the production of porous carbon in a one-step process  Multitude of characteristics control via combination of process conditions  Intensive energy consumption for IL recycling  Multifunctionalities of IL as solvent, template, and catalyst  Easy to incorporate doping and increase conductivity of product  Versatile for a variety of agriculture waste biomasses  Relatively mild conditions  Capacitive carbon exhibit high thermal stability, porosity and

16, 60, 64-69

17-18, 70-77

19, 7882

80, 8390


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method

ability  Easy for heteroatomic doping

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enhanced heat transfer


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Figure 4. Representation of products resulting from pyrolysis at different temperatures. Reproduced with permission from the RSC from ref

63.

Copyright (2012) Royal Society of

Chemistry.

There are various types of pyrolysis processes which differ in operating conditions, resulting in different yields of product within the three phases91. Slow pyrolysis occurs at lower temperatures (400°C), with lower heating rates (1–10 °C/s) and long residence time (>5 mins). This enables more time for secondary reactions to occur, generating more biochar64. Conversely, fast or flash-pyrolysis occurs at higher temperatures (500–600 °C), and is characterized by rapid heating (10–1000 °C/s) and short residence time of the generated vapours ( Cd2+ > Ni2+, with an outstanding removal of aqueous lead in both single and multi-metal systems. Similar results were reported for KOH activated hydrochar by Sun et al.156.

(b)

(a)

(c)

(d)

(e)

Figure 11. (a) SEM image of magnetic activated carbon (b) Magnetization curve of magnetic activated carbon at 300 K (The inset shows that magnetic activated carbon can be separated easily under an external magnetic field) (c) Image of activated carbon (d) SEM micrograph of activated carbon (e) Langmuir and Freundlich adsorption isotherms for Pb (II) ions. Adapted with permission from ref152,

154.

Copyright (2014) Royal Society of Chemistry, Copyright

(2017) Elsevier.


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Catalytic Applications Catalyst With

the

increasing

emphasis

to

synthesize

materials

through

greener

and

environmentally friendly methods, researchers have put in more efforts to look into the application of green catalysts. HTC followed by subsequent activation is capable of producing hydrochar with desirable surface area and modifiable properties to be used as catalysts or as catalyst support. Conventionally, 5-hydroxymethylfurral (HMF) is synthesized in a two-step process from insulin using traditional solid acid catalysts. In a work presented by Kang et al.157, carbonbased sulfonated catalysts produced from different biomasses at various hydrothermal temperatures exhibited excellent catalytic activity and were capable of producing HMF in a single step process instead. As a result, a high 47–65% overall HMF yield was achieved with the addition of catalysts. The high reusability and efficiency make biomass-derived catalysts a promising candidate for future industrial applications158. In another work by Gan and coworkers159, acidic hydrochar (Figure 12a) were synthesized via HTC of alkali lignin and was used as a catalyst for the hydrolysis of cellulose. Mass pine lignin was carbonized in acrylic acid followed with subsequent sulfonation, where the presence of SO3H-functional groups contributed to the solid’s high catalytic efficiency. A high yield of 75.4% had been observed upon the addition of carbonaceous catalyst was shown in Figure 12b. Furthermore, no significant decrease in catalytic activity had been observed even after recycling the catalyst


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for 5 times (Figure 12c). The high reusability and efficiency of these biomass-derived catalysts make them a promising candidate for future industrial applications. a

d

f

c

e

g

Figure 12. (a) FESEM of carbonaceous catalyst produced from HTC of pine lignin in acrylic acid and subsequent sulfonation (b) effect of LAHC-SO3H40 loading on TRS yield (c) catalyst recycles for MCC hydrolysis (d) Illustration of the reaction procedure undertaken for the steam gasification of sewage sludge (e) FE-SEM images of pristine hydrochar (f) TEM images of Ni1.0@HC at 900°C (g) Selectivity of gaseous products from the catalytic gasification of


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Nix@HC (x = 0.1, 0.5, 1.0) composites at 900°C. Adapted with permission from ref159-160. Copyright (2017) Springer, Copyright (2017) American Chemical Society.

Catalyst Support The supporting materials used by heterogeneous catalysts play an important role which greatly influences the catalytic performance. It is crucial that the supporting materials have a high surface area and porosity so as to expedite the reaction. Since hydrochars typically present such properties, many researchers have explored and exploited the use of hydrochars as supporting materials161. In a recent work by Hu et al.162, “hybrid fleece” structures comprising of uniform carbonaceous nanofibers had been implanted with metal nanoparticles during the HTC process. The synthesized nanostructures displayed excellent thermal, chemical and mechanical stability with high binary carbon-metal contact together with a highly specific metal surface area. Such properties enabled the nanostructures to perform as catalysts, which effectively converted CO to CO2 at low temperatures. It was also observed that the second trial run had surpassed the performance of the first whereby the authors attributed such occurrence to the formation of active species in the first heating and oxidation cycle. In another report documented by Gai et al.160, hydrochar supported Ninanoparticles was utilized to aid in process of converting sewage sludge into hydrogen-rich syngas. Sewage sludge was mixed with nickel nitrate solution and reacted hydrothermally to produce Ni-composites (Figure 12d-f). The resulting composite had a uniform dispersion of


50

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Ni nanoparticles with strong metal-support interaction and were subsequently applied to the steam gasification of sewage sludge to produce hydrogen-rich syngas. The hydrochar increased the catalytic activity of Ni, with a high yield of 78.7 g H2 per kg of hydrochar and a H2 selectivity of 72.5% (Figure 12g).

Energy conversion and storage applications Supercapacitors Supercapacitors are the energy storage devices well known for its high capacitance, extended life span and quick charge/discharge capabilities163. They are mainly categorized into two groups –one is electrical double layer capacitors (EDLC), where electrostatic charge builds up on the surface of the electrode. The other is Pseudo-capacitors, where capacitance stems from the reversible surface redox reactions. Carbon-based materials are commonly used for the electrode given its outstanding physiochemical properties164. Henceforth, increasing attention has been given for the manufacturing of carbon-based materials with excellent electrochemical properties by environmentally friendly methods165-169. In a study illustrated by Li and co-workers170, porous carbon-based materials were synthesized from corncob residues via a thermal activation treatment. The as-prepared porous carbons inherited a high specific surface area of 1210 m2/g, with a highly stabilized mesoporous structure. As a result, the carbon electrode exhibited an outstanding capacitance of 120 F/g in a symmetrical cell and lasted throughout 100,000 cycles (Figure 13). Besides its low economic costs and ecology impact, these carbon electrodes displayed a higher electrochemical


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performance versus synthetic polymer-based carbons. Despite the achievement of a rather high capacitance, the capacitance ability can be further boosted through the hydrochar synthesized via HTC process. In a separate study reported by Dekhoda et al.171, mesoporous hydrochars were prepared through HTC with subsequent KOH activation. The resultant hydrochar had surface areas ranging between 488 to 2670 m2/g and mesoporous volume ranging from 0.05–1.70 cm3/g. These carbons displayed an enhanced capacitance between 182–240 F/g as well as significantly lessened electrode resistance. Apart from KOH activation, Sevilla et al.172 used a mild alkaline, potassium bicarbonate (KHCO3) for activation of hydrochar derived from glucose. In comparison to KOH activation, KHCO3 activation had produced an additional 10% more activated carbon yield. Furthermore, unlike KOH activated hydrochars, KHCO3 activated hydrochars retained its spherical morphologies, and also had larger surface areas of 2300 m2/g with tunable pore distribution upto 1.4 cm3/g. The preserved spherical morphology ensured a better packing property and reduced ion diffusion distances such that KHCO3 activated carbons were capable of storing up to 3.6 Wh/kg versus 3.4 Wh/kg for KOH activated carbons at 17 kW/kg in H2SO4.


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Figure 13. Porous carbon derived from corncob residue with superior capacitative performance of 120 F/g in a symmetrical cell. Adapted with permission from ref170. Copyright (2015) Elsevier.

Solid Biofuels Solid biofuels typically refer to any renewable, biological materials which can undergo combustion to generate energy. Unlike the use of solid fuels like coals, solid biofuels appear to have economic and social benefits as well as a lower impact on the environment173. Hydrothermal treatment has been used to convert industrial wastes and sewage sludge into clean solid biofuels. In particular, Basso et al.174 looked into the application of grape marc, a by-product from winery industries for energy purposes. Grape marc was dehydrated via a bio-drying175 process before undergoing hydrothermal carbonization treatment at different temperatures and residence time. Experimental results revealed that the high carbon content in carbonaceous solids contributed to a high heating value, which ranges between 19.8–24.1


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MJ/kg. Additionally, minimal gaseous products, consisting mainly CO2 with traces of H2 and CH4, were found to be released. Such results signified the feasibility of exploiting carbonaceous solids as solid biofuel with low environmental impact. In another work, He et al.

176

evaluated the efficiency of hydrochar synthesized from sewage sludge as solid biofuel.

Similar to the work by Basso, the results unveiled that the obtained char was made up of mainly carbon with more than 60% of nitrogen and sulfur being removed through the HTC process. The newly synthesized hydrochar was not only a cleaner form of solid fuel due to a lowered NOx and SOx emission, but was also empowered with a good combustion performance with combustibility index standing at 3.4 x 10-8.

Biological Applications Carbon quantum dots (CQD) have garnered much attention for their fluorescent properties which can be employed in medical bioimaging practices to detect or cure diseases.177-178 Various techniques have been identified for the synthesis of CQD. For example, Yang et al.177 synthesized carbon nanoparticles (CNP) through the hydrothermal carbonization of silk. The resultant CNPs has a narrow size distribution between 4–7 nm with a similar fluorescence emission of 450 nm when excited at 370 nm. To evaluate its feasibility as a bioimaging material, the authors introduced the CNPs into CCD-112 CoN colon fibroblast cells and findings confirmed the low cytotoxicity and applicability for bioimaging purposes. In a similar work, Parvin and co-workers178 illustrated the synthesis of highly fluorescent nitrogen-doped carbon quantum dots (N-CQDs) and its applicability for biomedical and


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optical imagining purposes. The N-CQDs were products derived from the hydrothermal treatment of agarose with diameters averaging at 4.5 nm. Intense fluorescence was observed upon the incubation of quantum dots into human breast cancer MCF-7 cells. The biodistribution, clearance and toxicity factors were also analysed by injecting into mice. The results, as seen in Figure 14, showed an excellent biodistribution and rapid clearance efficiency within 6 days. The high stability, low toxicity and intense fluorescence make NCQD a suitable alternative for biomedical applications.

(e)

Figure 14. Fluorescence images of mice injected with N-CQDs at different time periods: (a) pre-injection (b) 12 hours post-injection, (c) 24 hours post-injection. (d) Fluorescence microscopy images of various organs and tissues under different wavelength of light taken


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after 1 hour from post-injected mice (e) Distributions of N-CQDs probe in different organs and tissues of nude mice at 1 to 7 days post-injection. Adapted with permission from ref178. Copyright (2016) Royal Society of Chemistry.

Conclusions and Perspectives With the depletion of traditional resources (such as coal, petroleum) and to reduce the amount of carbon dioxide pollution from the use of these materials, the search for a clean and renewable source is of great importance. Biomass is considered as the most sustainable and renewable source for the synthesis of carbonaceous materials. These materials have a variety of applications in the environmental, catalytic and energy conversion/storage fields. It was shown that large amount of biomass is generated annually with only a small percentage for human needs. The major constituents of biomass include cellulose, hemicellulose and lignin. The composition varies with the type of biomass, which eventually affects the yield and structure of the carbonization product. It was highlighted that the lignin content is major factor affecting the properties of the carbonaceous material. Different mechanism pathways during carbonization were attributed to the type of biomass used as well. In general, the biomass undergoes dehydration, decarboxylation and a series of polymerization and condensation reactions to produce the solid product. Conversion of biomass to carbonaceous materials by four methods, pyrolysis, HTC, ITC and MSC were discussed. Pyrolysis is one of the most conventional methods used for the production of activated carbons. However, one main disadvantage of pyrolysis is that it requires pre-drying


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of the biomass, which is energy-extensive. Hydrothermal carbonization is an alternative thermochemical process, where biomass is heated at lower temperatures under subcritical water. Besides the effect of types of biomass, the effect of reaction conditions on the yield and porosity development of the carbon materials produced was outlined. Although HTC materials generally have a low porosity, methods such as activation and templating methodologies can be employed to solve this problem. The carbon materials can also be further modified by changing the functional groups or removal of the existing groups. Ionothermal carbonization produces porous biomass-derived carbon materials in one step process using ionic liquids without any templates or additives. The use of different ionic liquids can cause pores to be formed in different ways, as well as generating various pore sizes. It can also introduce different heteroatoms for doping of carbon materials, which would benefit its use as a catalyst by providing more active sites. Molten salt carbonization offers a simple and environmentally sound way to convert waste biomass to highly porous carbon. As mentioned, carbonaceous materials derived from biomass have various applications. For environmental applications, it can be used for CO2 capture. It has been demonstrated in multiple experiments that functionalization of the carbon materials allows more efficient adsorption. Besides its use for CO2 capture, the porous carbon enables the adsorption of contaminants in soil and water. In addition, it has been demonstrated that hydrochar can be used for removal of heavy metals in water, especially for removal of Pb2+. Other applications include acting as a catalyst and catalyst support, in which embedding with metallic


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nanoparticles, produces high thermal, chemical and mechanical stability. Due to presence of mesopores in the carbon materials, transport of ion and electrolytes are favorable, leading to its exploitation for use as supercapacitors in the electrochemical field. It was noted that HTC is more sustainable and economical as it has a more efficient process and consumes lower amount of energy. Lignin is a feedstock of interest due to its high stability under low temperatures, resulting in a high yield of solid carbonaceous product. However, not much research has been done on the hydrothermal carbonization of lignin. Since biomass-derived carbon materials have successfully proven its use in a variety of applications, more research work on the hydrothermal carbonization of different types of lignin and the effect on its use in various applications can be carried out. ITC proves to be a sustainable and economical process since conversion of biomass by ITC results in porous carbon nanomaterials without the use of any templates or additives. Besides, most of the IL used could be recovered and reused. The carbon materials can also be doped by the used IL, reducing the need for extra modification steps. As such, scaling up of ITC process may be more economical since porous carbon can be produced from the ILs directly during the process. The carbonization methods of HTC, ITC and MSC showed promising results in converting biomass into carbonaceous materials with small scale. So far pyrolysis is still the most convenient, mature and cost-effective method in converting bulk biomass into carbonaceous materials with large scale production. Thus to foster the commercialization of HTC, ITC and MSC, much more efforts need to be put into HTC, ITC and MSC of biomass especially lignin with large scale production.


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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (81472001, 31400851), the Minjiang Scholars Program of Fujian Province, the Tongjiang Scholars Program of Quanzhou City, Quanzhou City Science & Technology Program of China, the Fourth Health Education Joint Development Project of Fujian Province (WKJ-2016-2-36). The publication was prepared with support from RUDN University Program 5-100.

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For Table of Contents Use Only Biomass-derived carbonaceous materials: recent progress in synthetic approaches, advantages and applications Da-Peng Yang, Zibiao Li, Minghuan Liu, Xiaoyan Zhang, Yisong Chen, Hun Xue, Enyi Ye, Rafael Luque


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Synopsis Biomass-derived carbonaceous materials: Towards the development of high performance carbon materials from sustainable and renewable source.


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Biomass-Derived Carbonaceous Materials: Recent Progress in

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