Research Article

Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX pubs.acs.org/journal/ascecg

Tin-Functionalized Wood Biochar as a Sustainable Solid Catalyst for

Glucose Isomerization in Biorefinery
Xiao Yang,†,‡ Iris K. M. Yu,† Dong-Wan Cho,† Season S. Chen,† Daniel C. W. Tsang,*,† Jin Shang,§
Alex C. K. Yip,∥ Lei Wang,† and Yong Sik Ok*,‡
†
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong,
P. R. China
‡
Korea Biochar Research Center, O-Jeong Eco-Resilience Institute (OJERI) & Division of Environmental Science and Ecological
Engineering, Korea University, Seoul 02841, Republic of Korea
§
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Joint Laboratory for Energy and Environmental Catalysis, School of Energy and Environment, City University of Hong Kong, Tat
Chee Avenue, Kowloon, Hong Kong, P. R. China
∥
Energy and Environmental Catalysis Group, Department of Chemical and Process Engineering, University of Canterbury,
Downloaded via MACQUARIE UNIV on February 22, 2019 at 05:08:56 (UTC).

Christchurch 8041, New Zealand

*
S Supporting Information

ABSTRACT: This study tailored a novel engineered biochar as a solid catalyst for
glucose isomerization by pyrolyzing Sn-functionalized wood waste under varying
hypothesis-driven selected conditions (i.e., 650, 750, and 850 °C in N2 and CO2
atmosphere). The results showed that properties of biochar support (e.g., porosity and
acid/base property) and chemical speciation of Sn were highly related to their catalytic
performance. Variations in pyrolysis temperature and feed gas modified the porous
structure and surface functionality of biochar as well as the valence state of doped Sn on
the biochar. For the N2 biochars, higher pyrolysis temperature enhanced the fructose
yield yet had trivial effect on the selectivity, where 12.1 mol % fructose can be obtained at
150 °C and 20 min using biochar produced at 850 °C. This was plausibly attributed to
the increased fraction of amorphous Sn structures and metallic Sn that were more
reactive than its oxide form. At the pyrolysis temperature of 750 °C, the use of CO2
increased the surface area by 40%, enlarged the pore volume from 0.062 to 0.107 cm3
g−1, and enriched the amorphous Sn structures compared to those for N2 biochar. This
probably accounted for the better catalytic performance of CO2 biochar than that of N2 biochar (∼50% and 100% enhancement
in fructose yield and selectivity, respectively). The Sn-biochar catalysts may have promoted glucose isomerization via both the
Lewis acid and Brønsted base pathways. This study paves a new way to design biochar as a sustainable and low-cost solid
catalyst for biorefinery applications.
KEYWORDS: Engineered biochar, Waste valorization/recycling, Biobased value-added chemicals, Sugar conversion,
Lignocellulosic biomass, Lewis acid

■ INTRODUCTION
Sugar isomerization is known as one of the most important
tactics in the catalytic bioeconomy chain.1 For example, the
isomerization of glucose into fructose not only plays a role in
high-fructose corn syrups production,2 but serves as a
thermodynamically favorable pathway in the synthesis of 5-
hydroxymethyl furfural (HMF)3,4 and levulinic acid (LA).5
These building blocks produced by biomass valorization can be
employed as renewable alternatives of fossil fuel derivatives as
well as feedstocks in the industrial production of fragrances,
food additives, and resins,6−9 which relieve our heavy reliance
on conventional petrochemical resources. The increasing use
of abundant and renewable biomass resources (approximately
220 billion tons of dry biomass a year, which is equal to 4500
EJ of energy content)10 is driven by both economic incentives
and environmental benefits.7,11−13
The glucose isomerization is an endothermic (ΔH = 3 kJ/
mol) and reversible reaction (Keq ≈ 1 at 298 K) and the use of
biological or chemical catalysts is necessary to accelerate
isomerization.14 Although the enzymatic process is recognized
as an effective method that can achieve 42 wt % fructose
yield,15 it incurs high cost owing to the demand for purified
feeding material, narrow operating conditions (pH and
temperature), and irreversible deactivation of spent enzymes.16
In comparison, chemical catalysts show the advantages of
significantly shorter reaction time and greater endurance to
impurities. Glucose isomerization can be catalyzed by Lewis
acids (i.e., electron pair acceptor such as Sn4+ and Al3+) via
Received: October 15, 2018
Revised: February 7, 2019
Published: February 12, 2019

© XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.8b05311

ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
intramolecular hydride shift from C-2 to C-1 or by Brønsted
bases (i.e., OH−) via hydrogen transfer from O-2 to O-1.3
Homogeneous catalysts provide good catalytic performance,17
but often raise concerns about equipment corrosion as well as
downstream product separation and solvent treatment, which
has promoted the development of heterogeneous solid
catalysts for biomass conversion.18,19 Recent studies have
suggested that the incorporation of Lewis acid metal species
into porous supporting materials (e.g., zeolite, silica−alumina
composite, metal−organic framework, and covalent organic
framework)20,21 can manufacture high-performance solid
catalysts for isomerizing glucose to fructose.22 However,
chemical-/energy-demanding synthesis conditions and use of
unsustainable chemicals and organic solvents may restrain the
large-scale application of these advanced solid catalysts.
Biochar is a low-cost pyrolytic solid produced from waste
biomass, which possesses tunable pore structure and surface
chemistry. These advantages render biochar attractive in a
variety of environmental applications such as soil remediation,
wastewater treatment, energy production (gasification), and
storage, as well as CO2 capture.23−25 Recent research
demonstrated that biochar-based materials could serve as
catalysts for transforming biomaterials to high-value products,
including esterification/transesterification of waste oils for
biodiesel production,26 tar cracking for improved syngas
production,27 and biomass hydrolysis for sugar and biofuel
synthesis.12 Hence, there is a high potential for biochar serving
as a sustainable and economical solid support of catalysts for
biorefineries as an emerging and value-added application.
The major challenge in designing a high-performance
biochar-based catalyst is to increase the selectivity toward
useful products, by accelerating the desired reaction pathways
and suppressing the side reactions. While soluble Sn4+ catalyst
provides Lewis acid sites for catalytic glucose isomerization, it
is uncertain that if the Lewis acid sites remain active when Sn is
immobilized on a biochar support. The forms of impregnated
metal species are contended to play an important role in
determining the active sites,28 which may vary with the
pyrolysis conditions such as temperature and purge gas. In
comparison to inorganic materials such as zeolite, biochar as an
organic carbon support is more reactive.26 Therefore, more
chemical interactions between biochar and metal can be
expected, which may also alter the speciation of the
impregnated metals. As biochar by itself contains alkali and
alkaline earth metals that are naturally present in waste
biomass, we hypothesize that base sites may appear in Sn-
functionalized biochar composite, promoting glucose isomer-
ization via the base-driven pathway. In addition, the physical
properties of biochar-based catalysts such as porosity and
surface area are critical to their performance.29
This work aims to synthesize Sn-functionalized biochar (Sn-
BC) catalysts using a facile and simple impregnation method.
A series of Sn-BCs with distinctive physicochemical properties
were produced under different conditions (pyrolytic temper-
ature of 650−850 °C in N2 or CO2 atmosphere). The Sn-BCs
were evaluated as a solid catalyst for the conversion of glucose
to fructose in water, to investigate the correlation between the
physicochemical properties of Sn-BCs and their catalytic
activity. The reusability of Sn-BCs was also examined. This
work elucidates the critical properties of biochar-based catalyst
in determining their catalytic performance, which can advance
the development of engineered biochars for sustainable
biorefineries in a wide context.
B DOI: 10.1021/acssuschemeng.8b05311
Research Article
■ EXPERIMENTAL SECTION
Sample Collection and Chemical Agents. Mixed waste wood
biomass generated from the Industrial Centre, the Hong Kong
Polytechnic University, was employed as initial feedstock for biochar
production. The wood waste was first pulverized into 2 mm size and
dried at 60 °C before use. The SnCl4·5H2O (98%, Sigma-Aldrich) was
used as the impregnating agent for Sn-BC synthesis. Pure glucose
(≥99.5%, Sigma-Aldrich, St. Louis, MO, U.S.A.) was used as the
substrate in the evaluation of catalytic performance of the biochars.
Model compounds including glucose, fructose (≥99%, Wako, Tokyo,
Japan), cellobiose (≥98%, Alfa Aesar, Ward Hill, MA, U.S.A.),
maltose monohydrate (≥98%, Wako), HMF (≥99%, Sigma-Aldrich),
levoglucosan (Fluorochem, Hadfield, UK), levulinic acid (LA; 98%,
Alfa Aesar), formic acid (FA; 98%, Alfa Aesar) and furfural (FF; 99%,
Sigma-Aldrich) were used for instrument calibration based on the
reported protocol.30 All the chemicals were used without any further
purification.
Synthesis of Sn-Functionalized Biochar. Wood waste (WW)
was soaked in a Sn aqueous solution (prepared from SnCl4·5H2O) at
a solid-to-liquid mass ratio of 1:5, with the Sn dosage equivalent to 20
wt % of biomass. The mixture was continuously agitated for 1 h,
followed by drying at 105 °C in an air-flowing oven until achieving
constant mass. The resulting dry solid (i.e., SnCl4-treated WW) was
pyrolyzed using a horizontal tubular furnace. Three types of biochars
produced at 650, 750, and 850 °C under N2 purging were denoted as
Sn-B650N, Sn-B750N, and Sn-B850N, respectively. The temperature
of 750 °C was selected to produce Sn-BC in CO2 environment (i.e.,
Sn-B750C) because Boudouard reaction is feasible at ≥710 °C,
enabling the CO2-promoted development of porosity and syngas
enrichment.31,32 The temperature of 850 °C in CO2 was excluded to
avoid the complete devolatilization of C (i.e., no black carbon but ash-
like residue was observed in the solid product in preliminary
experiments). The heating rate was set at 10 °C min−1, and the
designated temperature was held for 2 h with the gas flow rate
maintained at 150 mL min−1. After pyrolysis, the reaction zone was
naturally cooled down to ambient temperature with continuous gas
purging. All Sn-BCs were stored in a desiccator before subsequent
use.
Characterization of Sn-Functionalized Biochar. Thermogravi-
metric analysis (TGA, Rigaku Thermo plus EVO2) was performed to
investigate the weight loss of SnCl4-treated WW and Sn-BCs with
temperature increasing from 100 to 1000 °C at a ramp rate of 10 °C
min−1 in Ar environment. Surface morphology, pore structure, and
surface elemental distribution were analyzed using a scanning electron
microscopy coupled with energy dispersive X-ray spectroscopy (SEM-
EDX, TESCAN VEGA3 XM). The crystalline structure of pyrolyzed
products was characterized by an X-ray diffractometer (XRD, Rigaku
SmartLab) with a scanning zone ranged from 20° to 70° at 45 kV and
200 mA. The Brunauer−Emmett−Teller (BET) surface area and
porosity (pore size, pore volume) of Sn-biochars were measured using
a gas adsorption−desorption analyzer (Micromeritics, Gemini VII)
using N2 at 77 K. Before the measurement, the biochars were
subjected to degassing under N2 purging at 200 °C for 6 h. Acid−base
properties were determined using an autotitrator (Mettler, Easy Plus)
based on a simplified Boehm titration.33,34 Typically, 0.1 g of the
sample was suspended in 25 mL of 0.025 M sodium hydroxide or
0.025 M hydrochloric acid. The mixture was placed in a shaker for 24
h at 200 rpm. The liquid phase was then collected via filtration and
titrated against 0.025 M HCl and NaOH, respectively. The number of
base sites (proton acceptor) was calculated based on the assumptions
that HCl neutralizes the basic fraction of biochar. Similarly, the
number of acid sites (proton donor) was calculated from the amount
of NaOH consumed. The inductively coupled plasma mass
spectrometry (ICP−MS, SPECTROBLUE FMX36) was used to
quantify the doped Sn in each sample, which was completely digested
using US EPA Method 3051A.35
Catalytic Conversion Tests and Products Identification and
Quantification. The catalytic conversion of glucose was carried out
in a 100 mL microwave autoclave with the Ethos UP Microwave
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering Research Article

Reactor (Milestone, maximum power 1900 W). The microwave-

assisted system was operated in the same manner as in our previous
work.36,37 A temperature probe was inserted into one of the reaction
vessels during each run of experiment, which enables the programmed
control of the reaction temperature. Typically, 0.25 g biochar catalyst
was added into the 10 mL solution of 5 wt/v % glucose (substrate) in
deionized water (reaction medium). A 5 min magnetic agitation was
conducted to make a homogeneous mixture before reaction. The
reaction mixture was then subjected to microwave radiation at a
temperature range of 140−160 °C for 1−60 min. After conversion, 40
min of air-flow ventilation was carried out to cool the reactor to
ambient temperature. The reusability of Sn-BC was examined at 160
°C for 20 min following the above-mentioned protocol. After
reaction, the solid catalyst was separated from the mixture by
filtration, followed by washing with distilled water for four times to
remove water-soluble substances. The washed solid was oven-dried at
105 °C overnight, giving the recycled solid catalyst that was directly
used in the next run of catalytic conversion of glucose without
regeneration.
For the product analysis, the collected liquid phase was diluted and
filtered through a 0.22-μm membrane. The prepared liquid samples
were injected into a high-performance liquid chromatography
(HPLC, Hitachi) equipped with an Aminex HPX-87H column
(Biorad). The mobile phase was 0.01 M H2SO4 at a flow rate of 0.5
mL min−1 at 50 °C. The yield and selectivity of each product were
calculated based on the carbon number.38 The unit Cmol % allows for
the estimation of carbon efficiency and carbon balance, which are
important consideration in devising high-performance catalytic
systems.
C p × Vol × Np/M p
yield p (Cmol%) = × 100%
Gi × Vol × NG/MG (1)
Cf × Vol × Nf /M f
fructose selectivity (Cmol%) = × 100%
(Gi − Gf ) × Vol × NG/MG
(2)
where Cp and Cf (mg mL−1) denotes the concentrations of the
product and fructose after the reaction; Np, Nf, and NG represent the
numbers of C in the product, fructose, and glucose (substrate); Gi and
Gf (mg mL−1) are the concentrations of the glucose at the initial and
final stage; Mp, Mf, and MG refer to the molecular weights of the
product, fructose, and glucose; and Vol refers to the volume of the
reaction mixture, i.e., 10 mL, respectively.

■ RESULTS AND DISCUSSION

Thermogravimetric Analysis. Different stages of thermal
decomposition of SnCl4-treated WW can be described by its
TGA curve (Figure 1a), which could illustrate the thermal-
induced changes during Sn-BC synthesis. The mass decay at
<100 °C was attributed to free-water evaporation, followed by
a stable stage with marginal mass change at 100−200 °C. The
most significant mass loss took place at 200−400 °C according
to the differential thermogravimetry (DTG) curve, which
could be explained by the devolatilization of biomass and
emission of small gaseous molecules.39 A smaller mass decay at
400−1000 °C was observed, in which char formation, phase
transition (i.e., depolymerization and atomic rearrangement),
and ashing could have taken place.39 The pyrolyzed products
(i.e., Sn-BCs) exhibited distinctive profiles of mass changes as a
function of temperature (Figure 1b). The weight loss of Sn-
BCs in general was less significant at 100−650 °C than that at
>650 °C, because most of the thermally susceptible
components were lost during the synthesis of Sn-BCs. For
Sn-BCs produced under N2, approximately 74−82 wt %
residues remained at 1000 °C, which may comprise graphitic
carbon and noncombustible metal salts. Increasing pyrolysis
temperature would result in more solid residues of biochars in
C DOI: 10.1021/acssuschemeng.8b05311
Figure 1. TG, DTG, and DTA curves of SnCl4-treated WW (a) and
TG and DTG patterns of Sn-BCs (b,c).
the TGA analysis. The Sn-BC pyrolyzed in CO2 (i.e., Sn-
B750C) gave the least residue at 1000 °C among the samples
(67 wt %), suggesting the presence of more thermally unstable
moieties in the biochar.
Physicochemical Property of Sn-BCs. The SEM images
show that the ordered and vascular structure of raw WW
(Figure 2a,b) collapsed after the SnCl4 treatment before
pyrolysis, producing particles ≤50 μm (Figure 2c,d). This
finding is contradictory to our recent study on Al-impregnated
biochars, which reported smaller changes in the vascular
structures (i.e., particle >100 μm) even after pyrolysis at 500−
700 °C.28 Such comparison suggests that the selection of metal
precursor plays a more important role than the pyrolysis
temperature in causing the collapse of biomass structure. As
the hydrolysis constant of Sn4+ (pK1 = −1.6) is much higher
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering Research Article

Figure 2. SEM-EDX results of WW at magnification of 1500 and 5000 (a,b), SnCl4-treated WW (c,d), Sn-B650N (e,f), Sn-B750N (g,h), Sn-
B850N (i,j), and Sn-B750C (k,l).

than that of Al3+ (pK1 = ∼5),40,41 more acidic environment can

be created when SnCl4 undergoes partial hydrolysis releasing
corrosive hydrogen chloride during the pretreatment. It has
been demonstrated that mineral acids (e.g., H2SO4 and
H3PO4) would partly disrupt the fibrous ridged structure of
wood-based materials, altering the surface porosity and
morphological feature.29,38 The EDX results validated the
successful impregnation of Sn element onto the surface of
SnCl4-treated WW (Figure 2d).
After pyrolysis in N2 at 650−850 °C, the presence of Sn was
observed in two major forms, i.e., the Sn species attached to
biomass structures (72−87% C and 1.7−14% Sn) as well as
the Sn-rich spherical particles (7.6−10% C and 83% Sn)
(Figure 2e−j). The abundance and size of the latter increased
with the increasing pyrolysis temperature (i.e., ≤ 5 μm at 650
°C, 5−8 μm at 750 °C, and up to 20 μm at 850 °C). It is
speculated that the progressive biomass devolatilization with
increasing temperature results in the partial loss of carbon Figure 3. XRD patterns of the synthesized Sn-BCs and SnCl4-treated
support and thereby the aggregation of Sn into spherical WW.
structures. There was a low oxygen content of 0−7.3 wt % in
Sn-B750N and Sn-B850N (Figure 2h,j) implying the presence
of metallic Sn, which was confirmed by the XRD patterns was disrupted at higher temperatures to give amorphous
(Figure 3). In contrast, a mixture of SnO2 and Sn crystals was structures that cannot be detected by XRD. The differential
formed in Sn-B650N. It has also been reported that solid− thermal analysis (DTA) of SnCl4-treated WW shows an
solid and solid−gas carbothermal reduction of SnO2 was endothermic peak starting from ∼500 °C where the mass
feasible at 700 °C or above in Ar environment:42 change was relatively minor (Figure 1a), suggesting the
possible occurrence of phase transition that involved bond-
SnO2 + C → Sn + CO2 ; SnO2 + 2C → Sn + 2CO breaking reactions without significant mass loss. A drop in the
(3) crystallinity of Si−Sn−C ternary alloy has been similarly
SnO2 + 2CO → Sn + 2CO2 observed as the heating temperature reached 700−800 °C
(4)
depending on the elemental proportion in a recent study.43
In the current study, the carbon from WW could have reduced Further investigations are needed to trace the thermal stability
the SnO2 that was formed at the initial stage of pyrolysis to its of SnO2 in the biochar matrix under the pyrolysis conditions.
metallic form, as the pyrolysis temperature increased to 750− The formation of Sn-rich components was also observed in
850 °C. Another possibility is that the crystalline order of SnO2 the CO2 biochar (i.e., Sn-B750C) according to the SEM-EDX
D DOI: 10.1021/acssuschemeng.8b05311
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
Table 1. Surface Properties of Synthesized Sn-BCs
base site density acid site density BET surfaces area
mmol g−1 mmol g−1 m2 g−1
Sn-B650N 0.300 0.615 375.1
Sn-B750N 0.365 0.465 438.6
Sn-B850N 0.550 0.685 360.3
Sn-B750C 0.715 0.700 614.8
Figure 4. Product yields (a) and fructose selectivity (b) in the conversion of glucose at 140−160 °C for 20 min over Sn-BC catalyst produced at
650, 750, and 850 °C under N2.
results (Figure 2k,l). However, their oxygen content (27.6 wt
%) was significantly higher than that of Sn-B750N (0−11 wt
%). The XRD results confirmed a higher proportion of SnO2 to
metallic Sn in Sn-B750C (Figure 3). The presence of CO2 may
have suppressed the reduction of SnO2 to metallic Sn by
serving as an oxidizing agent in the O-containing environment,
although the enriched CO content in the syngas can serve as a
reductant (eq 4). These results highlight that by changing the
pyrolysis temperature and purge gas we can tune the form of
impregnated metal species, besides the porous structure of
biochar support. In the case of Sn-BCs, the formation of
metallic Sn was favored by high pyrolysis temperature and
suppressed by CO2 purging.
The acid−base properties of the Sn-BCs are shown in Table
1. Their total acid site density ranged from 0.465 to 0.7 mmol
g−1, which may be derived from the acidic surface functional
groups such as carboxyl and hydroxyl groups.12,29 The base
sites (0.3−0.715 mmol g−1) may be attributed to the alkaline
earth metals naturally present in WW. For the N2 biochars,
both acidity and basicity increased with the increase of
pyrolysis temperature. The CO2-pyrolyzed Sn-B750C had the
highest acid and base site density of 0.7 and 0.715 mmol g−1,
respectively, among the samples. When pyrolysis was
performed in CO2 at 750 °C, the Boudouard reaction (CO2
+ C(s) → 2CO; thermodynamically feasible at >710 °C) could
occur and intensify the thermal degradation of biomass.31 This
may increase the relative content of the naturally occurring
alkaline minerals.
According to the porosity analysis, the BET surface area
(SA) increased from 375 m2 g−1 for Sn-B650N to 439 m2 g−1
for Sn-B750N (Table 1). The external surface area and average
pore size also increased from 72 to 93 m2 g−1 and 2.67 to 2.82
nm, respectively, suggesting the more significant formation of
mesopores (2−50 nm) at 750 °C. The increase in pyrolysis
temperature is known to promote biomass decomposition and
improve porosity development.44 However, Sn-B850N showed
a decrease in BET SA to 360 m2 g−1 along with a decrease in
Research Article
t-plot micropore area t-plot external surface area pore volume average pore size
m2 g−1 m2 g−1 cm3 g−1 nm
303.0 72.1 0.047 2.67
346.1 92.5 0.062 2.82
285.7 74.6 0.054 3.10
451.9 163.0 0.107 2.55
the microporous area, indicating that biomass devolatilization
was excessive at 850 °C causing the collapse of micropores.39
Compared to Sn-B750N, Sn-B750C showed a higher BET SA
(615 m2 g−1) and larger pore volume (0.107 cm3 g−1), i.e.,
increases by 40.2% and 72.5%, respectively. The use of CO2
promoted the formation of both micropores (452 m2 g−1) and
meso/macro-pores (163 m2 g−1), which may enhance the site
accessibility of biochar-based catalysts.
Effect of Pyrolysis Temperature on the Catalytic
Performance of Sn-BCs. The synthesized Sn-BCs were
examined as the solid catalyst in glucose conversion. The
fructose yield generally increased with the increasing pyrolysis
temperature as well as the catalytic reaction temperature
(Figure 4a). For instance, the fructose yield for Sn-750N at
160 °C was approximately three times higher than that at 140
°C, while Sn-B850N gave fructose of 10.6−12.1 Cmol % at
150−160 °C which was notably higher than 5.4 Cmol % at 140
°C (20 min). However, a small amount of secondary products
such as LA, FA, and FF was also produced over Sn-B750N and
Sn-B850N at 150 and 160 °C, suggesting the promotion of
side reactions (e.g., rehydration) by high reaction temper-
atures. Changing the catalysts and reaction temperature
exerted marginal impact on the fructose selectivity (Figure 4b).
The product profiles of glucose conversion over Sn-B650/
750/850N for 60 min are illustrated in Figure 5. The three
kinetic patterns were similar, where fructose was produced at
the expense of glucose during the first 10 min of reaction, and
the fructose yield reached an equilibrium at ∼20 min.
However, the decrease of glucose content during the initial
stage of reaction was the steepest for Sn-B850N, followed by
Sn-B750N, and then Sn-B650N. This observation reinforces
the increasing catalytic activity of Sn-BCs with the pyrolysis
temperature. The carbon balance in the catalytic systems (160
°C, 20 min) followed the descending order: Sn-B650N (81.3
Cmol %) > Sn-B750N (59 Cmol %) > Sn-B850N (45.3 Cmol
%), suggesting that Sn-BCs with a higher catalytic activity also
promoted side reactions generating undetected byproducts.
E DOI: 10.1021/acssuschemeng.8b05311
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering Research Article

BCs. Therefore, we uphold the speculation that the content of

amorphous Sn species increased at higher pyrolysis temper-
atures, which were probably conducive to the improved
glucose conversion (Figures 4 and 5). This speculation is in
good agreement with the latest study on glucose conversion
using Sn-based composite catalysts that comprised amorphous
components.46 As for the metallic Sn existing in the effective
Sn-B750N and Sn-B850N, further investigation would be
needed to evaluate its catalytic activity for glucose isomer-
ization, which has not been reported in the literature. It is
plausible that Sn as an elemental metal is more reactive than its
oxide forms and partially leaches as soluble Sn2+ (with a
stronger Lewis acidity than Sn4+) and Sn4+ to the liquid phase
via the reactions: Sn + SnCl4 → 2SnCl2, 6Sn2+ + O2 + 4HCl →
2SnCl4 + 4Sn(OH)Cl,47 facilitating glucose conversion in the
reaction medium.
The investigation of glucose isomerization over Sn-modified
biochar catalysts is reported for the first time in this work. The
fructose yield of 12.1−15.2 Cmol % obtained over Sn-B850N
or Sn-B750C (150 °C, 20 min) is comparable with that of
morpholine as a homogeneous base catalyst (∼17%
fructose),48 although it is lower than that of triethylamine
and a few costly solid catalysts such as zeolite- and
hydrotalcite-based catalysts (∼30%).1,16,49 Using biomass
waste as a low-cost feedstock via fast and simple preparation
process makes the biochar-based catalyst a sustainable
alternative to the traditional heterogeneous catalysts. This
study articulates the linkages among the pyrolysis conditions,
physicochemical properties, and catalytic performance, provid-
ing new insights for the future development of high-
performance biochar-based catalysts.
Effect of Pyrolysis Atmosphere on the Catalytic
Performance of Sn-BCs. Figure 6 illustrates the product

Figure 5. Product yields in the conversion of glucose at 160 °C as a

function of reaction time over Sn-BC catalyst produced at 650, 750,
and 850 °C under N2.

The catalytic performance of the N2-pyrolyzed Sn-BCs may

be associated with their average pore size in the descending
order: Sn-B850N > Sn-B750N > Sn-B650N (Table 1). A larger
pore size could have promoted the diffusion of glucose and
products for enhancing the glucose conversion.28 Yet there is
no clear trend of fructose yield as a function of SA (Table 1),
suggesting SA as an insignificant factor in the current study.
The chemical properties may also contribute to the catalytic
performance, because the least active Sn-B650N contains a Figure 6. Product yields and fructose selectivity in the conversion of
mixture of SnO2 and metallic Sn, in contrast to Sn-B750N and glucose at 140−160 °C for 20 min over Sn-BC catalyst produced at
Sn-B850N where metallic Sn and/or amorphous Sn species are 750 °C under N2 and CO2.
abundant (Figure 3). These results highlight the unfavorable
presence of SnO2, which corroborates our recent findings that
SnO2 in conventional and green solvents was inactive toward yields and fructose selectivity over the Sn-BC catalysts
catalytic glucose isomerization.45 produced at 750 °C in N2 and CO2 environment. It is
As the pyrolysis temperature increased, SnO2 may have been interesting to note that Sn-B750C presented better catalytic
reduced to metallic Sn by carbothermal reduction and/or performance in terms of the fructose yield of 14.7−15.2 Cmol
transformed into amorphous structures that were undetectable % compared to its N2-pyrolyzed counterpart (i.e., 3.1−10.8
in the XRD analysis (Section 3.2). It has been suggested that Cmol % for Sn-B750N) at the studied temperatures (140−160
Al-impregnated biochars contained Lewis acidity in amorphous °C, 20 min), suggesting that CO2 atmosphere facilitates the
structures, which gave a higher fructose yield of 21.5 Cmol % production of active Sn-BCs. However, Sn-B750C is
compared to the Sn-BCs in this study.28 This points to the dominated by SnO2 according to the XRD pattern, in contrast
importance of the crystallinity to the catalytic activity of Sn- to Sn-B750N that possesses metallic Sn as the major species
F DOI: 10.1021/acssuschemeng.8b05311
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
(Figure 3). This comparison suggests that the elemental Sn
crystals may be the secondary contributor to a high catalytic
activity. It should be noted that Sn-B750C is more amorphous
than Sn-B750N in view of the peak broadening in the XRD
pattern of the former, probably because more aggressive
biomass degradation by the Boudouard reaction in CO2
environment reduces the crystallinity of Sn structures. This
further substantiates our postulation that the amorphous Sn
species can play a more important role than the crystalline
fraction in the catalytic glucose isomerization (Section 3.3.1).
The enrichment of both micropores and meso/macro-pores
of Sn-B750C in comparison to Sn-B750N (Table 1) could be
favorable for the improved accessibility of active Sn sites on the
biochar-based catalyst. It is known that the micropore imparts
stronger adsorption potential,50 while the meso/macro-pores
promote faster molecular diffusion of adsorbate and products.
The well-established hierarchical porous surface can enhance
the contact between the solid catalyst and dissolved reactants,
and hence potentially improve the electron transfer between
the entities.51 Moreover, it is noteworthy that fructose
selectivity of Sn-B750C was two times higher than that of
Sn-B750N (140 °C, 20 min) (Figure 6). The improved mass
transfer may have mitigated the retention of sugar products at
the active sites of Sn-BC, which helps to suppress the side
reactions due to excessive catalytic activity.
The finding that Sn-B750C has the base site density two-fold
higher than that of Sn-B750N appears as another possible
reason for the better performance of the former (Table 1). In
particular, the base site density of Sn-B750C (0.715 mmol g−1)
is comparable to that of the effective base catalysts reported in
the literature,52 suggesting that the Brønsted base-driven
pathway of glucose-fructose isomerization may also be feasible
over Sn-B750C. Therefore, the synergy between Lewis acid
sites and Brønsted base sites as well as the favorable site
accessibility renders Sn-B750C the most active among the
prepared biochar samples. A small amount of HMF (<5 Cmol
%) was detected in the case of Sn-B750C in the experiments at
150 and 160 °C, which may be ascribed to the presence of
Brønsted acids (e.g., carboxylic acid) as represented by the
measured acid site density of 0.7 mmol g−1 (Table 1).
Brønsted acids are essential catalysts for the thermodynami-
cally favorable production of HMF via the dehydration of
fructose (or glucose though less thermodynamically favorable).
These findings emphasize that the tunable physicochemical
properties of biochar-based catalysts can enable a wide
spectrum of catalytic applications in sustainable biorefineries.
Reusability of Sn-Functionalized Biochar. The reus-
ability of Sn-750N and Sn-750C was examined under the
reaction condition of 160 °C for 20 min. The yield of fructose
over the reused Sn-B750N (RSn-B750N) notably decreased to
∼35% of that of pristine biochar catalyst yet it subsequently
remained stable over the second and third cycle (Figure 7).
The fructose selectivity slightly decreased from 22% to 19−
20% on Sn-B750N while it gradually decreased from 29% to
25% and then 20−21% on Sn-B750C over the three cycles.
The ICP results showed that the doped Sn content decreased
by 20.2% in Sn-B750N and 15% in Sn-B750C after the first run
of experiment (Figure S1 of the Supporting Information, SI).
Such loss of Sn was possibly the major reason for the lowered
catalytic performance, corroborating recent findings.29 How-
ever, leaching was less significant in the second and third
cycles, which accounted for the marginal decrease in their
fructose yields. The loosely bound active Sn may leach during
G DOI: 10.1021/acssuschemeng.8b05311
Research Article
Figure 7. Product yields and fructose selectivity in the reusability test
of Sn-B750N and Sn-B750C at 160 °C for 20 min.
the first run under the hydrothermal condition, leaving the
more stable yet less active species in the recovered catalyst.
According to the TG-DTG analysis (Figure 8a,b), at above
600 °C, the DTG peak of reused biochar catalysts showed a
rightward shift relative to that of the pristine catalysts. This
confirmed the decrease of Sn content after reaction, on the
basis of the knowledge that a high level of metal in
carbonaceous material could promote its decomposition.50 In
addition, the XRD patterns (Figure 8c,d) show the emergence
of SnO2 and progressive disappearance of metallic Sn upon
recycling. This may suggest the release of free Sn4+ from
metallic Sn and the irreversible transformation of Sn to SnO2
(Sn + 2Cl− → SnCl2, 2SnCl2 + O2 → SnO2(s) + SnCl4).47
Some of the metallic Sn-rich particles may also have been lost
by physical disintegration during the recycling process. The
transformation and retention of Sn species in the biochar
catalysts needs further examination to verify the active species
and catalytic mechanisms.
The surface of Sn-BCs (Figure 2h,l) became rough due to
possible solid deposition after recycling experiments (Figure
S2b,d). The BET results show that the type H3 hysteresis loop
in pristine Sn-B750N and Sn-B750C disappeared after three
cycles of experiments, which is indicative of the blockage of
mesopores (Figure S3). The BET SA notably decreased by up
to two orders of magnitude, and the average pore size
increased by two to four times. The TG-DTG analysis (Figure
8a,b) suggested the presence of thermally unstable structures
in the recycled catalysts, which were degraded at the
temperature range of 120 to 480 °C. These structures may
have a low crystallinity, as broad peaks emerged in their XRD
patterns (Figure 8c,d). Such newly formed structures may be
assigned to humins deposited on the surface of Sn-BCs, which
could block the active sites, or to biochar fractions loosened
under hydrothermal conditions. This should be verified with
the use of isotopes in future studies.
Nevertheless, marginal decline in the fructose yield and
selectivity was observed in the second and third cycle
experiments, suggesting that the recycled catalysts were in a
stable state possibly due to the steady Sn content (Figure S1).
As the catalytic activity decreased, further formation of
precipitates and humins was reduced in the second and third
run, and thus their impacts on the catalytic performance
remained steady. After three cycles of reaction, there were
>70% Sn retained in the catalyst. Therefore, activating the
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering Research Article

Figure 8. Thermogravimetric analysis (a,b) and XRD pattern (c,d) of Sn-B750N and Sn-B750C and their reused samples, i.e., RSn-B750N and
RSn-B750C, respectively, after three cycles of reaction.

spent Sn and removing the humins deposit would be vital for

regeneration of Sn-functionalized biochar catalyst.
■
*
ASSOCIATED CONTENT
S Supporting Information

■ CONCLUSIONS
We proposed to valorize wood waste through a fast and simple
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b05311.
preparation process to produce a new biochar-based catalyst as The Sn content in pristine and reused catalysts; SEM
a low-cost and sustainable alternative to the traditional images of reused catalysts; and N2 isotherms of pristine
heterogeneous catalysts in biorefinery. We fabricated different and reused catalysts (PDF)

■
types of Sn-BCs under hypothesis-driven design of pyrolytic
temperatures and N2/CO2 atmosphere to elucidate the AUTHOR INFORMATION
linkages among the pyrolysis conditions, physicochemical
properties, and catalytic performance. In an N2 environment, Corresponding Authors
increasing the pyrolysis temperature resulted in the formation *E-mail: dan.tsang@polyu.edu.hk (D.C.W.T.).
of more reactive metallic Sn phase and increased the fraction of * E-mail: yongsikok@korea.ac.kr (Y.S.O.).
amorphous Sn structures, which were found to be conducive to ORCID
higher catalytic activity for the isomerization of glucose to Daniel C. W. Tsang: 0000-0002-6850-733X
fructose. Compared to N2 biochars, the use of CO2 created Jin Shang: 0000-0001-5165-0466
larger porosity, enriched surface reactivity, and mediated Alex C. K. Yip: 0000-0003-4042-7589
structure crystallinity, which further improved the catalytic Yong Sik Ok: 0000-0003-3401-0912
activity of Sn-BCs. Sn-750C gave the highest yield (15.2 Cmol Notes
%) and selectivity (29 Cmol %) of fructose at 160 °C in 20 The authors declare no competing financial interest.

■
min. Both Lewis acid and Brønsted base were present in Sn-
BCs to simultaneously catalyze glucose conversion. The ACKNOWLEDGMENTS
reusability test revealed that active site leaching and potential This work was supported by the Hong Kong Research Grants
pore clogging by humins and Sn precipitates compromised the Council (PolyU 15217818) and Hong Kong Environment and
catalytic function of Sn-BCs but the performance remained Conservation Fund (K-ZB78, 2016).

stable in the second and third cycle. This study devises Sn-BCs
for catalytic glucose isomerization for the first time, and more
importantly, provides new fundamental insights for fostering
the tunable design of engineered biochar as sustainable
catalysts in emerging applications for circular bioeconomy.
■
REFERENCES
(1) Moliner, M.; Román-Leshkov, Y.; Davis, M. E. Tin-containing
zeolites are highly active catalysts for the isomerization of glucose in
water. Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 6164−6168.

H DOI: 10.1021/acssuschemeng.8b05311
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
(2) Román-Leshkov, Y.; Moliner, M.; Labinger, J. A.; Davis, M. E.
Mechanism of glucose isomerization using a solid lewis acid catalyst in
water. Angew. Chem. 2010, 122, 9138−9141.
(3) Pagan-Torres, Y. J.; Wang, T.; Gallo, J. M. R.; Shanks, B. H.;
Dumesic, J. A. Production of 5-hydroxymethylfurfural from glucose
using a combination of lewis and brønsted acid catalysts in water in a
biphasic reactor with an alkylphenol solvent. ACS Catal. 2012, 2,
930−934.
(4) Nikolla, E.; Román-Leshkov, Y.; Moliner, M.; Davis, M. E. One-
Pot” synthesis of 5-(hydroxymethyl)furfural from carbohydrates using
tin-beta zeolite. ACS Catal. 2011, 1, 408−410.
(5) Fachri, B. A.; Abdilla, R. M.; Bovenkamp, H. H. V. D.;
Rasrendra, C. B.; Heeres, H. J. Experimental and kinetic modeling
studies on the sulfuric acid catalyzed conversion of D-fructose to 5-
hydroxymethylfurfural and levulinic acid in water. ACS Sustainable
Chem. Eng. 2015, 3, 3024−3034.
(6) Yu, I. K. M.; Tsang, D. C. W.; Yip, A. C. K.; Chen, S. S.; Ok, Y.
S.; Poon, C. S. Valorization of food waste into hydroxymethylfurfural:
dual role of metal ions in successive conversion steps. Bioresour.
Technol. 2016, 219, 338−347.
(7) Chen, S. S.; Yu, I. K. M.; Tsang, D. C. W.; Yip, A. C. K.; Khan,
E.; Wang, L.; Ok, Y. S.; Poon, C. S. Valorization of cellulosic food
waste into levulinic acid catalyzed by heterogeneous brønsted acids :
temperature and solvent effects. Chem. Eng. J. 2017, 327, 328−335.
(8) Román-Leshkov, Y.; Chheda, J. N.; Dumesic, J. A. Phase
modifiers promote efficient production of hydroxymethylfurfural from
fructose. Science 2006, 312, 1933−1937.
(9) Roman-Leshkov, Y.; Barrett, C. J.; Liu, Z. Y.; Dumesic, J. A.
Production of dimethylfuran for liquid fuels from biomass-derived
carbohydrates. Nature 2007, 447, 982−985.
(10) De Lasa, H.; Salaices, E.; Mazumder, J.; Lucky, R. Catalytic
steam gasification of biomass: catalysts, thermodynamics and kinetics.
Chem. Rev. 2011, 111, 5404−5433.
(11) Chen, S. S.; Maneerung, T.; Tsang, D. C. W.; Ok, Y. S.; Wang,
C. H. Valorization of biomass to hydroxymethylfurfural, levulinic acid,
and fatty acid methyl ester by heterogeneous catalysts. Chem. Eng. J.
2017, 328, 246−273.
(12) Xiong, X.; Yu, I. K. M.; Cao, L.; Tsang, D. C. W.; Zhang, S.;
Ok, Y. S. A review of biochar-based catalysts for chemical synthesis,
biofuel production, and pollution control. Bioresour. Technol. 2017,
246, 254−270.
(13) Ji, H.; Dong, C.; Yang, G.; Pang, Z. Valorization of
lignocellulosic biomass towards multi-purpose fractionation: furfural,
phenolic compounds and ethanol. ACS Sustainable Chem. Eng. 2018,
6, 15306−15315.
(14) Tewari, Y. B. Thermodynamics of industrially-important,
enzyme-catalyzed reactions. Appl. Biochem. Biotechnol. 1990, 23,
187−203.
(15) Bhosale, S. H.; Rao, M. B.; Deshpande, V. V. Molecular and
industrial aspects of glucose isomerase. Microbiol Rev. 1996, 60, 280−
300.
(16) Carraher, J. M.; Fleitman, C. N.; Tessonnier, J. P. Kinetic and
mechanistic study of glucose isomerization using homogeneous
organic Brønsted base catalysts in water. ACS Catal. 2015, 5,
3162−3173.
(17) Yu, I. K. M.; Tsang, D. C. W.; Su, Z.; Yip, A. C. K.; Shang, J.;
Ok, Y. S.; Kim, K. H.; Poon, C. S. Contrasting roles of maleic acid in
controlling kinetics and selectivity of Sn(IV)- and Cr(III)-catalyzed
hydroxymethylfurfural (HMF) synthesis. ACS Sustainable Chem. Eng.
2018, 6, 14264−14274.
(18) Sun, Z.; Cheng, M.; Li, H.; Shi, T.; Yuan, M.; Wang, X.; Jiang,
Z. One-pot depolymerization of cellulose into glucose and levulinic
acid by heteropolyacid ionic liquid catalysis. RSC Adv. 2012, 2, 9058−
9065.
(19) Peng, L.; Lin, L.; Zhang, J.; Zhuang, J.; Zhang, B.; Gong, Y.
Catalytic conversion of cellulose to levulinic acid by metal chlorides.
Molecules 2010, 15, 5258−5272.
(20) Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivos-
Suarez, A. I.; Sepúlveda-Escribano, A.; Vimont, A.; Clet, G.; Bazin, P.;
I DOI: 10.1021/acssuschemeng.8b05311
Research Article
Kapteijn, F.; et al. Metal-organic and covalent organic frameworks as
single-site catalysts. Chem. Soc. Rev. 2017, 46, 3134−3184.
(21) Guo, Q.; Ren, L.; Kumar, P.; Cybulskis, V. J.; Mkhoyan, K. A.;
Davis, M. E.; Tsapatsis, M. A chromium hydroxide/MIL-101(Cr)
MOF composite catalyst and its use for the selective isomerization of
glucose to fructose. Angew. Chem. 2018, 130, 5020−5024.
(22) Li, X.; Peng, K.; Liu, X.; Xia, Q.; Wang, Y. Comprehensive
understanding of the role of Brønsted and Lewis acid sites in glucose
conversion into 5-hydroxymethylfurfural. ChemCatChem 2017, 9,
2739−2746.
(23) Uchimiya, M.; Chang, S.; Klasson, K. T. Screening biochars for
heavy metal retention in soil: role of oxygen functional groups. J.
Hazard. Mater. 2011, 190, 432−441.
(24) Zhou, Y.; Gao, B.; Zimmerman, A. R.; Chen, H.; Zhang, M.;
Cao, X. Biochar-supported zerovalent iron for removal of various
contaminants from aqueous solutions. Bioresour. Technol. 2014, 152,
538−542.
(25) Igalavithana, A. D.; Mandal, S.; Niazi, N. K.; Vithanage, M.;
Parikh, S. J.; Mukome, F. N. D.; Rizwan, M.; Oleszczuk, P.; Al-Wabel,
M.; Bolan, N.; et al. Advances and future directions of biochar
characterization methods and applications. Crit. Rev. Environ. Sci.
Technol. 2017, 47, 2275−2330.
(26) Lee, J.; Kim, K. H.; Kwon, E. E. Biochar as a catalyst. Renewable
Sustainable Energy Rev. 2017, 77, 70−79.
(27) Anis, S.; Zainal, Z. A. Tar reduction in biomass producer gas via
mechanical, catalytic and thermal methods: a review. Renewable
Sustainable Energy Rev. 2011, 15, 2355−2377.
(28) Yu, I. K. M.; Xiong, X.; Tsang, D. C. W.; Wang, L.; Hunt, A. J.;
Song, H. C.; Shang, J.; Ok, Y. S.; Poon, C. S. Aluminium-biochar
composites as sustainable heterogeneous catalysts for glucose
isomerisation in a biorefinery. Green Chem. 2019, DOI: 10.1039/
C8GC02466A.
(29) Cao, L.; Yu, I. K. M.; Chen, S. S.; Tsang, D. C. W.; Wang, L.;
Xiong, X.; Zhang, S.; Ok, Y. S.; Kwon, E. E.; Song, H.; Poon, C. S.
Production of 5-hydroxymethylfurfural from starch-rich food waste
catalyzed by sulfonated biochar. Bioresour. Technol. 2018, 252, 76−82.
(30) Yu, I. K. M.; Tsang, D. C. W.; Yip, A. C. K.; Chen, S. S.; Wang,
L.; Ok, Y. S.; Poon, C. S. Catalytic valorization of starch-rich food
waste into hydroxymethylfurfural (HMF): controlling relative kinetics
for high productivity. Bioresour. Technol. 2017, 237, 222−230.
(31) Lee, J.; Yang, X.; Cho, S. H.; Kim, J. K.; Lee, S. S.; Tsang, D. C.
W.; Ok, Y. S.; Kwon, E. E. Pyrolysis process of agricultural waste using
CO2 for waste management, energy recovery, and biochar fabrication.
Appl. Energy 2017, 185, 214−222.
(32) You, S.; Ok, Y. S.; Tsang, D. C. W.; Kwon, E. E.; Wang, C. H.
Towards practical application of gasification: a critical review from
syngas and biochar perspectives. Crit. Rev. Environ. Sci. Technol. 2018,
1.
(33) Salame, I. I.; Bandosz, T. J. Surface chemistry of activated
carbons: combining the results of temperature-programmed desorp-
tion, Boehm, and potentiometric titrations. J. Colloid Interface Sci.
2001, 240, 252−258.
(34) Goertzen, S. L.; Thériault, K. D.; Oickle, A. M.; Tarasuk, A. C.;
Andreas, H. A. Standardization of the Boehm titration. Part I. CO2
expulsion and endpoint determination. Carbon 2010, 48, 1252−1261.
(35) Method 3051A: Microwave Assisted Acid Digestion of Sediments,
Sludges, Soils, and Oils; U.S. Environmental Protection Agency, U.S.
Government Printing Office: Washington, DC, 1998.
(36) Möller, M.; Harnisch, F.; Schröder, U. Microwave-assisted
hydrothermal degradation of fructose and glucose in subcritical water.
Biomass Bioenergy 2012, 39, 389−398.
(37) Yu, I. K. M.; Tsang, D. C. W. Conversion of biomass to
hydroxymethylfurfural: a review of catalytic systems and underlying
mechanisms. Bioresour. Technol. 2017, 238, 716−732.
(38) Xiong, X.; Yu, I. K. M.; Chen, S. S.; Tsang, D. C. W.; Cao, L.;
Song, H.; Kwon, E. E.; Ok, Y. S.; Zhang, S.; Poon, C. S. Sulfonated
biochar as acid catalyst for sugar hydrolysis and dehydration. Catal.
Today 2018, 314, 52−61.
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering Research Article

(39) Yang, X.; Kwon, E. E.; Dou, X.; Zhang, M.; Kim, K.-H.; Tsang,
D. C. W.; Ok, Y. S. Fabrication of spherical biochar by a two-step
thermal process from waste potato peel. Sci. Total Environ. 2018, 626,
478−485.
(40) Brown, P. L.; Sylva, R. N.; Ellis, J. An equation for predicting
the formation constants of hydroxo-metal complexes. J. Chem. Soc.,
Dalton Trans. 1985, 4, 723−730.
(41) Yu, I. K. M.; Tsang, D. C. W.; Yip, A. C. K.; Chen, S. S.; Ok, Y.
S.; Poon, C. S. Valorization of starchy, cellulosic, and sugary food
waste into hydroxymethylfurfural by one-pot catalysis. Chemosphere
2017, 184, 1099−1107.
(42) Levêque, G.; Abanades, S. Thermodynamic and kinetic study of
the carbothermal reduction of SnO2 for solar thermochemical fuel
generation. Energy Fuels 2014, 28, 1396−1405.
(43) Yano, S.; Yamaha, T.; Shimura, Y.; Takeuchi, W.; Sakashita, M.;
Kurosawa, M.; Nakatsuka, O.; Zaima, S. Solid-phase crystallization of
Si1‑x‑ySnxCy ternary alloy layers and characterization of their crystalline
and optical properties. Jpn. J. Appl. Phys. 2017, 56, 01AB02.
(44) Ahmad, M.; Ok, Y. S.; Kim, B. Y.; Ahn, J. H.; Lee, Y. H.; Zhang,
M.; Moon, D. H.; Al-Wabel, M. I.; Lee, S. S. Impact of soybean
stover- and pine needle-derived biochars on Pb and As mobility,
microbial community, and carbon stability in a contaminated
agricultural soil. J. Environ. Manage. 2016, 166, 131−139.
(45) Yu, I. K. M.; Tsang, D. C. W.; Yip, A. C. K.; Hunt, A. J.;
Sherwood, J.; Shang, J.; Song, H.; Ok, Y. S.; Poon, C. S. Propylene
carbonate and γ-valerolactone as green solvents enhance Sn(IV)-
catalysed hydroxymethylfurfural (HMF) production from bread
waste. Green Chem. 2018, 20, 2064−2074.
(46) Li, K.; Du, M.; Ji, P. Multifunctional tin-based heterogeneous
catalyst for catalytic conversion of glucose to 5-hydroxymethylfurfural.
ACS Sustainable Chem. Eng. 2018, 6, 5636−5644.
(47) Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements, 2nd
ed.; Butterworth-Heinemann, 1997.
(48) Liu, C.; Carraher, J. M.; Swedberg, J. L.; Herndon, C. R.;
Fleitman, C. N.; Tessonnier, J.-P. Selective base-catalyzed isomer-
ization of glucose to fructose. ACS Catal. 2014, 4, 4295−4298.
(49) Lee, G.; Kang, J. Y.; Yan, N.; Suh, Y. W.; Jung, J. C. Simple
preparation method for Mg-Al hydrotalcites as base catalysts. J. Mol.
Catal. A: Chem. 2016, 423, 347−355.
(50) Yang, X.; Jin, D.; Zhang, M.; Wu, P.; Jin, H.; Li, J.; Wang, X.;
Ge, H.; Wang, Z.; Lou, H. Fabrication and application of magnetic
starch-based activated hierarchical porous carbon spheres for the
efficient removal of dyes from water. Mater. Chem. Phys. 2016, 174,
179−186.
(51) Igalavithana, A. D.; Yang, X.; Zahra, H. R.; Tack, F. M. G.;
Tsang, D. C. W.; Kwon, E. E.; Ok, Y. S. Metal(loid) immobilization in
soils with biochars pyrolyzed in N2 and CO2 environments. Sci. Total
Environ. 2018, 630, 1103−1114.
(52) Chen, S. S.; Yu, I. K. M.; Cho, D. W.; Song, H.; Tsang, D. C.
W.; Tessonnier, J. P.; Ok, Y. S.; Poon, C. S. Selective glucose
isomerization to fructose via nitrogen-doped solid base catalyst
derived from spent coffee grounds. ACS Sustainable Chem. Eng. 2018,
6, 16113−16120.

J DOI: 10.1021/acssuschemeng.8b05311
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX