Chinese Journal of Chemical Engineering 28 (2020) 2084–2091

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Chinese Journal of Chemical Engineering

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Article

Systematic study of H2 production from catalytic photoreforming of

cellulose over Pt catalysts supported on TiO2
Lan Lan 1, Yan Shao 1,2, Yilai Jiao 3, Rongxin Zhang 1, Christopher Hardacre 1,⁎, Xiaolei Fan 1,⁎
1
Department of Chemical Engineering and Analytical Science, School of Engineering, The University of Manchester, M13 9PL, United Kingdom
2
School of Chemical and Environmental Engineering, Wuyi University, Jiangmen 52920, China
3
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

a r t i c l e i n f o a b s t r a c t

Article history: Hydrogen (H2) production from photocatalytic reforming of cellulose is a promising way for sustainable H2 to be
Received 1 February 2020 generated. Herein, we report a systematic study of the photocatalytic reforming of cellulose over Pt/m-TiO2 (i.e.
Received in revised form 19 March 2020 mixed TiO2, 80% of anatase and 20% of rutile) catalysts in water. The optimum operation condition was
Accepted 30 March 2020
established by studying the effect of Pt loading, catalyst concentration, cellulose concentration and reaction tem-
Available online 1 May 2020
perature on the gas production rate of H2 (rH 2) and CO2 (rCO 2), suggesting an optimum operation condition at 40
Keywords:
°C with 1.0 g·L−1 of cellulose and 0.75 g·L−1 of 0.16-Pt/m-TiO2 catalyst (with 0.16 wt% Pt loadting) to achieve a
Hydrogen (H2) production relatively sound photocatalytic performance with rH2 = 9.95 μmol·h−1. It is also shown that although the
Catalytic photoreforming photoreforming of cellulose was operated at a relatively mild condition (i.e. with an UV-A lamp irradiation at
Cellulose 40 °C in the aqueous system), a low loading of Pt at ~0.16 wt% on m-TiO2 could promote the H2 production effec-
Kinetics tively. Additionally, by comparing the reaction order expressed from both rH 2 (a1) and rCO 2 (a2) with respect to
Titanium dioxide (TiO2) cellulose and water, the possible mechanism of H2 production was proposed.
© 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd.
All rights reserved.

1. Introduction Lignocellulose is mainly comprised of three polymers which are

Lignocellulosic biomass has been regarded as the most abundant
biomass on Earth, with great potential to be converted into valuable
chemicals, such as glucose [1,2], sorbitol [3,4], lactic acid [5] and various
fuels such as methane [6,7], syngas (mixture of carbon monoxide, CO
and hydrogen, H2) [8,9] and H2 [6,9]. Hydrogen is an effective energy
carrier with a high heat value of ~ 140 kJ·g−1 in comparison with
conventional fossil fuels such as crude oil (~ 44 kJ·g−1) and natural
gas (~ 39 kJ·g−1) [10], as well as being a clean energy without green-
house gas emission from H2 combustion. It is a promising alternative
to conventional fuels for the purpose of relieving the stress resulted
from the increasing concern in energy demand and environmental
impact [11,12]. H2 can be obtained from lignocellulosic biomass by
various conversion technologies such as gasification (at N750 °C) and
pyrolysis (at 450–650 °C) which are energy intensive [13,14], or by
thermocatalytic reforming which is associated with the problems of cat-
alyst deactivation and by-product (e.g. CO) production [15]. Conversely,
H2 production via the photocatalytic reforming of biomass-derived lig-
nocellulosic substrates in aqueous phase is a more sustainable route
than the others regarding the energy source (i.e. the solar light)
required for driving the conversion.
⁎ Corresponding authors.
E-mail addresses: c.hardacre@manchester.ac.uk (C. Hardacre),
xiaolei.fan@manchester.ac.uk (X. Fan).
cellulose (N40% in wood stems), hemicellulose (20%–40%) and lignin
(b35%) [16]. Cellulose, the major component of lignocellulose, is a
polysaccharide of anhydroglucose monomers. As it is difficult to hy-
drolyse cellulose, the valorisation of cellulose is regarded as rather
limited [17]. In 1980, Kawai and Sakata first discovered that plants-
derived substrates such as sugar and cellulose could produce H 2
under the irradiation generated by a Xe lamp. In the presence of
water and photocatalysts such as RuO2 /TiO 2 /Pt [18] and Pt/TiO2
[19], H2 was generated with relatively low production rates at b 50
μmol·h−1 ·g−1cat (as shown in Table S1). Accordingly, efforts have
been made to improve the H 2 production via photocatalytic
reforming of cellulose, and the relevant experimental conditions
and results of the studies are summarised in Table S1. The majority
of the studies has focused on improving the photocatalytic
performance by either developing new photocatalysts such as TiO2/
NiOx@Cg [20], TiO2–S–Ni [21], CdS/CdOx quantum dots (QDs) [16],
cellulose@Pt/TiO2 [22] and NCNCNx with H2PtCl6 [23] or improving
the solubility of cellulose by introducing SO2−
4 to facilitate the acid
catalysed hydrolysis of cellulose. This generates soluble glucose
which is beneficial to quench the photo-generated holes which
were used to oxidise water to producing hydroxyl radicals, and solu-
ble glucose hence offering protons by the attack of hydroxide radi-
cals [21,24]. Accordingly, the photocatalytic activity of cellulose
reforming was improved considerably with improved H2 production

https://doi.org/10.1016/j.cjche.2020.03.030
1004-9541/© 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
 L. Lan et al. / Chinese Journal of Chemical Engineering 28 (2020) 2084–2091
rates of N1000 μmol·h−1·g−1 cat (as shown in Table S1). However, only
a few studies were attempted to investigate the kinetics of the pho-
tocatalytic reforming of plants-derived substrates [25,26], specifi-
cally cellulose [27,28,29]. The effect of the irradiation time,
concentration of catalyst and cellulose, system pH and water salinity
on H2 generation has been investigated in the cellulose-water sus-
pension over Pt/TiO2 catalyst [27]. The H2 yield was improved with
an increase in the irradiation time, concentration of catalyst and cel-
lulose before reaching the plateau, while the water salinity showed
insignificant effect on the yield of H2. The findings from the system-
atic investigation [23,27,28] on the cellulose-based photocatalytic
system were beneficial to explore the optimum operating condition
of the system. Therefore, in addition to the exploration of the opti-
mum operation condition of the relevant cellulose photoreforming
systems (by adjusting the reaction conditions), studies on the mech-
anism is also needed to understand the possible pathways of H2 gen-
eration from the systems.
This current work presents an investigation into the photocata-
lytic reforming of cellulose using Pt/m-TiO2 (m-TiO2 with 80% ana-
tase and 20% rutile phases) catalysts under UV irradiation in water
solution. m-TiO2 was used as the support to make the relevant cata-
lysts under study comparable with the reported catalysts based on
P25 [24–27] [29], as shown in Table S1. A systematic study was per-
formed to study the effect of Pt loading, concentration of catalyst and
cellulose in the reaction system, and reaction temperature on the
photocatalytic performance, aimed at (i) establishing the relevant
optimum reaction condition for improving the H2 production from
the catalytic photocatalytic reforming of cellulose in aqueous system
and (ii) obtaining the mechanistic understanding of the system, spe-
cifically, analysing the reaction orders to identify the steps for H2
Production.
2. Experimental
2.1. Chemicals and materials
m-TiO2, i.e. TiO2 with the mixed phase of rutile and anatase, was pur-
chased from Aldrich® and used as the catalyst support. Chloroplatinic
acid hexahydrate (H2PtCl6·6H2O, Honeywell Fluka®) was used as the
metal precursor for catalyst preparation. Microcrystalline cellulose
(Aldrich®) with a density of 0.6 g·cm−3 was used in the photocatalytic
reaction as the biomass source. Deionised water was obtained from the
Direct-Q 3UV ultrapure water system (Millipore®).
2.2. Preparation of photocatalyst
Platinum catalysts supported on m-TiO2 (Pt/m-TiO2) were prepared
by wet impregnation. 2 g m-TiO2 support was dispersed in X ml
deionised water in a beaker and stirred for 10 min. Then Y ml (X + Y
= 20 ml, X and Y were varied during the preparation to adjust the Pt
loading on the catalysts) of the metal precursor solution (Cmp =
0.01 g·ml−1, H2PtCl6·6H2O dissolved in deionised water) was added
into the TiO2 slurry. The mixture was stirred at 60 °C for 4 h, and the
resulting catalyst was dried at 150 °C for 2 h and calcined in air at 500
°C for 2 h. Pt/m-TiO2 catalysts with different theoretical metal loadings,
ranging from 0.08 wt% to 1.5 wt%, were prepared, named as 0.08-Pt/m-
TiO2, 0.16-Pt/m-TiO2, 0.50-Pt/m-TiO2, 1.00-Pt/m-TiO2 and 1.50-Pt/m-
TiO2, respectively. Prior to the catalytic tests, all Pt/m-TiO2 catalysts
were reduced in pure H2 at 200 °C for 30 min.
2.3. Characterisation of materials
The structure of the catalysts and cellulose was characterised using
powder X-ray diffraction (PXRD), transmission electron microscopy
(TEM) and scanning electron microscopy (SEM). XRD patterns of mate-
rials were obtained by PANalytical X'Pert Pro X-ray diffractometer using
2085
CuKα emission lines from a generator operating at 40 keV and 40 mA.
XRD scans were performed at 2θ from 10° to 90° with a step size of
0.033°. Crystallite sizes (D, nm) of the anatase and rutile phases were
calculated using the Scherrer equation (Eq. 1). Anatase-rutile propor-
tions were determined by considering the relative diffraction inten-
sities of the (101) at 25.3° and (110) features at 27.4° corresponding
to the anatase and rutile phase, respectively. TEM micrographs were
obtained with an FEI Tecnai G2 F20 electron microscope operated at
200 kV. Before the measurements, catalyst samples were dispersed
in ethanol and sonicated for 10 min, then followed by drop-casting
and drying the particle suspension on a copper TEM grid. SEM micro-
graphs of materials were obtained by FEI Quanta 250 FEG microscope
operating at 15 kV.
kd λ
D¼ ð1Þ
β cosθ
where kd is the dimensionless shape factor (kd = 0.943); λ is the X-
ray wavelength (λ = 0.154 nm); β is the line broadening in radians
at half the maximum intensity of the diffraction peak at θ.
The optical property of the catalyst and cellulose were characterised
by UV–visible diffuse reflectance spectroscopy (UV–Vis DRS, Shimadzu
UV-2600) in the spectral range of 200–800 nm. N2 adsorption–desorp-
tion analysis was performed at − 196 °C using a Micromeritics 3Flex
Surface Characterisation Analyser to determine the specific surface
area of the catalysts (based on the Brunauer–Emmett–Teller (BET)
method) and the pore size distribution of the catalysts (using the
Barrett–Joyner–Halenda (BJH) method). Inductively coupled plasma
optical emission spectroscopy (ICP-OES, PlasmaQuant PQ 9000 Elite)
was performed to determine the actual Pt loading on the catalysts. Be-
fore ICP-OES analysis, the sample (25 mg) was mixed with 12 ml aqua
regia (9 ml HCl: 3 ml HNO3) and digested using an ETHOS EASY micro-
wave digester at 220 °C for 20 min.
Temperature-programmed reduction (TPR) analysis of the catalysts
(~20 mg for each analysis) was measured under the 5% H2/Ar flow at
40 cm3·min−1. Prior to TPR, the catalyst was pre-treated in pure oxygen
(at 40 cm3·min−1) at 300 °C for 1 h. TPR analysis started at the initial
temperature of −80 °C, under the 5% H2/Ar flow, and the temperature
was then increased from − 80 °C to 800 °C with a heating rate of 10
°C·min−1. The consumption of H2 was monitored by a thermal conduc-
tivity detector (TCD) in the QuantaChrom ChemBET Pulsar TPR/TPD
Analyser.
2.4. Photocatalytic reforming of cellulose over Pt/TiO2 catalysts
The experimental rig for the photocatalytic reforming of cellulose
was composed of a jacketed flat-bottomed borosilicate glass flask (as
shown in the Support Information, SI, Fig. S1). During the experiment,
a circulating bath was used to circulate the heat transfer fluid through
the jacket of the flask to maintain a constant reaction temperature at
40 °C, 60 °C or 80 °C, respectively. On the top of the reactor, there are
two vent holes which can be used to sample gaseous products from
the reaction. For a typical photocatalytic reforming reaction experiment,
75 mg catalyst and 100 ml distilled water were placed in the reactor,
together with 100 mg cellulose. The mixture was stirred for 30 min at
room temperature, and the reactant mixture was purged with argon
(Ar) thoroughly for 1.5 h to remove the dissolved oxygen from the
system. After Ar purging, the reactor was sealed and irradiated by a
UV-A lamp (365 nm, 2 × 8 W, Thistle Scientific®) for 5 h. The initial
and final gaseous products from the headspace of the reactor were sam-
pled and analysed by gas chromatography (Perkin Elmer Clarus 580 GC,
fitted with 2 m inline HayeSep DB 100/120 mesh columns followed by a
2 m ShinCarbon ST 100/120 mesh column equipped with the TCD and
FID detectors). The average production rate of gas phase (rM) is
defined as the mole amount of the gas (M) generated per hour
(μmol·h−1).
2086 L. Lan et al. / Chinese Journal of Chemical Engineering 28 (2020) 2084–2091

3. Results and Discussion were calculated using the PXRD results, as presented in Table 1. Varia-
tion of the crystalline size of the supports, as well as the proportion of
3.1. Characterisation of materials the anatase and rutile phase in the support, was measured after Pt im-
pregnation, i.e. anatase crystalline size in the support increased slightly
The nature of crystalline phases in Pt impregnated m-TiO2 was stud- and anatase/rutile ratio decreased. Considering the variation of anatase/
ied by PXRD as shown in Fig. S2. The diffractograms show that the pris- rutile phase ratio in the commercial P25 TiO2 (i.e. between 4:1 and 9:1),
tine m-TiO2 has the typical diffraction peaks corresponding to anatase the ratio of the catalysts after Pt impregnation (with an average value of
and rutile phases at 2θ = 25.5° and 27.5°, respectively, and the positions 4.6:1) was in the range.
of diffraction peaks remained the same after the Pt impregnation, as ex- N2 physisorption analysis was performed on the m-TiO2 support and
pected. The diffraction peaks associated with Pt species (metal or ox- the prepared catalysts (with the relevant adsorption–desorption iso-
ides) were not detected by XRD possibly due to the dispersion of Pt as therms shown in Fig. S3), and the relevant BET data are shown in
small nanoparticles of b5 nm. The crystallite size of TiO2 supports and Table 1. The m-TiO2 had a specific surface area of 99 m2·g−1 (as
the relative proportion of the anatase and rutile phases in the supports shown in Fig. S4). Pt impregnation resulted in the decrease in the BET
area of the support, possibly due to the partial occupation of Pt nanopar-
ticles in the porous network of the TiO2 support. The accurate Pt loading
Table 1
of the catalysts by ICP analysis was summarised in Table 1, showing the
Properties of m-TiO2 support and photocatalysts according to BET, XRD and ICP analyses
comparable values to the theoretical loadings.
Support Pt loading amount of catalysts/% The morphology of the catalysts was characterised by TEM, as shown
m-TiO2 0.08 0.16 0.50 1.00 1.50 in Fig. 1 and Fig. S5. Uniformly distributed Pt nanoparticles can be iden-
BET surface area/m2·g−1 99 55 42 53 53 58 tified for the catalysts with the relatively high loadings (i.e. N 1% shown
Anatase crystalline size/nm 16.5 19.6 20.2 19.5 18.8 18.7 in Fig. 1 c-d). For the catalysts with the Pt loading b1% (i.e. 0.16% and
Rutile crystalline size/nm 31.9 30.9 31.5 31.5 32.0 32.4 0.50% Pt catalysts supported on m-TiO2), Pt nanoparticles could not be
Anatase/rutile ratio 5.6:1 5.2:1 5.5:1 4.1:1 4.1:1 3.9:1 observed (shown in Fig. 1 a-b). The average Pt particle sizes for 1.00-
ICP Pt loading ratio/wt% 0 0.10 0.15 0.41 0.73 1.36
Pt/m-TiO2, 1.50-Pt/m-TiO2 are 1.7 nm and 1.8 nm, respectively.

Fig. 1. TEM images of (a) 0.16-Pt/m-TiO2, (b) 0.50-Pt/m-TiO2, (c) 1.00-Pt/m-TiO2 and (d) 1.50-Pt/m-TiO2.
 L. Lan et al. / Chinese Journal of Chemical Engineering 28 (2020) 2084–2091
The light absorption property of the support and catalysts was deter-
mined by diffuse reflectance UV–Vis spectroscopy. Fig. S6 shows the
absorbance spectra over the range between 200 and 800 nm for the
commercial m-TiO2 and Pt/m-TiO2 catalysts with different metal load-
ings. The rapid increase in the absorption at wavelengths lower than
380 nm can be assigned to the band gap absorption for m-TiO2 (band
gap energy: ~3.2 eV [30]). In the UV region (200–400 nm), Pt supported
on m-TiO2 catalysts with Pt loadings from 0.16% to 1.5% show similar
absorbance intensities which are higher than that of m-TiO2 support
and 0.08% Pt/m-TiO2. In the visible light region (400–800 nm), com-
pared with the m-TiO2 support, all the Pt/m-TiO2 catalysts show the
absorption (as shown in insets in Fig. S6). Generally, the absorption of
visible light by the catalysts increases with an increase in the Pt loading,
which can be attributed to the localised surface plasmon resonance
absorption of Pt nanoparticles [31,32]. The optical absorption ability of
cellulose was also investigated, as shown in Fig. S6. Generally, cellulose
has no capability of absorbing the visible light, while it shows the insig-
nificant absorption of UV light (b 250 nm), which can be disregarded
when compared with the UV light absorption of the catalysts. This result
indicates that the photochemical degradation of cellulose during the
catalytic photoreforming can be disregarded.
The structure of the microcrystalline cellulose used in this study was
characterised by PXRD and SEM (as shown in Fig. 2). PXRD pattern of
cellulose shows a profile with the typical peaks centred at 15.0°, 16.3°
and 22.5°, respectively, representing the cellulose I structure [28]. The
crystallinity index (CrI) of the microcrystalline cellulose used is about
80% according to Eq. 2
CrI ¼ ðI002 −I AM Þ=I002  100%
where I002 represents the maximum intensity of the (002) lattice dif-
fraction (2θ = 22.5°), and IAM represents the intensity of diffraction
for the amorphous phase at 2θ = 18°.
CrI is deemed as an important structural parameter regarding the
conversion of cellulose since a relatively low degree of crystallinity
may result in the relatively fast hydrolysis of cellulose, leading to a com-
paratively easy interaction between the catalyst and the hydrolysed
parts from cellulose [33]. Accordingly, in comparison with other natural
cellulose substrate, such as cotton cellulose fibre (CrI = 80%–100%), the
use of microcrystalline cellulose (with the CrI of 80%) in photoreforming
can be advantageous. SEM micrograph of microcrystalline cellulose is
shown in Fig. 2b, showing that the average particle size of the cellulose
is approximately 100 μm together with a fraction of smaller particles.
In order to investigate the reducibility of the TiO2 supports and Pt/
TiO2 catalysts, hydrogen temperature-programmed reduction (H2-
TPR) analysis was carried out (as shown in Fig. S7). A H2 consumption
peak at around 80 °C was identified in the H2-TPR profiles for all the
Fig. 2. Characterisation of microcrystalline cellulose: (a) XRD diffractogram and (b) SEM image of cellulose.
2087
catalysts, representing the reduction of PtOx crystallites to metallic Pt
[34,35].
3.2. Effects of Pt loading, catalyst concentration, cellulose concentration and
reaction temperature on photocatalytic performance
The effect of Pt loading in the catalysts on the production rate of H2
and CO2 was first investigated to compare the catalysts in the catalytic
photoreforming system (using cellulose as the substrate) for H2 gener-
ation. As shown in Fig. 3a, the average production rate of H2 and CO2 (i.e.
rH 2 and rCO 2) over 5 h UV irradiation is plotted as a function of the Pt
loading in the catalysts (H2 and CO2 were the main products measured
in the gas phase, the overall gas composition of the systems is presented
in Table S2). For the system using the m-TiO2 support, low rates of H2
were produced over 5 h reaction together with a small amount of CO2
(rH 2 = 0.17 μmol·h−1, rCO 2 = 1.65 μmol·h−1). Pt/m-TiO2 catalysts sig-
nificantly promoted the rate of production of H2 and CO2, as shown in
Fig. 3a, while the rH 2 and rCO 2 show the maxima as an increase of the
Pt loading. For Pt/m-TiO2 catalysts, the maximum rates were measured
as about 9.95 and 3.75 μmol·h−1, respectively, for H2 and CO2, over the
0.16-Pt/m-TiO2 catalyst. Pt species on TiO2 act as the electron traps [36],
promoting the separation of photo-generated electrons and holes, and
thus improving the photocatalytic activity in photoreforming reactions.
Accordingly, an increase in the Pt loading on TiO2 leads to the initial
increase in the activity of the system. However, larger loadings of Pt
on the surface of TiO2 may also hinder the light irradiation, reducing
the generation of electrons and holes in the catalyst support. Therefore,
for the Pt/m-TiO2 catalyst, there is a trade-off between the two effects
ð2Þ incurred by supporting Pt species, leading to the existence of an opti-
mum Pt loading on TiO2 supports. Different from the most studies in
which the highest rates were observed at Pt loadings higher than 0.5%
[27–29], the highest rates were observed at a Pt loading of only
0.16 wt% in this study. The performance of the 0.16-Pt/m-TiO2 catalyst
in the photoreforming of cellulose under UV irradiation, represented
by the normalised rH 2 (by the mass of catalyst) at 132.6 μmol·h−1·g−1 cat ,
was comparable with the reported state-of-the-art catalysts (shown
in Table S1) such as 0.50 wt% Pt/TiO2 (Hombikat TiO2, anatase/rutile
(a/r) ratio = 19:6, under the irradiation of UV light at room temperature
in water solution, 40 μmol·h−1·g−1 cat ) [29] and 0.50 wt% Pt/TiO2 (Evonik
P25 TiO2, a/r ratio = 41:9, under the irradiation of UV light in water so-
lution, 225 μmol·h−1·g−1 cat ) [27]. The operation conditions over the 0.16-
Pt/m-TiO2 catalyst and those two 0.50 wt% Pt/TiO2 catalysts are similar,
which are relatively mild compared with the conditions over other cat-
alysts (under the irradiation of Xe lamp in basic or acid solution at high
temperature (N60 °C), shown in Table S1). Therefore, the possible rea-
son behind the variation of the photocatalytic performance among
them could be the differences in TiO2 supports. The 0.16-Pt/m-TiO2
2088 L. Lan et al. / Chinese Journal of Chemical Engineering 28 (2020) 2084–2091

Fig. 3. Gas production rates as a function of (a) Pt loadings on m-TiO2 (conditions: 0.75 g·L−1 Pt/m-TiO2, 1 g·L−1 of cellulose, under the irradiation of 5 h UV-A lamp for 5 h at 40 °C),
(b) catalyst concentrations (conditions: 0.16-Pt/m-TiO2, 1 g·L−1 of cellulose, under the irradiation of UV-A lamp for 5 h at 40 °C), (c) cellulose concentrations (conditions: 0.75 g·L−1
0.16-Pt/m-TiO2, cellulose, under the irradiation of UV-A lamp for 5 h at 40 °C), and (d) reaction temperature (conditions: 0.16-Pt/m-TiO2, 1 g·L−1 of cellulose, under the irradiation of
UV-A lamp for 5 h at 40 °C, 60 °C and 80 °C).

catalyst was employed in the following studies to investigate the effect from the reaction between photogenerated electrons (e−) and H+ in
of other parameters (including the catalyst concentration, the concen- the system. For the cellulose photoreforming system under study, H+
tration of cellulose and reaction temperature) on the photocatalytic per- is produced by oxidation of water and oxidation of cellulose. CO2 is pro-
formance since it gave the comparatively best performance during the duced from the oxidation of cellulose by hydroxyl radical (·OH) which
initial activity tests. is produced by H+ induced water oxidation. Once ·OH radicals are gen-
The concentration of 0.16-Pt/m-TiO2 catalyst was varied over range erated on the surface of the catalysts, they diffuse to the surface of the
of 0 to 1.5 g·L−1 to study its effect on the photocatalytic activity of the cellulose and are consumed by the cellulose. The consumption of ·OH
system (Fig. 3b). For the system with cellulose only (i.e. catalysts radicals increase with increasing the concentration of cellulose, how-
concentration = 0 g·L−1), CO2 and H2 were not produced under UV ever, when ·OH radicals are consumed completely, excess cellulose
irradiation due to the insignificant UV absorption of cellulose (Fig. S6). results in no increase in the CO2 production, thus leading to the plateau
By increasing the catalyst concentration in the system, the rH 2 and rCO 2 of the rCO 2.
showed a maximum. A relatively high concentration of the catalyst cor- The overall reaction of cellulose with water over Pt/m-TiO2 catalyst
responds to the improved UV light absorption, leading to the enhanced can be understood as follows:
photocatalytic activity. The increase in rH 2 and rCO 2 peaked at 9.95
μmol·h−1 and 3.75 μmol·h−1, respectively, up to 0.75 g·L−1. Further in- ðC6 H10 O5 Þn þ 7n H2 O→6n CO2 þ 12n H2 : ð3Þ
creases in the catalyst concentration from 0.75 g·L−1 to 1.5 g·L−1
caused the decrease in the photocatalytic performance which can be at- It was operated in a batch system; therefore, the overall rate law for
tributed to the hindered light absorption [37,38]. At high concentrations the process can be expressed by rH2 as:
of the catalyst, the resulting turbidity impedes the light penetration into
the inner section of the reactor, thus decreasing the light absorption by r H2
−r ¼ ¼ kC a1 C bH2 O ð4Þ
the photocatalyst in the bulk solution. 12n
Fig. 3c presents the effect of the cellulose concentration on rH 2 and
or it can also be expressed by rCO 2 as:
rCO 2 over the 0.16-Pt/m-TiO2 catalyst under UV irradiation. The photo-
catalytic activity was measured as insignificant for the system without r CO2
cellulose. By increasing the cellulose concentration in the reaction −r ¼ ¼ kC a2 C bH2 O ð5Þ
6n
system from 0.125 to 2 g·L−1, the H2 production increased sharply
and then decreased slightly to 2 g·L−1. Conversely, rCO 2 of the system where r is the overall reaction rate, C is the concentration of cellulose, a
plateaued at around 3.7 μmol·h−1 at 0.5 g·L−1 cellulose. H2 is produced (a1 for H2 and a2 for CO2) and b are the reaction orders with respect to
 L. Lan et al. / Chinese Journal of Chemical Engineering 28 (2020) 2084–2091
cellulose and water, respectively, n is the corresponding degree of poly-
merisation of cellulose, and k is the rate constant. As the water in system
is excessive,CH 2O is considered unchanged, the Eq. 4 and Eq. 5 could be
simplified as:
r H2 ¼ 2kobs C a1
r CO2 ¼ kobs C a2
where kobs = 6nkCbH2O. In order to compare a1 and a2, the logarithm of
Eq. (6) and Eq. (7) has been taken at both sides of the equation and
the representation of ln (rH 2) (or ln (rCO 2)) versus ln (C) leads to a linear
fit (shown in Fig. S8), and its slope corresponds to the reaction order a1
(or a2) with respect to cellulose:

holes in the semiconductor are excited by photons, either the recombi-
ln r H2 ¼ 1:661 ln ðC Þ þ 2:202;
 
R2 ¼ 0:979; 0:25bC g  L−1 b1

steps, such as adsorption/desorption dynamics, diffusion of adsorbed
ln r CO2 ¼ 0:222 ln ðC Þ þ 1:556;
 
R2 ¼ 0:971; 0:125bC g  L−1 b0:5
where the reaction order expressed by rH 2 (a1 = 1.661 in Eq. (8)) is
around 8 times higher than that of the reaction order expressed by
rCO 2 (a2 = 0.222 in Eq. (9)).
The reaction order expressed by rCO 2 (a2 = 0.222) suggests that the
reaction is near-zero order with respect to cellulose, meaning that the
concentration of cellulose has a minor effect on rCO 2. Caravaca et al.
[28] suggested that photoreforming of cellulose I under the Xe lamp
irradiation was near zero-order, and this was also reported by Chang
et al. [29] when using both cellulose I polymorph or cellulose II poly-
morph in the catalytic photoreforming system. However, in the latter
studies, rH 2 was used solely to determine the reaction order, and on
the correlation between rCO 2 and the cellulose concentration is lacking.
According to the previous research [28,37–39], during the process of
cellulose photoreforming, the hydrolysis of cellulose under the photo-
irradiation leads to the production of glucose, which was subsequently
oxidised by the •OH, giving aldehyde R-CHO such as glyceraldehyde
[38] and acid R-COOH such as formic acid [37,38]. Finally, H2 and CO2
were produced simultaneously via the oxidation of formic acid [39].
Accordingly, based on this mechanism, i.e. the co-production of H2 and
CO2 via the oxidation reaction, the relevant reaction orders (i.e. a1 and
a2) should be comparable. Conversely, it was found at the first time
from the findings of the current kinetic analysis of the data, i.e. a1 ≈ 8
a2, additional reaction routes exist in the photoreforming system in ad-
dition to the final step oxidation of formic acid, likely the reactions
Fig. 4. Schematic model of the photocatalytic reforming of cellulose over Pt supported on TiO2 catalysts.
2089
between the H+ derived from the oxidation of R-CHO into R-COOH
and the photogenerated e−.
The thermal effect (40, 60 and 80 °C, respectively) on the photocat-
alytic performance of the reaction system was also investigated, and the
result is illustrated in Fig. 3d. It is observed that an increase in the reac-
ð6Þ tion temperature resulted in a decrease of rH 2 from 9.95 to 7.04
μmol·h−1, whereas it showed an insigfnicant influence on the rCO 2. By
ð7Þ increasing the solution temperature from 40 °C to 80 °C, the photo-
driven reaction steps cannot be affacted as the thermal energy kBT (kB
is Boltzmann constant = 8.617 × 10−5 eV·K−1, T in K) in the tempera-
ture range under study is too low (0.027 to 0.031 eV) to excite the semi-
conductor (bandgap energy ≈ 3.2 eV) [40]. One plausible explanation of
the measured thermal effect on the activity (i.e. the reduced rH 2 due to
the temperature rise) has been propsoed based on the time-resolved
spectroscopic study [41]. It was found that, once the electrons and
nation or transfer to appropriate redox pairs is initiated, which is faster
ð8Þ
than diffusion and desorption of absorbed products on the catalyst.
Accoridngly, the production rate should be limited by “dark” catalytic
species, etc. [26]. It could be concluded that the production of H2 is
ð9Þ affected by the non-photo reaction steps which could be influenced by
the thermal effect. However, CO2 is produced at the final step during
the non-photo reaction step, it could be influenced by the thermal effect
but it is insignificant.
Based on the systematic study of the catlytic photocatalytic
reforming of cellulose, it was found that the investigated paremeters
indeed have influences on the performance of the photoreforming in
aqueous system. Accoridng to the findings, the catalytic photoreforming
system using cellulose is suggested being operated at 40 °C with
1.0 g·L−1 of cellulose and 0.75 g·L−1 of 0.16-Pt/m-TiO2 catalyst to
achieve the optimum photocatalytic performance (rH 2 = 9.95
μmol·h−1 and rCO 2 = 3.75 μmol·h−1).
Based on the finding from this study, in combination with the existing
knowledge for the photoreforming of cellulose and glucose, the mecha-
nism of H2 production from the catalytic photoreforming of cellulose
was proposed, as shown in Fig. 4. The photocatalytic reaction is initiated
by photons with energy (hv) equal to or higher than the bandgap energy
of the TiO2 support (Eg = 3.2 eV), leading to the generation of the e−-H+
pairs. Subsequently, the photo-generated e− and H+ transfer to the sur-
face of the TiO2 to participate in redox reactions. This hypothesis is
based on the fact that (i) the CB potential of TiO2 (around − 0.41 eV
[42]) is more negative than the H+ reduction potential (0 V vs. the normal
hydrogen potential, HNE) and (ii) the VB potential of TiO2 (around
3.15 eV [43]) is more positive than the H2O oxidation potential (1.23 V
vs. NHE). Concerning the role of Pt species on TiO2, they act as the electron
sink to promote the separation of e− and H+ pairs, and hence avoiding
their recombination to some extents. Those photo-generated carriers
2090 L. Lan et al. / Chinese Journal of Chemical Engineering 28 (2020) 2084–2091
may promote the water-splitting reactions in the first place to create H+
and ·OH from water (Fig. 4(a) process). The H+ and ·OH produced by the
oxidation of water then participate in the hydrolysis of cellulose, leading
to the production of glucose (Fig. 4 (b) process). The ·OH radicals
would attack glucose, resulting in the generation of R-CHO and H+
(Fig. 4 (c) process), and the R-CHO would further be oxidised by ·OH rad-
icals to R-COOH and H+ (Fig. 4 (d) process). Finally, the CO2 and H+
would be produced by the oxidation of R-COOH (Fig. 4 (e) process), and
the H+ produced during the whole process would react with
photogenerated e− to produce H2 (Fig. 4 (f) process). During the whole
procedure, step (a) and (f) are the photo-driven reaction steps, affecting
the production of H2, however, steps (b) to (e) are the non-photo reaction
steps which could be affected by thermal effect, influencing the produc-
tion of H2 as well as CO2.
4. Conclusions
In this work, a systematic study of the H2 production from the
photocatalytic reforming of cellulose in aqueous systems over Pt cata-
lysts supported on m-TiO2 (Pt/m-TiO2) was performed in order to un-
derstand the photocatalytic behaviour of the system. The effect of Pt
loading (up to 1.50 wt%), catalyst concentration (0–1.5 g·L−1), cellulose
concentration (0–2.0 g·L−1) and reaction temperature (40–80 °C) on
the photocatalytic activity of Pt/m-TiO2 was investigated to to identify
the optimum operation condition for the system, i.e. at 40 °C with
1.0 g·L−1 of cellulose and 0.75 g·L−1 over 0.16% Pt/m-TiO2 catalyst to
produce H2 at 9.95 μmol·h−1. The result suggested that even though
the cellulose photoreforming was operated in a relatively moderate
condition (UV-A lamp irradiation at 40 °C in pure water solution), a
low loading amount of Pt (0.16 wt%) on m-TiO2 support could result
in a sound average hydrogen production rate at 132.6 μmol·h−1·g−1.
By comparing the reaction order a1 (expressed by rH 2) and a2
(expressed by rCO 2) with respect to cellulose and water, a1 is eight
times as much as a2, suggesting the additional H2 production from the
oxidation reaction during the photoreforming process in addition to
the co-production of H2/CO2 from photoreforming of cellulose in aque-
ous system. Overall, the findings in this work established the optimum
operation condition for photoreforming cellulose over the Pt/m-TiO2
catalyst, as well as sheding light on the addtional mechanism for H2 gen-
eration in the system.
Nomenclature
a, b Reaction orders with respect to cellulose and water
C Concentration of solution, g·l−1
Cmp Metal precursor concentration, g·ml−1
CrI Crystallinity index, %
D Crystallite size, nm
Eg Bandgap energy, eV
IAM Intensity of diffraction for the amorphous phase
I002 Maximum diffraction intensity of the (002) lattice
k The rate constant in the overall rate law
0
kλ
k′ Dimensionless shape factor, k′ = 0.943 in D ¼
β cosθ
kB Boltzmann constant = 8.617 × 10−5eV·K−1
ln (rM) Logarithm of the M production rate
n Corresponding degree of polymerisation of cellulose
r Overall reaction rate, μmol·h−1
rM The production rate of a gas phase M, μmol·h−1
β Line broadening at half the maximum intensity of the diffrac-
tion peak at 2θ, rad
θ Diffraction angle, (°)
λ Wavelength of the light, nm
Acknowledgements
LL thanks the China Scholarship Council (CSC, file no. 201706950035)-
University of Manchester joint studentship for supporting her PhD
research. YS thanks the CSC for her academic visiting fellowship at The
University of Manchester (file no. 201708440477) and the Foundation
of Department of Education of Guangdong Province (No.
2017KZDXM085, 2018KZDXM070).
Supplementary Material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cjche.2020.03.030.
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