Sustainable Materials and Technologies 24 (2020) e00162

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Sustainable Materials and Technologies

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Sustainable development of inexpensive visible-range CuO\\TiO2

nano-photocatalysts deploying in situ recovered glass fiber
and Cu(CH3COO)2 from waste printed wiring board: Optimal
lignin photo-degradation for valuable products
Debnil Bose, Sourav Barman, Rajat Chakraborty ⁎
Department of Chemical Engineering, Jadavpur University, Kolkata 700032, India

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

Article history: Inexpensive glass fiber (GF) support as well as copper acetate precursor recovered in situ from waste printed wir-
Received 6 November 2019 ing boards (WPWB) have been utilized for preparation of GF supported CuO-TiO2nano-photocatalyst (NP)
Received in revised form 25 January 2020 through sequential sol-gel and wet-impregnation methodology deploying solar-resembling quartz-halogen radi-
Accepted 14 March 2020
ation (SRQHR) (wavelength: 0.32–1.1 μm).The optimal NP (QGF-CuO-TiO7.5 2 ) possessed finer nano TiO2 and CuO
crystalline phases (7.31 nm) and higher BET surface area (62.107 m2.g−1) compared to conventionally prepared
Keywords:
NP (crystallite size: 33.38 nm, surface area: 42.170 m2.g−1); thus, advocating the supremacy of SRQHR over con-
Nano-photocatalyst ventional thermal-energy. Furthermore, UV–Vis-NIR diffuse spectroscopy revealed that QGF-CuO-TiO7.5 2 was ca-

Lignin degradation pable of absorbing light in the visible spectrum, owing to its low bandgap energy (2.26 eV). Taguchi orthogonal
Sustainable process design was used to investigate and optimize the efficacy of the prepared NPs in lignin (rice straw extracted)
photo-degradation process employing an energy-efficient SRQHR assisted rotating batch reactor (RBR). The
optimal QGF-CuO-TiO7.5 2 rendered a significantly higher lignin photo-degradation (89.73%) compared to the con-
ventionally prepared NP (54.53%) at optimal conditions (70 °C; 50 min; 200 rpm). Moreover, lignin photo-
degradation in RBR exhibited higher degradation percentage (89.73%) compared to that (67.78%) achieved in a
conventionally agitated reactor. Overall sustainability of lignin photo-degradation process for production of
lignin-derivatives (vanillin, syringaldehyde, vanillic acid) analysed via life cycle assessment (LCA) study evi-
dently revealed that the QGF-CuO-TiO7.5 2 catalysed process resulted less environmental impacts in comparison
with its conventional counterpart and commercial nano-TiO2 catalyst.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction discovered till date due to complexity in separation of its constituents

Waste Printed Wiring Boards (WPWB) are one of the most viable
and abundant wastes which needs to be recycled or converted to valu-
able chemicals to avoid its harmful effects on land, water and soil [1].
Every year, large amounts of WPWBs are being landfilled or incinerated
without having any track of their whereabouts [2,3].WPWB contains
several other precious and valuable metal ingredients such as copper,
nickel, iron etc. which if extracted and separated can be utilized for sev-
eral applications which in turn can in many ways improve the socio-
economic conditions of the society [4,5]. At the same time, WPWB also
contains several non-metallic ingredients such as brominated epoxy
resins, flame retardants, glass fiber etc. which despite having harmful
effects, rapid development in its recycling abilities hasn't been properly
⁎ Corresponding author.
E-mail address: rajat.chakraborty@jadavpuruniversity.in (R. Chakraborty).
present in varying numbers [6].
Several extraction and recycling methodologies of metallic and non-
metallic ingredients from WPWBs have been revealed by researchers
over the years. They include thermal degradation methods (gasification
and pyrolysis) [7,8]; extraction methods using inorganic (HCl, H2SO4
and HNO3) and organic acids (acetic acid, citric acid) [9,10], organic sol-
vents (Dimethyl sulfoxide (DMSO) and N-N Dimethylformamide
(DMF)) [11,12]; mechanical treatments using ultrafine grinders, hydro-
metallurgical treatments, bioleaching methodologies etc. [13] Verma
et al. [14] reported significant advantages of using DMF as an organic
solvent to extract the non-metallic ingredients because of its low spe-
cific heat, low hygroscopicity, and low viscosity as compared to other
solvents. Extraction of metallic ingredients from WPWBs using strong
acids like HCl, H2SO4 and HNO3 etc. has been significantly investigated
by a number of researchers over the years [15]. However, focus has
been shifted towards using mild acidic reagents like acetic acid, citric
acid etc.to extract the metallic parts [16,17]. Guo et al. [17] reported

https://doi.org/10.1016/j.susmat.2020.e00162
2214-9937/© 2020 Elsevier B.V. All rights reserved.
2 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162
Fig. 1. Schematic diagram of SRQHR assisted RBR.
that use of acetic acid buffer solution rendered higher leaching of copper
as compared to strong inorganic acids like H2SO4 and HNO3. In addition,
application of certain oxidizing agents like H2O2 along with mild organic
acidic reagents has also been investigated [18]. Moreover, removal of
chemical coatings from WPWB also needs to be addressed to further en-
hance the separation of metallic as well as non-metallic parts [19].
In recent times, application of electromagnetic radiation in prepara-
tion of catalysts has been explored by several researchers [20,21]. Previ-
ous literature reviews have revealed that usage of electromagnetic
radiation showed significant beneficial effects in the preparation of
nano catalysts [22,23]. Application of TiO2 as photo-catalyst has been
significantly investigated because of its greater chemical stability, and
resistance to photo-corrosion. However, TiO2 has higher band gap
which restricts its ability to absorb light in the visible region. Efficient
doping on TiO2 with metallic species e.g. Au@ Ag core–shell bimetallic
nanoparticles grafted on TiO2 [24] as well as by coupling an effective
support viz. graphene [25] nanostructure with TiO2would enhance the
photocatalytic performance of the prepared nano composites to a signif-
icant level. Singh et al. [26] demonstrated sustainable photocatalytic ap-
plication of waste mutton bone derived hydroxyapatite (HAp) as an
effective support in the development of highly efficient supported
TiO2 nanoparticles. Recently, Barman et al. [27] reported usage of
waste printed circuit board (WPCB) derived glass fiber-epoxy resin as
an effective support for preparation of supported Mo-Cu doped catalyst
for efficient production of glucose from jute fiber. Notably, usage of
WPWB derived glass fiber as a support for preparation of GF supported
nano metal oxide (TiO2, CuO) doped photo-catalyst has not been re-
ported till date.
Lignin, an important constituent of lignocellulosic biomass, which
can be degraded employing suitable catalysts for production of various
valuable chemicals e.g. vanillin, vanillic acid, syringaldehyde etc. [28].
Rice straw being an abundantly available lignocellulosic biomass can
be considered as a promising source of lignin [29]. Previously, lignin
was extracted from lignocellulosic biomass via kraft process,
organosolvent extraction, and alkaline processes. Oxidation of recalci-
trant lignin substrates such as kraft lignin [30], lignosulfonates [31],
organosolv lignin [32] etc. was extensively studied over the past. Kansal
et al. [33] utilized TiO2 and ZnO catalysts to study the effects of photo-
catalytic degradation of kraft lignin. The study revealed that the rate of
lignin degradation was enhanced at pH 11 and oxidant (sodium hypo-
chlorite) concentration of 12.2 × 10−6 M. Another work pertaining to
degradation of lignosulfonates was investigated by Machado et al.
[34]. The result showed that the addition of H2O2 oxidant could increase
the degradation efficiency by 173.5% in presence of TiO2 (Degussa, P-
25). Moreover, it is worthwhile to note that although few works have
been reported on photocatalytic degradation of organosolv lignin in
visible range [35], however no scientific works using glass fiber sup-
ported CuO-TiO2 as visible range photo-catalyst has been reported.
Previous literature indicated doping of TiO2 with any transition
metal as well as semiconductor for enhancement of the absorption
spectra to a visible range [36]. Yin et al. [37] reported the role of plati-
num (Pt) nanoparticles doped onto TiO2 nanotubes (Pt-TiO2 compos-
ites) in photocatalytic water splitting using UV as the light source. A
significant enhancement in the photocurrent densities (10–20 times)
was observed in the presence of Pt/TiO2 nano-composites as compared
to pure TiO2. However, no support derived from WPWB has been re-
ported to prepare CuO-TiO2 photocatalysts till date.
Life cycle assessment methodology has been widely used to assess
the environmental impact of systems, products [38,39]. Literature re-
view revealed that life cycle assessment analysis on waste derived cata-
lyst preparation [40,41] and vanillin production from kraft-lignin [42,
43], have been investigated by several researchers. However, there is
no scientific reports available on LCA analysis of WPCB derived GF sup-
ported CuO-TiO2 photocatalyst preparation as well as vanillin produc-
tion from lignin using heterogeneous photocatalyst to the best of our
knowledge.
The present work primarily focuses on effective separation of glass
fiber and Cu from WPWB using mild organic acid (acetic acid) along
with an oxidizing agent (H2O2) under energy-efficient electromagnetic
radiation and subsequent application of extracted glass fiber and Cu to
produce a cost-effective nano CuO-TiO2 doped glass fiber photo-
catalyst. Solar-resembling quartz-halogen radiation (SRQHR) (150 W;
0.32–1.1 μm) was applied in preparation of nano CuO-TiO2 doped
glass fiber supported nano-photo catalyst. The efficacy of the prepared
catalyst has been investigated in rice straw derived organosolv lignin
photo-degradation process using SRQHR assisted rotating batch reactor
(RBR). The photo- degradation process was also optimized using
Taguchi orthogonal design (TOD) to maximize the lignin photo-
degradation products. Finally, “cradle-to-grave” LCA analysis (Catalyst
preparation, application and final treatment) was performed to evalu-
ate and compare the life cycle environmental impact of the SRQHR acti-
vated catalyst and conventionally prepared catalyst for production of
valuable chemicals from lignin at optimized conditions.
2. Materials and methods
2.1. Materials
For this study, WPWBs were procured from a local scrap market in
Kolkata, West Bengal, India. Hydrogen peroxide (30% (w/w) in H2O),
vanillin, acetic acidglacial (≥99.85%), titanium isopropoxide, N-N
 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162 3

dimethylformamide purchased from Merck were of analytical grade. Table 1

The rice straw was collected from a local paddy field. Self-governing process parameters for degradation of extracted lignin in RBR under
SRQHR.

2.2. Preparation of glass fiber (GF) support Factors Units L−1 Level L0 Level L1 Level

All the unnecessary parts viz. conductive tracks, RAM etc. was dis-
mantled and removed manually from the WPWB. After that, the
WPWBs were grinded in an ultrafine grinder viz. drum sander through
a 200-mesh screen. After that, the ferrous materials present in WPWB
were removed by using a wet magnetic stirrer (100 W) for 0.5 h.
Heavy particles consisting of tin, aluminium, zinc, lead etc. were par-
tially removed by sedimentation. Further, concentrated alkaline treat-
ment (with 100 ml of 10 M NaOH solution at 80 °C for a time period
of 3 h under magnetic stirring) was conducted for the resultant mix
(50 g) to remove remaining materials like tin, zinc, aluminium etc.
through dissolution. Following this, the resultant mixture consisting of
glass fiber, epoxy resin, copper etc. were washed and collected through
filtration. After that, DMF (Di-Methyl Formamide) was added to the re-
sultant powder to remove epoxy resin from it. Subsequently, copper
was completely extracted by stirring the sample with 1 M acetic acid
and5 ml of H2O2 (30% w/w in H2O) solution over 2 h. After extracting
copper as copper acetate, the glass fiber was thoroughly washed and
collected. The extracted glass fiber (GF) was further treated with
ultrasonicator (100 W) for 3 h for size reduction and collected by filtra-
tion. Finally, the GF was dried in a hot air oven at 105 °C and used as a
support for catalyst preparation.
2.3. QGF-CuO-TiO2 catalyst preparation
Different copper-titanium nano-gels were prepared by varying the
titanium precursor (Titanium Isopropoxide [Ti(OCH(CH3)2)4]) loading
(5, 7.5, 10 wt% of GF) with fixed amount of WPWB derived Cu precursor
(Cu(CH3COO)2: purity 97.8 wt%; with trace amounts of silica (1.3 wt%)
and alumina (0.9 wt%); measured using Inductively-coupled plasma op-
tical emission spectrometry (ICP-OES) (PerkinElmer, Optima-8000)
analysis [42]) loading (2 wt%) employing sequential sol-gel and wet im-
pregnation methodology. This sol-gel method was accomplished by ro-
tating (200 rpm (Fig. 1S); 100 W) the Ti (OCH (CH3)2)4 in ethanol and
Cu (CH3COO)2 at a temperature of 70 °C using the SRQHR assisted RBR
(Fig. 1) (SRQHR: 150 W; 0.32–1.1 μm) for a time period of 4 h to obtain
the Ti-Cu nanogel. Subsequently, in wet-impregnation, a measured
amount of GF (as support) was impregnated with the nanogel through
rotating the resultant mixture (200 rpm) for 3 h and the resultant mix
was left to age for 24 h. After aging, the resultant mix is washed with de-
ionized water to remove organic and unreacted compounds, impurities,
etc. and then dried in a hot-air oven (105 °C). Eventually, the oven-dried
powder was calcined at a temperature of 500 °C for 3 h. The prepared
SRQHR activated catalysts were termed as QGF-CuO-TiO52 (TiO2 loading
5 wt%), QGF-CuO-TiO7.5 2 (TiO2 loading 7.5 wt%), QGF-CuO-TiO2 (TiO2
10
loading 10 wt%). In order to study the effects of quartz-halogen radia-
tion system on the properties and performance of the prepared catalyst,
the optimum GF supported catalyst was also prepared by applying con-
ventional thermal energy (named as CGF-CuO-TiO7.5 2 ) deploying a
heating mantle (500 W) at optimal TiO2 loading (7.5 wt%).
Temperature (γT) °C 50 60 70
Titanium precursor Loading (γTi) wt% 5.0 7.5 10
Catalyst Concentration (γC) wt% 2.5 5.0 7.5
Time (γt) Min 30 50 70
the EL [44] for determination of hemicellulose concentration (wt%) in
EL; this in turn, could measure the lignin percentage (purity) in EL. Fi-
nally, the extracted organosolv lignin was collected by filtration and
dried over P2O5.
2.5. Photocatalytic degradation of extracted lignin and design of experiment
Photocatalytic degradation of organosolv lignin (purity 96.7 wt%)
extracted from rice straw was also performed in the same solar-
resembling quartz–halogen radiator (SRQHR) (150 W; 0.32–1.1 μm)
assisted rotating batch reactor (RBR). Aqueous solution (50 ml) of ex-
tracted lignin (0.2 g/ml) with a measured amount of prepared
photocatalyst and 0.5 ml of H2O2 solution as oxidizing agent was
taken in the one-necked flask (250 ml) of the RBR (200 rpm). Before
photocatalytic reaction, the reaction mix was kept in dark condition at
room temperature (25 °C) for 20 min to attain the adsorption equilib-
rium (Fig. 2S). Thereafter, the SRQHR was applied and the RBR temper-
ature was maintained by a PID controller for the photocatalytic
degradation. The photo-degradation was monitored by varying four in-
dependent process parameters i.e. reaction temperature (γT), time (γt),
catalyst concentration (γC) and titanium precursor loading (γTi)
[Table 1].
The effects of four process factors on lignin degradation process
were assessed and optimized through nine experimental runs
employing L9 TOD (Minitab Inc. USA for Windows 7) [Table 2]. The op-
timal process factors corresponding to maximum lignin degradation
(LRBR) were determined through evaluation of signal-to-noise (S/N) ra-
tios (employing the “larger is better” criterion) (Eq. 1) and analysis of
variance (ANOVA).
!
S 1X n
¼ −10 log 1=LRBR;m 2 ð1Þ
N n m¼1
where, n is the number of experimental runs performed at a particular
set condition [Table 2], m is the number of replications, and LRBR,m is
LRBR corresponding to run n.
In order to assess the efficacy of QGF-CuO-TiO2 catalysts, photocata-
lytic lignin degradation process was also conducted using convention-
ally prepared CGF-CuO-TiO7.5 2 catalyst at other TOD derived optimized
condition. The photocatalytic lignin degradation percentage was evalu-
ated using UV-VIS Spectroscopy (PerkinElmer, Lamda-365) by

Table 2
2.4. Lignin extraction from rice straw TOD Layout for extracted lignin degradation process using QGF-CuO-TiO2 catalyst.

The procured rice straw was thoroughly washed with hot water and Trial no γT/(°C) γTi/(wt%) γC/(wt%) γt/(min) LRBR/(%) Std. SN ratio

was grinded to uniform fine particles (200 mesh screen). Afterwards, 1 50 5.0 2.5 30 40.12 ±0.02 32.0672
lignin was extracted and purified from rice straw by following the pro- 2 50 7.5 5.0 50 58.16 ±0.14 34.5117
3 50 10 7.5 70 66.93 ±0.11 39.0617
cedure reported by Watkins et al. [43].50 g rice straw was treated with
4 60 5.0 5.0 70 71.24 ±0.16 37.0545
100 ml acetic acid and H2O2 mix solution (9: 1) at 80 °C for 3 h to isolate 5 60 7.5 7.5 30 78.39 ±0.21 35.7733
lignin. Subsequently, the dissolved lignin in the extracted liquor (EL) 6 60 10 2.5 50 68.91 ±0.28 37.8028
was precipitated by diluting with three times additional deionized 7 70 5.0 10 50 89.76 ±0.15 36.0541
water. After precipitation, the composition of the diluted liquor part 8 70 7.5 2.5 70 75.31 ±0.08 37.3163
9 70 10 5.0 30 69.43 ±0.14 36.8309
was analysed using HPLC to quantify the hemicellulose derivatives in
4 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162
Fig. 2. Process flow diagram and system boundaries for LCA.
comparing the difference of absorbance at 280 nm of lignin solution be-
fore and after reaction.
2.6. Characterization of the prepared catalyst and lignin degradation
product
XRD analysis of the calcined GF support and the prepared catalysts
were performed using a Cu Kαsource coupled with an Inel CPS 120
hemispherical detector and the infrared spectra of the corresponding
samples were performed using FTIR-SHIMADZU (Alpha) ranging from
400 to 4000 cm−1 at 2θ ranging from 10° to 90° at a scanning speed of
1° min−1. The specific surface area, pore size and pore volume were
quantified by BET and BJH methods using Quantachrome Instruments,
Nova 4000e. For BET analysis, the samples were initially pre-treated
and degassed (temperature 150 °C) for removal of moisture from the
surface. In addition, TGA analyses of calcined GF support and the pre-
pared catalysts were conducted in a Perkin-Elmer TGA analyser (Pyris
Diamond TG/DTA) comprising of nitrogen atmosphere (20 ml.min−1)
in which temperature was increased from 30 to 900 °C at the rate of
15.0 °C• min−1.The acidity of the samples was measured through NH3-
TPD analysis (Quantachrome Instruments), TPR win v2. Furthermore,
high resolution transmission electron microscopy (HR-TEM) analysis
of the requisite samples were performed in a JEOL 3010 instrument
with a UHR pole piece at an accelerating voltage of 300 kV. The lattice
spacing of the crystallites was determined with the help of a “GATAN
digital micrograph” through processing the micrographs. XPS analysis
of the optimal catalyst was conducted to determine the binding energy
of Ti 3d and Cu 2p of the optimal catalyst. Photocatalytic properties of
Table 3
Δ value and S/N Ratio of Process Parameters for lignin degradation process.
Level γT/(°C) γTi/(wt%) γC/(wt%)
L−1 34.62 36.06 35.46
L0 37.24 36.90* 36.39
L1 37.81* 36.70 37.82*
Delta 3.19 0.84 2.36
Rank 1 4 2 3
Asterisk signifies the “optimum level of process parameter”.
CGF-CuO-TiO7.5 7.5
2 and the optimal QGF-CuO-TiO2 catalyst was analysed
by using Perkin Elmer LAMBDA 950 UV-VIS-NIR Spectrophotometer in
the range of 200–900 nm having tungsten halogen lamp as light source.
Moreover, efficacy of the quartz halogen radiation system over conven-
tional thermal system in preparation of titanium-copper nano gel (at
optimum loading, 7.5 wt%) was also analysed in UV-VIS spectropho-
tometer (Perkin Elmer LAMBDA 950).
The photocatalytic lignin degradation percentage was evaluated
using UV-VIS Spectrophotometer (Perkin Elmer, Lamda-365) at
280 nm wavelength. The products obtained from oxidative treatment
of extracted lignin from rice straw were detected and eventually quan-
tified using gas chromatography mass spectroscopic analysis (Thermo
fisher scientific, USA) along with a TG-5MS column (30 m * 0.25 mm in-
ternal diameter; 0.5 μm film thickness). Helium has been used as the
carrier gas with a flow rate of 1 ml/min. The column temperature pro-
gram was kept as 50 °C (6 min); 50–320 °C (10 °C• min−1, hold time:
6 min). The transfer line and the ion source temperatures were main-
tained at 200 and 250 °C respectively. The products were quantified
by monitoring the electron ionization mass spectroscopy in the range
of 30–600 (m/z). The NMR spectra were detected using a Bruker
AVANCE 500 MHz spectrometer at 25 °C using CD3Cl as the solvent.
2.7. LCA methods and modelling
In order to establish the sustainability of the optimized process de-
sign for utilization of SRQHR over conventional thermal-energy in prep-
aration of WPCB derived GF supported TiO2-CuO nano-photocatalyst, a
comparative environmental impact assessment analysis was investi-
gated using OpenLCA 1.9.0 software. Furthermore, the potential
environmental impacts associated with the optimized lignin photo-
degradation process using fresh QGF-CuO-TiO7.5 2 catalyst was also
γt/(min) assessed and compared with the reused catalyst. Ecoinvent database
3.5 and life cycle impact assessment (LCIA) methodology “ReCiPe
35.59
37.04* Midpoint (H) V1.13” was applied to assess the potential environmental
37.03 impacts [45].
1.45 The schematic representation of the system boundaries for these
LCA is depicted in Fig. 2 The 1st system boundary for life cycle analysis
(LCA) includes the chemicals transport, WPCB processing, GF support
 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162 5

Fig. 3. Interaction plots for the lignin photo-degradation process parameters.

preparation and GF supported TiO2-CuO nano-photocatalyst prepara- 3. Result and discussion

tion, where LCIA results were evaluated based on 1 kg QGF-CuO-TiO7.5 2
nano-photocatalyst production. The 2nd system boundary covers all 3.1. Optimal process conditions of extracted lignin degradation process
the processes in 1st system boundary along with lignin extraction
from rice straw, lignin photo-degradation process using QGF-CuO- Individual ranks of process parameters based on their effects on the
TiO7.5
2 catalyst and final treatment of spent catalyst. Moreover, 1 kg of response variable (LRBR) have been presented in Table 3. The process pa-
vanillin production is considered as functional unit for LCA study of rameter corresponding to the maximum Δ-value has most significant
the 2nd system boundary. Economic allocation was considered for the
multioutput processes (Table 5S, Table 9S–11S).
The outcomes of the research work were scaled up according to
functional units and served as database for the Life Cycle Inventory
(LCI). The detailed LCI information regarding the GF support prepara-
tion, GF supported catalyst preparations and lignin photo-degradation
can be found in the supplementary information [Table 4S–11S]. Notably,
database regarding Ti (OCH (CH3)2)4 is not present in the Ecoinvent da-
tabase, hence, Ti(OCH (CH3)2)4 preparation process from Ti(Cl)4 was
modelled according to Caramazana-González et al., 2017 [46]. All elec-
trical energy used in the entire process considered to be dissipated as
waste heat to air (Except calcination process, where partial heat loss
was assumed (18% heat loss)) [47]. Furthermore, the process waste
viz., spent GF supported TiO2-CuO photocatalyst and waste water was
considered to be disposed via hazardous waste treatment (under-
ground deposition) and waste water treatment respectively.

Fig. 5. XRD patterns of (a) QGF-CuO-TiO10 7.5

2 , (b) QGF-CuO-TiO2 , (c) QGF-CuO-TiO2 ,
5.0

(d) CGF-CuO-TiO7.5
2 and (e) GF [characteristic peaks due to TiO2 ( ), CuO ( ), SiO2 ( ),
Fig. 4. TGA analyses of (a)GF (b) QGF-CuO-TiO7.5 7.5
2 (c) CGF-CuO-TiO2 . Na2O-Al2O3-SiO2 ( ), MgO ( )].
6 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162
Table 4
Effects of Titanium precursor loading on the properties of the prepared catalyst.
Catalyst BET analysis
Surface area/(m2.g−1) Total pore volume/(cc.g−1)
QGF-CuO-TiO5.0
2 62.682 0.134
QGF-CuO-TiO7.5
2 62.107 0.132
QGF-CuO-TiO10
2 49.622 0.122
7.5
CGF-CuO-TiO2 42.170 0.113
effect on LRBR whereas highest S/N ratio represents the optimum level
for that process factor. Thus, from Table 3, it may be concluded that L1
of γT(70 °C), L0 of γTi (7.5 wt%), L1 of γC (7.5 wt%), and L0 of γt
(50 min) were the optimum process values (indicated by * in Table 3)
rendering maximum lignin degradation. Moreover, ANOVA analysis
[Table 1S] for photo-catalytic lignin degradation process revealed that
the degradation temperature (γT) and catalyst concentration (γC)
were statistically significant process parameters at 95% confidence
level (p-value b.05).
3.2. Individual and interactive effects of process parameters on lignin
degradation
Fig. 3S demonstrates the individual parametric effects on LRBR (based
on S/N ratio), keeping other factors at their optimum levels. It could be
observed that the degradation of lignin is enhanced by increasing the γT
as higher temperature facilitates the generation and transportation of
charge carriers between TiO2-CuO surface and reaction medium which
eventually accelerates the production of hydroxyl radicals [48]. Further-
more, the degradation process was also performed up to 90 °C, to under-
stand the influence of temperature on LRBR. However, upon additional
increase in temperature, the degradation rate started to decrease
which might be due to accelerated thermally-assisted decomposition
of H2O2. Fig. 3S also demonstrates an enhanced LRBR at higher γC due
to greater availability of catalyst's active sites. On the other hand,
Fig. 3S also reveals that lignin degradation rate could be augmented
through increasing γTi up to 7.5 wt%; whereas, above 7.5 wt%, a negative
impact on LRBR was observed. Above 7.5 wt% of γTi, the increased nano-
particle size resulted in blocking of the GF support's pore and drastically
Fig. 6. FTIR analyses of (a) QGF-CuO-TiO10 7.5
2 , (b) QGF-CuO-TiO2 , (c) QGF-CuO-TiO2 ,
(d) CGF-CuO-TiO7.5
2 and (e) GF.
NH3-TPD/(mmol NH.3(g catalyst)−1) XRD and HRTEM
Pore diameter /(nm) Average crystallite size /(nm)
5.53 1.724 5.42±0.02
5.47 1.872 7.31±0.01
4.91 1.890 10.29±0.01
4.68 1.532 33.38±0.02
reduced the overall surface area of the catalyst (BET analysis and XRD).
Moreover, the increased particle size has also reduced the lignin adsorp-
tion rate on catalyst surface which clearly corroborated well with lignin
degradation results [49]. Notably, it was observed that on increasing γt
up to 50 min degradation of lignin increases considerably. However, fur-
ther increment of γt had little effect on LRBR.
Parametric interactions for the photocatalytic lignin degradation
process have been depicted in Fig. 3 Interaction between catalyst con-
centration and temperature (maintaining two other parameters at the
optimum level) revealed that an increment in catalyst concentration re-
sulted in higher lignin degradation (LRBR) [Fig. 3b] at all levels of temper-
ature, which clearly suggested that the prepared QGF-CuO-TiO2 catalyst
immensely facilitated the lignin degradation process. A similar trend
was observed for all values of reaction time. On the other hand, Interac-
tion between catalyst concentration and titanium precursor loading has
an antagonistic effect on LRBR because of the formation of larger nanopar-
ticles at higher precursor loading during catalyst preparation [Fig. 3d].
Moreover, to investigate the beneficial effects of rotating action on
lignin degradation, the degradation process was also conducted in a
SRQHR assisted mechanically stirred batch reactor (SBR) at TOD derived
optimal conditions over a speed range from 50 rpm to 400 rpm (Fig. 4S).
The experimental results revealed that the SBR renders relatively low
LSBR (67.28%) compared to the RBR when operated at same speed of
200 rpm. However, a further increase in rpm above 200 rpm, an oppo-
site trend was observed. At higher rotational speed (above 200 rpm),
the decreasing trend of LRBR in RBR corroborated well to the formation
of central vortex which results in inefficient mixing of reactants and cat-
alyst, therefore, lowering the overall lignin degradation in RBR.
3.3. Catalyst characterization
3.3.1. TGA
Thermo-gravimetric analyses of the GF, QGF-CuO-TiO7.5 2 and CGF-
CuO-TiO7.5
2 [Fig. 4] were carried out to determine the thermal stability
5.0
Fig. 7. NH3-TPD analyses of (a) QGF-CuO-TiO10 7.5 5.0
2 (b) QGF-CuO-TiO2 (c) QGF-CuO-TiO2
(d) CGF-CuO-TiO7.5
2 (e) GF.
 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162
Fig. 8. (a) Light absorbance profile of QGF-CuO-TiO7.5
2 [inset shows the band gap of QGF-CuO-TiO2 ], (b) reflectance (%) of QGF-CuO-TiO2 and CGF-CuO-TiO2 .
when heated over a wide range prevalent from 30 to 900 °C. The sam-
ple weight% vs. temperature plot showed a major weight loss of 12.5%
in the temperature range of 30–450 °C observed in case of CGF-CuO-
TiO7.5
2 . A weight loss of 7% was observed in the case of QGF-CuO-
TiO7.5
2 over the temperature range of 30–450 °C. The occurrence of
this phenomenon could be best ascribed due to the evaporation of
adsorbed water and thermal decomposition of copper and titanium
precursors. Furthermore, the TGA plot of QGF-CuO-TiO7.5 2 rendered
4% weight loss within the temperature range of 400–450 °C owing
to the decomposition of the titanium precursor (Titanium
Isopropoxide [Ti (OCH (CH3)2)4]) (decomposition temperature
400 °C) [50]. In addition, a small percentage of weight loss (1.5%)
over 180–290 °C in QGF-CuO-TiO7.52 catalyst occurs due to the decom-
position of copper acetate [51]. On the other hand, GF showed 3.5%
weight loss over the same temperature range of 30–450 °C. Notably,
the TGA plot of CGF-CuO-TiO7.5
2 showed better thermal stability over
CGF-CuO-TiO7.5
2 which in turn substantiated the better thermal superi-
ority of SRQHR over conventional hydrothermal treatment. Further-
more, as the lignin photo-degradation temperature (70 °C) was
much lower than the calcination temperature (500 °C), thermal de-
composition of catalysts was unlikely to occur during lignin photo-
degradation.
3.3.2. X-ray diffraction
Fig. 5 depicts the X-Ray diffraction pattern of the prepared support
as well as the prepared catalysts i.e. GF support, QGF-CuO-TiO52, QGF-
CuO-TiO7.5 10 7.5
2 , QGF-CuO-TiO2 and CGF-CuO-TiO2 [Table 4]. The XRD
diffractogram of all the catalysts showed peaks at 32.442°, 35.550°,
38.694°, 58.160°, 74.972° (JCPDS card no. 45–0937) corresponding to
Fig. 9. (a)Pore volume vs relative pressure (P/PO) of the optimum QGF-CuO-TiO7.5
2 catalyst [inset: BJH pore size distribution for thedetermination of modal pore diameter] (b) Cumulative
pore volume vs. pore diameter for the QGF-CuO-TiO7.5 2 catalyst.
7
7.5 7.5 7.5
crystalline phase of copper oxide and peaks at 25.260°, 37.790°,
48.10°, 62.135°, 70.305° (JCPDS card no. 21-1272; JCPDS card no. 21-
1276) representing the crystalline phase of titanium dioxide. Further-
more, peaks representing the SiO2 crystal (26.602°, 50.069°,
54.838°and 65.621°) (JCPDS card no. 39-1425) were also found in all
the catalysts ascribing the presence of GF. It is worthwhile to mention
here that with increasing concentrations of Titanium Isopropoxide pre-
cursor, the peaks corresponding to TiO2 strongly increased in the QGF-
CuO-TiO2 catalyst. The diffraction pattern of GF support depicts the
presence of Na2O-Al2O3-SiO2 (21.092°) (JCPDS Card no. 48-0038) and
MgO (42.949°) (JCPDS Card no. 89-7746) revealing the constituent
phases of the GF support.
3.3.3. FTIR spectra
Fig. 6 depicts the Fourier Transform Infrared (FTIR) spectrum of GF
support and catalysts (QGF-CuO-TiO52, QGF-CuO-TiO7.5 10
2 , QGF-CuO-TiO2
7.5
and CGF-CuO-TiO2 ). FTIR analyses of the catalysts and support showed
a broad peak at 3447.62 cm−1 due to the presence of strong OH
stretching mode of absorbed water [52]. Peaks corresponding to wave
numbers of 1401.83 cm−1 and 463.09 cm−1 showed the presence of
Ti-O-Ti stretching modes in the prepared catalysts [53]. Furthermore,
spectra of all catalysts also exhibited peaks at 957.55 cm−1 which corre-
sponds to vibration of Ti-O-Si. It could also be perceived that the peak
intensity increases gradually with increasing loading of TiO2 precursor
[54]. In addition to this, vibrational modes at 667.99 cm−1 could be
assigned to the Cu-O stretching in Cu-O-Si bonds in the prepared
catalyst [55].
8 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162

Fig. 10. TEM images of (a) QGF-CuO-TiO7.5 7.5

2 (with particle size distribution) (b) CGF-CuO-TiO2 (with particle size distribution) (c) GF.

3.3.4. NH3-TPD analyses
NH3-TPD analyses of calcined GF support and prepared catalyst
[Fig. 7] indicated that within the temperature range of 100–900 °C
several weak (signal maxima at 180–200 °C), medium (signal max-
ima at 350–390 °C) and strong (signal maxima at 730–780 °C) acidic
sites were distributed for all the prepared catalysts, whereas only
strong acidic site (signal maxima at 590 °C) was observed for cal-
cined GF support. Moreover, with increase in titanium precursor
loading, it could be observed that NH3 desorption peak increased in
lower temperature zone while depicting lower peaks in higher tem-
perature zone, which clearly indicated that the concentration of weak
acidic sites increases with increment in titanium precursor loading
[56]. Notably, weak acidic sites could be beneficial for lignin
depolymerisation as strong acidic sites could promote the re-
polymerisation of degraded lignin [57].
3.3.5. UV–Vis-NIR diffuse spectroscopy
The UV–Vis-NIR spectrophotometric analysis of optimal QGF-CuO-
TiO7.5
2 catalyst showed a large absorbance peak at a wavelength of
239.40 nm indicating the presence of TiO2 in the prepared photo-
catalyst. In addition, Fig. 8a also exhibits a long absorbance hump in
the visible range as well as near infrared range (up to the wavelength
of 860.52 nm). Notably, the absorption band in the range of
600–800 nm indicated the presence of CuO in crystalline phase [58].
The band gap energy (Eg = 2.26 eV) of QGF-CuO-TiO7.5 2 was computed
from reflectance spectra utilizing Kubelka–Munk equation and Tauc

Fig. 11. HRTEM image of (a) QGF-CuO-TiO7.5 2 ; (b) magnified view of the red rectangle section for CuO [inset shows the fast Fourier transform (FFT) of the enclosed region]; (c) magnified
view of the red rectangle section for TiO2 [inset shows the FFT of the enclosed region]; and (d), (e) are crystal structure of {004} crystal planes of CuO and {211} crystal planes of TiO2
respectively [60].
 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162
Fig. 12. XPS Survey spectrum of QGF-CuO-TiO7.5
2 catalyst.
plot (Fig. 8b). It could be inferred that the presence of copper ions con-
siderably shifted a major part of the absorbance spectrum towards the
visible and near infrared range leading to enhancement of the photocat-
alytic activity of the catalyst. Furthermore, with reference to the Fig. 8b,
the diffuse reflectance spectra of CGF-CuO-TiO7.5 2 and QGF-CuO-TiO2
7.5
clearly indicated the higher absorption ability of the latter one, which
in turn advocates that the SRQHR rendered better hydrothermal activa-
tion during sol-gel process compared to conventional protocol.
3.3.6. BET analyses
The specific surface area of the prepared catalysts and the support
were assessed through BET (Brunauer-Emmett-Teller) analyses. From
Table 4, it could be observed that the specific surface area of the pre-
pared catalyst were a little lower in cases of both QGF-CuO-TiO5.0 2 1272; JCPDS card no. 21-1276) of TiO2 crystallites respectively [Fig. 11].
(62.682 m2.g−1) and QGF-CuO-TiO7.5 2 (62.107 m g
2. −1
) catalysts com-
pared to the GF support (67.318 m2.g−1) whereas for QGF-CuO-TiO10 2 3.3.8. XPS analysis
(49.622 m2.g−1), a substantial decrease in specific surface area was ob-
served. Evidently, at a higher precursor loading, the size of the nanopar-
ticles increased which partially blocked the GF support's pore and
rendered lower overall surface area of the QGF-CuO-TiO10 2 catalyst
[Table 4]. The adsorption isotherm of the optimal catalyst QGF-CuO-
TiO7.5
2 corroborated with type II isotherm (IUPAC) [Fig. 9a] implying
Fig. 13. XPS spectra of Cu 2p and Ti 2p of QGF-CuO-TiO7.5
9
Fig. 14. Lignin photo-degradation using QGF-CuO-TiO7.5 7.5
2 , CGF-CuO-TiO2 and TiO2 at
optimal condition.
unrestricted multilayer adsorption. BJH method was employed to calcu-
−1
late the QGF-CuO-TiO7.52 catalyst pore volume (0.132, 0.141 cc.g for
GF) and modal pore diameter (5.47, 5.76 nm for GF) [inset of Fig. 9a]
representing mesoporous catalyst. Furthermore, Fig. 9b revealed that
15.61% micropores and 84.39% mesopores were present in the optimum
QGF-CuO-TiO7.5 2 catalyst. Reasonably, the mesoporous structure of
QGF-CuO-TiO7.5 2 favoured diffusion of larger lignin molecules [3.5 nm]
inside the pore structure which augmented the lignin degradation
reaction [59].
3.3.7. HR-TEM
Transmission electron microscopic analyses of GF, QGF-CuO-TiO7.5 2
and CGF-CuO-TiO7.52 were performed to interpret their structural pat-
tern as shown in Fig. 10. It could be clearly observed from Fig. 10 that
there was a clear and distinct visual enhancement after titanium and
copper precursors were doped onto GF. Furthermore, a meticulous as-
sessment of the FigS. [10a, b, c] evidently revealed the presence of
more porous sites in QGF-CuO-TiO7.5 2 as compared to CGF-CuO-TiO2 .
7.5
The lattice spacing of 0.127 nm revealed the presence of 004 plane
(JCPDS card no. 45-0937) of CuO crystallites; whereas the lattice spacing
of 0.166 nm was due to the presence of 211 plane (JCPDS card no. 21-
The XPS diagram of the optimal QGF-CuO-TiO7.5 2 catalyst [Fig. 12]
depicted the XPS spectra of catalyst support's constituents (Si 2p, C
1 s, Al 2 s, Ca 2p and O 1 s) and Ti 2p and Cu 2p. The binding energies
located at 463.33 and 457.45 eV evidenced the presence of Ti 2p1/2
and Ti 2p3/2 spin-orbital splitting photoelectrons which could be as-
cribed to Ti4+ in a tetragonal structure [Fig. 13] [61].To discuss further,
2 catalyst.
10 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162
Fig. 15. UV-VIS Spectroscopy of (a) Titanium-copper nano gel produced under SRQHR
(b) Titanium-copper nano gel produced under conventional heating.
it is interesting to note that the binding energy at 932.65 eV and
952.56 eV depicted the presence of Cu 2p3/2 orbital and Cu 2p1/2 orbital
respectively, whereas one satellite peak lies at 941.63 eV, which re-
vealed that only CuO phase was present in the catalyst framework [62].
3.4. Catalytic performance of the QGF-CuO-TiO7.5
2 catalyst in lignin degra-
dation process
Photo-catalytic efficiencies of the optimum QGF-CuO-TiO7.5 2 , CGF-
CuO-TiO7.52 , and commercial TiO2 in rice straw derived lignin degrada-
tion process were investigated at the TOD derived optimal condition.
QGF-CuO-TiO7.5 2 showed better photo-catalytic activity in terms of lignin
degradation (89.76%) over CGF-CuO-TiO7.5 2 (LRBR: 54.53%); TiO2 (LRBR:
28.46%) at an optimum time of 50 min [Fig. 14]. The superior catalytic
activity of QGF-CuO-TiO7.52 over TiO2 could be attributed to the better
light-absorbing ability of the prepared catalyst due to the presence of
CuO (UV spectra).
To have a better understanding of the effects of SRQHR over conven-
tional heating on catalyst preparation, the prepared titanium-copper
nano gel was also analysed in UV-VIS spectrophotometer, which re-
vealed that higher concentration of titanium-copper nano gel (which
increases the acidic sites in the prepared catalyst) was rendered by
SRQHR [Fig. 15]. On the other hand, lower particle size (from XRD and
HRTEM) of the SRQHR activated QGF-CuO-TiO7.5 2 also enhanced the ad-
sorption efficiency of the lignin particles on catalyst surface. Thus, high
acidic sites as well as lower particle size of the SRQHR activated QGF-
Fig. 16. UV-VIS spectroscopy analysis of (a) initial lignin solution and degrdation products at optimal condition using (b) CGF-CuO-TiO7.5
(e) time dependent absorption spectra of QGF-CuO-TiO7.5 2 photocatalyzed lignin degrdation.
CuO-TiO7.5 7.5
2 made it a superior catalyst compared to CGF-CuO-TiO2 . No-
tably, the QGF-CuO-TiO7.5
2 catalyst facilitated almost same LRBR(89.76%;
degradation time: 50 min) compared to the LRBR reported in the previ-
ous work by Rangel et al., 2015 (92.46%; degradation time: 120 min)
within a much shorter time [63].
3.5. Product characterization
The lignin degradation in presence of prepared nano-photocatalysts
has been monitored through UV-VIS spectroscopy at 280 nm wave-
length [Fig. 16]. Fig. 16e depicted the time dependent photocatalytic lig-
nin degradation percentage in presence of optimal QGF-CuO-TiO7.5 2
nano-photocatalysts. Furthermore, composition of the optimally de-
graded lignin mix was quantified using GC–MS in which identifiable
degradation product viz., vanillin, syringaldehyde, vanillic acid were
retained at 16.74 min, 18.37 min, 12.86 min respectively [Fig. 17]
[mass list of the identifiable products is given in Table 2S]. The phenolic
compounds concentration were remarkably higher (vanillin: 11.5 wt%;
syringaldehyde: 0.63 wt%; vanillic acid: 1.23 wt%) in case of lignin deg-
radation using QGF-CuO-TiO7.5 7.5
2 compared to CGF-CuO-TiO2 (vanillin:
7.9 wt%; syringaldehyde: 0.84 wt%; vanillic acid: 0.73 wt%)and TiO2
(vanillin: 3.41 wt%; syringaldehyde: 0.54 wt%; vanillic acid: 0.52 wt%),
which confirmed the superiority of QGF-CuO-TiO7.5 2 for selective degra-
dation of lignin.
3.6. 1H-NMR analysis
The products obtained from lignin degradation using QGF-CuO-
TiO7.5 1
2 was examined by H NMR analysis as shown in Fig. 5S. Table 3S
shows the different chemical shifts and the assignments of these signals
to different functional groups of lignin degradation products. The sharp
peak having chemical shift of 9.542 ppm belongs to the region of
aldehyde-protonic groups, with the major compounds presumed to be
benzaldehyde type units obtained from light-intensified degradation
of lignin [64]. Chemical shifts at 7.318 and 7.404 ppm can be attributed
to aromatic protons of p-hydroxyphenyl units whereas chemical shifts
around 7.108 ppm and 6.921 ppm are attributed to aromatic protons
in guaiacyl units [65].
3.7. Catalyst reusability
The catalyst reusability was investigated by taking 10th consecutive
experimental runs at the TOD derived optimal condition using the opti-
mal photocatalyst QGF-CuO-TiO7.5 2 . After each batch lignin photo-
7.5
2 ; (c) QGF-CuO-TiO2 ; (d) baseline (water)
 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162 11

Fig. 17. GC of products derived from lignin degradation using (a) QGF-CuO-TiO7.5 7.5
2 and (b) CGF-CuO-TiO2 .

degradation, the catalyst could be easily recovered by membrane filtra-
tion and subsequently oven-dried at105 °C for 1.5 h. The LRBR decreased
from 89.76 to 87.53% after 7th recycle while no further decrease in LRBR
was observed in subsequent three more reaction cycles. Inductively
coupled plasma (ICP) optical emission spectroscopy of the reused
photocatalyst revealed that an insignificant number of active sites
(0.14 ppm of Ti) was leached from QGF-CuO-TiO7.5 2 , while CGF-CuO-
TiO7.5
2 suffered leaching up to 2.36 ppm of Ti, which further reinforces
the superiority of SRQHR over conventional heating system. Thus, the
optimal QGF-CuO-TiO7.5 2 catalyst demonstrated appreciable reusability
attributes. Noticeably, the presence of slight amount of leached Ti spe-
cies in the reaction mix also ensured storage stability of the product at
room temperature.
3.8. Lignin extraction and photo-catalytic degradation pathways
Peracetic acid catalysed delignification of rice straw mainly occurs
due to hydrolytic cleavages of α - and β -aryl ether linkages (mainly
β-O-4 linkage; as it is the most is the most common linkage in lignin)
between the lignin monolignols (Fig. 18). In the primary step, dehydra-
tion of hydroxyl groups in α- or γ-carbon occurs; then the proton (H+)
hydrolyse the β-O-4 linkage and produce ferulic acid, eugenol and
isoeugenol compounds [66,67].
In the lignin photo-degradation step, the extracted lignin derivatives
form rice straw was oxidized according to Fig. 19 in presence of glass
fiber supported CuO-TiO2 photocatalyst. In presence irradiation, the
QGF-CuO-TiO2 photocatalyst generates hydroxyl radicals (OH−) and
anionic superoxide (O− 2 ) [68]. Moreover, presence of CuO in the pre-
pared catalyst facilitates the decomposition of H2O2 and also generates
hydroxyl radicals [69]. Subsequently, the generated hydroxyl groups
were incorporated in the aromatic rings, which intern facilitates hy-
droxylation [70] of extracted lignin derivatives and produce vanillin,
vanillic acid and syringaldehyde.
3.9. Life cycle impact assessment (LCIA)
The results of the environmental impact assessment according to the
ReCiPe Midpoint (H) V1.13 are presented in Figs. 20 and 21. The results

Fig. 18. Proposed reaction pathways for lignin extraction from rice straw using peracetic acid.
12 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162

Fig. 19. Proposed reaction pathways for peracetic acid treated rice straw derived lignin photo-oxidation using QGF-CuO-TiO7.5
2 .

revealed that the most prominent midpoint impact indicators were cli-
mate change (GWP100), fossil depletion (FDP), human toxicity (HTP
inf), ionising radiation (IRP_HE), metal depletion (MDP), water deple-
tion (WDP) for both system boundaries. Fig. 20a illustrates comparative
potential environmental impacts of optimized lignin photo-degradation
process (2nd system boundary) under different catalytic systems,
which clearly revealed that the QGF-CuO-TiO7.5 2 catalysed lignin
photo-degradation process resulted less impacts in all categories in
comparison with TiO2 and CGF-CuO-TiO7.5 2 catalysed lignin photo-
degradation process. Furthermore, from Fig. 20b, it can be seen that
sub-processes viz., lignin extraction (contribution rages:
59.17–74.98%), waste water treatment (contribution rages:
35.56–14.06%), catalyst preparation process (contribution rages:
11.82–5.64%) are the major contributors to the overall impacts in
QGF-CuO-TiO7.5 2 catalysed lignin photo-degradation process. Uses of
large amount of water and acetic acid in lignin extraction process ap-
pear to be main factors which made this process as largest contributor
to the total impacts. Fig. 21a clearly demonstrated the sustainability of
catalyst preparation process employing SRQHR compared to conven-
tional catalyst preparation process (1st system boundary) as it depicted
less environmental impacts due to the lower energy demand. Finally,
the lignin photo-degradation process involving 10 cycles of catalyst
recycling also displayed less environmental impacts in contrast with
fresh catalyst (Fig. 21b).

Fig. 20. (a) comparative environmental impacts assessment of lignin photo-degradation process under different catalytic system (QGF-CuO-TiO7.5 7.5
2 , CGF-CuO-TiO2 , TiO2) at optimized
condition; (b) relative percentage contributions of sub-processes (in QGF-CuO-TiO7.5
2 catalysed lignin photo-degradation process) to produce 1 kg of vanillin.
 D. Bose et al. / Sustainable Materials and Technologies 24 (2020) e00162
Fig. 21. (a) comparative environmental impacts assessment between SRQHR activated catalyst preparation and conventional catalyst preparation; (b) comparative environmental impacts
assessment of reused QGF-CuO-TiO7.5 7.5
2 catalyst over fresh QGF-CuO-TiO2 in lignin photo-degradation process.
4. Conclusion
WPWB derived GF can be effectively deployed as a promising inex-
pensive support for preparation of QGF-CuO-TiO2 and CGF-CuO-TiO2
nano-photocatalysts by utilizing solar-resembling quartz-halogen radi-
ation (SRQHR) and conventional hydrothermal treatment respectively.
The experimental results clearly indicated that the SRQHR activated
QGF-CuO-TiO2 catalyst was more efficient in terms of lignin degradation
as compared to conventionally activated catalyst. Furthermore, XRD
analysis confirmed the presence of much smaller nanoparticles in
QGF-CuO-TiO7.5 7.5
2 compared to CGF-CuO-TiO2 authenticating the advan-
tage of using SRQHR. Notably, comparative environmental impacts
analyses of optimized lignin photo-degradation process for production
of value-added chemicals (vanillin, syringaldehyde, vanillic acid)
under different catalytic systems, evidently demonstrated that the
QGF-CuO-TiO7.52 catalysed lignin process resulted much lower environ-
mental impacts in comparison with commercial nano-TiO2 and CGF-
CuO-TiO7.5
2 catalysed lignin photo-degradation processes. Thus, utiliza-
tion of WPWB for development of inexpensive, recyclable nano-
photocatalyst with enhanced performance under solar-resembling radi-
ation could open-up new avenues and foundations of sustainable syn-
thesis of valuable lignin-derived chemicals.
Declaration of Competing Interest
The authors have no conflicts of interest.
Acknowledgements
The financial support of Department of Science & Technology and
Biotechnology (ST/P/S&T/4G-2/2018) (Government of West Bengal,
India) and RUSA 2.0 (Ref. No. R-11/481/19) Jadavpur University, India
are gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.susmat.2020.e00162.
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