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Liquid phase oxidation of benzyl alcohol to

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DOI: 10.1016/j.cej.2012.01.051

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Chemical Engineering Journal 187 (2012) 232238

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Liquid phase oxidation of benzyl alcohol to benzaldehyde with novel uncalcined

bioreduction Au catalysts: High activity and durability
Guowu Zhan, Jiale Huang , Mingming Du, Daohua Sun, Ibrahim Abdul-Rauf, Wenshuang Lin,
Yingling Hong, Qingbiao Li
Department of Chemical and Biochemical Engineering, and National Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, and Key Lab for Chemical Biology of
Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, PR China

a r t i c l e

i n f o

Article history:
Received 24 June 2011
Received in revised form 5 January 2012
Accepted 10 January 2012
Keywords:
Bioreduction
Gold catalysts
Benzyl alcohol
Benzaldehyde
Oxidation

a b s t r a c t
An environmentally benign bioreduction method was used to prepare Au catalysts for liquid phase oxidation of benzyl alcohol to benzaldehyde. The catalysts were characterized by N2 physisorption, X-ray
diffraction, transmission electron micrograph, thermogravimetric analysis and X-ray photoelectron spectroscopy. The performance of uncalcined bioreduction Au catalysts is evaluated with H2 O2 as oxidant
and without any base or organic solvent. Having investigated the effects of different reaction conditions
(time, temperature, amount of catalyst and molar ratio of H2 O2 to benzyl alcohol) on the catalytic performance, the optimum conditions were found to be 6 h, 80 C, 0.3 g and 1.25, respectively. In terms of
the catalyst parameters, gold loading of 0.3% and support Si/Ti molar ratio of 35 were demonstrated to
be optimum. Under optimal conditions, benzyl alcohol conversion of 67% and benzaldehyde selectivity
of 84% were achieved. Recycling tests of the catalysts manifested their durability and reusability, traits
vital for industrial prospects.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Benzaldehyde (BzH), an important ne chemical and intermediate to many organic compounds, is widely used in the
pharmaceutical, dyestuff, perfumery, and agrochemical industries
[1]. Commercially, it is obtained mainly through the hydrolysis of
benzal chloride and the oxidation of toluene [2,3]. However, BzH
produced from the former route inevitably suffered from the problem of chlorine contamination while the selectivity in the latter
is very poor. Currently, liquid phase oxidation of benzyl alcohol
(BzOH) is the practically preferred reaction route for the production of chlorine-free BzH with high selectivity [4]. This process
has gained acceptance and earned praises for being eco-friendly
and economically efcient. Lately, noble metals (Pt, Pd, Au, Ag,
Ru, Rh, etc.) have attracted tremendous interests and are widely
used as heterogeneous catalysts in the oxidization of alcohols to
corresponding aldehydes [57]. In particular, considerable studies
have been focused on Au-based catalysts due to their excellent catalytic performance (high activity and selectivity) for liquid phase
oxidation of BzOH to BzH [811].
For Au-based catalysts, commonly, they are prepared by the
depositionprecipitation (DP) technique, since it has the ability to

Corresponding authors. Tel.: +86 592 2189595; fax: +86 592 2184822.
E-mail addresses: cola@xmu.edu.cn (J. Huang), kelqb@xmu.edu.cn (Q. Li).
1385-8947/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2012.01.051

produce small-size Au particles [12] with intimate metalsupport

interactions [13,14]. Nevertheless, this basic method has numerous
variable parameters, such as pH, time, temperature, type of bases,
concentration of HAuCl4 , washing condition, heat pretreatment
and the like, resulting in poor reproducibility of the active catalysts [15,16]. Again, Au capture efciency of this technique is low
(<60%) and Au recovery from the ltrate is almost impracticable,
thus restricting scaling-up for industrial applications and environmental concerns [12,17]. Biological approach (green chemistry)
using plant extracts is probably an alternative to the DP for the
production of Au catalysts. It represents the combination of biosynthesized Au nanoparticles (AuNPs) with the support materials,
offering facile preparation processes and being environmentally
benign [18]. Although researchers working on the biosynthesis of
AuNPs have made great progress [19,20], the direct fabrication of
Au catalysts from biosynthesized AuNPs remained, to date, a great
challenge. The application of bioreduction catalysts was reported
previously by Zepedas group [21] and our group [22], but these
works were focused on the gas phase reaction. Considering the
fact that plant extract played dual roles as reductant and protective agent in the production of AuNPs [20], liquid phase reactions
would be the preferable application choice in order to avoid overprotection. Herein, we prepared Au catalysts using biosynthesized
AuNPs utilizing plant extract and applied them (catalysts) in the
liquid phase oxidation of BzOH to BzH with H2 O2 (30 wt.%) as oxidant without any base or organic solvent. We then investigated the

G. Zhan et al. / Chemical Engineering Journal 187 (2012) 232238

233

Fig. 1. Nitrogen adsorption/desorption isotherms (I) and the corresponding pore size distributions (II) for bioreduction catalysts varying Au loading: (a) 0%, (b) 0.1%, (c) 0.3%,
(d) 0.5%, (e) 0.7%, and (f) 0.9%.

inuences of various reaction conditions and catalyst parameters

on the catalytic performance of the bioreduction Au catalysts. To
our knowledge, this is the rst report on liquid phase oxidation of
BzOH using bioreduction Au catalysts.
2. Experimental details
2.1. Materials
All chemicals were purchased from Sinopharm Chemical
Reagent Co. Ltd., China and used as received. Cacumen Platycladi
(CP) was purchased from Xiamen Jiuding Drugstore, China.
2.2. Catalyst preparation
Au
catalysts
were
prepared
via
an
Bioreduction
adsorptionreduction method in which aqueous HAuCl4 was
reduced with CP extract and TS-1 was used as support. Firstly,
an amount of support was immersed in aqueous HAuCl4 (30 mL,
0.3 mM) for 1 h. Then 30 mL CP extract was added immediately
into the mixture solution under stirring. The color of the solution
changed from pale yellow to purple red due to the reduction of the
adsorbed Au ions by the extract. After 2 h the slurry was ltered,
the solid was washed thoroughly with distilled water, dried in
vacuum oven at 50 C overnight and catalytically tested (without
calcination).
2.3. Catalyst characterization
N2 physisorption isotherms were recorded on a porosimetry analyzer (Micromeritics TriStar 3000) at 77 K. Transmission
electron microscopy (TEM) observations were performed on an
electron microscope (Phillips Analytical FEI Tecnai 30) at an
accelerating voltage of 300 kV. Powder X-ray diffraction (XRD) patterns were recorded on a diffractometer (Panalytical Xpert PRO)
equipped with Cu-K radiation (40 kV, 30 mA). X-ray photoelectron spectra (XPS) were collected on a spectrometer (PHI-Quantum
2000) employing a monochromatized microfocused Al X-ray
source. Thermogravimetric (TG) and differential thermogravimetric (DTG) analysis were carried out on a thermo balance (Netzsch
TG209F1) under atmospheric air at a heating rate of 10 K min1 .
2.4. Catalytic tests
The oxidation of BzOH was carried out in a magnetically stirred
glass reactor (50 mL) by dispersing the catalysts in 10 mL aqueous
medium composed of BzOH and H2 O2 . To investigate the inuence

of reaction parameters, different reaction conditions (temperature,

3595 C; reaction time, 0.524 h; catalyst, 00.5 g; molar ratio of
H2 O2 /BzOH, 0.51.75) were implemented. Samples (from the reactor) were taken periodically (with a syringe) and centrifuged to
separate the catalyst from the mixture. The products were analyzed by a gas chromatography, equipped with FID detector (SE-30
capillary column) and identied by comparison with known standards [23]. External calibration method was used for quantitative
analysis of the amounts of reactants consumed (conversion) and
products generated (selectivity) [23]; with BzH selectivity dened
as the amount of BzH produced divided by the amount of BzOH
consumed.
3. Results and discussion
3.1. Characterization of the bioreduction catalysts
N2 physisorption was used to measure the mesoporous structure of the bioreduction catalysts. Fig. 1(I) and (II) shows the
N2 adsorption/desorption isotherms and pore size distributions,
respectively. All the samples followed Langmuir type IV isotherms
with hysteresis loop at the high P/P0 ; revealing the typical mesoporous material [24]. Pore structure parameters, viz. specic area
(SBET ), pore volume (VP ) and pore diameter (DP ), are listed in Table 1.
The SBET and VP decreased slightly after the incorporation of the
AuNPs into the mesoporous channels of the support. SBET decreased
from 388 to 364 m2 g1 and VP decreased from 0.31 to 0.25 cm3 g1 ,
as comparing the catalyst (Au loading of 0.9%) with the pristine TS1 support. However, the pore size distribution (Fig. 1(II)) and the
mean pore diameter (Table 1) both indicate the slight increase of
DP (from 4.5 to 5.3 nm), probably due to the extension role of the
AuNPs consistent with literature [25].
TEM was used to determine the morphology and particle size of
the bioreduction catalysts. Images of the AuNPs over the support
and the size distribution are presented in Fig. 2. As illustrated, all

Table 1
Structural property of the bioreduction catalysts.
Samplea

SBET (m2 g1 )

VP (cm3 g1 )

DP (nm)

TS-1
Au/TS-1(0.1%)
Au/TS-1(0.3%)
Au/TS-1(0.5%)
Au/TS-1(0.7%)
Au/TS-1(0.9%)

388
383
372
372
368
364

0.31
0.28
0.26
0.26
0.27
0.25

4.5
5.2
4.7
6.0
5.1
5.3

The numbers in parenthesis represent Au loading.

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G. Zhan et al. / Chemical Engineering Journal 187 (2012) 232238

Fig. 2. Representative TEM images of Au catalysts with Au loading of 0.3%. The inset in (b) indicates the size distribution of the AuNPs thereof.

catalysts presented the spherical Au particles distributing well on

the support, regardless of the Au loading (only catalyst with Au
loading of 0.3% shown in Fig. 2). Measurement of size distribution
based on the images showed a mean particle size of 3.0 nm and a
narrow distribution range of 2.34.3 nm.
The crystalline phase of the catalyst was characterized by powder XRD. The XRD patterns of the bioreduction catalysts along with
the pure support are shown in Fig. 3. As shown, the orthorhombic
MFI structures of the catalysts were kept without obvious change
after loading the Au on the support [26] but the intensity of the
diffraction peak at 38.2 corresponding to the (1 1 1) diffraction
planes of cubic Au (JCPDS No. 03-065-2870) increased with increasing Au loading, indicating the presence of metallic gold phase. On
the other hand, the diffraction peaks due to cubic Au are quite weak
due to the high dispersion of the AuNPs within the TS-1 framework
[24].
XPS technique was used to determine the electronic state of
Au [21] and the spectra of Au 4f region are presented in Fig. 4.
The spectrum of the catalyst precursor (viz. pure support adsorbed
chloroauric acid) with an Au 4f7/2 signal around 85.5 eV (Fig. 4a)
conrmed Au species had not been reduced yet. However, the
fresh catalysts showed the Au 4f7/2 signal with a lower position
at 83.7 eV (Fig. 4b), which indicated Au ions were reduced to the
metallic phase. Particularly, metallic gold was the only gold species
observed from the catalysts sample, suggesting complete reduction by the plant biomass (CP extract). Besides, the XPS spectra for
the catalysts before and after the reaction are identical (Fig. 4c)
suggesting that Au maintained Au0 state in the recycled catalysts.

TG and DTG analysis were conducted to examine the residual

plant biomass on the bioreduction Au catalysts. Evidently, Fig. 5
shows that the biomass accounts for 2% of the total weight of
the catalyst (Au loading 0.3%); consistent with the theory that
biomass adheres to AuNPs as a faint thin layer and acts as protective agents preventing the aggregation of the AuNPs [20,27].
The decomposition temperature of the biomass was in the range

Fig. 3. Powder XRD patterns of pure TS-1 (a) and catalysts with various Au loading:
(b) 0.1%, (c) 0.3%, (d) 0.5%, (e) 0.7%, and (f) 0.9%; () Au (1 1 1).

G. Zhan et al. / Chemical Engineering Journal 187 (2012) 232238

Fig. 4. XPS spectra of Au 4f regions recorded on (a) pure support adsorbed chloroauric acid, (b) bioreduction catalyst with Au loading of 0.3% before reaction, and (c)
after reaction.

of 400800 K (inset), showing the capping action of some complicated biomolecules over the catalysts. Actually, catalysts with other
gold loadings all showed the same biomass amount, demonstrating
that the amount of residual biomass on catalyst was dependent on
the CP dosage during the preparation of the catalysts.

3.2. Catalytic activity studies

3.2.1. Effect of reaction time
The conversion of BzOH and the product selectivity were monitored at different reaction intervals. As illustrated in Fig. 6, 21%
BzOH conversion and 96% BzH selectivity were obtained at 0.5 h;
and after allowing the reaction to last for 12 h, 76% conversion and
80% selectivity were determined. The main product was BzOH with
benzoic acid (BzA) and benzyl benzoate (BzB) as by-products; indicating that the oxidation of BzOH occurs within the consecutive
reactions in Scheme 1 [3]. Based on the reaction route, to increase
the conversion of BzOH, the reaction time needs to be prolonged.
However, the BzH selectivity will decrease due to subsequent reaction of BzH to BzA. There was no signicant difference in the BzOH
conversion as increasing the time beyond 6 h, whereas the BzH
selectivity decreased continuously. The BzH selectivity of only 75%
was attained at 24 h, while that of BzA (a by-product) increased to
22%.

Fig. 5. TG and DTG proles of pure support (a) and bioreduction Au catalyst with
Au loading of 0.3% (b).

235

Fig. 6. Effect of reaction time on the conversion of BzOH and product selectivity.
(Conditions: BzOH 29 mmol, H2 O2 36 mmol, catalyst 0.3 g, temperature 80 C, Au
loading 0.3%, and Si/Ti molar ratio 35.)

3.2.2. Effect of reaction temperature

Fig. 7 shows the effect of temperature (3595 C) on the oxidation of BzOH over bioreduction Au catalysts. It can be seen that
BzOH conversion largely increased but BzH selectivity signicantly
decreased with increasing temperature. Particularly, the BzOH conversion was only 20% at 35 C owing to thermal effect on the kinetics
(kinetically controlled) [28]. Therefore, high temperature favors
the reaction as the BzOH conversion increased from 20% to 75%
when the temperature was elevated from 35 C to 95 C. Nevertheless, rapid decomposition of H2 O2 coupled with further oxidation
of BzH at the high temperature, led to lower selectivity to BzH.
The selectivity of BzH decreased from 97% at 35 C to 80% at 95 C.
Therefore, 80 C was considered the optimum reaction temperature considering the tradeoff between BzH selectivity and BzOH
conversion.
3.2.3. Effect of catalyst amount
The BzOH conversion and the selectivities of BzH, BzA and BzB
as a function of catalyst amount are shown in Fig. 8. It is noteworthy
that catalytic activity is directly proportional to the amount of the
catalysts. A negligible conversion of BzOH (only 2%) was obtained
in the absence of the catalysts, indicating that the catalyst is necessary for the BzOH oxidation. The conversion increased from 19%
to 74% by increasing the catalyst amount from 50 to 500 mg. The
higher the catalyst amount, the better the chances for the reactants
(BzOH and H2 O2 ) to react before diffusing out of the catalysts surface. However, the increase inevitably led to the decrease of BzH
selectivity. This was attributed to the further oxidation of BzH in

Fig. 7. Effect of reaction temperature on the conversion of BzOH and product selectivity. (Conditions: BzOH 29 mmol, H2 O2 36 mmol, catalyst 0.3 g, time 6 h, Au loading
0.3%, and Si/Ti molar ratio 35.)

236

G. Zhan et al. / Chemical Engineering Journal 187 (2012) 232238

Scheme 1. The reaction route of BzOH oxidation over bioreduction Au catalyst.

H2 O2 (H2 O2 /BzOH molar ratio of 1.25), whereas inferior activity

was as a result of either excessive or inadequate amount of H2 O2 .

Fig. 8. Effect of catalysts amount on the conversion of BzOH and product selectivity.
(Conditions: BzOH 29 mmol, H2 O2 36 mmol, temperature 80 C, time 6 h, Au loading
0.3%, and Si/Ti molar ratio 35.)

the excess catalysts. In fact, side reactions are also facilitated by

the catalysts; hence 300 mg is considered the optimum amount of
the catalyst.
3.2.4. Effect of H2 O2 amount
The catalytic performance of BzOH oxidation as a function of
H2 O2 amount is depicted in Fig. 9. The amount of H2 O2 plays a crucial role in the BzOH oxidation, especially when the H2 O2 /BzOH
molar ratio is lower than the stoichiometric ratio. The data (from
Fig. 9) clearly indicates that the conversion of BzOH was signicantly higher with high H2 O2 amount. Nevertheless, higher amount
of H2 O2 is accompanied by over oxidation of BzH and the decomposition of H2 O2 to water. As a result, higher amount of H2 O2 has
a detrimental effect on the BzH selectivity. The BzOH conversion
remained about 67% after adjusting the H2 O2 /BzOH molar ratio
from 1.25 to 1.5. However, it turned to decrease noticeably as the
H2 O2 amount was increased to the highest (molar ratio of 1.75).
Thus, the optimal activity was achieved with medium amount of

Fig. 9. Effect of H2 O2 amount on the conversion of BzOH and product selectivity.

(Conditions: BzOH 29 mmol, catalyst 0.3 g, temperature 80 C, time 6 h, Au loading
0.3%, and Si/Ti molar ratio 35.)

3.2.5. Effect of Au loading

The catalytic performance of the bioreduction catalysts with
various Au loading (0.10.9%) is shown in Fig. 10. It can be seen that
Au loading had a remarkable effect on BzOH conversion while little
on product selectivity. The turnover frequency (TOF) values, based
on the molar of converted BzOH per molar Au per hour, are 1777,
709, 368, 258 and 194 for 0.1, 0.3, 0.5, 0.7 and 0.9% Au loadings,
respectively. In fact, the catalyst properties are closely associated
with two factors: the amount of Au active sites and the size of Au.
Higher loading obviously ensures sufcient active Au sites; however, larger Au particles are usually obtained at higher Au loading
even with the same preparation method [29]. We found almost no
observable Au particles in the TEM images at low Au loading (0.1%)
but many invisible Au clusters might be entrapped within the
support, which are beyond the range of TEM observations. Therefore, we conclude that the bioreduction catalysts with very low Au
loading had very small Au size (below 1 nm). Liu et al. found that the
catalytic activity for BzOH oxidation decreased monotonically with
increasing Au particle size; indicating that small Au particles were
responsible for the high catalytic activity [30]. Consequently, the
optimal Au loading is 0.3% as it was the best compromise between
the Au active sites and particle size.
3.2.6. Effect of Si/Ti molar ratio
Fig. 11 shows the comparison of catalytic performance of six catalysts with different Si/Ti molar ratios. The Si/Ti molar ratio of the
catalysts is another important factor inuencing the catalytic performance (from Fig. 11). The catalyst with a Si/Ti molar ratio of 100
gave rise to BzOH conversion of only 35% whilst that with a ratio
of 35 resulted gave much higher conversion of 66%. To our knowledge, the acidity of the catalysts depends strongly on the amount
of Ti atoms (Lewis acid sites) in the MFI framework [24]. Lewis
acid sites are reported to be favorable to the catalytic oxidation of
BzOH with H2 O2 [31]. Therefore, increasing the amount of Ti atoms
would enhance the catalytic ability for selective oxidation of BzOH

Fig. 10. Effect of Au loading on the conversion of BzOH and product selectivity.
(Conditions: BzOH 29 mmol, H2 O2 36 mmol, catalyst 0.3 g, temperature 80 C, time
6 h, and Si/Ti molar ratio 35.)

G. Zhan et al. / Chemical Engineering Journal 187 (2012) 232238

237

Table 2
The comparison of BzOH oxidation catalyzed by Au catalysts.
Catalyst

Yielda (%)

TOFb (h1 )

Ref.

Bioreduction Au
Au/C
Au/zeolite-Y
Au/HMS
Au/TiO2
Au/SBA
Au/U3 O8

56
4
94
41
39
2
85

709
1676
11
98
6348
1937
128

This work
[23]
[9]
[32]
[10]
[11]
[33]

BzH yield = the product of BzOH conversion and BzH selectivity.

Measured on the basis of ratio of moles of converted BzOH per mole of Au per
hour.
b

Fig. 11. Effect of Si/Ti molar ratio on the conversion of BzOH and product selectivity.
(Conditions: BzOH 29 mmol, H2 O2 36 mmol, catalyst 0.3 g, temperature 80 C, time
6 h, and Au loading 0.3%.)

to BzH. However, too many Ti atoms (Si/Ti molar ratio of 10 or 20)

may result in loss of catalytic activity due to the decreasing catalyst crystallinity by the extra framework of Ti sites [24]. Hence, the
optimum Si/Ti molar ratio is 35.
3.2.7. Durability of the bioreduction catalysts
One major problem of heterogeneous catalysts is the leaching
of metal, which leads to loss of catalyst activity on subsequent
uses. In order to assess the durability of the bioreduction Au catalysts, recycle tests were conducted. The catalysts after reaction
were recovered by centrifugation and washed with ethanol, then
dried and reused for another reaction under the same conditions.
Shown in Fig. 12, the conversion of BzOH and selectivity of BzH
remained the same (within experimental error) during ve consecutive cycles, indicating the remarkable stability of the bioreduction
Au catalysts. It gave a total turnover number (TON) of 21,270 after
ve recycles and a TOF of 709 h1 in 6 h. Note that the bioreduction
Au catalysts were not calcined (to remove the plant biomass on the
catalysts (Fig. 5)). In contrast, Au catalysts prepared by chemical
processes (with PVA as protecting agents and NaBH4 as reductants)
are subjected to the heat treatment for the removal of protecting
agents (PVA) from the surface of the Au to increase its accessible
surface area [10]. Therefore, we proposed that the plant biomass, as
both the protecting and reducing agents, adhered to the AuNPs as a
faint thin layer, is able to prevent the leaching of Au and yet does not
offer overprotection; thereby contributing to excellent durability of
the bioreduction Au catalysts.

3.2.8. Comparison of bioreduction catalyst with analogous

catalysts
The yield of BzH and the TOF for liquid phase BzOH oxidation
with the bioreduction Au catalysts herein and other Au-based catalysts reported in the literatures are compared in Table 2. Obviously,
the catalytic performance of the bioreduction Au catalysts is comparable and superior (in some cases) to that of catalysts prepared
by conventional chemical methods (DP, impregnation, etc.). Higher
BzH yield and higher TOF values were simultaneously achieved
with the bioreduction Au catalysts.
4. Conclusions
In conclusion, an efcient and eco-friendly process for the
oxidation of BzOH to BzH over bioreduction Au catalyst was demonstrated in this work. The most suitable conditions, reaction time
of 6 h, temperature of 80 C, catalyst amount of 0.3 g, H2 O2 /BzOH
molar ratio of 1.25, Au loading of 0.3% and support Si/Ti molar ratio
of 35, were obtained. The catalysts were recyclable for up to ve
runs consecutively without any appreciable loss of activity and
selectivity. The plant biomass contributes to the durability of the
bioreduction catalyst by immobilizing the AuNPs and preventing
leaching. Since the bioreduction Au catalyst is able to oxidize BzOH
to BzH with high activity, highly recyclable, remarkably stable and
above all, environmentally friendly, they hereby are promising for
the industrial application.
Acknowledgments
This work was supported by the Fundamental Research Funds
for Central Universities (No. 2010121051), the NSFC projects
(Nos. 21036004, 21106117 and 20976146), the Research Fund
for the Doctoral Program of Higher Education of China (Nos.
20100121110032 and 20110121120018), and the NSF-Fujian
projects (Nos. 2010J05032 and 2010J01052).
References

Fig. 12. The catalytic performance of recycling bioreduction catalysts. (Conditions:

BzOH 29 mmol, H2 O2 36 mmol, catalyst 0.3 g, temperature 80 C, time 6 h, Au loading
0.3%, and Si/Ti molar ratio 35.)

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