Visible-Light-Induced Efficient Selective Oxidation of Nonactivated Alcohols over {001}-Faceted TiO2 with Molecular Oxygen

Article abstract of DOI:10.1002/asia.201601064

In the presence of molecular oxygen, a {001}-faceted nanocrystalline anatase TiO₂ catalyst enabled the selective oxidation of nonactivated aliphatic alcohols to the corresponding aldehydes or ketones under visible light. The reaction shows excellent conversion and selectivity towards the formation of the carbonyl products without over-oxidation to the corresponding carboxylic acids. The exceptional reactivity of the catalyst is possibly due to the absorption of visible light originating from a stronger interaction of alcohol with the {001} facet, which facilitates the modification of the band structure of TiO₂, thus facilitating the photogenerated hole transfer and subsequent oxidation processes. The experimental results have also been corroborated by first-principles quantum chemical DFT calculations.

Full text of DOI:10.1002/asia.201601064

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Visible light induced Efficient Selective Oxidation of Non-Activated Alcohols
over 001 Faceted TiO2 with Molecular Oxygen
Authors: Subhash Chandra Ghosh; Raji Vadakkekara; Abul Kalam Biswas; Tapan
Sahoo; Provas Pal; Biswajit Ganguly; Asit Baran Panda
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To be cited as: Chem. Asian J. 10.1002/asia.201601064
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Chemistry - An Asian Journal
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Visible light induced Efficient Selective Oxidation of Non-
Activated Alcohols over {001} Faceted TiO2 with Molecular
Oxygen
Raji Vadakkekara, Abul Kalam Biswas, Tapan Sahoo, Provas Pal, Bishwajit Ganguly,* Subhash
Chandra Ghosh* and Asit Baran Panda*
Abstract: In the presence of molecular oxygen, a {001} faceted
nanocrystalline anatase TiO2 catalyst enables the selective oxidation
of non-activated aliphatic alcohols to the corresponding aldehydes or
ketones in presence of oxygen under visible light. The reaction
shows excellent conversion and selectivity towards the formation of
the carbonyl products without over-oxidation to the corresponding
carboxylic acids. The exceptional reactivity of the catalyst is possibly
due to the absorption of visible light originating from stronger
interaction of alcohol with (001) facet, which facilitates the
modification of band structure of TiO2, thus facilitating the photo-
generated hole transfer and subsequent oxidation processes. The
experimental results have also been corroborated by first principal
quantum chemical DFT calculations.
Thus, it is essential to develop a simple, energy efficient catalytic
procedure for selective oxidation of non-activated alcohols.
In recent years, harvesting of solar energy to obtain
chemical energy, i.e., visible light driven chemical conversion
(photocatalysis) has been triggered worldwide, as it is the only
sustainable energy resource on earth and is produced through
clean and economical path.[7] In the direction of sustainable
development, heterogeneous room temperature based
photocatalytic routes for selective oxidation of alcohols to the
corresponding carbonyls in combination with O2 as oxidant,
without over oxidation to carboxylic acids, have been introduced
and a number of photocatalysts have been developed, including
CdS, carbon nitride, TiO2, Ta2O5.[8-13] Although, all the catalysts
showed moderate to good results for different activated alcohols
(benzylic or allylic), however to the best of our knowledge, there
has been no report on selective oxidation of non-activated
aliphatic/cyclic alcohols.
Introduction
Among the developed photocatalysts, TiO2 has been studied
extensively, as it is cheap, abundant and chemically stable.[8-11] It
is well documented that activity of TiO2 is highly controlled by its
polymorph, exposed facet, size, shape and surface area.[14]
Specifically, nanocrystalline anatase TiO2 with exposed high
energy {001} facet is catalytically more active than other.[15]
However, Lu et.al.,[10] reported that there are no distinct facet
selective effect of TiO2 nanocrystals for selective oxidation of
alcohol under VU light. Here, it is noteworthy to mention that for
alcohol oxidation TiO2 is active in both UV and visible light, but
their energy (habsorption mechanism is different. Under UV
light, it absorbs energy directly through band excitation, whereas
under visible light, through modified band structure originate
from alcohol adsorbed on the TiO2.[9] Thus, it is expected to have
a distinct facet selective catalytic activity under visible light, as it
is supposed to vary the extent of adsorption of alcohol on TiO2
surface with specific surface energy, in turn catalytic activity.
Thus, there remains a definite possibility to develop efficient
visible light driven photocatalytic process for selective oxidation
of non-activated aliphatic/cyclic alcohols to the corresponding
carbonyl compounds using a specific phase and facet selective
nanocrystalline TiO2.
Herein, we have developed nanocrystalline (001) faceted
anatase TiO2 as an efficient visible light active photocatalyst for
selective oxidation of non-activated aliphatic/cyclic alcohol to
corresponding aldehyde/ketone. The origin of superior activity of
(001) faceted anatase TiO2 over other TiO2 nanoparticles have
also been corroborated by first principal quantum chemical DFT
calculations. Based on our knowledge, this is the first report on
photocatalytic selective oxidation of non-activated alcohol to
aldehyde/ketone. Here it is essential to mention that simple
house hold 40W CFL lamp is used to make the procedure easier.
The selective oxidation of non-activated alcohols to
corresponding aldehydes or ketones is a fundamental synthetic
transformation given the abundance of the resulting carbonyl
compounds in numerous fine chemicals, pharmaceuticals,
flavour and fragrances, and biologically active compounds.[1-2] In
general, stoichiometric strong oxidants are used to accomplish
the reaction in-turn producing hazardous wastes.[3] With ever
growing environmental concern, development of simple room
temperature (RT) protocols using O2 as a stoichiometric oxidant
is highly in demand as an attractive alternative to the traditional
approach because, it generates mainly water as a by-product.[4]
Thus, numerous transition metal based homogeneous and
heterogeneous catalysts have been developed for the
purpose.[4b,5-6] However, homogeneous catalysts require
additives and/or bases and are not reusable.[5] Whereas, most of
the heterogeneous catalysts are based on costly metals.
Catalytic efficiencies of non-noble metal based catalysts are
low.[6] Both the catalytic system required temperature and
Dr. R. Vadakkekara, Mr. A. K. Biswas, Mr. T. Sahoo, Dr. P. Pal, Dr.
B. Ganguly, Dr. S. C. Ghosh, Dr. A. B. Panda
Central Salt and Marine Chemicals Research Institute (CSIR-
CSMCRI) and CSMCRI-Academy of Scientific and Innovative
Research
G. B. Marg, Bhavnagar-364002, Gujarat,
India.
E-mail: abpanda@csmcri.org, scghosh@csmcri.org ;
ganguly@csmcri.org
Supporting information for this article is given via a link at the end of
the document.
selective oxidation of non-activated alcohols are rarely reported.
1
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Chemistry - An Asian Journal
10.1002/asia.201601064
The use of CFL helped to avoid the required precautions to
manage the heat generated from the generally used Xe-lamp
for good activity. Synthesized {001} faceted anatase TiO2 is too
active to give excellent results under the used CFL lamp.
compared to other tested facet and phase selective TiO2
nanoparticles while commercial P25 showed lowest activity. The
{001} faceted TiO2 nanoparticles ended with >90% conversion
(GC) of 1-octanol with 100% selectivity of 1-octanal after 24h of
reaction. No over oxidation product was detected in GC/GC-MS,
which indicates the 100% selectivity of octanal. Furthermore, ~
85% isolated yield confirmed the extremely high selectivity of the
performed reaction. The photocatalytic activity of facet selective
TiO2 follows the following order (001)>>(101)>(100) of reactivity.
The calculated reaction rate (10 µmol h-1), turn-over frequency
(8.9 h-1) and turnover number of 215 for (001) faceted TiO2 are
reasonably higher compared to that of other tested TiO2 (Table
S1, Supporting Information). Further, systematic solvent
screening experiments evidenced the BTF to be ideal solvent for
the performed alcohol oxidation (Figure 2). This is most probably
due to the superior oxygen storage capacity of BTF. The catalyst
is reusable at least 6 times for consecutive cycles (Figure S5,
Supporting Information). The obtained yield is quite superior to
that of literature reported results for selective octanol oxidation
Results and Discussion
From the above mentioned alcohol oxidation reactions, varying
phase and specific facet exposed TiO2 nanoparticles were
synthesized using previously reported methods. {001} faceted
highly truncated octahedral TiO2 nanoparticles and layered
titanate were synthesized following our recently developed
fluorine free protocol under hydrothermal conditions, using
aqueous soluble peroxo-ammonium carbonate complex solution
as precursor.[15] {100} and {101} faceted anatase, rutile and
brookite TiO2 nano particles were synthesized using the method
as reported by Liu et al.[10] The detailed synthetic methods and
corresponding characterization results are presented in
Supporting Information (Supporting experimental procedures
and Figure S1-S3, Supporting Information).
to
octanal
using
transition/noble
catalysts
metal
at
based
homogeneous/heterogeneous
elevated
temperatures (Table S2, Supporting Information).
Afterward, the scope and limitations of the presently
developed and optimized protocol were evaluated by using a
large variety of non-activated aliphatic / cyclic primary,
Figure 1. Visible light driven photocatalytic activity of different nanostructured
facet selective anatase TiO2 (TiO2-A) and other polymorphs of TiO2 (Rutile:
TiO2-R, Brookite: TiO2-B) for selective oxidation of octanol to octanal.
Figure 2. Visible light induced photocatalytic performance of (001) faceted
TiO2 in oxidation for selective conversion of 1-Octanol to 1-Octanal in different
solvents.
All the synthesized TiO2 nano particles were used for visible
light driven photocatalytic selective oxidation of non-activated
alcohols to corresponding carbonyl compounds under 40W
simple house hold CFL lamp. To find out an active catalyst
capable of oxidizing non-activated alcohols efficiently and
selectively in the presence of molecular oxygen as oxidant,
octanol (C8H17OH, simple C8 long chain alcohol) was initially
chosen as a model substrate and BTF (benzotrofluoride) as
solvent. It was observed that the concentration of photo-formed
octanal, corresponding aldehyde, was increased gradually with
the time of exposure to visible light for the whole reaction system.
However, the reactivity varied with the phase and corresponding
exposed facet. All the catalysts ended with 100% selectivity of
octanal (Figure 1, Figure S4 and Table S1 Supporting
Information). From the Figure 1, it is evident that the {001}
facetted anatase TiO2 nanocrystals showed superior catalytic
activity, with respect to conversion and rate of reaction,
2
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Chemistry - An Asian Journal
10.1002/asia.201601064
the TiO2 showed similar trend of photocatalytic activity for benzyl
alcohol oxidation as obtained for octanol oxidation and {001}
faceted TiO2 showed superior activity (Figure S6, Supporting
Information). However, the rate of photocatalytic oxidation of
benzyl alcohol is much faster than that of octanol and completed
(100% conversion) within
6 h with 100% selectivity of
benzaldehyde. The calculated rate of reaction is 71.1 µmolh-1,
almost 7 times higher than octanol oxidation. Difference in
photocatalytic activity of (001) faceted TiO2 for benzyl alcohol
oxidation is more prominent and the reaction rate more than
double than that of other TiO2. The obtained photocatalytic
activity of (001) faceted TiO2 in terms of overall rate and yield is
much superior to that of other literature reported photo-catalysts,
including TiO2, as well as other homogeneous/heterogeneous
thermo-catalyst (Table S3, Supporting Information). {001}
faceted TiO2 nano particles were also applied for visible light
driven selective oxidation of other activated benzylic/allylic
alcohols to evaluate the scope and limitations of the developed
protocol and the results are summarized in Scheme 2. It is
important to mention that both electron-donating and electron-
withdrawing substituents at ortho-, meta- and para- position
work excellently and almost quantitative yield of corresponding
aldehydes were obtained (Scheme 2, 4b-h). Oxidation of
cinnamyl alcohols also worked smoothly (4m-n). Benzylic
secondary alcohols, were also converted to the corresponding
keto compounds (4o-q) with good to excellent yields. Methanol’s
bearing heterometic substituents also underwent the desired
oxidation (4s-u).
Scheme 1. Visible light driven aerobic oxidation of non-activated
aliphatic/cyclic alcohol using over (001) faceted TiO2 in presence of O2;
Substrate: 0.5mmol, BTF (solvent): 1.5ml; Atmosphere: oxygen; Catalyst TiO2:
15mg.
Mechanistic Study.
To understand the mechanism of the performed reaction and
origin of superior activity of {001} faceted TiO2, we did some
additional control experiments, as well as theoretical studies
(DFT calculations). In control reactions, under dark condition
and without catalyst, no product was formed in both the cases,
confirming that the reaction took place only when exposed to
light (Table S1). During alcohol oxidation, TiO2 adsorbed visible
light through energy level modification by alcohol adsorption.
Thus, it is observed that the extent of adsorption is prime
controlling factor for its activity.[9] The light absorption
characteristic of octanol absorbed TiO2 dispersed in BTF was
investigated. All the pure TiO2 showed similar absorption
characteristics and was adsorbed only in UV region. Whereas, a
threshold absorption in visible region was observed for octanol
adsorbed TiO2 (Figure 3). However, the extent of visible light
absorption was observed to vary with TiO2. Both the {001} and
{101} faceted TiO2 absorbed visible light strongly than that of
other TiO2. These absorption characteristics imply that the
extent of binding of octanol in {001} and {101} facets of TiO2 is
more and should give high catalytic activity. Practically, similar
trend of catalytic activity is found. In another set of controlled
experiments for octanal oxidation reactions with as-synthesized,
dried (200°C), calcined (500°C) {001} faceted and HF treated
TiO2 showed that the as-synthesized TiO2 ended with maximum
secondary, branched alcohols under the optimized reaction
conditions (optimized for octanol) and the results are
summarized in Scheme 1. Most of the simple long chain and
branched primary aliphatic alcohols were converted into the
corresponding aldehydes with high to excellent yields (>85%,
2a-d, 2f-g), except hexadecane-1-ol. Hexadecane-1-ol
converted to palmitaldehyde (2e) with 45% conversion and the
yield is lower due to the solubility of the hexadecane-1-ol in the
reaction medium. Secondary aliphatic alcohols were also
converted to corresponding ketones with moderate yield (>60%,
2h-i). Alcohols with unsaturated group (alkene and alkyne) were
converted to the corresponding aldehyde/ketone giving an
excellent yield without affecting alkene and alkyne groups (2j-m).
Cyclic aliphatic alcohols
were also converted to the
corresponding aldehyde/ ketone compounds in excellent yields
(2j-m).
Although the obtained results for visible light driven
photocatalytic selective oxidation of non-activated alcohols to
the corresponding carbonyl compound are excellent, but it is not
possible to compare the activity with literature reported results,
as there are no such reports available. All the reports are on
selective oxidation of activated benzylic/allylic alcohol.[17] With
the promising results for aliphatic/cyclic aldehyde/ketone
synthesis, further exploration was done to check the possibility
to extend the alcohol oxidation reaction towards selective
oxidation of activated benzylic/allylic alcohols to the
corresponding aldehydes/ketones, which are more prone to
over-oxidation to corresponding carboxylic acid. All the tested
TiO2 for the oxidation of benzyl alcohol had been well utilized. All
3
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Chemistry - An Asian Journal
10.1002/asia.201601064
replacement of hydroxyl group by fluoride in the calcined and HF
treated samples, respectively. As-synthesized TiO2 having
maximum hydroxyl groups showed higher activity due to higher
concentration of surface hydroxyl groups facilitate to absorb
reactant molecules. . 36% conversion of octanol after 24h for
photocatalytic
oxidation
of
octanol
in
nitrogen
atmosphere(withoutoxygen) was obserev which confirmed that
the reaction undergoes photocatalytic way (Table S1,
Supporting Information). Photocatalytic activity of TiO2 is mainly
related to the formation of electrons and holes in conduction and
valence bands, respectively, through the adsorption of photon
energy. Subsequently, oxidation took place in valence band
through the transformation of photo-generated holes to the
surface adsorbed octanol and resulted in the oxidized product
octanal. During photo-induced selective oxidation of octanol to
octanal under nitrogen atmosphere, TiO2 acts as acceptor for
electrons and protons. Li et.al.,[8] showed the presence of
enhanced Ti3+ and surface hydroxyl group of the used catalyst
under N2 environment due to the acceptance of electrons and
protons. However, this process is slow and in-turn the reaction
proceeds slowly. Whereas, in presence of oxygen, oxygen acts
as acceptor and as a result the reaction rate is high. Selective
photocatalytic oxidation of octanol to octanal is a two electron
transfer process. However, enormous electron-hole pair is
generated continuously on photo-irradiation. Thus, there is a
definite probability of over oxidation of oxidized product, but here
only first oxidation product was obtained, i.e., octanal selectively
and the obtained carbon balance was >98%.
Scheme 2. Visible light driven aerobic oxidation of activated benzylic- / allylic-
alcohol using over (001) faceted TiO2 in presence of O2; Substrate: 0.5mmol,
BTF (solvent): 1.5ml; Atmosphere: oxygen; Catalyst TiO2: 15mg.
Thus, to understand the origin of high selectivity of carbonyl
compound, without over oxidation, and superior reactivity of
{001} faceted TiO2, we performed the DFT calculations to
evaluate the possible electronic interaction of benzyl alcohol and
benzaldehyde on {001} and {101} facet of TiO2. Both the alcohol
and aldehyde groups can coordinate through the oxygen atom of
the functional group with TiO2 surface and corresponding
adsorption energy (Figure 4) has been calculated. The
calculated adsorption energies of benzaldehyde on {001} &
{101} surface are -26.0 & -5.9 kcal/mol respectively and the
adsorption energies of benzyl alcohol on {001} & {101} surface
are -28.9 & -7.4 kcal/mol, respectively Energy calculations
suggest that benzaldehyde is bounded weakly to the TiO2
surface than the benzyl alcohol. These results suggested that
the benzaldehyde can be released easily from the TiO2 surface
immediately after transformation of alcohol to aldehyde and
restricts over oxidation.[18] Such process is termed as “self-
adjustable photo-oxidation system”.[8] Further, reasonably high
absorption energy of benzyl alcohol on {001} surface (28.9
kcal/mol) compared the most stable {101} (-7.4 kcal/mol) implies
that benzyl alcohol interacts with {001} surface. Such preference
might facilitate the hole transfer process, i.e., oxidation and
resulted in much higher visible light driven photocatalytic activity.
Therefore, the DFT results suggest that the transformation of
alcohol to aldehyde would be more preferred in {001} TiO2
surface than {101} surface and hence the adsorption can affect
the reactions and products. Thus the DFT calculated results
corroborate the experimental findings.
Figure 3. UV-vis absorption spectra of octanol absorbed different facet
selective anatase TiO2 and TiO2 with different phase dispersed in BTF.
conversion with 100% selectivity of octanal (Table S4,
Supporting Information). This is due to the variation of
concentration of surface hydroxyl groups, as the adsorption of
octanol on TiO2 surface takes place through interaction with
surface hydroxyl group and act as active sites. FTIR spectra of
corresponding TiO2 samples are also evident that as-
synthesized and dried TiO2 contains maximum surface hydroxyl
group (Figure S7, Supporting Information). Surface hydroxyl
group was reduced for de-hydroxylation during calcination or
4
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Chemistry - An Asian Journal
10.1002/asia.201601064
alcohol to corresponding carbonyl compound over (001) faceted
TiO2 at room temperature using O2 as oxidant and simple house
hold 40W CFL lamp as visible light source. {001} faceted
anatase TiO2 nanocrystals showed 90% conversion of 1-octanol
with 100% selectivity of 1-octanal which is superior than that of
other phase and facet selective TiO2. Experimental results
evidenced that {001} faceted TiO2 showed superior activity due
to absorption of light in visible range through stronger adsorption
of alcohol in {001} facet of TiO2. This was further corroborated
by computational DFT calculations and showed adsorption
energy of alcohol on {001} facet to be quite higher than that of
{101} facet. Further, due to lower adsorption energy of aldehyde
(product), the photo-generated aldehyde went out from TiO2
surface and restricted over oxidation. The obtained catalytic
activity is much higher than that of other reported metal based
homogeneous /heterogeneous catalyst as well as photocatalysts.
Thus, it is expected that the synthesized {001} faceted TiO2
should have
a wide range of potential applications in
Figure 4. The optimized geometries of TiO2-absorbed systems: (a) (101) TiO2-
benzyl alcohol, (b) (001) TiO2-benzyl alcohol, (c) (101) TiO2-benzaldehyde, (d)
(001) TiO2-benzaldehyde and corresponding absorption energies in kcal/mol.
photocatalytic organic transformation.
Acknowledgements
From the above discussed experimental results and
theoretical study, a probable path has been proposed for the
performed selective oxidation of octanol to octanal using {001}
faceted nanocrystalline TiO2 under visible light (Scheme 5). In
the first step, alcohol adsorbed on TiO2, generate a new energy
level through charge transfer which is capable of absorbing
visible light (hγ) and hence generate photo-excited electron hole
pairs in the new band structure. Then, adsorbed alcohol
transformed into its oxidized state through transformation of
photo-generated hole from VB. Successively, the oxidized state
of alcohol was converted to corresponding carbonyl compound
by releasing protons and electrons. Simultaneously, oxygen (O2)
acted as acceptor of electrons and formed superoxide radical
CSIR-CSMCRI Communication No. 054/2016. Authors earnestly
acknowledge the financial support from the Science and
Engineering Research Board, New Delhi, India in form of a
research grant (NO:EMR/2014/001219) to carry out the reported
investigation. The authors also acknowledge the ‘‘AD&CIF’’ of
CSMCRI for providing instrumentational facilities. R.V. is
thankful to UGC for Post-doctoral research fellowship.
Keywords: aliphatic alcohol • nanoparticles • Photooxidation •
TiO2 • visible light
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5
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10.1002/asia.201601064
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Chemistry - An Asian Journal
10.1002/asia.201601064
Entry for the Table of Contents
FULL PAPER
Visible light induced efficient
photocatalytic selective oxidation of
non-activated aliphatic/cyclic
alcohols over {001} faceted TiO2
nanoparticles in the presence of
molecular oxygen is presented. The
superior activity of {001} faceted TiO2
has also been corroborated by first
principal quantum chemical DFT
calculations.
Raji Vadakkekara, Abul Kalam Biswas,
Tapan Sahoo, Provas Pal, Bishwajit
Ganguly,* Subhash C. Ghosh* and Asit
Baran Panda*
Page No. – Page No.
Visible light induced Efficient
Selective Oxidation of Non-
Activated Alcohols over {001}
Faceted TiO2 with Molecular Oxygen
7
This article is protected by copyright. All rights reserved