Accepted Manuscript

Effect of electrochemical reduction on the structural and electrical properties of anodic

TiO2 nanotubes

Muhammad Asim Rasheed, Kamran Ahmad, Nilem Khaliq, Yaqoob Khan,

Muhammad Aftab Rafiq, Abdul Waheed, Attaullah Shah, Arshad Mahmood, Ghafar
Ali
PII: S1567-1739(18)30001-4
DOI: 10.1016/j.cap.2018.01.001
Reference: CAP 4655

To appear in: Current Applied Physics

Received Date: 8 November 2017

Revised Date: 24 December 2017
Accepted Date: 3 January 2018

Please cite this article as: M.A. Rasheed, K. Ahmad, N. Khaliq, Y. Khan, M. Aftab Rafiq, A. Waheed, A.
Shah, A. Mahmood, G. Ali, Effect of electrochemical reduction on the structural and electrical properties
of anodic TiO2 nanotubes, Current Applied Physics (2018), doi: 10.1016/j.cap.2018.01.001.

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 ACCEPTED MANUSCRIPT

Effect of Electrochemical Reduction on the Structural and Electrical

Properties of Anodic TiO 2 Nanotubes

Muhammad Asim Rasheed*1, Kamran Ahmad2, Nilem Khaliq2, Yaqoob Khan3, Muhammad Aftab

Rafiq1, Abdul Waheed4, Attaullah Shah5, Arshad Mahmood5, Ghafar Ali*6

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Department of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and Applied

Sciences (PIEAS), Islamabad 45650, Pakistan

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Department of Physics and Applied Mathematics, Pakistan Institute of Engineering and Applied

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Sciences (PIEAS), Islamabad 45650, Pakistan
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Nanosciences and Catalysis Division, National Centre for Physics, Islamabad 45320, Pakistan
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Department of Physics, Islamia College, Peshawar 25120, Pakistan
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National Institute of Laser and Optronics (NILOP), Islamabad 45650, Pakistan
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Nanomaterials Reasearch Group, Physics Division, PINSTECH, Islamabad 45650, Pakistan
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*masimr22@gmail.com, *ghafarali@kaist.ac.kr
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Abstract
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The effect of electrochemical reduction on the structural and electrical properties of

amorphous as well as annealed TiO2 nanotubes (TNTs) is investigated under ambient

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conditions. TNTs were prepared by anodizing titanium sheet in ethylene glycol electrolyte

containing NH4F and de-ionized water at 40 V for 6 h. Electrochemical reduction is carried

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out in 1 M aqueous KOH solution for ~15 second at 3 V. TNTs are characterized by SEM,
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XRD, XPS and impedance spectrometer. XRD results confirm an increase in d-spacing for

(101) and (200) planes, after electrochemical reduction. XPS data reveal that electrochemical

reduction produced prominent shifts of ~0.7-1.0 eV in the binding energies of TNTs.

Interestingly, these shifts recover completely (in case of amorphous TNTs) and partially (in

case of anatase TNTs) within ~ 7 days after reduction process due to oxygen uptake. Partial

recovery in the binding energies of anatase TNTs is due to the fact that the oxygen vacancies
are thermodynamically more stable compared to amorphous TNTs. Similarly, the
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electrochemical reduction process decreases the impedance values of TNTs by more than

three orders of magnitudes (from MΩ to kΩ). The impedance values also recover to the

similar values before reduction in a span of ~7days.

Key words: Anodization; TiO2 nanotubes; electrochemical reduction; oxygen uptake

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1. Introduction ACCEPTED MANUSCRIPT
TiO2 has been synthesized in various shapes and morphologies such as nanotubes [1-

10], nanoporous structure [11], nanowires [12], nanoparticles [13-15], thin films [14, 16-19]

and nanobelts [20]. Recently TiO2 nanotubes (TNTs) prepared by anodization attracted

considerable interest due to its self-organized, highly-ordered and vertically oriented

morphology [10]. Among all the existing morphologies, nanotubes are known for their large

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surface area [21], which makes them useful for a large number of applications such as solar

cells [22], water splitting [23], photo-catalysis [20, 24], gas sensing [25] and drug delivery [7,

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26, 27]. Generally, larger surface area of TNTs provides higher probability of interaction with

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ambient species. Reduced TNTs have also been demonstrated as a promising candidate for

water splitting [23], super capacitors [28], and photocatalytic activity [29]. One of its

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applications as oxygen scavengers has been recently demonstrated by Close et al. [30]. They
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have studied the effect of electrochemical reduction process and subsequent oxygen uptake

on the DC resistivity of TNTs. They have shown that electrochemically reduced TNTs
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reversibly scavenge oxygen at room temperature in a far superior way than the commercial
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oxygen scavengers [30]. It has been found that amorphous TNTs scavenge oxygen better than
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anatase TNTs.

Different phases of TNTs such as anatase and rutile have been synthesized and
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explored for various applications such as photocatalysis and solar cells [21]. However,
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anatase TNTs have demonstrated more promising results than rutile TNTs with regards to
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aforementioned applications [21]. On the other hand, amorphous phase TNTs have not been

probed well [24, 29, 31, 32]. Recent finding of Close et al. regarding the better oxygen

scavenging ability of electrochemically reduced amorphous TNTs compelled us to further

explore its oxygen uptake behavior in a systematic way. To the best our knowledge, there is

no report available on the effect of oxygen uptake on the structural (XPS) and electrical

(impedance) properties of the electrochemically reduced amorphous as well as anatase TNTs.

Therefore, an effort has been made to explore the time dependent XPS and impedance
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responses of electrochemically reduced amorphous and anatase TNTs.

Self-organized and vertically oriented TNTs were prepared by anodizing titanium sheet

in ethylene glycol electrolyte containing NH4F and de-ionized water at 40 V for 6 h. The

synthesized pristine and anatase TNTs were electrochemically reduced in 1 M KOH aqueous

solution at 3 V for ~15 second. After electrochemical reduction process the TNTs were

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studied for the effect of oxygen uptake behavior with time. XPS was performed for

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electrochemically reduced amorphous and anatase TNTs after 1 hour and 7 days,

respectively. The impedance data was taken before, as well as, 5 minutes, 15 minutes, 25

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minutes, 50 minutes, 1 hour and 7 days after electrochemical reduction for amorphous and

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anatase TNTs. AN
2. Materials and Methods

2.1 Materials
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Titanium sheet (Ti, Good fellow England, 0.2 mm thickness, 99.6% purity),
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ammonium fluoride (NH4F, Sigma-Aldrich, 98+ %), ethylene glycol (Sigma-Aldrich, 98+
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%), potassium hydro-oxide (KOH, Sigma-Aldrich) were used in their as-received form

without further treatment.

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2.2 Fabrication of TNTs (TNTs)

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TNTs were fabricated by anodization of Ti-sheet in ethylene glycol (EG) electrolyte

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containing 0.5 wt% NH4F and 0.2 wt% deionized (DI) water (18.2 MΩ-cm) as reported in

[33]. Prior to anodization, Ti-sheets were cleaned by sonicating in acetone and ethanol for 10

min each. Subsequently the Ti-sheets were rinsed with DI water and dried using air blower.

The samples were anodized at 40 V for 6 h in two electrodes system with gold sheet as a

counter electrode and Ti-sheet as an anode. Anodization produced TNTs on the surface of Ti-
sheet exposed to the electrolyte. The pristine nanotubes were annealed at 450 ˚C for 2 h with
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a heating rate of 10 ˚C/min and cooling rate of 3 ˚C/min.

2.3 Electrochemical Reduction

Electrochemical reduction process of TNTs was carried out in 1M aqueous KOH

solution at 3 V for ~15 second using two-electrode system under ambient conditions. An

amorphous or annealed TiO2 nanotube was used as a cathode and gold sheet was used as

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anode. The samples were cleaned with DI water after electrochemical reduction process.

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2.4 Characterization/Measurements
The structural morphology of TNTs was examined by a field emission scanning electron

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microscope (FESEM, TESCAN Mira3, Czech Republic). The crystal structure and phase
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purity of the nanotubes were determined by a high power X-ray machine BRUKER D8 -

Discover (Germany) X-ray diffractometer with Cu Kα radiation (λ =1.54056 A˚). The X-ray
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source was set at an operating voltage of 40 kV and current of 40 mA. X-ray photoelectron
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spectroscopy (XPS) analysis was carried out on an Omicron nanoscience instrument

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(Germany) using an Al Kα X-ray (1486.7 eV) mono energetic source energized to 300 watts.

For XPS scans, the analyzer pass energy was kept constant at 20 eV. Analyzer’s work
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function was 4.5 eV and it was operated in CAE mode, with step size of 0.5 eV. The data

acquisition was performed with Matrix v3.2 software and data analysis was performed with
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Casa XPS and Origin. In order to avoid the sample charging effects during XPS analysis, the
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binding energies were calibrated using C1s peak (284.8eV). Impedance spectra were

collected using Potentiostat /Galvanostat/ZRA reference 3000, from Gamry instruments.

Measurements were performed using home-made spring loaded assembly (with 0.3 cm2

contact area) under ambient conditions. Frequency range from 0.1-106 Hz was used with an

ac excitation voltage of 100 mV.

3 Results and Discussion
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3.1 XRD analysis
XRD patterns of the as-anodized and annealed TNTs are shown in Figure 1a. It can be

seen from the XRD pattern that the as-anodized sample shows only peaks related to titanium

(red line) confirming the amorphous nature of TNTs. The data is matched with JCPDS card

No. 44-1294 indicating that titanium has hexagonal structure with lattice parameters a =

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2.9505 Å and c = 4.6828 Å. When the amorphous TNTs were annealed at 450 ˚C for 2 h,

peaks related to the anatase phase appeared in the XRD pattern (black line). The anatase

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phase has a tetragonal crystal structure with lattice parameters a = 3.7694 Å and c = 9.4306

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Å. The peaks matched well with JCPDS card No. 21-1272 and were in agreement with the

literature [34]. Figure 1b shows comparison of XRD pattern of anatase TNTs before and 1h

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after the electrochemical reduction process. It has been found that electrochemical reduction
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shift the anatase peaks toward lower angle (inset 1(b)). Such changes have also been

observed for TiO2 nanocrystals by others [35]. It is known that electrochemical reduction
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process creates oxygen vacancies in TNTs [30], as a result changes in lattice parameters
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occurs [35]. Due to peak shift of (101) and (200) planes toward the lower 2θ values (Figure
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1b (inset)), an increase in the d-spacing for these planes has been observed (Table 1). The

lattice parameters calculated for the anatase TNTs after electrochemical reduction are
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therefore, a = 3.7852 Å and c = 9.5643 Å. The effect of electrochemical reduction process on

the peak shifting of anatase phase is summarized in Table 1.

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Figure 1. XRD patterns of (a) amorphous and annealed TNTs, (b) annealed nanotubes before
and after electrochemical reduction. The asterisk (*) in (a) indicate titanium peaks. Inset in

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(b) highlights a shift in (101) and (200) peaks due to electrochemical reduction.

Table 1. Summary of XRD results for the anatase phase of annealed TNTs before and
after electrochemical reduction.

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Anatase TNTs Electrochemically reduced anatase TNTs Change

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°2θ d-spacing (Å) FWHM (2θ) °2θ d-spacing (Å) FWHM (2θ) ∆d (Å)

25.354 25.256
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3.5129 0.2755 3.5263 0.1968 0.0134
(101) (101)

48.203 47.780
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1.8878 0.3936 1.9036 0.5510 0.0158

(200) (200)
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3.2 Sanning eletron microscopy (SEM)

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Figure 2 shows SEM images of amorphous and anatase TNTs before and after

electrochemical reduction. It reveals the formation of vertically oriented TNTs with average
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diameter of ~ 120 nm and wall thickness of ∼20 nm. It is worth mentioning that

electrochemical reduction did not affect the morphology of TNTs (Figure 2(b, d)) as observed
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by others [30].
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Figure 2. SEM images of TNTs (a) amorphous, (b) electrochemically reduced amorphous,

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(c) annealed and (d) electrochemically reduced annealed.

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3.3 XPS analysis
XPS studies of the amorphous and anatase TNTs before and after electrochemical

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reduction was performed and the results are shown in Figure 3. It is observed that the
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electrochemical reduction process shift the binding energies of amorphous as well as anatase

TNTs. The magnitude of the induced shifts range from 0.7 eV to 1 eV toward lower values,
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in O 1s and Ti 2p peaks for both amorphous as well as anatase TNTs (Figure 3 (a,b)).
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Figure 3. XPS data showing (a) O1s peaks and (b) Ti2p peaks for amorphous and annealed
TNTs before and after electrochemical reduction.

Similar shift of ~ 0.7 eV to lower binding energies is reported by Q. Kang et al. for the

chemically reduced annealed TNTs [23]. Interestingly, our XPS results show that the binding

energy shift caused by electrochemical reduction is completely and partially recoverable for
amorphous and anatase TNTs respectively as indicated in Figure 3(a,b). This recovery in
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binding energies for the electrochemically reduced TNTs is not reported earlier to the best of

our knowledge. As mentioned earlier, the electrochemical reduction creates oxygen vacancies

in the TNTs. The binding energy recovery effect is due to the ability of electrochemically

reduced TNTs to scavenge oxygen from the environment as observed by Close et al. [30].

The de-convoluted XPS data of the amorphous TNTs before and after electrochemical

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reduction is shown in Figure 4. The high resolution XPS spectrum of O1s (amorphous TNTs)

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show a main peak at 530.1 eV along with a shoulder peak at 532.5 eV (Figure 4a). The peak

located at 530.1 eV corresponds to O-Ti while the shoulder peak at 532.5 eV correspond to

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Ti-OH [36]. The shoulder peak shifted to a lower value after the annealing process (Figure

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5a). The complete recovery of peak related to Ti-O in O1s from 529.1 eV (Figure 4b) to its
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original value before electrochemical reduction (530.1 eV) can be seen in the Figure 4(c) in

~7 days after electrochemical reduction. This is attributed to the oxygen scavenging

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phenomena of TNTs [30]. The high resolution XPS spectra related to Ti2p before and after

electrochemical reduction of amorphous TNTs are shown in Figure 4(d-f) and summarized in
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Table 2. In the as-prepared TNTs two peaks located at 458.5 eV and 464.3 eV, as shown in
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the Figure 4d, correspond to Ti2p3/2 and Ti2p1/2 respectively [37]. Interestingly, it has been

found that the electrochemical reduction process result in the formation of new energy state
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in the amorphous TNTs. The creation of new energy states (Ti+3) has been observed at a
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binding energy of ~ 465.3 eV and ~ 464.6 eV for reduced amorphous TNTs after 1 h and 7
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days respectively (Figure 4 (e,f)). This state has not been reported earlier in electrochemically

reduced amorphous TNTs. Surprisingly, the Ti+3 states exist even ~7 days after

electrochemical reduction (Figure 4f) with a shift in the binding energy. This shift is due to

the oxygen uptake by electrochemically reduced amorphous TNTs from the environment

over a period of ~7 days [30]. It is worth mentioning that the peak related to Ti+4 2p3/2

recovers completely while the one corresponding to Ti+4 2p1/2 recovers partially to the values
before electrochemical reduction. A 0.2 eV difference in the binding energy has been
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observed for Ti+4 2p1/2 compared to its value before electrochemical reduction (Table 2). This

partial recovery of the binding energy might be due to the creation of Ti+3 states as a result of

electrochemical reduction. In contrast to the amorphous TNTs, the binding energy shift

induced by electrochemical reduction in O1s and Ti2p of anatase nanotubes doesn’t recover

completely as depicted in Figure 5(a-f). The binding energy data for 1 hour after

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electrochemical reduction indicate a shift of ~ 0.7 eV in peaks related to O1s (Figure 5(b))

and Ti2p (Figure 5(e)). These values do not recover even ~7 days after electrochemical

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reduction and are 0.5 eV less than anatase TNTs before reduction (Figure 5(c,f)). The

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incomplete recovery in binding energy values of electrochemically reduced anatase TNTs is

due to the fact that oxygen vacancies are thermodynamically more stable compared to

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amorphous TNTs [30]. This partial recovery also corroborates the finding that anatase
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nanotubes are not good oxygen scavengers compared to amorphous TNTs [30]. The summary

of XPS analysis is given in Table 2.

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Figure 4. The de-convoluted XPS data of the amorphous TNTs fitted with Gaussian function
for O1s peak and Ti2p peaks (a) & (d) before electrochemical reduction, (b) & (e) 1 hour
after electrochemical reduction, (c) & (f) ~7 days after electrochemical reduction.
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Figure 5. The de-convoluted XPS data for annealed TNTs fitted with Gaussian function for
O 1s peak and Ti 2p peaks (a) & (d) before electrochemical reduction, (b) & (e) 1 hour after

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electrochemical reduction, (c) & (f) ~7 days after electrochemical reduction.

Table 2. Summary of XPS data based on fitting of de-convoluted spectra for amorphous and

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annealed TNTs before and after electrochemical reduction.

Electronic levels Ti+4 Ti+3 O

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P3/2 P1/2 P3/2 P1/2 1s
(eV) (eV) (eV) (eV) (eV)
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Amorphous TNTs 458.5 464.3 ___ ___ 530.1 532.5
(TNTs)
Reduced amorphous 457.7 463.5 ___ 465.3 529.1 530.3
TNTs after 1 h
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Reduced amorphous 458.5 464.1 __ 464.6 530.1 532.0

TNTs after ~7 days
Annealed TNTs 458.8 464.6 --- --- 530.1 531.1
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Reduced annealed 458.1 463.9 --- --- 529.4 530.3

TNTs after 1 h
Reduced annealed 458.3 464.1 --- --- 529.6 530.9
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TNTs after ~7 days

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3.4 Impedance Spectroscopy

Impedance spectroscopy of amorphous and anatase TNTs was carried out before and
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after electrochemical reduction. Representative Nyquist plots of amorphous and anatase

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TNTs before electrochemical reduction are shown in Figure 6(a) and Figure 7(a) respectively.

The impedance values of amorphous and anatase TNTs are in the range of 25-35 MΩ and 10-

20 MΩ respectively. The high impedance values of TNTs are due to less free carrier

concentration [14]. It is also observed that impedance values of amorphous TNTs are

generally higher than anatase TNTs. This is due to their disordered structure and high

resistance to charge transport. Electrochemical reduction process decreases the impedance of

TNTs by at least three orders of magnitude (to kΩ range) as depicted in Figure 6(b) and
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Figure 7(b). The decrease in impedance values of TNTs is due to the fact that electrochemical

reduction produces localized states of oxygen vacancies below conduction band [28].

Consequently, donor level concentration increases in the reduced TNTs which facilitate the

charge transport and as a result the impedance values decrease. Nyquist plots (Figure 6(b)

and Figure 7(b)) also indicate a striking increase in the radius of semi-circles with time after

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electrochemical reduction process. A three-fold increase in the impedance values is observed

in the reduced amorphous TNTs within 1h as shown in Figure 6b. This is due to the reason

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that the electrochemically reduced TNTs continuously absorb oxygen from environment with

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time, as a result the number of donor states decrease [38]. Generally, TNTs walls contain

some porosity, so absorption of oxygen takes place inside the walls. The absorbed oxygen

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captures the free electrons from the donor states of reduced TNTs thereby decreasing their
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concentration [30]. The process of oxygen uptake continues and within ~7 days the

impedance values of reduced amorphous and anatase TNTs recover to their values before
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electrochemical reduction as shown in Figure 6(c) and Figure 7(c) respectively. Figure 6(d)
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and Figure 7(d) represent the capacitance values of the reduced amorphous and anatase TNTs
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extracted from the Nyquist plots (Figure 6(b) and Figure 7(b)). It is found that the capacitance

of electrochemically reduced TNTs decrease with time. Capacitance of the reduced

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amorphous nanotubes, at a frequency of 1 kHz, decrease from ~ 16 nF to 4 nF within 1 hour

(Figure 6(d)). While the capacitance of reduced anatase nanotubes at a frequency of 4 kHz
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decrease from ~190 nF to 50 nF within the same duration (Figure 7(d)). From these plots, it is
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also observed that the rate at which capacitance decrease under ambient conditions after

electrochemical reduction is higher for amorphous TNTs compared to anatase. It has been

reported by others that supercapacitors based on electrochemically reduced anatase TNTs

show three orders of magnitude higher capacitance than un-reduced TNTs [28]. However, our

finding shows that after electrochemical reduction the capacitance does not remain constant
and it changes with time due to oxygen uptake phenomena. Therefore, for the applications of
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electrochemically reduced TNTs in supercapacitors and solar cells, the oxygen uptake

phenomena should be considered, as it strongly influences the electrical properties.

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Figure 6. Impedance plots of amorphous TNTs (a) before, (b) after electrochemical reduction
under ambient conditions up to 1 hour, (c) 7 days after reduction. (d) Capacitance changes

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observed for electrochemically reduced amorphous TNTs with reference to capacitance value
extracted from peak of initial reading.
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Figure 7. Impedance plots for annealed TNTs (a) before (b) after electrochemical reduction
under ambient conditions up to 1 hour, (c) 7 days after reduction. (d) Capacitance changes
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observed for electrochemically reduced annealed TNTs with reference to capacitance value
extracted from peak of initial reading.
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4 Conclusions
In summary, we have reported the effect of electrochemical reduction process on the

structural and electrical properties of amorphous and anatase TNTs under ambient conditions.

XRD results confirm that electrochemical reduction process increase the d-spacing of (101)

and (002) planes. This is due to creation of oxygen vacancies in the lattice. XPS and
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impedance studies show the oxygen scavenging behavior of TNTs. It is found that

electrochemical reduction process shifts the binding energies of TNTs towards lower values

which completely or partially recover within ~7 days. This is attributed to the oxygen uptake

phenomena. The partial recovery in the binding energy values of reduced anatase TNTs is

due to the fact that the oxygen vacancies are thermodynamically more stable compared to

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amorphous TNTs. In addition, electrochemical reduction process decreases the impedance

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values of TNTs by more than three orders of magnitudes (from MΩ to kΩ). Similarly the

impedance values of electrochemically reduced TNTs recover in ~7 days to its values before

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the reduction process. Capacitance values of reduced amorphous TNTs decreases from 16 nF

to 4 nF while for reduced anatase TNTs it decreases from 190 nF to 40 nF within 1 hour. For

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the applications of electrochemically reduced TNTs in supercapacitors and solar cells, the
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oxygen uptake phenomena should be considered, as it strongly influences the electrical
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properties.

Acknowledgements
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PIEAS, NCP, and NILOP are gratefully acknowledged.

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Highlights

• Effect of electrochemical reduction on structural and electrical properties of anodic TNTs

• Recovery behavior of TNTs under ambient conditions due to oxygen uptake

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Amorphous TNTs show full, anatase show partial recovery based on time dependent XPS

• Impedance changes from MΩ to KΩ and recover back to MΩ range in ~ 7 days

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