中美自然科学基金双边会 议 2009.10.

16 ~ 19 ,江苏 常州

Developments of Solar Energy Materials Based Nanotubular TiO2
Changjian Lin (林昌健)
cjlin@xmu.edu.cn

State Key Laboratory of Physical Chemistry of Solid Surfaces, and College of Chemistry and Chemical Engineering , Xiamen University, Xiamen 361005, China

Highlights
 Photogenerated Cathodic Protection  Hydrogen Production by

Photoelectrocatalytic Water Splitting
 Photoelectrochemical Solar Cell

( DSSC )
 Orderly nano-micro structured biomaterials

A Photoelectrochemical Study of TiO2-based Nanotube Arrays as the Photoanodes for Cathodic Protection of Metals

Washington, DC, Oct. 7-12, 2007

Introduction
ee- ehν Metallic substrates

Photoelectrochemistry

e-

CB

Photocatalysisphotodegredations

e- h+ h+ eTiO2

VB

Wettability- Superhydrophilic Superhydrophobic

“Green” Cathodic protection No Supply current

Photo-generated cathodic protection

Consume light metals(Mg,Al,Zn)

TiO2 + hν→h+ + e-

Main critical technical problems
 e-h+ precursor in TiO2 is created only under an irradiation of UV light due to its large energy band-gap.  Because of short excition diffusion lengths and high recombination of e-h+ pairs, the photoreactivity and quantum efficiency of TiO2 remains low.  Pure TiO2 coatings cannot provide with a sustainable cathodic protection under dark conditions.

Aim and Motivation
 To enhance the photoabsorption to a visible light  To increase the photoreactivity of TiO2  To last the cathodic protection in dark conditions.

Electrochemical Anodization & Doping
Potentiostat

anode : 2H2O → O2 + 4e- + 4H+ Ti + O2 → TiO2 TiO2 + 6F− + 4H+ → TiF62− + 2H2O

Platinum Cathode Ti metal anode Bath

two-electrode electrochemical cell

Highly ordered nanostructure of TiO2 N, Fe-doped TN

self-organized anodization in fluorinated electrolyte (H2SO4/ HF, Na2SO4/NaF containing
different nitrogen, iron sources).

wet methods

Morphologies of TN Array
a (a), b b

(b) a

(a),(b) N-TN layers anodizeded in IMH2SO4+0.15wt%HF under 20V for 4h sintered at 4500C

100nm

100nm

diameter: ~ 90 nm length : ~ 500 nm
(c),(d) N-TN layers anodizeded in 0.2MNa2SO4+0.15wt%NaF under 20V for 6h annealed at 5000C

cc

d d

100nm

200nm

Typical SEM top views(a,c) and cross-sectional (b,d) images for the N-doped TiO2 nanotubular layers anodized in different electrolyte.

diameter: ~ 100 nm length : ~1.5 μm

Chemical Compositions of the N-TN
XPS total spectrum(a) and N1s high resolution spectrum (b) of the n-doped TN calcined at 4500C for 2h

400±0.2eV : chemisorbed γ- N2 on TiO2

surface  396±0.2eV: atomic β-N (interstitial state)  concentration of N: ~2.7 atom%.
 Wet doping procedure : distribute

the N-dopant within the outer layer of the TN film  Nitrogen: implanted in the nanotubular structure, presenting in a chemically bonded state.

Chemical Compositions of the Fe-TN
XPS spectra of Fe doped TN arrays anodized in 0.5%(w)NaF+0.2 mol·L-1 Na2SO4 containing 0.1M Fe2+ annealed at 500 0C

459.8eV: Ti2p3/2 (anatase-type TiO2 ) 724.3eV: Fe(Ⅲ)2p1/2 710.7eV: Fe(Ⅲ)2p3/2 (γ–Fe2O3)

 Anodization and anneal Fe(Ⅱ) was oxidized to Fe(Ⅲ)  Fe ion or mixed titanium oxide-iron concentrated on the surface layer of the TN films.

Photocurrent of the N-TN
nanotubular

(A) Photocurrent spectra of the pure TN film and the nanoparticles film a: anodized in 0.2MNa2SO4+0.15wt%NaF,4h b: anodized in IMH2SO4+0.15wt%HF, 2h c: nanoparticle films prepared by sol-gel d: blank Ti substrates e: n-doped TiO2 nanoparticle films.

N-doped

(B) A comparison of photocurrent spectra of the samples a,b,c: n-doped TN films recorded under the different bias voltages:a-1V,b-3V,c-300mV d: no-n-doped TN films.

N intercalation : absorption edge extends into the visible region.  Nanotubular films: harvest UV or visible light much more effectively than the irregular structure.

Photocurrent Fe-TN
Sharply increasing absorption in 625-650 nm.  Band gap energy: 1.9~ 2.0 eV

A comparison of photocurrent spectra of the Fe-doped TN films anodized in 0.2MFe2+ /0.15wt %HF +1MH2SO4 and the nanoparticles film sintered at 500 0C, for different times, a-7h,b5h,c-4h,d-2h,e-sol-gel

Photocathodic protection-N-TN
Time dependence of OCP for 316 SS coupled with the TiO2 nanotube layers and nanoparticle films under dark and illumination conditions.

1: TiO2 nanotubular electrodes; 2: TiO2 nanoparticle films.

 n-doped TN

exhibiting a higher photoeffect on UV, the OCP drops immediately to -300mV  the recovery is very slight (~0.039mV/s)  the negative value can keep for several hours  remain a complete cathodic protection for the SS in the dark condition.

Photocathodic protection N-TN
A comparison of the OCP shifts for 316L SS coupled with the Ndoped TiO2 nanotube electrodes under irradiation and dark condition 1: visible light , λ=540nm 2: UV illumination, λ=350nm

 Visible light  N-TN electrode  Dark condition

OCP reaches a more negative value (- 400mV) compared to the sample under UV. exhibits a much higher photoresponse to visible light illumination. the negative OCP shift maintains for a period and the photocathodic protection can last for a reasonable time.

Solar-hydrogen production by photoelectrocatalytic water splitting using highly ordered nanotubular TiO2 arrays

TiO2 photocatalysts for hydrogen production
Potentiostat

A eeH+ H2
membrane

B
e- H2O
H2+OH-

SCE

eh
+

+0.0 V E0(H3O+/H2)

CB

e- H2O
H2+OH-

H2O

D+
+1.23 V E (H2O/O2)
0

Pt

O2
ligh t
Anodized nanotubular TiO2 arrays

O2+H3O+

D

e-

eH2O

VB

Schematic illustrating the process of hydrogen generation using annealed nanotubular TiO2 arrays.

Potential energy diagrams for photochemical water splitting at pH = 0;(A) single semiconductor system (B) with an electron donor.

Electrochemical anodization

• The highly ordered TiO2 arrays constructed by Potentiostat electrochemical anodization are using as photoanode for hydrogen production in photoelectrochemical cell.

Platinum cathode

Ti anode electrolyte

Ti - 4e

Ti4+

Ti4+ + 2H2O → TiO2 + 4H+ (or: Ti4+ + 4H2O → Ti(OH)4↓+ 4H+ Ti(OH)4 → TiO2 + 2H2O) TiO2 + 6F- + 4H+ TiF62- + 2H2O

Schematic illustration of two-electrode electrochemical cell for the electrochemical anodization of Ti .

Nanotubular TiO2 (TNT) arrays
• Dimethylsulfoxide electrolyte
a b c

d

e

f

Highly ordered TiO2 array: tubelength of 18 µ m, pore diameter of 100 nm, wall thickness of 20 nm

Nanotubular TiO2 (TNT) arrays
notable highly ordered TiO2 arrays by multi-anodization in ethylene glycol electrolyte

Normal TNT arrays

smooth nanotubes

nanoporous morphology with 55nm wall thickness

Multi-step anodization

Notable highly ordered TNT arrays

Structure and photoelectrochemical activities

25

Photocurren Density (mA/cm2)

20

350 C o 450 C o 550 C o 650 C

o

15

10

5

0

-0.9

-0.6

-0.3

0.0

0.3

0.6

0.9

Potential (V vs SCE)

Photocurrent densities generated from the nanotubular TNT arrays by third anodization in 0.5 M KOH with a 300 W Xenon lamp.

Hydrogen production
potentiostat
to RE W E C E

PV = n R T
P,V,T known

O2

vacuomete r gas collection

Thermoelectric couple

H2 H2
Reaction cell

Cooling flask

Pump

SCE TNT arrays photoanode Pt electrode

Remove water vapor

Illustrative drawing of a threeelectrode photoelectrochemical cell for hydrogen production by water splitting.

A gas-closed circulation system equipped with a three electrodes reaction cell and a volumetric device with a vacuum line.

Photoelectrochemical activities
Enhanced photocatalytic activities for hydrogen production by multi-anodization.
400 µ mol·h-1 ·cm-2
2000

H2 generation amount(µmol⋅h ⋅cm )

Photocurrent Density (m A/cm2)

1500

T5(1.2 µm) S5(1.2 µm) F90 (1.2 µm) F300 (10 µm)

-2

25

20

T5 (1.2 µm ) S5 (1.2µm ) F90 (1.2 µm) F300 (10 µm)

-1

15

1000

10

5

500

0

-0.9

-0.6

-0.3

0.0

0.3

0.6

0.9

0

Potential (V vs SCE)
0 1 2 3 4 5

Time (h)

The amount of hydrogen generated as a function of time using the sample T5, S5, F90 and F300 in 2 M KOH with 0.5 M ethylene glycol.

UV-Vis photocurrent densities generated from the annealed nanotubular TNT arrays sample T5, S5, F90, F300 in 0.5 M KOH. T, S, F represent third, second and first anodization respectively.

Composite nanostructures of TiO2
Ti foils Degreased Ti foils

(a)

(b)

Treatment in an oxidizing agent Potentiostatic anodization nanocomposite TiO2 film Bamboo leaf-like TiO2

(c)

(d)

Schematic presentation of the two-step fabrication process used to synthesize nanocomposite TiO2 film.

The bamboo leaf-like TiO2 are uniform and dense with film thickness of 400 nm.

Composite TiO2 nanostructures
(a) (b) bamboo leaf-like TiO2

(c)

TNT arrays

(d)

Enhanced photocurrent densities of 150% higher than those of the two components alone.
Photocurrent Density (mA/cm2)
18 15 12 9 6 3 0

composite TiO2 nanotubular TiO2

Structure of composite TiO2 consists of highly ordered TNT arrays of 1.5 µ m and bamboo leaflikeTiO2 films of 0.1 µ m on top surface.

-1.0

-0.5

0.0

0.5

1.0

Potential (V vs SCE)

Hydrogen production
The combination of TNT arrays and bamboo leaf-like TiO2 enhance the hydrogen production rate significantly up to 150 µ mol·h-1 ·cm-2 . The O2 evolution was lower than the stoichiometric (H2 : O2=2:1) (a)
Generation amount(µmol⋅h ⋅cm )
-2 -1

800 700 600 500 400 300 200 100 0

(b)
composite TiO2

Generation amount(µmol⋅h ⋅cm )

normal TNT arrays bamboo leaf-like TiO2

700
-2

H2 O2

600 500 400 300 200 100 0

0

1

2

3

4

5

Time (h)

-1

0

1

2

3

4

5

Time (h)

The separate evolution of H2 and O2 by photoelectrocatalytic water splitting using composite TiO2 films under UV-Vis irradiation in 2 M Na2CO3+0.5 MCH3OH.

The evolution of H2 using three morphologies TiO2 materials under UV-Vis irradiation in 2 M Na2CO3+0.5 M CH3OH.

Summary
 The notable highly ordered TNT arrays by multi-step anodization show excellent photocatalytic activities for H2 production by photoelectrocatalytic water splitting.  The nanocomposite of TiO2 photoanode is capable of enhancing the photocatalytic activities for water splitting with H2 evolution rate of 150 µ mol•h-1•cm-2. The prepared highly ordered nanocomposite titania possess good stability, and it is expected to become an efficient photoanode materials for water splitting.

Electrochemical Solar Cell ( DSC ) based on Nanotubular TiO2

Structure and principle

Table 1 Performances of Main Solar Cells
Type of cell Crystalline silicon Multicrystalline silicon Amorphous silicon CuInSe2 Dye-sensitized solar cells Efficiency (%) Cell 24 18 13 19 Research and technology needs Module 10-15 Higher production yields, lowering of cost and energy content 9-12 7 12 Lower manufacturing cost and complexity Lower production costs, increase production volume and stability Replace indium (too expensive and limited supply), replace CdS window layer, scale up production Improve efficiency and high-temperature stability, scale up production Reduce materials cost, sale up Improve stability and efficiency

10-11

7 -

Bipolar AlGaAs/Si 19-20 photoelectrochemical cell Organic solar cell 2-3

M. Grätzel, Photoelectrochemical cells, Nature 2001(414), 338

Why- DSSC?
High cost Rare materials
Complex fabrication

Low cost

Si—DSC

Cheap materials Easy fabrication green

pollution

PEC or DSSC new generation of solar cells ?

Important Issues for DSC
TiO2 , ZnO , SnO2 , Nb2O5 等

photoanodes

Organic/ inorganic dyes Organic or inorganic dyes L, S, q-S < 1% Pt, C

Electrolytes Counter Electrode

7.1%

10%

Grätzel team

11.18%

Preparation of TiO2 Photoanode
TiO2 Nanocrystalline

Sol-gel synthesized hydrolyzate of TiCl4 Screen Printing Electrochemical deposition .................
megnetron sputtering

光 阳 极

Tio 2
1-D Nanostructures

from up to down from down to up free-standing

PVD Ion beam evaporation

templated assisted Hydrothermal Synthesis

1.1-1.2μm

5.6-5.9μm

3min

5min

20min

0.8-0.9μm

3min

5min

20min

SEM images of the nanoporous TiO2 films after third anodization at 50V in ethylene glycol system including NH4F and H2O for 3min,5min and 20min with different film thickness.

modified with Pd-QD nanoparticles

modified with Pt-QD nanoparticles

a

b

100nm

100nm

c

d

100nm

100nm

Photocurrent (a.u.)

TiO2 CdS dc - 2 min dc - 10 min sono - 2 min sono -10 min

250
f
CdS

300

350
(a)

400

450

500

e

Wavelength (nm)

100nm

100nm

SEM images of TiO2 nanotube array electrode (a, b) and CdS-TiO2 nanotube array electrodes after CdS sonoelectrochemical deposition at 0.5 mA/cm2 for 2 min (c), 5 min (d) and 10 min (e, f), respectively.

Photocurrent spectra of TiO2 nanotube array (black), CdS layer (blue) and six types of CdS modified TiO2 nanotube array electrodes, respectively(a). The main charge-transfer process between TiO2 and CdS after being excitated by the light (b)

A1

10min

A2

20min

A3

30min

B1

10min

B2

20min

B3

30min

TiO2/ZnO nanocomposite and heterojunction structures

Large-Scale, Noncurling, and Free-Standing Crystallized TiO2 Nanotube Arrays for Dye-Sensitized Solar Cells

0.25 wt % NH4F 50 V

0.25 wt % NH4F 12 V

Fig 13: SEM images of the membranes with different thicknesses of 9 μm (a,d), 25 μm (b,e), and 42 μm (c,f) Procedure for Preparing Free-Standing Crystallized TNT Arrays J. Phys. Chem. C, 113, 15, 2009

Design of structures of DSSC based on TiO2 nanotube arrays

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