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Abstract

We synthesized Zn and Pd Co-Modified TiO2 photocatalyst using a facile sol-gel method. The

photocatalyst was characterized by various characterization technology and ab-initial calculation

to investigate the crystalline structure, surface microscopic structure and band structure. The

photoreduction activity of CO2 into CH4 is investigated and the structure-activity relationship and

photocatalytic mechanism are elucidated detailly.

Introduction

The photo-reduction of CO2 and H2O into CH4 via semiconductor has been investigated by

many researchers since it applies solar light to convert CO2into valuable carbon fuels,

methane.TiO2 is one of the most promising and investigatedphotocatalystsfor thephoto-

reduction,due to its active performance, photo-stability and nontoxicity 1-5. However, the

efficiency of TiO2 is still limited for practical photocatalytic applications because of its large

band gap (3.2 eV) and rapid charge carrier recombination rate. Therefore, it is of great

importance to improve the photocatalytic activity of the TiO 2 based photocatalysts on photo-

reduction of CO2 into CH4under visible irradiation.

Doping or modification with noble metal elements, such as Au6-8, Ag9-10 and Pd11-16, is usually

regarded as quite an effective method to improve the photocatalytic performance of TiO 2 based

catalyst. Among these noble elements, Pd is most commonly used metal with a low cost. Li et al.

found that the modification of PdO had an effect on the optical properties and photocatalytic

performance of the TiO215-16. Kuvarega and his co-workers found the presence of Pd would

enhance the absorption and promote the separation of photogenerated charge carriers 14. Recently,

we also found out that the TiO2 modified with O-Pd-O surface speciesshow strong absorption in

visible region and exhibit remarkable photocatalytic activity 12. Moreover, it has been
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demonstrated by our previous work that the unique O-M-Cl (M= In, Ni or Sn) species would

extend the absorption into visible region and suppress the recombination of photoindcued

electrons and holes efficiently17-19. The existence of unique O-Zn-Cl species on the surface of

TiO2 is also confirmed and its opti-electric properties remain uninvestigated. We would like to

combine the advantage of both O-Pd-O and O-Zn-Cl species into TiO 2 system, so as to obtain a

highly reactive photocatalyst on reduction of CO2 into CH4.

Herein, we introduce zinc into PdO modified TiO 2 samples via a simple sol-gel method. It is

revealed that the introduced Zn and Pd exist as O-Zn-Cl and O-Pd-O species on the surface of

TiO2 nanoparticles. The introduction of O-Zn-Cl species could further enhance the visible light

response and improve the photocatalytic activity significantly on photo-reduction CO 2 and H2O

into CH4.

Experimental Details

Catalyst Preparation. All chemicals used were of analytical grade and the water was deionized

water (>18.2 Mcm). At room temperature, certain amount of PdCl 2 solution and Zn(NO3)2

were dissolved into 40 mL of ethanol. After mixing for half an hour, 1 mL HCl solution

(12mol/L) and 12 mL of Ti(OC4H9)4was added dropwise into the mixture under vigous stirring.

Then 1 mL of deionized waterwas added for further hydrolysis. The pH value of the mixture is

evaluated to be 0.5. The mixture was stirred until the formation of TiO2 gel. After aging for 24

hours, the TiO2 gels were dried at 373K for 10 h and annealed at 723K in a muffle for 2.5h. The

obtained samples were denoted as TiO2-Pd-Zn, where the nominal molar ratio of Zn 2+ and Pd2+to

Ti4+ (Zn/Ti and Pd/Ti) is 5% and 1.5%, respectively. Pure TiO 2, Zn modified TiO2 (TiO2-Zn) and

Pdmodified TiO2 (TiO2-Pd) were prepared using the same procedure without the addition of
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corresponding precursor. Different nominal molar ratio of Zn and Pd co-modified TiO 2 samples

are also prepared which is shown in the supporting information.

Characterization.

X-Ray diffraction (XRD) patterns were acquired on a Rigaku D/max 2500 X-ray diffraction

spectrometer (Cu Ka, =1.54056) at a scan rate of 0.02 2 s-1. The average crystal size was

calculated using the Scherrer equation (D=k/Bcos). After degassing at 180 C, the BET surface

area was determined via the measurement of nitrogen adsorptiondesorption isotherms at 77 K

(Micromeritics Automatic Surface Area Analyzer Gemini 2360, Shimadzu). X-Ray photoelectron

spectroscopy (XPS) measurements were carried out with an ESCA Lab 220i-XL spectrometer by

using an unmonochromated Al Ka X-ray source(148.6 eV). All spectra were calibrated using the

binding energy(BE) of the adventitious C1s peak at 284.8 eV. Diffuse reectance UV-vis

absorption spectra (UV-Vis DRS) were collected with a UV-vis spectrometer (U-4100, Hitachi).

Photoluminescence (PL) spectra were acquired by using the 325 nm line of a nano-second

Nd:YAG laser (NL303G) as excitation source. The experimental setup consists of a spectrometer

(Spex 1702), a photomultiplier tube(PMT, Hamamatsu R943), a lock-in amplier, and a

computer for data processing. All of the measurements were carried out at room temperature

(252C). The surfacephotovoltage spectroscopy (SPS) was measured on a solid-

junctionphotovoltaic cell of indium tin oxide (ITO)/sample/ITO equippedwith a lock-in amplifier

(Model SR830, DSP) and synchronized witha light chopper. The monochromatic light was

obtained by passinglight from a 500W xenon lamp (CHF-XQ 500W) through a doubleprism

monochromator (WDG30-2).

Evaluation of Photocatalytic Activity.

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The photo-reduction of CO2 and H2O into CH4 is carried out as follows:in the photocatalytic

reduction of CO2,150 mg photocatalysist was uniformly dispersed on the nanoparticulate film

with an area of 9.4cm2 which was placed at the bottom of a sealed Pyrex glass reaction vessel

(410 mL). 2mL of deionized water was injected into the reaction system as reducer. A 500W

Xenon arc lamp was used as the light source of photocatalytic reaction. Prior to the illumination,

the high purity of CO2 gas (99.99%),via a flow controller, was followed into the reaction setup

for 45 min for reaching ambient pressure. During irradiation, about 0.4 mL of gas was

continually taken from the reaction cell every 2h for subsequent CH4 and CO concentration

analysis by using a gas chromatograph (Techcomp GC-7890F, equipped with a 1 m 3 mm

TDX-01 packed column and a flame ionization detector (FID)].N2 was used as the carrier gas.

Since FID cannotdetect CO and CO 2, an additional converter (Techcomp converter loadedwith

Ni catalyst) was attached to the GC system between thecolumn and detector, which can reduce

CO to methanol(CO + H2 CH4OH) and CO2 to methane (CO2 + 4H2CH4 + 2H2O). Hence,

CO and CO2 could be analyzedsimultaneously.

Results and Discussion

Figure 1 CH4 generation over TiO2(P25), TiO2, TiO2-Pd, TiO2-Zn and TiO2-Pd-Zn.
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The photo-reduction of CO2 into CH4 in the presence of water under Xe lamp irradiation is

applied to the evaluated the photocatalytic activity of the obtained TiO 2samples. The commercial

available TiO2 (Degussa P25) is also applied for comparison. In this experiment, CO is the

intermediate product (Figure S1) and CH4 is the final product, shown in Figure 1. The

photocatalytic experiment results of the TiO 2 based photocatalysts are presented in Figure 1 and

Table 1. After 8 hours irradiation, only 0.350 and 0.358 molof CH 4 is detected in the presence

of self-made pure TiO2 sample and commercial TiO2 (Degussa P25). The Zn modified TiO2

sample(TiO2-Zn) exhibit a limited photocatalytic activity and about 0.851mol of CH 4 is

produced. After the modification with Pd, the photocatalytic performance of TiO 2-Pd is enhanced

effectively and 3.59mol of CH4 is generated. After the introduction of Zn andPdinto TiO 2, TiO2-

Pd-Zn samples exhibit the best photocatalytic activity on photo-reduction of CO2 into CH4. There

is about 7.99 mol of CH 4 is detected, whose specific photocatalytic activity is almost twice as

that for TiO2-Pd and twenty time higher than that for P25. These photocatalytic experiment

results indicate that the co-modification with Pd and Zn is quite an efficient and effective method

to improve the photocatalytic activity of TiO2 based photocatalysts.

Table1Photocatalytic activity of pure TiO2, TiO2-Zn, TiO2-Pd and TiO2-Pd-Zn samples under Xe
lamp irradiation
specific
CH4generation specific photocatalytic CO generation photocatalytic
Sample
amount(mol) activity b(molg-1h-1) amount(mol) activity c (molg-1h-
1
)
blank a 3.1410-7 - 2.3410-6 -

TiO2(P25) 3.5810-7 2.9810-7 1.0210-5 8.510-6

TiO2 3.5010-7 2.9110-7 8.9910-6 7.4910-6

TiO2-Zn 8.5110-7 7.0910-7 8.5310-6 7.1110-6

TiO2-Pd 3.5910-6 2.9910-6 4.2710-7 3.5610-7

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TiO2-Pd-Zn 7.9910-6 6.6610-6 3.8810-6 3.2310-6

a
Blank is the photolysis of CO2;bspecificphotocatalytic activity of CH4, CH4 generation amount per unit mass catalyst

per hour;
c
specificphotocatalytic activity of CO, CO generation amount per unit mass catalyst per hour

Figure 2XRD patterns of pure TiO2(curve a), TiO2-Pd (curve b), TiO2-Zn (curve c) and TiO2-Pd-

Zn (curve d) samples. Inset shows the enlargement of (101) plane.

To investigate the crystal structure of the obtained samples, Figure 2 shows the XRD patterns

of the TiO2(curve a), TiO2-Pd (curve b), TiO2-Zn (curve c) and TiO2-Pd-Zn (curve d) samples. It

is clear that all samples exhibit typical anatase structure and there is no other phase, such as ZnO,

ZnTiO3 and PdO, observed in the XRD patterns. The lattice parameters, cell volumes and crystal

size are calculated and summarized in Table 2, derived from the XRD patterns of all four

samples.For metal oxide, there are usually two doping mode, substitutional mode and interstitial

mode.As the ionic radius of Zn2+ ions (74 pm) and Pd2+ ions (85 pm) are much larger than that

for Ti4+ ions (68 pm), it is hard for Zn 2+ ions or Pd2+ ions to be weaved into TiO 2 lattice in

interstitial mode. Moreover, an increase of lattice parameters and cell volume is expected if the

lattice Ti4+ ions are substituted by the introduced Zn2+ ions or Pd2+ ions, corresponding to the shift

to lower diffraction angle for XRD diffraction peaks. Inset of Figure 2 is the enlargement of the
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diffraction peaks of anatase (101) plane for all samples. It is noted that no shift of the diffraction

peaks is observed and the lattice parameters as well as the cell volume almost remain unchanged

for the TiO2-Pd (curve b), TiO2-Zn (curve c) and TiO2-Pd-Zn (curve d) samples, compared with

pure TiO2 (curve a). Therefore it becomes reasonable to deduce that neither Pd 2+ ions nor Zn2+

ions are doped into TiO2 lattice in substitutional mode. The introduced Pd2+ ions and Zn2+ ions

may exist as some kinds of species on the surface of TiO 2. Furthermore, after the introduction of

foreign metal ions, the BET specific surface areas increase in the order of TiO 2< TiO2-Zn < TiO2-

Pd < TiO2-Pd-Zn. The crystallite sizes also increasein the order of TiO 2-Pd-Zn< TiO2-Pd< TiO2-

Zn< TiO2, which is consistent with the changes for surface areas.In addition, the increase of

surface areas are in favor of the enhancement of photocatalytic activity.

Table 2Lattice parameters, cell volume, crystal size and specific surface areas of the TiO 2, TiO2-Pd, TiO2-Znand
TiO2-Pd-Znsamples
Lattice parameter ()
cell crystal SBET
Samples
volume (3) size (nm) (m2 g-1)
a b c

TiO2 3.7857 3.7857 9.5118 136.32 12.4 56.9353

TiO2-Pd 3.7842 3.7842 9.5042 136.10 9.6 74.6179
TiO2-Zn 3.7876 3.7876 9.4963 136.23 8.9 63.4306
TiO2-Pd-Zn 3.7851 3.7851 9.4875 135.93 7.7 79.2025
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Figure 3 (A) XPS Cl 2p spectra of TiO2, TiO2-Pd, TiO2-Zn and TiO2-Pd-Zn; (B) Zn 2p and (C)

Pd 3d spectra of TiO2-Pd and TiO2-Pd-Zn.

The detailed chemical states of Zn and Pd in all samples are investigated by the XPS

technique. As shown in Figure 3A, the peak centered at about 198.1 eV for TiO 2 and TiO2-Pd is

ascribed to the O-Ti-Cl species. It has been demonstrated by our previous work that the Cl - ions

link with the surface unsaturated Ti sites to form the O-Ti-Cl species which shows no visible

response and hardly influence the photocatalytic activity 19-21. In comparison with pure TiO2, the

peak intensity of Cl 2p spectrum for TiO 2-Pd remains almost unchanged. For the TiO 2-Zn and

TiO2-Pd-Zn samples, the peak intensity of the Cl 2p increase significantly and the peaks are

centered at about 198.9 eV and 198.7 eV, respectively, locating between that of TiCl 4 (198.2 eV)

and ZnCl2 (199.7 eV)22. This suggests that the Cl- ions may links with only Zn2+ ions to form Zn-

Cl bonds on the surface of TiO2. Moreover, the center of the Zn 2p3/2 peakfor the Zn 2p spectra of

TiO2-Zn (1022.1 eV) and TiO2-Pd-Zn (1022.0 eV) locates between that of ZnO (1021.5 eV)23 and

ZnCl2 (1022.5 eV)24, indicating the Zn2+ ions link with the unsaturated O sites and Cl- ions to

exist as O-Zn-Cl species24. For the Pd 3d spectra (Figure 3C), the peak of Pd 3d 5/2 for TiO2-Pd
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and TiO2-Pd-Zn locates at about 336.7 eV, attributed to the O-Pd-O structure on the surface of

TiO2(one Pd2+ ions linked with two unsaturated O2- ions)21. Hence, it is concluded that the

introduced Pd ions exist as O-Pd-O species and the introduced Zn ions exist as O-Zn-Cl species

on the surface of TiO2. None of the introduced metal ions are weaved into TiO 2 lattice, which is

in good agreement with the XRD results.

Figure 4. Raman spectra of TiO2, TiO2-Zn, TiO2-Pd and TiO2-Pd-Zn. Inset shows the

enlargement of Zn and Pd co-modified TiO2 samples with different Zn content(3%, 5% and 7%).

To further confirm the existence of surface O-Zn-Cl species, the Raman spectra of all samples

are plotted in Figure 4. All samples show the typical characteristic bands at about 142 cm -1, 195

cm-1, 395 cm-1, 515 cm-1 and 637 cm-1, attributed to the Eg, B1g, A1g, B2g and Eg vibrational modes

of anatase25, respectively. In addition, two additional Raman peaks at about 256 cm -1 and 333 cm-
1
are observed for the Zn modified TiO2 as well as the Pd and Zn co-modified TiO2samples (Inset

of Figure 4), ascribed to stretching modes of Zn-Cl and Zn-O bonds, respectively 26. These

Raman spectra further demonstrated the existence of O-Zn-Cl species on TiO2 surface.
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Figure 7.Projected density of states (PDOS) for the TiO2 and TiO2-Pd.

To investigate the band structure of TiO 2 modified with O-Pd-O species, theoretical

calculation based on density functional theory are carried out, as shown in Figure 7. The

conduction band of TiO2 consist of Ti 3d and a small fraction of O 2p orbitals, and the valence

band of TiO2 is made up of O 2p with a small fraction of Ti 3d orbitals. For the TiO 2-Pd samples,

new doping energy level occurred owing to the introduction of Pd. The doping energy bands are

composed of Pd 3d orbitals, strongly hybridized with O 2p and Ti 3d electric states, which

corresponds to the O-Pd-O species on the surface of TiO 2 and is consistent with the experiment

results discussed above.

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Figure 5.(A) absorption spectra and (B) surface photovoltaic spectra of TiO 2, TiO2-Zn, TiO2-

Pd and TiO2-Pd-Zn.

The absorption spectra and surface photovoltaic spectra (SPS) are carried out to investigate the

opti-electric properties of the photocatalysts, which is closely related to the photocatalytic

activity. The diffuse reectance UVvisible absorption spectra of all samples are plotted in

Figure 5A. TiO2 shows no visible response because of the large band gap (3.1 eV). The TiO 2-Zn

shows a weak broad threshold absorption from 400 nm to 600 nm, caused by the electron

transition from the valence band to the surface energy level of O-Zn-Cl species. The position of

the absorption maximum is at about 450 nm, indicating the surface energy level of O-Zn-Cl
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locates at 0.35 eV below the conduction band. The visible response is enhanced significantly

after the introduction of Pd (TiO2-Pd) contributed from the surface O-Pd-O species 21. The

absorption maximum is at about 477 nm, suggesting the energy level of O-Pd-O is 0.5 eV below

the conduction band of TiO2. Moreover, it is found from the XPS valence band spectra that the

valence band top is determined to be at 2.6 eV (+2.2 eV, vs NHE), hence the energy level of the

conduction band bottom, O-Zn-Cl and O-Pd-O species are at about -0.9 eV, -0.55 eV and -0.4 eV

(vs NHE), respectively.As we expect, the co-modified TiO 2 sample (TiO2-Pd-Zn) represent the

strongest absorption in visible region, which is owing to synergistic effect of introduced O-Pd-O

and O-Zn-Cl spceies. Moreover, the TiO2-Pd-Zn sample also exhibits the highest visible light

surface photovoltaic spectroscopic (SPS) response in the visible region (from 400 nm to 800

nm). At the same time, the TiO2-Zn and TiO2-Pd exhibit poor SPS response in visible region and

pure TiO2 almost shows no SPS response from 800 nm to 400 nm. These SPS results suggest that

the introduction of O-Zn-Cl species into TiO2-Pd system is an effective method to enhance the

visible response, resulting in as improvement of the photocatalytic performance. Moreover, in

comparison with the other samples, TiO 2-Pd-Zn sample exhibits the strongest absorption in

visible region and also presents the enhanced photocatalytic activity, suggesting the visible

response is the key factor in this experiment.

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Figure 6. Photoluminescence (PL) spectra of TiO2, TiO2-Zn, TiO2-Pd and TiO2-Pd-Zn.

For metal oxides, the photoinduced electrons in the conduction band would fall into the

oxygen vacancies through a nonirradiative process and recombine with the holes via an

irradiative process then, leading to the emission of fluorescence. Hence, the quench of the

photoluminescence (PL) spectra usually indicates suppression of the recombination

forphotoinduced charge carriers. Figure 6 shows the PL spectra of TiO 2, TiO2-Zn, TiO2-Pd and

TiO2-Pd-Zn. It can be easily seen that the emission intensity of TiO 2-Zn is weakened compared

with pure TiO2, as the photoinduced electrons could transfer into the surface energy level of O-

Zn-Cl species. For TiO2-Pd, the PL spectrum is quenched significantly because of the O-Pd-O

species. And the PL emission for TiO 2-Pd-Zn is further quenched owing to the contribution from

both the O-Zn-Cl and O-Pd-O species. These PL result suggest that the photoinduced electrons

and holes are separated efficiently for the Zn and Pd co-modified TiO 2 samples, benefitting the

enhancement of photocatalytic activity on photo-reduction of CO2 into CH4.

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Table 4.Values of the Calculated Decay Time Constant 1 and 2 through Double Exponential
Decay Fitting for theCorresponding Samples

TiO2 Zn5-TiO2 Pd1.5 -TiO2 Pd1.5/Zn5-TiO2

1(ns) 0.295 0.298 0.294 0.291

2(ns) 3.059 3.876 4.038 4.382

Figure 8.Schematic band structure of TiO2-Pd-Zn as well as the photocatalytic mechanism

(not drawn to scale).

According to the discussion above, the enhancement of the photocatalytic mechanism could be

explained with the assistance of schematic diagram band structureof TiO2-Pd-Zn, shown in

Figure 8.The mechanism of photo-reduction CO2 into CH4 via photocatalysis can be summarized

as follows:

Photocatalyst + hv e- + h+ (1)

2H2O + 4h+ O2 + 4H+ Eo=0.82V (vs NHE) (2)

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CO2 + 8e- + 8H+ CH4 + 2H2O Eo=-0.24V (vs NHE) (3)

Under illumination, the photocatalysts are excited and the photoinduced electrons and holes

are generated in the conduction band and valence band, respectively. The photoinduced holes

react with the adsorbed H2O to form H+ and oxygen. Meanwhile, the exited electrons would be

captured directly by the surface adsorbed CO2 molecules to form CO and oxygen. The resultant

CO would further react with electrons and H + to generate the final product, CH4. For pure TiO2

sample, quite a few electrons and holes can be excited by irradiation and the recombination rate

of the charge carriers are relatively high, resulting in a poor photocatalytic activity on reduction

of CO2 into CH4. Owing to the introduction of O-Zn-Cl surface species, electrons can be excited

from the valence band of TiO 2 to the surface energy level of O-Zn-Cl, located below the

conduction band of TiO2. At the same time, the electrons on the conduction band of TiO 2 would

transfer to energy level of O-Zn-Cl species other than recombine with the holes, suppressing the

recombination of electrons and holes. Therefore, the TiO 2-Zn sample represents a better

photocatalytic activity than pure TiO2, owing to the formation of O-Zn-Cl species. Owing to the

surface O-Pd-O species on the surface of TiO 2, TiO2-Pd sample shows strong absorption in

visible region, accompanied with an efficient separation of charge carriers, resulting in a

remarkably enhanced photocatalytic activity. Moreover, for TiO 2-Pd-Zn sample, owing to co-

existence of O-Pd-O and O-Pd-Cl species, the density of the energy states below the conduction

band of TiO2 increased significantly, accompanied with strongest visible response. Because of

the synergetic effect of surface O-Zn-Cl and O-Pd-O species, morephotoinduced electrons and

holes are generated and separated efficiently, benefiting the photocatalytic activity. As the

energy level of O-Zn-Cl (-0.55 eV, vs NHE) and O-Pd-O (-0.4 eV, vs NHE) locate above the

redox potential of reaction (3) (-0.24 V, vs NHE), the separated electrons in the surface energy
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level and holes in the valence band of TiO 2 are able to take part in the photocatalytic reaction on

reduction of CO2 into CH4. Hence, TiO2-Pd-Zn samples exhibit much better photocatalytic

activity than the other samples.

Conclusion

According to the discussion above, the TiO2-Pd-Zn sample represent the best photocatalytic

performance on reduction of CO2 and H2O into CH4. Owing to the O-Zn-Cl and O-Pd-O surface

species, the opti-electric response of the photocatalyst is enhanced significantly in visible region

and the photoinduced carriers are separated efficiently. As a result, more electrons and holes

participate the photo-reduciton of CO2 and H2O into CH4, leading to remarkable improved

photocatalytic activity. It is believed that the introduction of surface species is effective method

to improve the photocatalytic activity, which can be applied in many fields, such as

photosynthesis, photodegradation and solar cells.

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