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Advanced Materials Research Vols. 183-185 (2011) pp 1842-1846 Online available since 2011/Jan/20 at www.scientific.

net (2011) Trans Tech Publications, Switzerland doi:10.4028/

Preparation of C doped TiO2 photocatalysts and their photocatalytic reduction of carbon dioxide Li-mei Xue1,2,a,Feng-hua Zhang2,b,Hui-juan Fan3,c and Xue-feng Bai1,3,d*

College of Materials Science and chemical engineering, Harbin Engineering University, harbin 150027, China 2 School of Resource and Environment, Heilongjiang Science and Technology University, harbin 150027, China 3 Institute of Petrochemistry, Heilongjiang Academy og Sciences, harbin 150040, China a, b,, d *Corresponding

Key words: Carbon doping; Photocatalysis; Reduction; Carbon dioxide

Abstract.TiO2 doped with C was obtained by way of immersion and calcinations method by using citric acid (CA) as dopant material.and characterized by using XPSXRD, UV-Vis, FT-IR and SPS. The results of analysis and characterization showed that C substituted partial Ti atoms in the lattice of TiO2 and formed Ti-O-C structure. The photocatalytic properties of C-TiO2 photocatalysts had been evidently improved as a result of a noticeable shift to visible region and the enhancement of the charge separation efficiency. The doped carbon lowers the band gap and expends the absorption of visible light region. CO2 was photocatalytically reduced to form HCOOH by the best C-TiO2-3/1-600 nanoparticles under the irradiation of the simulated daylight lamp. Methanoic acid yield may achieve 2633.98mol/g-Cat when irradiation time is six hours. Introduction Currently, the shortage of energy and basic chemical raw materials is a serious problem, while carbon dioxide is a potential carbon resources, researchers begin to study. Carbon dioxide is the largest contributor among greenhouse gases. The atmospheric concentration of CO2 has recently increased owing to human activity; it accelerates the greenhouse effect further. The photocatalytic process can convert CO2 into other chemical commoditier such as methanol, methane and ethanol. If solar energy can be used to reduce CO2 to reasonable hydrocarbon resources would benefit humans and the environment. The advantages of photocatalysis technology indicate a promising application potential for photoreduction of CO2 and a positive impact on climate change [1]. At present, some novel photocatalysts includingcalcium-titanium oxides, tunnel frame, molecule sieves, organism and bioenzyme, TiO2, CdS and iron oxides were used in reduction of CO2 [2]. Zirconium oxide is found to be active for photocatalytic reduction of carbon dioxide to carbon monoxide with hydrogen in the gas phase [3]. CoPcTiO2 catalyst were used for the photoreduction of CO2 in NaOH solution, under the optimal conditions, the gross photocatalytic reduction of CO2 was 1032 lmol (g cat)-1 [4]. The ZrO2 was used for the photocatalytic reduction of CO2 [5]. Many researchers found that spinel-type composite oxide (AB2O4), whose band gap is narrow, is the photocatalyst with great potential application.The photocatalytic reduction of CO2 on ptype CaFe2O4 powder has been studied in water. In this work, TiO2-P25 and citric acid are materials, TiO2 is modified by doping C to get the C-TiO2 nano-powder, its optical activity, microstructure and photocatalytic reduction activity of carbon dioxide were studied.

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Advanced Materials Research Vols. 183-185


Experimental procedure Materials.The following analytical grade chemicals were purchased from Tianjin Kemiou Chemical Reagent Co. and used without further purification. Preparation of C-TiO2.TiO2 doped with C was obtained by way of immersion and calcinations method by using citric acid (CA) as dopant material. First, weighing 3g citric acid (CA) dissolved in 50mL aqueous solution, and weighing 1gTiO2-P25 dispersed in citric acid (CA) solution, milling 1 h, vacuum drying at 95 , then calcined for 2 h at 600 , that the full ground C-TiO2-3/1-600 catalyst, 3/1 was the weight ratio of the CA/TiO2-P25. By the same method to synthesize the catalyst is C-TiO2-1/1-600, C-TiO2-2/1-600, and C-TiO2-4/1-600. Evaluation of photocatalytic reduction activity .Photocatalytic experiments were carried out in a three-concentric cylindrical quartz reactor. The outermost layer is the reaction pool, which was filled with reaction solution; the middle layer is quartz cold trap; the innermost layer is the light source (175W high pressure mercury lamp). The photocatalytic activity of C-TiO2 nanoparticles was evaluated by the reduction efficiency of CO2. Products are mainly HCOOH. The yield of HCOOH was determined as follows: the reaction solution was taken off from the reactor, and then sediments of the solution were separated by centrifuge. The pH of the supernatant liquid of the reaction solution was adjusted to 2 by using Phosphoric acid. The solution was distilled at normal pressure. The distillates at 90 C were collected into a 25 mL colorimetric tube, while taking 1.0ml 0.1mol / L NaOH solution as a blank solution. adding 100mg of magnesium tape respectively, placing the colorimetric tube in cold bath, slowly adding 1.0mL concentrated hydrochloric acid, then adding 5% chromotropic acid and 5.0 mL vitriol oil, heating 30min in boiling water, then cooling to room temperature, adding 10mL ultrapure water, using visible light spectrophotometer at 574.5 nm measured absorbance. Fig.1 is the formic acid ion in UV-Vis absorption spectra; Fig.2 shows a good linear relationship between absorbance and the concentration of HCOOH, which is used as a standard curve for HCOOH content calculations. The yield of HCOOH (mHCOOH) was calculated by Eq. 2:
A = 0 . 0046 C + 0 . 0053 ( R

= 0 . 9999 )


(2) Where mHCOOH is the amount of HCOOH produced in the photocatalytic reaction (mol/g); V0 is the volume of the reaction solution; m is the amount of the catalyst used in the photocatalytic reaction.
0 .1 0


( mol / g Cat ) =

( A 0 . 0053 ) V 0 10 3 0 . 0046 M ( HCOOH ) m ( C at )

0 .5
0 .0 8

A = 0 .0 0 4 7 C + 0 .0 0 4 2 3 2 R = 0 .9 9 9 6


0 .4

550 600 650

0 .0 6

0 .3 0 .2 0 .1 0 .0 0 20 40

0 .0 4

0 .0 2

0 .0 0 500

H C O O (m g /L )



W a v e le n g th /n m

Fig.1 UV-Vis absorption spectrum of HCOO-

Fig.2 Working Standard curve of HCOO-


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Results and discussion X-ray diffraction studies.Fig.3 was the XRD spectra of the C-TiO2-R-600. It can be seen that there is no different between anatase and rutile when the R values of C-TiO2 was different. They were the anatase and rutile mixed phase. After C doped, the peak intensity of the anatase was weakened before doping C, while the peak intensity of the rutile increased. The result showed that the catalyst occurred phase transfer when it was calcined at high temperature.

C -T iO 2-1 /1

C -T iO 2-2 /1 C -T iO 2-3 /1 C -T i O 2 -4 / 1 T iO 2-P 25

10 20 30 40 50 60 70

2 /

Fig.3 XRD patterns of C-TiO2 R-600 According to a formula of Bragg, the cell parameters of the catalyst can be seen at table 1. Compared with the TiO2-P25, C-TiO2 unit cell parameters are changed, which indicated that C-element which doped into TiO2 lattice, replaced Ti4+, so that cell volume is expansion. Table.1 the unit cell parameters of C-TiO2 R-600 Sample TiO2-P25 C-TiO2-3/1-600 Unit cell parameters (a/nm) 3.7906 3.7906 Unit cell parameters (c/nm) 9.4885 9.7103

XPS studies.Fig.4 is the the XPS spectra of C-TiO2. Fig. 4 (a), in C-TiO2 spectrum we can see the characteristic peak of Ti2s, Ti2p, Ti3s, Ti3p, O1s and C1s. From Fig. 4 (b), we learn, Ti2p in 464.5ev and 458.8ev has two peaks which correspond to the absorption peak of anatase TiO2 in Ti4+2p1/2 and Ti4+2p3/2, TiO2-P25 has peaks in the 459.7ev, the Ti2p peaks is occurred blue shift. From Fig.4 (c), we learn, C1s in 288.6ev and in 284.6ev has two characteristic peaks, 284.6ev should correspond to the carbon pollution (instrument calibration), in 288.6ev the peaks illustrate it is the C-O, so that Ti in the TiO2 lattice may be replaced by the C, a Ti-O-C structure is formed [6].
O1S a: C-TiO2-3/1
b: Ti 2p 2P3/2458.8
c: C1s 284.6






















Binding Energy/ev

Binding Energy/ev

Binding Energy/ev

(b) (c) Fig.4 XPS spectras of C-TiO2 (a) C-TiO2; (b) Ti2p; (c) C1s UV-Vis studies.Fig.5 is the UV - visible diffuse reflectance spectra of the C-TiO2-R-600. The absorption edge of C-TiO2-R-600 has a degree of red shift compared with the TiO2-P25. The oxygen atom in the TiO2 lattice is replaced by carbon atom, up the TiO2 valence band there has a new band, so that system can be reduced.

Advanced Materials Research Vols. 183-185


0 .1 5

0 .1 2 C - T iO 2 - 1 /1 - 6 0 0


0 .0 9 C -T iO 2 - 4 /1 -6 0 0 0 .0 6 C - T iO 2 - 2 /1 - 6 0 0 C - T iO 2 -3 /1 - 6 0 0 0 .0 3 T iO 2 - P 2 5 0 .0 0 250 300 350 400

W a v e le n g th /n m

Fig.5 the UV-Vis diffuse spectras of C-TiO2-R-600 FT-IR studies.Fig.6 is the FT-IR spectra of C-TiO2-R-600. Compared with the TiO2-P25, the C-TiO2 has the new peaks. before and after doping TiO2-P25 in 3400 cm-1 and 1650 cm-1 has absorption peaks, at 3400 cm-1 it is the stretching vibration absorption peaks of OH group, at 1650 cm-1 it is the deformation vibration absorption peak of physical adsorbed water O-H bond, the results shows that C doping does not lead to changes in TiO2 surface-OH. In 500-700 cm-1 it is Ti-O bond vibration absorption peak. A series of C-TiO2-R-600 in the vicinity of 1150 cm-1 have new absorption peaks, the result shows that C doping process has an effect on the structure of TiO2.
0.8 0.7 C-TiO2-3/1-600


0.6 0.5 0.4 0.3 0.2 0.1 0.0 4000 3500 3000 2500 2000 1500

C-TiO2-1/1-600 C-TiO 2-4/1-600 TiO2-P25 C-TiO2-2/1-600




Fig.6 FT-IR spectras of C-TiO2 R-600 SPS studies.Fig.7 is the SPS spectrum of the C-TiO2-3/1-600. It can be seen that, the absorption peak intensity of C-TiO2-3/1-600 was significantly higher than TiO2-P25. The result shows after doping the charge separation efficiency of the catalyst is heightened.

C -T iO 2 -3 /1 -6 0 0

T iO 2 -P 2 5








W a v e len g th /n m

Fig.7 the SPS spectras of C-TiO2-3/1-600 Photocatalytic reduction of CO2 studies.Fig.8 shows the photocatalytic reduction of CO2 by using C-TiO2-3/1-600 nanoparticles as catalysts and Na2SO3 as the electron donor. It can be seen that the catalyst has obvious photocatalytic activity, and which can make HCOOH yield maximum in 5h .The produced HCOOH could also be decomposed into CO2 and H2O because of the strong oxidation capacity of spinel-type photocatalyst. The HCOOH concentration was stabilized when the reduction of CO2 and the oxidation of HCOOH were balanced. In addition, the NaHCO3 was decompounded when the reaction temperature was high, and the part of the decomposition of gaseous CO2 escaped from internal pressure reactor. In the reaction system, the HCO3-and CO32concentrations were lower. The HCOOH concentration was decreased when the reaction time was


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longer, therefore, methanoic acid yield may achieve 2610.98mol/g-Cat when irradiation time was five hours, and the activity of C-TiO2-3/1-600 had best.
3000 2500 Yield of HCOOH(mol/g-Cat) 2000 1500 1000 500 0 1 2 3 4 5 6 C -TiO 2 -3/1-600 C-TiO 2 -1/1-600 C-TiO 2 -2/1-600

C-TiO 2 -4/1-600 TiO 2 -P 25

Irradiation time (h)

Fig.8 Yields of HCOOH in the photocatalytic reduction of CO2 by C-TiO2-R-600 Two conditions must be well controlled to enable the photoreduction of CO2: first, the end of the conduction band is higher than the oxidation-reduction potential of H2CO3 / HCOOH; second, the top of the valence band must be lower than the oxidation-reduction potential of O2/H2O. In the reaction system, amount of Na2C2O4 plays a great role in promoting. Na2SO3 as a reductant has a low oxidation-reduction potential, which can promotes oxidation of the four catalysts in the valence band hole. According to the wavelength of light absorption, CO2 was reduced by the photoelectrons excited by the photocatalysts. The reduction of was described using Eq.5.
photocatalyst h 2CO 2 + 2H 2 O + 2CHOOH + O 2


Summary TiO2 doped with C was obtained by way of immersion and calcinations method by using citric acid (CA) as dopant material. The investigation showed that the C-TiO2-R-600 photocatalysts all had better activity. Methanoic acid yield may achieve 2610.98mol/g-Cat when irradiation time was 5 h, and the activity of C-TiO2-3/1-600 wad best. References [1] S Krischok, O Heofft, V Kempter, The chemisorption of H2O and on TiO2 surfaces: studies with MIES and UPS(He/)Surface Science, 2002, (5):69-73 [2]Hiromi Yamashita, Yo Fuchi, Ichihashi, Shu Gou Zhang, Keita Ikeue, Dal Ryung Park, Keiko Koyano, Takashi Tatsumi, Masakazu AnPo, Selective formation of CH3OH in the photocatalytic reduction of CO2 with H20 on titanium oxides highly dispersed within zeofites and mesoporous molecular sieves, Catalysis Today, 1998, (45):221-227 [3]Ikeue KNozaki SOgawa M etal.CharaCterization of self-standing Ti-containing porous silica thin films and their reactivity for the photocatalytic reduction of CO2 with H2O.Catal.TOd.,2002,74:241-248 [4] Shioya Y,Ikeue K,Ogawa M,etal.Synthesis of transparent Ti-containing mesoporous silica thin film material sand their unique photocatalytic activity for the reduction of CO2 with H2O.Appl.Catal.A2003254:251-259. [5] Sasirekha N,Basha S J S,Shanthi K.Photocata1ytic performance of Ru doped anatase mounted on silica for reduction of carbon dioxide.Appl.Catal.B200662(1-2):169-180 [6]Ren Wenjie, Ai Zhihui, Jia Falong, et al. Appl. Catal., B: Environmental, 2007, 69(3-4): 138-144

Environmental Biotechnology and Materials Engineering doi:10.4028/ Preparation of C Doped TiO<sub>2</sub> Photocatalysts and their Photocatalytic Reduction of Carbon Dioxide doi:10.4028/