Asymmetric Photocatalytic Membranes for Hydrogen Production: Preparation of TiO2-based Membranes and Their Properties

Dmitry E. Tsydenov, Alexander V. Vorontsov, Valentin N. Parmon Boreskov Institute of Catalysis SB RAS, Novosibirsk 630090, Russia; Novosibirsk State University, Novosibirsk 630090, Russia;
Description Membrane photocatalytic system (MPS) is one of the promising ways for water splitting and separation of gaseous products. The MPS has layered structure Pt/chemically loaded TiO2/filtration loaded TiO2/porous polymer membrane/support. Influence of MPS preparation conditions on its TiO2 content, permeability, diffuse reflectance spectra, mechanical stability, Pt loading and membrane morphology was investigated. Chemical bath deposition of TiO2 could provide mechanical stability of the TiO2 layer on the membrane. Further aging of the TiO2 layer leads to high activity in hydrogen production. Optimum mass of TiO2 and loading with photodeposited Pt were found for high rate of H2 generation. The presence of gas phase at one side of MPS results in higher rate of H2 generation (quantum efficiency ~ 13%). Objective Developing MPS preparation methods and study of their activity for hydrogen production from water in the presence of ethanol. To solve this task we used Pt/TiO2 composition as a photocatalyst and PTFE filter MMFK-3 with reinforced polypropylene support as a substrate.

Preparation steps

Fig. 1. Schematic representation of the MPS being developed for separate hydrogen and oxygen evolution.

Fig. 2. Schematic representation of the MPS preparation steps

Fig. 3. The membrane reactor with lamp DRSH-1000.

Membrane characterization
0,08
16

Photocatalytic hydrogen production

4

0,06

W(H2),ml/h

12 8 4 0

m(Pt), mg

0,04 0,02 0,00 0 100 200 C(H2PtCl6), M 300

W(H2), ml/h
0.00 0.03 0.06 0.09 m(Pt), mg 0.12

1 0 1 2 3 4 5 6 7 8

m ( TiO2) , mg

Fig. 4. Amount of platinum photodeposited on membrane as a function of initial concentration of H2PtCl6.

1000 800

Fig. 7. Rate of hydrogen production on the amount of photodeposited platinum on membrane loaded with 12 mg TiO2 by filtration. Only IC was filled.

Fig. 8. The effect of the mass of TiO2 loaded by CBD on the rate of hydrogen generation. Only IC was filled

6 5
Memb rane

For two compartment liquid filled reaction

Amount of chemically precipitated TiO2, mg 0.5 1 3 5 7 LT, s KH2 KC Kcom

LT, s

600 400 200 0

W(H2), ml/h

4 3
100 105 102 103 104

m, mg

-1 0

4 5 t, h

36 46 390 270 900

6.6 0,8 18.9 1.1 20.8 0.8 0.66 0.16 0.73 0.17

8,3 17.2 26.7 4,1 4,2

Fig. 5. Dependence of leakage time (LT) on amount of TiO2 loaded by CBD.

Fig. 9. Influence of the aging time on the rate of hydrogen production. Only IC was filled.

Table 1. Product ratios for photocatalytic hydrogen production from ethanol during 100 min over CBD loaded membranes with 0.06 mg of photodeposited Pt.

Fig. 6. SEM images of empty membrane, membrane filled TiO2 by filtration, membrane after CBD.

vs
NC IC NC IC

The rate of hydrogen production was up to 3 times higher for configuration, when only IC was filled with liquid , compared with configuration, when only both compartments filled.

Conclusions: A method of preparation of a stable photoactive layer based on TiO2 over the porous polymer membrane MFFK-3 has been developed. Relationships were established between the conditions of preparation of the membranes and their properties. The influence of platinum amount, mass and composition of the applied layer of TiO2 and aging time on the rate of hydrogen evolution in ethanol solution was determined.

Acknowledgements
The work was supported by RAS Presidium grant 24.49.