Startseite Determination of Photochemical, Electrochemical and Photoelectrochemical Efficiencies in a Photoelectrocatalytic Reactor
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Determination of Photochemical, Electrochemical and Photoelectrochemical Efficiencies in a Photoelectrocatalytic Reactor

  • Javier Marugán EMAIL logo , Rafael van Grieken , Cristina Pablos , Cristina Adán und Ruud Timmers
Veröffentlicht/Copyright: 20. Juni 2013
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International Journal of Chemical Reactor Engineering
Aus der Zeitschrift International Journal of Chemical Reactor Engineering Band 11 Heft 2

Abstract

The relation between the amount of incident photons, absorbed photons, oxidant species, reaction products and electrons in the external circuit should be analyzed individually to determine the step limiting the efficiency of the global photoelectrocatalytic processes. This work discusses the evaluation of three different titania electrodes for the oxidation of methanol in a photoelectrocatalytic reactor. The electrode prepared with three titania coating cycles shows a high efficiency in terms of photochemical (photons to product molecules), electrochemical (product molecules to electrons) and photoelectrochemical (photons to electrons) what explain its high activity for the photoelectrocatalytic oxidation of methanol.

Keywords: photoelectrocatalysis; TiO2 electrode; photonic efficiency; electrochemical efficiency; IPCE

Appendix: Values of the efficiencies

Table 5

Photonic efficiencies of formaldehyde formation during the photoelectrocatalytic oxidation of 0.1 M aqueous solutions of methanol in 0.1 M Na2SO4 at increasing potential bias with the three studied electrodes. Values calculated with eq. [2] using the incident radiation value estimated by actinometry (1.01 × 10−6 Einstein s−1).

E (V)ξ (molHCHO Einstein−1)
1-TiO2/ITO2-TiO2/ITO3-TiO2/ITO
Open circuit0.0224 (±0.0070)0.0381 (±0.0076)0.0465 (±0.0093)
0.40.0276 (±0.0055)0.0462 (±0.0092)0.0732 (±0.015)
0.60.0126 (±0.0050)0.0367 (±0.0073)0.0893 (±0.018)
0.80.0169 (±0.0058)0.0469 (±0.0094)0.0637 (±0.013)
1.00.0070 (±0.0039)0.0350 (±0.0070)0.0780 (±0.016)
1.40.0124 (±0.0050)0.0359 (±0.0072)0.0655 (±0.013)
Table 6

Minimum quantum efficiencies of formaldehyde formation during the photoelectrocatalytic oxidation of 0.1 M aqueous solutions of methanol in 0.1 M Na2SO4 at increasing potential bias with the three studied electrodes. Values calculated with eq. [3] using the absorbed radiation values estimated by radiometry (Table 4).

E (V) (molHCHO Einstein−1)
1-TiO2/ITO2-TiO2/ITO3-TiO2/ITO
Open circuit0.0601 (±0.019)0.0720 (±0.014)0.0792 (±0.016)
0.40.0738 (±0.015)0.0873 (±0.018)0.1247 (±0.025)
0.60.0337 (±0.013)0.0693 (±0.014)0.1520 (±0.030)
0.80.0453 (±0.016)0.0885 (±0.018)0.1085 (±0.022)
1.00.0188 (±0.010)0.0661 (±0.013)0.1329 (±0.027)
1.40.0333 (±0.013)0.0679 (±0.014)0.1115 (±0.022)
Table 7

Electrochemical efficiencies of formaldehyde formation during the photoelectrocatalytic oxidation of 0.1 M aqueous solutions of methanol in 0.1 M Na2SO4 at increasing potential bias with the three studied electrodes. Values calculated with eq. [4] using the photocurrent densities registered during the reactions (Table 3).

E (V)ε (molHCHO mole−−1)
1-TiO2/ITO2-TiO2/ITO3-TiO2/ITO
0.40.365 (±0.110)0.466 (±0.093)0.318 (±0.064)
0.60.337 (±0.067)0.452 (±0.090)0.435 (±0.087)
0.80.137 (±0.054)0.359 (±0.072)0.504 (±0.100)
1.00.199 (±0.069)0.382 (±0.076)0.386 (±0.077)
1.40.065 (±0.036)0.244 (±0.049)0.423 (±0.085)
Table 8

Incident photon-to-current efficiencies during the photoelectrocatalytic oxidation of 0.1 M aqueous solutions of methanol in 0.1 M Na2SO4 at increasing potential bias with the three studied electrodes. Values calculated with eq. [5].

E (V)IPCE (mole− Einstein−1)
1-TiO2/ITO2-TiO2/ITO3-TiO2/ITO
0.40.076 (±0.023)0.099 (±0.020)0.230 (±0.046)
0.60.037 (±0.007)0.081 (±0.016)0.205 (±0.041)
0.80.124 (±0.049)0.131 (±0.026)0.126 (±0.025)
1.00.035 (±0.012)0.092 (±0.018)0.202 (±0.040)
1.40.192 (±0.106)0.147 (±0.029)0.155 (±0.031)

Notation

CHCHOformaldehyde molar concentration, mol cm−3
surface rate of photon absorption, Einstein cm−2 s−1
Epotential bias, V
FFaraday constant, C mol−1
Jphotocurrent density, A
kzero-order kinetic constant, mol cm−2 s−1
P0incident irradiation power, Einstein s−1
qradiation flux, Einstein cm−2 s−1
rHCHOformaldehyde formation reaction rate, mol cm−2 s−1
electrode surface area, cm2
ttime, s
VTtotal working volume, cm3

Greek letters

εelectrochemical efficiency, molHCHO mole−−1
monochromatic quantum yield, molHCHO Einstein−1
λwavelength, nm
ηpolychromatic quantum efficiency, molHCHO Einstein−1
ξphotonic efficiency, molHCHO Einstein−1

Subscripts

λindicates a dependence on wavelength
minindicates the minimum value

Special symbols

〈 〉indicates average value

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Published Online: 2013-06-20

©2013 by Walter de Gruyter Berlin / Boston

Artikel in diesem Heft

  1. Masthead
  2. Masthead
  3. Editorial
  4. In Honor of Alberto E. Cassano: Researcher, Engineer, and Academic
  5. Articles
  6. From Ideal Reactor Concepts to Reality: The Novel Drum Reactor for Photocatalytic Wastewater Treatment
  7. Synthesis, Characterization, and Comparison of Sol–Gel TiO2 Immobilized Photocatalysts
  8. Determination of Kinetic Parameter in a Unified Kinetic Model for the Photodegradation of Phenol by Using Nonlinear Regression and the Genetic Algorithm
  9. Mass Transfer and Conservation from a Finite Source to an Infinite Media
  10. Modelling and Simulation of Gas–liquid Hydrodynamics in a Rectangular Air-lift Reactor
  11. Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor
  12. Role of Aspect Ratio and Joule Heating within the Fluid Region Near a Cylindrical Electrode in Electrokinetic Remediation: A Numerical Solution based on the Boundary Layer Model
  13. Solar Water Disinfection Using NF-codoped TiO2 Photocatalysis: Estimation of Scaling-up Parameters
  14. A Simple and Semi-Empirical Model to Predict THMs Generation in Water Facilities Including pH Effects
  15. On the Standardization of the Photocatalytic Gas/Solid Tests
  16. Microalgae Technology: A Patent Survey
  17. Influence of Physical and Optical Parameters on 2,4-Dichlorophenol Degradation
  18. Factors Capable of Modifying the Response of Pseudomonas aeruginosa to the Inactivation Induced by Heterogeneous Photocatalysis
  19. Enhanced Antibacterial Activity of CeO2 Nanoparticles by Surfactants
  20. Determination of Photochemical, Electrochemical and Photoelectrochemical Efficiencies in a Photoelectrocatalytic Reactor
  21. Correlations between Molecular Descriptors from Various Volatile Organic Compounds and Photocatalytic Oxidation Kinetic Constants
  22. Role of Joule Heating in Electro-Assisted Processes: A Boundary Layer Approach for Rectangular Electrodes
https://doi.org/10.1515/ijcre-2012-0014
Schlagwörter für diesen Artikel
photoelectrocatalysis; TiO2 electrode; photonic efficiency; electrochemical efficiency; IPCE

Artikel in diesem Heft

  1. Masthead
  2. Masthead
  3. Editorial
  4. In Honor of Alberto E. Cassano: Researcher, Engineer, and Academic
  5. Articles
  6. From Ideal Reactor Concepts to Reality: The Novel Drum Reactor for Photocatalytic Wastewater Treatment
  7. Synthesis, Characterization, and Comparison of Sol–Gel TiO2 Immobilized Photocatalysts
  8. Determination of Kinetic Parameter in a Unified Kinetic Model for the Photodegradation of Phenol by Using Nonlinear Regression and the Genetic Algorithm
  9. Mass Transfer and Conservation from a Finite Source to an Infinite Media
  10. Modelling and Simulation of Gas–liquid Hydrodynamics in a Rectangular Air-lift Reactor
  11. Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor
  12. Role of Aspect Ratio and Joule Heating within the Fluid Region Near a Cylindrical Electrode in Electrokinetic Remediation: A Numerical Solution based on the Boundary Layer Model
  13. Solar Water Disinfection Using NF-codoped TiO2 Photocatalysis: Estimation of Scaling-up Parameters
  14. A Simple and Semi-Empirical Model to Predict THMs Generation in Water Facilities Including pH Effects
  15. On the Standardization of the Photocatalytic Gas/Solid Tests
  16. Microalgae Technology: A Patent Survey
  17. Influence of Physical and Optical Parameters on 2,4-Dichlorophenol Degradation
  18. Factors Capable of Modifying the Response of Pseudomonas aeruginosa to the Inactivation Induced by Heterogeneous Photocatalysis
  19. Enhanced Antibacterial Activity of CeO2 Nanoparticles by Surfactants
  20. Determination of Photochemical, Electrochemical and Photoelectrochemical Efficiencies in a Photoelectrocatalytic Reactor
  21. Correlations between Molecular Descriptors from Various Volatile Organic Compounds and Photocatalytic Oxidation Kinetic Constants
  22. Role of Joule Heating in Electro-Assisted Processes: A Boundary Layer Approach for Rectangular Electrodes
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