Photoelectrochemical reduction of carbon dioxide

Photoelectrochemical reduction of carbon dioxide, also known as photoelectrolysis of carbon dioxide, is a chemical process whereby carbon dioxide is reduced to carbon monoxide or hydrocarbons by the energy of incident light. This process requires catalysts, most of which are semiconducting materials. The feasibility of this chemical reaction was first theorised by Giacomo Luigi Ciamician, an Italian photochemist. Already in 1912 he stated that "y using suitable catalyzers, it should be possible to transform the mixture of water and carbon dioxide into oxygen and methane, or to cause other endo-energetic processes."
Furthermore, the reduced species may prove to be a valuable feedstock for other processes. If the incident light utilized is solar then this process also potentially represents energy routes which combine renewable energy with CO₂ reduction.

Thermodynamics

Thermodynamic potentials for the reduction of CO₂ to various products is given in the following table versus NHE at pH = 7. Single electron reduction of CO₂ to CO₂^●− radical occurs at E° = −1.90 V versus NHE at pH = 7 in an aqueous solution at 25 °C under 1 atm gas pressure. The reason behind the high negative thermodynamically unfavorable single electron reduction potential of CO₂ is the large reorganization energy between the linear molecule and bent radical anion. Proton-coupled multi-electron steps for CO₂ reductions are generally more favorable than single electron reductions, as thermodynamically more stable molecules are produced.

+ 2 + 2 e⁻ → CO +	E⁰ = −0.53 V
+ 2 + 2 e⁻ →	E⁰ = −0.61 V
+ 4 + 4 e⁻ → HCHO +	E⁰ = −0.48 V
+ 6 + 6 e⁻ → +	E⁰ = −0.38 V
+ 8 + 8 e⁻ → + 2	E⁰ = −0.24 V
+ e⁻ →	E⁰ = −1.90 V

Kinetics

Thermodynamically, proton coupled multiple-electron reduction of CO₂ is easier than single electron reduction. But to manage multiple proton coupled multiple-electron processes is a huge challenge kinetically. This leads to a high overpotential for electrochemical heterogeneous reduction of CO₂ to hydrocarbons and alcohols. Even further heterogeneous reduction of singly reduced CO₂^●− radical anion is difficult because of repulsive interaction between negatively biased electrode and negatively charged anion.
Figure 2 shows that in case of a p-type semiconductor/liquid junction photo generated electrons are available at the semiconductor/liquid interface under illumination. The reduction of redox species happens at less negative potential on illuminated p-type semiconductor compared to metal electrode due to the band bending at semiconductor/liquid interface. Figure 3 shows that thermodynamically, some of the proton-coupled multi-electron CO₂ reductions are within semiconductors band gap. This makes it feasible to photo-reduce CO₂ on p-type semiconductors. Various p-type semiconductors have been successfully employed for CO₂ photo reduction including p-GaP, p-CdTe, p-Si, p-GaAs, p-InP, and p-SiC. Kinetically, however, these reactions are extremely slow on given semiconductor surfaces; this leads to significant overpotential for CO₂ reduction on these semiconductor surfaces. Apart from high overpotential; these systems have a few advantages including sustainability, direct conversion of solar energy to chemical energy, utilization of renewable energy resource for energy intensive process, stability of the process etc. A different approach for photo-reduction of CO₂ involves molecular catalysts, photosensitizers and sacrificial electron donors. In this process sacrificial electron donors are consumed during the process and photosensitizers degrade under long exposure to illumination.

Solvent effect

The photo-reduction of CO₂ on p-type semiconductor photo-electrodes has been achieved in both aqueous and non-aqueous media. Main difference between aqueous and non-aqueous media is the solubility of CO₂. The solubility of CO₂ in aqueous media at 1 atm. of CO₂ is around ≈ 35 mM; whereas solubility of CO₂ in methanol is around 210 mM and in acetonitrile is around 210 mM.

Aqueous media

Photoreduction of CO₂ to formic acid was demonstrated on an p-GaP photocathode in aqueous media. Apart from several other reports of CO₂ photoreduction on p-GaP, there are other p-type semiconductors like p-GaAs, p-InP, p-CdTe, and p⁺/p-Si have been successfully used for photoreduction of CO₂. The lowest potential for CO₂ photoreduction was observed on p-GaP. This may be due to high photovoltage excepted from higher band gap p-GaP photocathode. Apart from formic acid, other products observed for CO₂ photoreduction are formaldehyde, methanol and carbon monoxide. On p-GaP, p-GaAs and p⁺/p-Si photocathode, the main product is formic acid with small amount of formaldehyde and methanol. However, for p-InP and p-CdTe photocathode, both carbon monoxide and formic acid are observed in similar quantities. Mechanism proposed by Hori based on CO₂ reduction on metal electrodes predicts formation of both formic acid and carbon monoxide in aqueous media. This same mechanism can be evoked to explain the formation of mainly formic acid on p-GaP, p-GaAs and p⁺/p-Si photocathode owing to no adsorption of singly reduced CO₂^●− radical anion to the surface. In case of p-InP and p-CdTe photocathode, partial adsorption of CO₂^●− radical anion leads to formation of both carbon monoxide and formic acid. Low catalytic current density for CO₂ photoreduction and competitive hydrogen generation are two major drawbacks of this system.

Non-aqueous media

Maximum catalytic current density for CO₂ reduction that can be achieved in aqueous media is only 10 mA cm⁻² based solubility of CO₂ and diffusion limitations. The integrated maximum photocurrent under Air Mass 1.5 illumination, in the conventional Shockley-Quiesser limit for solar energy conversion for p-Si, p-InP, p-GaAs, and p-GaP are 44.0 mA cm⁻², 37.0 mA cm⁻², 32.5 mA cm⁻² and 9.0 mA cm⁻², respectively. Therefore, non-aqueous media such as DMF, acetonitrile, methanol are explored as solvent for CO₂ electrochemical reduction. In addition, Methanol has been industrially used as a physical absorber of CO₂ in the Rectisol method. Similarly to aqueous media system, p-Si, p-InP, p-GaAs, p-GaP and p-CdTe are explored for CO₂ photoelectrochemical reduction. Among these, p-GaP has lowest overpotential, whereas, p-CdTe has moderate overpotential but high catalytic current density in DMF with 5% water mixture system. Main product of CO₂ reduction in non-aqueous media is carbon monoxide. Competitive hydrogen generation is minimized in non-aqueous media. Proposed mechanism for CO₂ reduction to CO in non-aqueous media involves single electron reduction of CO₂ to CO₂^●− radical anion and adsorption of radical anion to surface followed by disproportionate reaction between unreduced CO₂ and CO₂^●− radical anion to form CO₃²⁻ and CO.