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Molecules 2020, 25, 3653 8 of 23 2.4. Photoelectrocatalysis Since there is an inexhaustible solar energy supply in nature, it should be fully utilized in different ways. Photoelectrocatalysis, which combines the advantages of photocatalysis and electrocatalysis, is considered to be an ideal strategy for the selective conversion of CO2 into gaseous (such as CO, methane, etc.) and liquid products (such as formic acid, methanol, ethanol, etc.) under sunlight irradiation, and has therefore attracted great attention [88–90]. Photoelectrocatalysis makes the best use of solar energy to produce photoelectrons. The photogenerated electrons are transferred to the electrode surface under the action of an applied electric field, and finally obtained by CO2 for catalytic reduction. The applied electric field can effectively facilitate charge separation in the photocatalytic process [59], promote electron migration, and significantly improve the intrinsic activity and energy efficiency of CO2 molecules [91]. The efficient utilization of solar energy in photoelectrocatalysis can effectively overcome the problem of high energy consumption in the electrocatalysis of CO2. In order to promote rapid charge transfer and improve the performance of photoelectrocatalysis, Ding and coauthors [92] patterned a photocathode through photolithography to expose a third of the surface, which is an effective and robust Si–Bi interface formed by Bi3+-assisted chemical etching of Si wafers and completed the reduction of CO2. This method increased the current density and facilitated the reduction of CO2 based on high product selectivity. TiO2 is one of the most employed semiconductor in photo-assisted processes. Castro et al. [93] loaded different amounts of TiO2 on the photoanode using a Cu plate as the photocathode to build a photoelectric chemical device, and combined this with an electrochemical filter-press cell. This device was employed to continuously convert CO2 into alcohol with reducing energy consumption due to less external energy demand. Comparing the alcohol produced under different conditions, the TiO2 photoanode system exhibited enhanced alcohol production and reduced energy consumption under ultraviolet light irradiation. Different photocathodes have different light absorption capabilities, which essentially depend on the optical characteristics of the semiconductor. Table 1 lists and compares the performance of different photoelectrochemical systems of CO2 reduction from the latest literature. The efficiency of CO2 conversion is a criterion of photoelectric conversion efficiency, which can be calculated by the following equation. Faradaic Efficiency (FE): FE can be understood as the percentage of actual product/theoretical product. FE(%) = eoutput × 100 = n(mol) × m × 100 (1) In the above equation, n is the actual moles of product, m is the number of reaction electrons, Q is the calculated electric charge, and F is the Faraday constant (96,485 C/mol). Applied Bias Photon-to-Current Efficiency (ABPE): ABPE is used to measure the efficiency when an external voltage (Vbias) is applied. einput Q(Coulomb) F(Coulomb/mol) J mA/cm2×∆E◦(V)−V (V)×FE ph bias Psolar(mW/cm2) ◦ whereJphisthephotocurrentdetectedundertheexternalvoltage,∆E isthethermodynamicenergy stored in the PEC reactor, and Psolar is the power density of light. ABPE = (2)PDF Image | Research Progress in Conversion of CO2 to Valuable Fuels
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