Photocatalytic Reduction of Carbon Dioxide on TiO2 Heterojunction Photocatalysts-A Review.

The photocatalytic reduction of carbon dioxide to renewable fuel or other valuable chemicals using solar energy is attracting the interest of researchers because of its great potential to offer a clean fuel alternative and solve global warming problems. Unfortunately, the efficiency of CO2 photocatalytic reduction remains not very high due to the fast recombination of photogenerated electron-hole and small light utilization. Consequently, tremendous efforts have been made to solve these problems, and one possible solution is the use of heterojunction photocatalysts. This review begins with the fundamental aspects of CO2 photocatalytic reduction and the fundamental principles of various heterojunction photocatalysts. In the following part, we discuss using TiO2 heterojunction photocatalysts with other semiconductors, such as C3N4, CeO2, CuO, CdS, MoS2, GaP, CaTiO3 and FeTiO3. Finally, a concise summary and presentation of perspectives in the field of heterojunction photocatalysts are provided. The review covers references in the years 2011-2021.

Photocatalytic Decomposition of N2O Over Ceramics Cordierite/CeO2 Nanoparticles.

The study is focused on the testing of the photocatalytic ability to decompose nitrous oxide (N2O) over cordierite/CeO² nanoparticles ceramic photocatalysts. The activity of ceramic materials was compared with the activity of industrially produced TiO² (Evonik photocatalyst). Photocatalytic decomposition of N2O over the ceramic samples and the TiO² Evonik was performed in annular batch reactor illuminated with 8 W Hg lamp (λ ═ 254 nm wavelength). Reaction kinetics was well described by pseudo 1st rate law. Photocatalytic activity of cordierite/CeO² was better in comparison with TiO² Evonik P25. The highest N2O conversion (56%) after 20 h of irradiation in inert gas was achieved over the sample with higher amount of CeO². This photocatalyst sample was examined for photocatalytic activity in the decomposition of N2O in the three various gaseous feed mixtures. The gaseous feed mixtures were: N2O enriched with O² (6.5 mol.%); N2O enriched with H2O(25 mol.%) and N2O enriched with mixture of O² and H2O(6.5 mol.% and 25 mol.%, respectively). It is assumed that the reduced conversion of N2O (47%) observed in the flow of the mixture of N2O and H2Ocould be affected by the sorption of water vapor on/onto the photocatalyst "active sites" causing less penetration of light and thus reducing the efficiency of photocatalytic decomposition of N2O. The presence of oxygen in the N2O mixture had only little effect to photocatalytic decomposition of N2O.

Photocatalytic CO2 Reduction by Mesoporous Polymeric Carbon Nitride Photocatalysts.

In this paper, a sol-gel derived mesoporous polymeric carbon nitride has been investigated as a photocatalyst for CO2 photocatalytic reduction. Noble-metal Pt nanoparticles were deposited on carbon nitride (sg-CN) in order to investigate the performance of both Pt-sg-CN and sg-CN for photocatalytic CO2 reduction. Physicochemical properties of prepared nanocomposites were comprehensively characterized by using powder XRD, N2 physisorption, UV-Vis DRS, ICP-AES, FTIR, solid-state NMR, SEM, TEM and photoelectrochemical measurements. Compared with pure sg-CN, the resulting Pt-loaded sg-CN (Pt-sg-CN) exhibited significant improvement on the CO2 photocatalytic reduction to CH4 in the presence of water vapor at ambient condition under UV irradiation. 1.5 wt.% Pt-loaded sg-CN (Pt-sg-CN) photocatalyst formed the highest methane yield of 13.9 µmol/gcat. after 18 h of light irradiation, which was almost 2 times and 32 times improvement in comparison to pure sg-CN and commercial TiO2 Evonik P25, respectively. The substantial photocatalytic activity of Pt-sg-CN photocatalyst for the yield product of the CO2 photocatalytic reduction was attributed to the efficient interfacial transfer of photogenerated electrons from sg-CN to Pt due to the lower Fermi level of Pt in the Pt-sg-CN hybrid heterojunctions as also evidenced by photo-electrochemical measurements. This resulted in the reduction of electron-hole pairs recombination for effective spatial charge separation, consequently increasing the photocatalytic efficiency.

Novel TiO2/C3N4 Photocatalysts for Photocatalytic Reduction of CO2 and for Photocatalytic Decomposition of N2O.

TiO2/g-C3N4 photocatalysts with the ratio of TiO2 to g-C3N4 ranging from 0.3/1 to 2/1 were prepared by simple mechanical mixing of pure g-C3N4 and commercial TiO2 Evonik P25. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, Raman spectroscopy, infrared spectroscopy, transmission electron microscopy, photoelectrochemical measurements, and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic reduction of carbon dioxide and photocatalytic decomposition of nitrous oxide. The pure g-C3N4 exhibited the lowest photocatalytic activity in both cases, pointing to a very high recombination rate of charge carriers. On the other hand, the most active photocatalyst toward all the products was (0.3/1)TiO2/g-C3N4. The highest activity is achieved by combination of a number of factors: (i) specific surface area, (ii) adsorption edge energy, (iii) crystallite size, and (iv) efficient separation of the charge carriers, where the efficient charge separation is the most decisive parameter.

Photocatalytic Hydrogen Formation from Ammonia in an Aqueous Solution Over Pt-Enriched TiO2-ZrO2 Photocatalyst.

The aim of this study was to remove ammonia from an aqueous solution by its decomposition to valuable products such as H2 and harmless N2 under UV light. The decomposition of ammonia by photocatalytic process represents an emerging and interesting way of its removal since beside the need of its reduction from the drinking and wastewaters with the respect to its negative impact on human and mammals health, it can lead to generation of hydrogen as an alternative fuel. A laboratory-synthesized Pt/TiO2-ZrO2 photocatalyst was studied and its photocatalytic activity was compared with the activity of commercial TiO2 Evonik P25. The Pt/TiO2-ZrO2 photocatalyst was prepared by combining a sol-gel process controlled within reverse micelles of nonionic surfactant Triton X-114 in cyclohexane, impregnation under vacuum and calcination. Explored photocatalysts were characterized by organic elementary analysis, nitrogen physisorption, XRD, FESEM and UV-Vis spectroscopy. The real platinum content in the Pt/TiO2-ZrO2 photocatalyst was determined by ICP-MS. The photocatalytic decomposition of ammonia was investigated in the time range of 0-12 h. During the first two hours the generation of hydrogen was almost negligible. The generation of hydrogen increased after 4 h of irradiation. Based on time dependences of ammonia decomposition the kinetic rate constants for Pt/TiO2-ZrO2 and TiO2 Evonik P25 photocatalysts were calculated. The ammonia photocatalytic decomposition was described well by the first order kinetic equation. The photocatalytic ammonia decomposition over the platinized TiO2-ZrO2 photocatalyst was proving 2 times higher photocatalytic performance than Evonik P25 (1241 µmol/g(cat) and 665 µmol/g(cat), respectively).