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We demonstrated that controlled periodic illumination (CPI) is unable to increase the quantum yield (or photoefficiency) of the photocatalytic process. Nevertheless, choosing the appropriate experi...

The photocatalytic activity of graphitic carbon nitride (g-C3N4) is actually a hot topic in the field of photocatalysis, as more than one thousand papers have been published in 2019 regarding the photocatalytic properties of this material. Here, we critically evaluated the state-of-the-art focusing on (i) the photophysical and electrochemical properties of this organic semiconductor; (ii) the proposed methods of synthesis that affect dramatically its properties starting from the stoichiometry and the p- or n-type nature; (iii) the features of the heterojunctions in g-C3N4-based hybrid heterostructures (binary, ternary, or also of higher complexity); (iv) its photocatalytic and photochemical applications; and (v) its uses in processes and technologies beyond (photo)catalysis (e.g., analytical applications). The photocatalytic applications of g-C3N4 are reviewed in the light of its overall semiconducting properties and chemical reactivity, focusing on the water photosplitting, the artificial photosynthesis, and photocatalytic CO2 reduction, its use in advanced oxidation processes for the abatement of (bio)recalcitrant pollutants and for photocatalytic disinfection, and last, as photoactivated catalyst for the synthesis of value-added compounds in organic syntheses. Some conclusions regarding the properties of this material and its more promising applications are drawn, together with some general perspectives of this organic semiconductor in the field of photocatalysis.

The light absorption and scattering play a prominent and often underrated role in the overall photocatalytic process and heavily affect the rate. This is particularly important for the choice of the catalyst in addition to other chemical and physical parameters usually considered for their catalytic role. Here we propose an approximated but easy-to-apply method to evaluate the light harvested by the photocatalyst slurry and its scattering/absorption coefficients, which does not require the use of complex spectrophotometric tools and the complicated radiative transport equation. The optical properties are obtained with the lamp and in the experimental setup employed in the photocatalytic batch tests. Among the four TiO2 specimens considered, we characterized Evonik P25 and Hombikat UV100. The obtained scattering and absorption coefficients helped in rationalizing the experimental results on the degradation of formic acid at low concentration. From the rate dependence on the catalyst concentration, this approach allowed further understanding of the role of catalyst-specific properties affecting the overall catalytic performance. This approach is proposed as a starting point for fixing conditions to compare different photocatalysts.

Different amounts of graphene oxide were chemically reduced with hydrazine in the presence of nanometric TiO 2 and SiO 2 . The photocatalytic performance of the resulting hybrid materials was compared with pristine supports using phenol and methylene blue (MB) under two different irradiation conditions (UV–vis and Vis only light). MB is strongly adsorbed on the hybrid materials. Significant MB degradation rates were observed on pristine TiO 2 and hybrid TiO 2 -reduced graphene oxide (rGO) material under both irradiation conditions. In the presence of the hybrid catalyst, the degradation of MB under Vis is due to the dye-sensitized mechanism, while under UV–vis there is an additional semiconductor-based photocatalytic mechanism. Conversely, the presence of rGO reduces the rate of photocatalytic transformation for the poorly adsorbed phenol under UV irradiation, and a negligible degradation rate was observed under Vis. The UV–vis absorption spectra of aqueous suspensions of hybrid materials with different rGO loading indicate a strong interaction of the two materials and a reduction of the light absorption due to the presence of rGO. Among many mechanisms reported on the role of rGO, it is inferred that the working mechanism involves electron transfer from photoexcited states of rGO onto the titania, and holes migration from titania to rGO, where adsorbed substrates are oxidized. This oxidation is possible only if the substrate HOMO has higher energy (less positive standard redox potential) than the empty states of excited rGO, supposedly for MB and not for phenol. Then, reduced graphene is advantageous when substrates are adsorbed and when the charge separation is possible (coupled with a proper semiconductor like TiO 2 ). Alone, or coupled with low work function oxides like SiO 2 , rGO could be ineffective.

p-Type organic semiconductors are attractive to develop new photo- and photoelectro-catalytic systems, particularly if the conduction band is located at negative redox potentials. An easy synthetic route to produce carbon-doped carbon nitride (Cn>3N4) with a stable p-type semiconducting character was optimized. The precursors used were melamine and triaminopyrimidine. The p-type Cn>3N4 exhibited a remarkable photoactivity under visible light compared with pristine C3N4, which is a stable n-type organic semiconductor deeply studied as heterogeneous photocatalyst for many environmental applications. The photoelectrochemical features of the synthesized p-type materials and pristine C3N4 were deeply investigated with chronopotentiometry and cyclic voltammetry, in the dark and under different illumination conditions, and then compared with the photocatalytic activity using 2-fluorophenol as substrate and different radiation sources. The p-doping with carbon of C3N4 reduces the band gap, slightly moves the potential of the valence band, and increases the conduction band to more positive potentials, thus precluding the application of these materials when large negative redox potentials are needed.

It has been often reported that an efficient and green photocatalytic dissociation of water under irradiated semiconductors likely represents the most important goal for modern chemistry. Despite decades of intensive work on this topic, the efficiency of the water photolytic process under irradiated semiconductors is far from reaching significant photocatalytic efficiency. The use of a sacrificial agent as hole scavenger dramatically increases the hydrogen production rate and might represent the classic “kill two birds with one stone”: on the one hand, the production of hydrogen, then usable as energy carrier, on the other, the treatment of water for the abatement of pollutants used as sacrificial agents. Among metal oxides, TiO2 has a central role due to its versatility and inexpensiveness that allows an extended applicability in several scientific and technological fields. In this review we focus on the hydrogen production on irradiated TiO2 and its fundamental and environmental implications.

The photocatalytic performance of pristine and rare earth elements (La, Ce, Pr, Er, Yb) doped zinc oxide was tested toward the abatement of a model pollutant in MilliQ water and wastewater matrices. ZnO doped with Ce, Er and particularly with Yb exhibited photoactivity higher than bare zinc oxide and the benchmark TiO2 P25, especially in wastewater matrix. Several electrochemical investigations were performed via chronopotentiometry and cyclic voltammetry aimed to shed light on the reasons why the diverse materials behaved differently. From the overall data a complex picture emerged, where there is not a single property of the materials evidently outperforming the others. Nonetheless, from the analysis of whole data a limited role of doping emerged for La and Pr, doping with Er improved the photocurrent, doping with Yb favored a better accumulation of photoelectrons, and doping with Ce promoted a faster electron transfer.

The addition of graphene nanoplatelets (GNP) to TiO2 nanoparticles (NPs) has been recently considered as a method to improve the photocatalytic efficiency of TiO2 by favoring charge carrier separation. Here, we show that it is possible to improve the efficiency of GNP-TiO2 composites by controlling the shape, stability, and facets of TiO2 NPs grown on GNP functionalized with either COOH or NH2 groups, while adding ethylendiamine (EDA) and oleic acid (OA) during a hydrothermal synthesis. We studied the photocatalytic activity of all synthesized materials under UV-A light using phenol as a target molecule. GNP-TiO2 composites synthesized on COOH-functionalized GNP, exposing {101} facets, were more efficient at abating phenol than those synthesized on NH2-functionalized GNP, exposing {101} and {100} facets. However, neither of these composites was stable under irradiation. The addition of both OA and EDA stabilized the materials under irradiation; however, only the composite prepared on COOH-functionalized GNP in the presence of EDA showed a significant increase in phenol degradation rate, leading to results that were better than those obtained with TiO2 alone. This result can be attributed to Ti-OH complexation by EDA, which protects GNP from oxidation. The orientation of the most reducing {101} facets toward GNP and the most oxidizing {100} facets toward the solution induces faster phenol degradation owing to a better separation of the charge carriers.

This work reports the effect of doping zinc oxide with lanthanide ions on structural, EPR and UV visible properties. Bare and doped samples were synthesized using the simple and green hydrothermal process. Different rare earth ions (RE = La, Ce, Pr, Er and Yb) with 1% molar ratio RE/Zn were used. The samples have been studied using X Ray Diffraction, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and UV visible diffuse reflectance spectroscopy. Finally, electron paramagnetic resonance (EPR) spectroscopy, was used to assess the materials photoactivity under UV irradiation, both in solid state, to see the charge carriers’ generation and in solution, evaluating the OH• radical formation using the DMPO (5,5-Dimethyl-1-Pyrroline-N-Oxide) spin trapping technique. The results suggest that the synthesized materials could be interesting systems for the photocatalytic abatement of emerging organic persistent pollutants in wastewater treatment plants.

Particle aggregation and agglomeration influence the optical properties of materials and therefore their ability to absorb and scatter the incoming radiation, also affecting their photocatalytic activity [1] , [2] , [3] , [4] , [5] , [6] , [7] . We have studied the correlation between aggregation and photocatalytic activity for titanium dioxide by means of experimental measurements of extinction and photocatalytic activity and calculations of their optical properties (extinction, absorption and scattering cross-sections). This approach can be adopted to quantitatively assess the quantum yields of the heterogeneous photocatalytic systems. The study was performed on TiO2 PC105 Cristal ACTiV™, made of aggregated (and agglomerated) primary particles of anatase. The size of the aggregates has been reduced with ultra-sonication. Aqueous suspensions of the obtained materials were characterized by measuring the optical properties (UV–vis extinction), the sizing properties (DLS) and the photocatalytic activity (degradation of phenol under standard conditions). The extinction and absorption spectra of the suspensions were derived from the calculated coefficients, considering also the size distributions measured with DLS, and revealed that light absorption is maximized when particle aggregation and agglomeration are avoided, while diffusion of the incoming radiation dominates when large aggregates and agglomerates are present. The present paper represents a valuable approach to the accurate and reproducible measurement of the photocatalytic activity of TiO2 nanoparticles suspensions, thus allowing a more reliable comparison of the properties of different materials.

The photoinduced transformation of 2,4,6-triamino-1,3,5-triazine (melamine) was studied by using different advanced oxidation technologies under a variety of experimental conditions. The systems involving homogeneous hydroxyl radicals, as generated by H2O2/hν, Fenton reagent, and sonocatalysis are ineffective. However, melamine is degraded under photocatalytic conditions or by SO4 − (S2O82−/hν). The time evolution of long-living intermediates, such as 2,4-diamino-6-hydroxy-1,3,5-triazine (ammeline) and 2-amino-4,6-dihydroxy-1,3,5-triazine (ammelide), has been followed, being 2,4,6-trihydroxy-1,3,5-triazine (cyanuric acid) the final stable product. During both photocatalytic and S2O82−/hν experiments, in the early steps, a fairly stable intermediate evolving to ammelide is observed in a large extent. This intermediate was identified as 2,4-diamino-6-nitro-1,3,5-triazine. This indicates that the primary photocatalytic event is the oxidation of the amino-group to nitro-group through several consecutive fast oxidation steps, and that a hydrolytic step leads to the release of nitrite in solution. To elucidate the nature of the oxidant species hole scavengers such as methanol and bromide ions were added to the irradiated TiO2. They completely stop the degradation, whereas chloride and fluoride ions decrease the degradation rate. The study of the photocatalytic degradation rate of melamine at increasing concentrations using two different commercial titanium dioxides, such as P25 and Merck TiO2, showed an intriguing behavior. A drastic abatement of the melamine transformation rate was observed when coagulation of the P25 slurry occurs due both to the pH change and melamine concentration effect that increase melamine adsorption. In the presence of TiO2 (Merck) the melamine initial degradation rates are significantly lower than those observed in the presence of P25 but are not depressed at larger concentrations. The experimental evidences (e.g., absence of melamine adsorption onto TiO2 surface at low concentrations or at acidic pH or due to the catalyst surface texture, and the lack of reactivity toward OH free and bound) suggest that the effective photocatalytic mechanism is based on an outer sphere direct hole transfer to the melamine. Its formal potential lies in the range 1.9–2.3 V vs NHE. Then, the photodegradation of melamine is an efficient tool to evaluate the direct hole transfer ability of a photocatalyst.

TiO2 inverse opals present increased photocatalytic production of H2. TiO2 inverse opals with different pore size and TiO2 macroporous structures with disordered arrangement of the pores have been tested in the photocatalytic production of hydrogen in aqueous solution with a formate buffer as hole scavenger. TiO2 inverse opals belong to the family of metamaterials and exhibit unique catalytic properties arising from their peculiar interaction with light. To discriminate the effects of slow photons the hydrogen photoproduction experiments were carried out at two different wavelengths, at 365 nm where the effect of slow photons is maximized, and at 254 nm where it is negligible. The resulting hydrogen production rates suggest a strong effect of the slow light and of the polymer template used in the synthesis of the TiO2 powders. The chemical properties of the polymeric sacrificial template determine the crystalline phase of the sample and as a consequence affect the catalytic performances of the resulting TiO2 structures.

The effects of the highly fluorescent 4-piperidinyl-1,8-naphthalimide (PNI) chromophore on the CO2 reduction catalytic properties of rhenium-based catalysts are investigated herein. In particular, the electro- and photocatalytic CO2 reduction features of [Re(CO)3(bpy)Cl] (bpy = 2,2′-bipyridine) are compared with the activity of [Re(CO)3(phen–PNI)Cl] (phen = 1,10-phenanthroline), which is known for its long excited-state lifetime. Moreover, another Re complex, namely [Re(CO)3(bpy–Ph–PNI)Cl], has been synthesized and tested as an electro- and photocatalyst. The catalytic properties of the selected compounds were studied by means of electrochemical (cyclic voltammetry and controlled-potential electrolysis) and photophysical measurements together with DFT calculations. [Re(CO)3(bpy–Ph–PNI)Cl] showed good electrocatalytic efficiency toward selective CO2 reduction to CO, as well as reduced electrocatalytic overpotential.

The study of the photocatalytic activity of TiO(2) inverse opals showed that these structures behave as metamaterials: their properties arise principally from the 3D periodic structure of the material and marginally from porosity, reflectivity and scattering.