Cobalt Impregnation on Titania Photocatalysts Enhances Vis Phenol Photodegradation

One of the main challenges of photocatalysis is to find a stable and effective photocatalyst, that is active and effective under sunlight. Here, we discuss the photocatalytic degradation of phenol as a model pollutant in aqueous solution using NUV-Vis (>366 nm) and UV (254 nm) in the presence of TiO2-P25 impregnated with different concentrations of Co (0.1%, 0.3%, 0.5%, and 1%). The modification of the surface of the photocatalyst was performed by wet impregnation, and the obtained solids were characterized using X-ray diffraction, XPS, SEM, EDS, TEM, N2 physisorption, Raman and UV-Vis DRS, which revealed the structural and morphological stability of the modified material. BET isotherms are type IV, with slit-shaped pores formed by nonrigid aggregate particles and no pore networks and a small H3 loop near the maximum relative pressure. The doped samples show increased crystallite sizes and a lower band gap, extending visible light harvesting. All prepared catalysts showed band gaps in the interval 2.3–2.5 eV. The photocatalytic degradation of aqueous phenol over TiO2-P25 and Co(X%)/TiO2 was monitored using UV-Vis spectrophotometry: Co(0.1%)/TiO2 being the most effective with NUV-Vis irradiation. TOC analysis showed ca. 96% TOC removal with NUV-Vis radiation, while only 23% removal under UV radiation.


Introduction
Many activities, such as agriculture, medicine, or industry, release pollutants into the environment, creating one of the most serious problems we currently face: environmental pollution. Water pollution, in particular, poses important risks to human health and the environment. Therefore, the control of pollutants released into aqueous media has led to increasingly restrictive environmental regulations. Phenol is considered a major pollutant because of its toxicity, bioaccumulation, low biodegradability, and carcinogenicity [1]. It causes an unpleasant taste and odor in drinking water [2], and it is harmful to living organisms at low concentrations, toxic and mutagenic, being absorbed through the skin at high concentrations [3]. The main sources of anthropogenic phenols in the aquatic environment are wastewaters from manufactures of resins, chemicals, dyes, polymers, pesticides, coal conversion, and petrochemical industries [4].
Considerable efforts have been devoted to developing approaches aiming to a complete removal of organic pollutants. However, the application of conventional methods, such as membrane filtration, adsorption on activated carbon, ion exchange on synthetic resins, purification by chemical coagulation systems, etc., are not cost effective and may generate wastes that require further treatment stages and additional costs [5,6]. Conversely, TiO 2 -P25 was from Evonik (ca. 70:30% anatase:rutile with a small amount of amorphous phase): surface area of 55 ± 15 m 2 ·g −1 [28] and particle size of ∼30 nm [29]. Cobalt (II) sulfate heptahydrate (CoSO 4 ·7H 2 O, ≥97%) was from Aldrich, and phenol (C 6 H 5 OH, 99.5%) from Sigma. Acetonitrile (HPLC grade) was from J.T. Baker. O 2 gas (purity ≥ 99.995%) was used in some experiments. All chemicals were used without further purification. Distilled water was obtained from a Millipore apparatus (Milli-Q water), resistivity of 18.2 MΩ at 298.0 K and total organic carbon (TOC) less than 5 µg·L −1 .

Catalyst Synthesis
Wetness impregnation was used to immobilize Co(II) on the surface of TiO 2 nanoparticles to prepare Co/TiO 2 photocatalysts [30] with enhanced photocatalytic properties. CoSO 4 ·7H 2 O was dissolved in distilled water and impregnated on Degussa TiO 2 -P25 nanoparticles under vigorous stirring.
This suspension was stirred for 24 h, and then dried in an oven at 50 • C to dry it completely. Then, the photocatalysts were calcined in a furnace (Paragon model HT-22D, Thermcraft) at 600 • C for 4 h with a ramp rate of 10 • C·min −1 . Finally, the so-prepared catalysts were ground thoroughly and labeled as Co(X%)/TiO 2 , where X denotes the Co(II) mass percent relative TiO 2 , X = 0.1%, 0.3%, 0.5%, and 1%. TiO 2 particles turned from white to yellowish as the cobalt percentage increased. The samples were placed in water under stirring for 2 h to test for potential Co n+ leaching; after filtration, the solution was analyzed using ICP/MS and the dry solid by XRD. No evidence of Co n+ leaching was found (Table 1).

Characterization
X-ray diffraction (XRD) measurements were conducted with a Bruker Siemens D5000 diffractometer following Bragg-Brentano geometry and θ/2θ configuration and equipped with a graphite monochromator. The optics consist of primary and secondary 2 • Soller slots, a variable output slot, a 1mm receiver slot, a 0.2 mm monochromator slot, and a 0.6 mm detector slot. The detector was a scintillation counter. The acquisition conditions were a sweep range (2θ): 2-80 • , a jump size (step): 0.050 • , and the acquisition time at each jump was about 2.5 s (time per jump). The DiffracPlus software v. 8.0.0.2 (Socabim) was used for data processing.
The morphology of TiO 2 -P25 and Co(X%)/TiO 2 were studied using a Jeol JSM-IT100 scanning electron microscope (SEM) equipped with an energy dispersive X-ray (EDX) system to obtain information on the surface elemental composition. The samples were deposited on thin films of amorphous carbon and coated with gold (2 nm). Transmission electron microscopy (TEM), using a Jeol JEM 1100 instrument, operating at an acceleration voltage of 80 kV, was also employed to examine the photocatalysts' surface morphology. Samples were prepared by depositing a few drops of nanoparticle suspension on carboncoated copper grids (electron microscopy, 200 mesh) and air drying.
Textural characterization was carried out using adsorption/desorption isotherms of N 2 , as adsorption gas, at 77.4 K (Tristar II Plus-Micromeritics, automatic station with 3 simultaneous measurement ports). Helium was used for the measurement of the dead volume of the sample holders. Isotherms were measured in the range P/P 0 = 0.1-1.0. The range of the BET area used for the calculation of the specific surface area was P/P 0 = 0.05-0.3. "Microactive for Tristar II Plus", v.2.03 (Micromeritics), was the software for control, acquisition, and data processing.
Raman measurements of the dried samples on glass were performed using a Witec Alpha 300 R confocal Raman system equipped with 633 and 785 nm excitation laser lines and a grating of 600 gr·cm −1 . Raman spectra were acquired at room temperature using a 20× objective over the spectra range of 90-2500 and 90-1800 cm −1 for 633 and 785 nm, respectively, laser powers at the samples of 21 mW (633 nm), 28 and 35 mW (785 nm), and acquisition times in the range of 0.5-5 s with 10 accumulation. The Raman spectra were processed with the Project5.2 Witec software for peak assignment including position, height, and FWHM. SpectraGryph 1.2 software was used for spectral processing involving baseline, background removal (i.e., Raman spectrum of glass was subtracted for the spectra acquired using a 785 nm laser line), and cosmic ray removal correction. Raman shift calibration was performed using a silicon wafer (peak at 520 cm −1 ). The spectra were normalized to the E g peak (146 cm −1 ) for a better comparison between samples.
Co(0.1%)/TiO 2 photocatalyst was analyzed by X-ray photoelectron spectroscopy (XPS) using a Thermo Scientific K-Alpha ESCA instrument equipped with an Al Kα monochromatized radiation (hν = 1486.7 eV) X-ray source. Measurements were carried out in a Constant Analyzer Energy mode with a 100 eV pass energy for survey spectra, and 20 eV pass energy for high-resolution spectra. The spot size selected was 400 µm and K-Alpha's charge compensation system was employed during analysis. In data analysis, C 1s = 285.0 eV was taken as the binding energy reference. Surface elemental composition was determined using the standard Scofield photoemission cross sections.
The UV-Vis diffuse reflectance spectra (DRS) (200-800 nm) of the solid photocatalyst was measured on a JASCO V-560 UV-Vis spectrophotometer with a double monochromator and double beam optical system, equipped with an integrating sphere attachment (JASCO ISV-469, Oklahoma City, OK, USA). Reflectance spectra were converted to equivalent absorption Kubelka-Munk units.

Photocatalytic Activity
The photocatalytic activity of the synthetized samples was tested in an axial photoreactor, under UV and near-UV-Vis light (NUV-Vis), monitoring changes in phenol (C 6 H 5 OH) concentration in aqueous solution. Two types of photocatalytic experiments were carried out. The first was performed under NUV-Vis light, in which the photoreactor was equipped with a Heraeus TQ 150 medium-pressure Hg-vapor lamp, with intense emission lines at 254, 313, 366, 405, 436, 546, and 578 nm. A Duran 50 ® glass jacket, filled with water, was used to cut off the radiation below 366 nm. For the second experiment, the photoreactor was equipped with a Heraeus TNN 15/32 low-pressure Hg-vapor lamp, with a single intense emission line at 254 nm, located inside a quartz tube. The photon flux at 366 nm, as determined by potassium ferrioxalate actinometry, [31] was 2.38 × 10 −6 Einstein·s −1 , and at 254 nm, it was of 8.33 × 10 −8 Einstein·s −1 .
The photocatalytic reactions were performed under a coherent magnetic stirring of 200 mL phenol solution, with an initial concentration of 50 mg·L −1 to facilitate monitoring, mixed with 200 mg of photocatalyst under controlled O 2 pressure. All samples were kept in the dark for 30 min, to ensure adsorption-desorption equilibrium. The heterogeneous suspensions, at natural pH, were exposed to UV irradiation for 60 min and to NUV-Vis irradiation for 300 min at ca. 25 • C, maintained by water flow from a thermostat-cryostat. Samples of aqueous phenol and photocatalysts were taken at time intervals and filtered through Sartorius NY 0.45 ™ filters.
Phenol concentration was monitored using a Biochrom Libra S70 spectrophotometer to measure the UV-Vis absorbance at 270 nm and using HPLC UV-Vis at 210 and 270 nm, in a Thermo Fisher instrument equipped with a 6000 LP UV detector, an AS 3000 autosampler, and a P4000 solvent pump. A KROMAPHASE C18 column (4.6 mm × 150 mm × 5 µm) was used, with a volume of 50 µL injected, a flow rate of 1.0 mL·min −1 , at 30 • C, the mobile phase being acetonitrile and water (25:75, v/v). Replicate experiments showed differences in rate constants within 5% error.

Results and Discussion
Crystallite size was calculated using the Scherrer equation [38]. The observed trend with both polymorphs is to increase in size continuously from TiO 2 -P25 to the doped photocatalyst, with a tendency to reduce in size as the doping percentage increases. A similar behavior has been reported for rutile [39]. Doping, within the used percentages, does not affect cell parameters (Table 2), which is consistent with the substitution of Ti 4+ by Co 2+ in the doped photocatalyst, provided they show relatively similar radii (74.5 vs. 79 pm, respectively, considering low spin Co 2+ and 6-coordination) [40]. The fact that cell parameters are not affected is in agreement with doping taking place mainly on the surface and not on the bulk.
As stated above, 1 g of a Co(0.1%)/TiO 2 sample in 1 L of distilled water was stirred for 2 h. The solid recovered after filtration and drying was XRD analyzed. The same diffraction peaks of Co(0.1%)/TiO 2 were found before and after the test ( Figure S1 of Supplementary Materials); therefore, similar values were obtained for the derived parameters, thus confirming the stability of the as-prepared photocatalyst. Figure 2 shows the Raman spectra of Co(0.1%)/TiO 2 , which are compared with the Raman spectrum of undoped TiO 2 , acquired using two different lasers, 633 and 785 nm, and two laser powers. Anatase polymorph, a tetragonal structure, is present. The Raman active "lattice vibrations" shown in Table 3 are assigned based on the D 4h point group.

Raman Spectroscopy
interband states which means a reduction in the band gap, boosting the photocatalytic activity under Vis radiation.
Crystallite size was calculated using the Scherrer equation [38]. The observed trend with both polymorphs is to increase in size continuously from TiO2-P25 to the doped photocatalyst, with a tendency to reduce in size as the doping percentage increases. A similar behavior has been reported for rutile [39]. Doping, within the used percentages, does not affect cell parameters (Table 2), which is consistent with the substitution of Ti 4+ by Co 2+ in the doped photocatalyst, provided they show relatively similar radii (74.5 vs. 79 pm, respectively, considering low spin Co 2+ and 6-coordination) [40]. The fact that cell parameters are not affected is in agreement with doping taking place mainly on the surface and not on the bulk.
As stated above, 1 g of a Co(0.1%)/TiO2 sample in 1 L of distilled water was stirred for 2 h. The solid recovered after filtration and drying was XRD analyzed. The same diffraction peaks of Co(0.1%)/TiO2 were found before and after the test ( Figure S1 of Supplementary Materials); therefore, similar values were obtained for the derived parameters, thus confirming the stability of the as-prepared photocatalyst. Figure 2 shows the Raman spectra of Co(0.1%)/TiO2, which are compared with the Raman spectrum of undoped TiO2, acquired using two different lasers, 633 and 785 nm, and two laser powers. Anatase polymorph, a tetragonal structure, is present. The Raman active "lattice vibrations" shown in Table 3 are assigned based on the D4h point group. The very low intensity band at ca. 445 cm −1 , E g mode of the rutile phase, does not allow a rough estimation of the weight ratios of anatase phase to rutile phase from the Raman spectrum. The table also includes Ti-O and Ti-Ti bond lengths calculated using covalence/length/frequency relations [41]. Values obtained for Co(0.1%)/TiO 2 are similar to those reported for P25, which agrees with the tiny structural effect of 0.1% Co doping observed using XRD. The method of preparation of the doped photocatalysts determines its particle size, which has to do with oxygen vacancies and electron-phonon coupling. Both factors may influence shifts and broadening of Raman peaks. Contrary to Co-doped TiO 2 synthetized using sol-gel [42], the as-prepared photocatalyst does not show a wavenumber shift upon the excitation of 785 nm laser line at any of the power laser values used. The FWHW of the most intense peak is the same for the undoped and doped (Co(0.1%)/TiO 2 ) sample ( Figure 2d, Table S1), the corresponding phonon lifetime being 0.34 ps. Interestingly, a red shift of 6 cm −1 was observed in the peak centered at 141 cm −1 , while the peaks centered at 517 and 640 cm −1 displayed a blue shift of 4-5 cm −1 (Figure 2c and Table S1 for peak at 141 cm −1 ) upon the excitation of 633 nm with a laser power of 21 mW. However, these shifts were not observed at lower powers of the 633 nm laser (Figure 2c,d, Table S1 for peak at 141 cm −1 ). This laser-induced phase transition (e.g., low crystallinity or phase transformation) in Co-doped anatase TiO 2 nanoparticles was previously reported [43]. This laser power dependence was not observed with the 785 nm laser line since its energy is lower than that of the 633 nm one. Figure S2 shows that the intensity of the well-defined peaks is higher for the Co-doped photocatalyst using both laser lines (see Table S1 for the most intense peak in Supplementary Materials), such enhancement has been previously described [44,45].

Scanning Electron Microscopy and Energy Dispersive Spectroscopy
The morphology and elemental analysis of the Co(X%)/TiO 2 samples were studied using scanning electron microscopy/energy dispersion spectroscopy (SEM/EDS). SEM images, Figure 3, show the crystals' shape and size of all cobalt-loaded samples are similar to those of unmodified P25-TiO 2 [17], with an average crystal size of 30 nm, in agreement with the value obtained from XRD data (vide supra). EDS analysis shows the percent of cobalt matches the initial doped amount at the lowest percentages, while at higher Co/TiO 2 doping percentages, the presence of Co is lower on the surface (Table 4), which could be attributed to Co ions diffusing into inner layers of the photocatalyst, a process that is facilitated by oxygen vacancies. The EDS-mapping images of the doped photocatalysts' surfaces revealed a homogeneous distribution of cobalt ions [35]. Considering typical penetrations of X-rays in SEM/EDS, the Co ions reached depths of not less than 2 µm below the surface. The presence of Co with an optimal concentration (0.1%) prevents the TiO 2 -P25 particles from agglomerating, probably due to the development of a surface charge. Large aggregates can decrease photocatalytic activity by reducing the exposed surface and shading active sites from exciting radiation [23]. photocatalysts' surfaces revealed a homogeneous distribution of cobalt ions [35]. Considering typical penetrations of X-rays in SEM/EDS, the Co ions reached depths of not less than 2 m below the surface. The presence of Co with an optimal concentration (0.1%) prevents the TiO2-P25 particles from agglomerating, probably due to the development of a surface charge. Large aggregates can decrease photocatalytic activity by reducing the exposed surface and shading active sites from exciting radiation [23].   Co(X%)/TiO2 samples were analyzed using XPS, in an attempt to understand the bonding states of the surface elements on the doped photocatalyst. The survey XPS spectrum is shown in Figure 4. The atomic composition of C 1s, Ti 2p, O 1s, and Co 2p of the Co/TiO2 photocatalyst was 27.8%, 20.1%, 50.3%, and 1.8%, respectively. The characteristic satellite (shake up) of Co at around 786 eV is evidence of the presence of Co(II). The high-resolution Co 2p spectrum showed spin-orbit splitting into 2p1/2 and 2p3/2 components ( Figure S2a). The Co 2p spectrum is close, or quite similar, to the Co(OH)2 compound [46]. The dominant Ti 2p3/2 peak is located at 458.8 eV binding energy and Ti 2p1/2 at 464.5 eV, i.e., with a spin-orbit splitting value of 5.7 eV, corresponding to Ti(IV) [47], Figure S2b. XPS Ti 2p peaks appear at slightly higher binding energy than in the case of P25 (458.6 and 464.2 eV, respectively). Electron density is transferred from Ti(IV) to Co(II), due to the higher Pauling electronegativity of the latter, and the binding energy increases. The peak at ca. 530 eV (O 1s, Figure S2c) is characteristic of the Ti-O lattice bond of TiO2 [48].

XPS Analysis
Co(X%)/TiO 2 samples were analyzed using XPS, in an attempt to understand the bonding states of the surface elements on the doped photocatalyst. The survey XPS spectrum is shown in Figure 4. The atomic composition of C 1s, Ti 2p, O 1s, and Co 2p of the Co/TiO 2 photocatalyst was 27.8%, 20.1%, 50.3%, and 1.8%, respectively. The characteristic satellite (shake up) of Co at around 786 eV is evidence of the presence of Co(II). The high-resolution Co 2p spectrum showed spin-orbit splitting into 2p 1/2 and 2p 3/2 components ( Figure S2a). The Co 2p spectrum is close, or quite similar, to the Co(OH) 2 compound [46]. The dominant Ti 2p 3/2 peak is located at 458.8 eV binding energy and Ti 2p 1/2 at 464.5 eV, i.e., with a spin-orbit splitting value of 5.7 eV, corresponding to Ti(IV) [47], Figure S2b. XPS Ti 2p peaks appear at slightly higher binding energy than in the case of P25 (458.6 and 464.2 eV, respectively). Electron density is transferred from Ti(IV) to Co(II), due to the higher Pauling electronegativity of the latter, and the binding energy increases. The peak at ca. 530 eV (O 1s, Figure S2c) is characteristic of the Ti-O lattice bond of TiO 2 [48].

Textural Properties
The N2 adsorption-desorption isotherm of Co(0.1%)/TiO2 is displayed in Figure 5, which according to the IUPAC classification belongs to type IV with a very small hysteresis loop H3 (ca. 0.75-0.9 P/P0), suggesting the mesoporous nature of the photocatalyst [49]. The adsorption isotherm does not level off at high pressure, which implies the existence of slit-shaped pores formed by nonrigid aggregate particles and no pore networks according to BJH [50].

Textural Properties
The N 2 adsorption-desorption isotherm of Co(0.1%)/TiO 2 is displayed in Figure 5, which according to the IUPAC classification belongs to type IV with a very small hysteresis loop H3 (ca. 0.75-0.9 P/P 0 ), suggesting the mesoporous nature of the photocatalyst [49]. The adsorption isotherm does not level off at high pressure, which implies the existence of slit-shaped pores formed by nonrigid aggregate particles and no pore networks according to BJH [50].

Textural Properties
The N2 adsorption-desorption isotherm of Co(0.1%)/TiO2 is displayed in Figure 5, which according to the IUPAC classification belongs to type IV with a very small hysteresis loop H3 (ca. 0.75-0.9 P/P0), suggesting the mesoporous nature of the photocatalyst [49]. The adsorption isotherm does not level off at high pressure, which implies the existence of slit-shaped pores formed by nonrigid aggregate particles and no pore networks according to BJH [50].  The BET isotherm was used to calculate the surface area (SBET-multipoint), and the textural properties were analyzed based on the Barrett, Joyner, and Halenda (BJH) model [50] (Table 5). The observed texture is different from that of Co(0.1%/TiO 2 ) as prepared by the hydrothermal method, where the isotherm, also type IV, shows a large H3 hysteresis loop (0.4-0.8 P/P 0 ), and the reported values of SBET (22.8 m 2 ·g −1 ) and pore volume (0.033 cm 3 ·g −1 ) are smaller than those of the as-synthesized photocatalyst [51]. Pore size distribution shows a maximum at 22 Å, just in the lower mesopore limit.

UV-Vis Diffuse Reflectance Spectroscopy
The UV-Vis DRS spectra of TiO 2 -P25 and the prepared photocatalysts are shown in Figure 6a. The absorption band of TiO 2 -P25, occurring from 200 to 380 nm, is associated with the O 2− (2p) → Ti(IV) (3d) transitions and tetrahedral symmetry [52]. In the case of Co(II)-doped TiO 2 samples, band tailing appears at ca. 400 nm; such light absorption increase in the Vis region, as compared to pure TiO 2 -P25, relates to the charge transfer from O 2− to Co(II) [53] and to the Vis absorption of the electrons from the defect states, the intensity being directly related to the number of defect states [54]. Visible light absorption increases as less energy is required to move electrons to the conduction band. The band gap (E g ) was obtained using the Tauc plot, Figure 6b [55]. For pure TiO 2 -P25, the band gap was found equal to 3.3 eV in agreement with the literature [56]. For cobalt-doped TiO 2 photocatalysts, E g narrows and depends on Co concentration (Table 6), with values around 2.3-2.4 eV. Table S2 lists the band gap of several Co-doped TiO 2 photocatalysts. It follows that the band gap depends on the synthetic method and on the nature of the starting material. The E g narrowing, observed as an absorption onset shift to the visible region, is due both to the substitution of Ti(IV) by Co(II), which implies new d-states coming from Co-in the forbidden band of TiO 2 , and to the addition of energy levels in the same zone from oxygen vacancies [36].  The presence of cobalt energy levels over the Fermi level enables visible light absorption and prevents e − /h + pair recombination, thus enhancing the photocatalytic efficiency, but an excess of dopant facilitates hole-electron pair recombination, reducing the photocatalytic activity [36,37].

Kinetics of Phenol Photodegradation
The photocatalytic activity of TiO2 and Co-TiO2-doped samples was tested by monitoring phenol photodegradation upon UV and NUV-Vis radiation. After irradiation, e − /h + pairs are formed according to the usual scheme of photocatalysis with semiconductors, [57,58] and the dopant Co(II) traps e − , thus reducing the probability of recombination. O2 and H2O/HO − adsorbed onto the photocatalyst surface scavenge the trapped e − and h + to form reactive oxygen species (hydroxyl, HO • , hydroperoxy, HO2 • , and superoxide, O2 • − , radicals, and H2O2), which are involved in the oxidative photodegradation of phenol, same as h + .
In the case of pure TiO2, the degradation of phenol was found to be effective under UV light; which was not the case under NUV-Vis light (Figure 7). The same results were found for the photodegradation under NUV-Vis light, of dyes [18,59], drugs [60], and phenol [19]. In fact, the large band gap of TiO2 makes the absorption of visible light photons ineffective, minimizing its photoactivity [61].  The presence of cobalt energy levels over the Fermi level enables visible light absorption and prevents e − /h + pair recombination, thus enhancing the photocatalytic efficiency, but an excess of dopant facilitates hole-electron pair recombination, reducing the photocatalytic activity [36,37].

Kinetics of Phenol Photodegradation
The photocatalytic activity of TiO 2 and Co-TiO 2 -doped samples was tested by monitoring phenol photodegradation upon UV and NUV-Vis radiation. After irradiation, e − /h + pairs are formed according to the usual scheme of photocatalysis with semiconductors, [57,58] and the dopant Co(II) traps e − , thus reducing the probability of recombination. O 2 and H 2 O/HO − adsorbed onto the photocatalyst surface scavenge the trapped e − and h + to form reactive oxygen species (hydroxyl, HO • , hydroperoxy, HO 2 • , and superoxide, O 2 •− , radicals, and H 2 O 2 ), which are involved in the oxidative photodegradation of phenol, same as h + .
In the case of pure TiO 2 , the degradation of phenol was found to be effective under UV light; which was not the case under NUV-Vis light (Figure 7). The same results were found for the photodegradation under NUV-Vis light, of dyes [18,59], drugs [60], and phenol [19]. In fact, the large band gap of TiO 2 makes the absorption of visible light photons ineffective, minimizing its photoactivity [61]. In the case of Co(X%)/TiO2 photocatalysts, phenol photodegradation was found to be totally different from pure P25-TiO2 ( Figures S4 and S5). Figure 8 shows the absorbance vs. time curves for phenol photodegradation in the presence of TiO2-P25 and Co(%)/TiO2 photocatalysts. The as-prepared photocatalysts slightly degrade phenol under UV light, whereas complete phenol photodegradation was observed under Vis light. Table 6 summarizes the obtained pseudo first order rate constants. Although, under UV irradiation, the rate constants are higher with Co-doped TiO2, there is only a very small phenol disappearance; a similar behavior was observed with Cu-doped titanium [32]. On the other hand, under NUV-Vis radiation, the rate constant increases when the band gap decreases, which runs parallel to Co content. The photocatalytic effect was more important with the lowest concentration of doped metal, i.e., Co(0.1%)/TiO2. As stated above, the fastest phenol photodegradation happen with the Co(0.1%)/TiO2 photocatalyst, probably due to a better dispersion of metal ions on the TiO2-P25 surface (as found by SEM, Section 3.1.3). The same results were found by previous authors with Cu-doped titania [62]. At higher Co concentrations, the rate constants decreased slowly; in agreement with the well-known fact that above the optimal In the case of Co(X%)/TiO 2 photocatalysts, phenol photodegradation was found to be totally different from pure P25-TiO 2 ( Figures S4 and S5). Figure 8 shows the absorbance vs. time curves for phenol photodegradation in the presence of TiO 2 -P25 and Co(%)/TiO 2 photocatalysts. The as-prepared photocatalysts slightly degrade phenol under UV light, whereas complete phenol photodegradation was observed under Vis light. Table 6 summarizes the obtained pseudo first order rate constants. Although, under UV irradiation, the rate constants are higher with Co-doped TiO 2 , there is only a very small phenol disappearance; a similar behavior was observed with Cu-doped titanium [32]. On the other hand, under NUV-Vis radiation, the rate constant increases when the band gap decreases, which runs parallel to Co content. In the case of Co(X%)/TiO2 photocatalysts, phenol photodegradation was found to be totally different from pure P25-TiO2 ( Figures S4 and S5). Figure 8 shows the absorbance vs. time curves for phenol photodegradation in the presence of TiO2-P25 and Co(%)/TiO2 photocatalysts. The as-prepared photocatalysts slightly degrade phenol under UV light, whereas complete phenol photodegradation was observed under Vis light. Table 6 summarizes the obtained pseudo first order rate constants. Although, under UV irradiation, the rate constants are higher with Co-doped TiO2, there is only a very small phenol disappearance; a similar behavior was observed with Cu-doped titanium [32]. On the other hand, under NUV-Vis radiation, the rate constant increases when the band gap decreases, which runs parallel to Co content. The photocatalytic effect was more important with the lowest concentration of doped metal, i.e., Co(0.1%)/TiO2. As stated above, the fastest phenol photodegradation happen with the Co(0.1%)/TiO2 photocatalyst, probably due to a better dispersion of metal ions on the TiO2-P25 surface (as found by SEM, Section 3.1.3). The same results were found by previous authors with Cu-doped titania [62]. At higher Co concentrations, the rate constants decreased slowly; in agreement with the well-known fact that above the optimal The photocatalytic effect was more important with the lowest concentration of doped metal, i.e., Co(0.1%)/TiO 2 . As stated above, the fastest phenol photodegradation happen with the Co(0.1%)/TiO 2 photocatalyst, probably due to a better dispersion of metal ions on the TiO 2 -P25 surface (as found by SEM, Section 3.1.3). The same results were found by previous authors with Cu-doped titania [62]. At higher Co concentrations, the rate constants decreased slowly; in agreement with the well-known fact that above the optimal value the presence of dopant reduces the photoactivity, charges are trapped and/or recombination centers are formed [25].

Total Organic Carbon (TOC) Analysis
To determine the degree of mineralization during photocatalysis, TOC analyses were carried out after 60 min of photoirradiation under UV light and 240 min under NUV-Vis light (Figure 9). The initial phenol concentration of 50 mg·L −1 with a measured TOC value of 48 mg·L −1 was used. value the presence of dopant reduces the photoactivity, charges are trapped and/or recombination centers are formed [25].

Total Organic Carbon (TOC) Analysis
To determine the degree of mineralization during photocatalysis, TOC analyses were carried out after 60 min of photoirradiation under UV light and 240 min under NUV-Vis light (Figure 9). The initial phenol concentration of 50 mg·L −1 with a measured TOC value of 48 mg·L −1 was used. TOC values decreased drastically upon photocatalysis, from 48 to 1.97 mg·L −1 under NUV-Vis light in the presence of Co(X%)/TiO2 photocatalysts, i.e., a 96% TOC removal whereas the observed removal was much lower (23%) under UV light. For both irradiation conditions, the maximum TOC removal was observed for the lowest dopant content (Co(0.1%)/TiO2), and in accordance with kinetics results, it decreased as the Co percent was increased.
TOC results are in agreement with kinetic results; the observed absorbance decay follows the same pattern found for TOC, irrespective of the irradiation wavelength: smal decay and TOC reduction with UV and almost complete elimination with NUV-Vis.

Photodegradation and Energetic Efficiency of the Process
Using the light intensity (Iλ/Einstein·L -1 ·s -1 ) at the irradiation wavelength (λ), the molar absorptivity at λ (ελ/mol·dm -3 ·cm -1 ), the pathlength of the photoreactor (l/cm), and the apparent pseudo first order rate constant (k/s -1 ), the photocatalysis quantum yield (Φphotodegradation) can be calculated (Table 7) [28]; likewise, taking into account the apparent pseudo first order rate constant (k/s -1 ), the electric power consumed by the lamp (P/kW) and the solution volume (V/L), the energy efficiency parameter (EEO/kW·L -1 ·s -1 ), i.e., the energy required to reduce the pollutant concentration per volume and time unit, can be obtained [32] (Table 7). TOC values decreased drastically upon photocatalysis, from 48 to 1.97 mg·L −1 under NUV-Vis light in the presence of Co(X%)/TiO 2 photocatalysts, i.e., a 96% TOC removal, whereas the observed removal was much lower (23%) under UV light. For both irradiation conditions, the maximum TOC removal was observed for the lowest dopant content (Co(0.1%)/TiO 2 ), and in accordance with kinetics results, it decreased as the Co percent was increased.
TOC results are in agreement with kinetic results; the observed absorbance decay follows the same pattern found for TOC, irrespective of the irradiation wavelength: small decay and TOC reduction with UV and almost complete elimination with NUV-Vis.

Photodegradation and Energetic Efficiency of the Process
Using the light intensity (I λ /Einstein·L -1 ·s -1 ) at the irradiation wavelength (λ), the molar absorptivity at λ (ε λ /mol·dm -3 ·cm -1 ), the pathlength of the photoreactor (l/cm), and the apparent pseudo first order rate constant (k/s -1 ), the photocatalysis quantum yield (Φ photodegradation ) can be calculated (Table 7) [28]; likewise, taking into account the apparent pseudo first order rate constant (k/s -1 ), the electric power consumed by the lamp (P/kW), and the solution volume (V/L), the energy efficiency parameter (E EO /kW·L -1 ·s -1 ), i.e., the energy required to reduce the pollutant concentration per volume and time unit, can be obtained [32] (Table 7). The large value of the UV photodegradation quantum yield suggests the contribution of secondary processes, possibly chain processes. On the other hand, EEO is much more favorable with UV radiation. At first glance, the choice would be to use UV radiation if the irradiation source is to be solely powered by electric current. The advantage of using the prepared photocatalyst, under NUV-Vis, is a much higher level of TOC removal and the use of sunlight, which would make the process more sustainable and reduce energy-associated costs.
As mentioned above (vide supra), the catalyst can be washed with no lixiviation or structural consequences after use, and when reutilized, it showed similar kinetic and TOC reduction results.

Conclusions
The degradation of phenol was investigated using cobalt-impregnated TiO 2 samples with different concentration, Co(X%)/TiO 2 , with X = 0.1%, 0.3%, 0.5%, and 1.0%, under NUV-Vis (>366 nm) and UV (254 nm) radiation. The TiO 2 -P25 surface was impregnated, and the obtained solids were characterized by XRD, Raman, XPS, SEM, EDS, and TEM. Crystallite size increased in the doped samples, where Ti(IV) was substituted by Co(II) and oxygen vacancies were created as well as interband states, which reduced the band gap as found with UV-Vis DRS measurements. The N 2 adsorption isotherm corresponds to type IV with a small H3 loop near the maximum relative pressure. The photocatalytic activity over phenol photodegradation was found to be the best for Co(0.1%)/TiO 2, at the lowest found band gap (E g ca. 2.3-2.4 eV) , when using NUV-Vis radiation. The TOC test showed an approximately complete removal (96%) for phenol photodegradation under NUV-Vis radiation and Co(0.1%)/TiO 2 , while it only removed 23% under UV radiation.
In summary, we easily prepared, by impregnation, and characterized a Co-doped TiO 2 (P25) photocatalyst showing extended light harvesting into the Vis region and were able to completely photodegrade phenol in an aqueous solution (50 ppm) after 3 h under NUV-Vis irradiation. The so-prepared catalyst was found to be chemically and mechanically stable and showed similar kinetic and TOC results upon reutilization.