J. Mater. Sci. Technol. ›› 2022, Vol. 112: 239-262.DOI: 10.1016/j.jmst.2021.09.057
• Research Article • Previous Articles Next Articles
Ying Lianga, Guohe Huangb,c,*(), Xiaying Xind, Yao Yaoe, Yongping Lia, Jianan Yine, Xiang Lia, Yuwei Wue, Sichen Gaoe
Received:
2021-07-13
Revised:
2021-09-02
Accepted:
2021-09-08
Published:
2021-12-26
Online:
2021-12-26
Contact:
Guohe Huang
About author:
* E-mail addresses: huang@iseis.org, huangg@uregina.ca (G. Huang).Ying Liang, Guohe Huang, Xiaying Xin, Yao Yao, Yongping Li, Jianan Yin, Xiang Li, Yuwei Wu, Sichen Gao. Black titanium dioxide nanomaterials for photocatalytic removal of pollutants: A review[J]. J. Mater. Sci. Technol., 2022, 112: 239-262.
Fig. 1. Schematic diagram of photocatalytic mechanism in (a) pristine TiO2, (b) black TiO2, (c) non-metal and metal doped black TiO2, and (d) black TiO2/other semiconductor heterojunction.
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | InitialConcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
MB | Black TiO2 | Hydrogenation in 20.0 bar H2 at about 200 °C for 5 d | 0.005 | solar: ∼1 sun power | Optical density is ∼1.0 | 8 min: ∼100% | 8 cycles | [ |
MB | H-TiO2 | Hydrogenation in atmospheric purity H2 at 400 °C for 10 h | 1 | vis-UV: 250 W mercury lamp | 10 | 150 min: > 90% | - | [ |
MB | Ti3+ self-doped TiO2 | H2O2 oxidized TiH2 followed with calcination at 630 °C for 3 h in Ar | 1.67 | solar: Solar simulator | 10-5 M | 20 min: ∼100% | 6 cycles | [ |
MB | Ti3+ self-doped TiO2 | H2O2 oxidized TiH2 | 0.67 | visible: 300 W Xe lamp | 5 × 10-4 M | 40 min: ∼100% | 10 cycles | [ |
MB | H-TiO2 (M) | Hydrogenation in H2 at 300 °C for 3h | 0.5 | visible | - | 80 min: 0.6 h - 1 | - | [ |
MB | H-TiO2 | H2 plasma treatment | 0.25 | solar: 300 W Xe lamp | 3 × 10-5 M | 12 min: 100%, 0.291 min-1 | - | [ |
MB | H-TiO2-x | Water plasma | - | visible: 150 W Xe lamp | 5 | 180 min: 90%, 9.30 × 10-3 min-1 | 4 cycles | [ |
MB | Black TiO2 | Annealing in vacuum at 400 °C for 3 h | 0.5 | visible: 800 W Xe lamp | 4 × 10-5 M | 220 min: 66% | - | [ |
MB | Ar-TiO2 | Ar plasma treated | 0.5 | solar/visible: 300 W Xe lamp | 10 | 120 min: 3.78 h - 1/150 min: 1.05 h - 1 | - | [ |
RhB | Black TiO2 | Treating meatal Ti in an ionic liquid containing LiAc and HAc under mild ionothermal conditions | 1 | visible: 300 W Xe lamp | 10 | 4 h: >40% | 4 cycles | [ |
RhB | Black TiO2 | Pulsed laser irradiation | 0.33 | visible: green LED/Red LED | - | 5 h: 33% / 12% | - | [ |
RhB | Ti3+ self-doped TiO2 | Microwaving for 4 min and then rising the temperature to about 200 °C | 0.5 | visible: 500 W Xe lamp | 10-5 M | 120 min: 0.0957 min-1 | - | [ |
RhB | H-TiO2 | H2 plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: ∼100% | - | [ |
RhB | Ti3+ self-doped TiO2 | HF oxidized TiCl3 and TTIP | 2 | visible: 500 W halogen lamp | 10 | 120 min: 89.4%, 0.0166 min-1 | 5 cycles; No change in XRD, Raman, and EPR. | [ |
RhB | Reduced TiO2 | NaBH4 reduction assisted heat treatment | 1 | solar: Ultra vitalux 300W | 5 | 50 min: 100%, 0.125 min-1 | - | [ |
RhB | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: ∼100% | 7 cycles | [ |
RhB | Black TiO2 | UV irradiation followed by annealing at 300 °C for 3 h in N2 | 0.25 | visible: 800 W Xe lamp | 4 × 10-5 M | 160 min: 0.046 min-1 | - | [ |
RhB | Black TiO2 | Annealing in vacuum at 400 °C for 3 h | 0.25 | visible: 800 W Xe lamp | 4 × 10-5 M | 150 min: >90% | - | [ |
RhB | H-TiO2 | Plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 180 min: ∼80%, 1.42 h - 1 | - | [ |
RhB | Ar-TiO2 | Ar plasma treated | 0.5 | solar/visible: 300 W Xe lamp | 10 | 120 min: 4.10 h-1/150 min: 3.17 h - 1 | - | [ |
RhB | Ti3+ self-doped TiO2 | SMMW | 5 | visible: 500 W Xe lamp | 20 | 180 min: degrated ∼3.5 ppm | - | [ |
RhB | Ti3+ self-doped TiO2 | SMMW | - | visible: 200 W Xe lamp | 5 | 300 min: ∼60% | - | [ |
RhB | hollow-shell black TiO2 | NaBH4 reduction | 0.12 | visible: 300 W Xe lamp | 50 min: >90%, 0.038 min-1 | 5 cycles | [ | |
MO | black TiO2 | Sol-gel method to prepared TiO2 and subsequent heat treatment in H2/N2 | 0.13 | visible: visible lamp | 1 | 150 min: >60%, ∼0.026 min-1 | - | [ |
MO | Blue TiO2 | TiH2 reduction | 1 | solar: 300 W Xe lamp | - | 8 min: 100% | - | [ |
MO | Blue TiO2 | NaBH4 reduction with annealing in N2 | 0.8 | visible: 35 W Xe lamp | 15 | 90 minn: 100% | - | [ |
MO | Ar-TiO2 | Dielectric barrier discharge plasma treatment under Ar atmosphere | 0.5 | solar/visible: 300 W Xe lamp | 10 | 30 min: 5.38 h - 1/150 min: 2.14 h - 1 | - | [ |
MO | Ti3+ self-doped TiO2 | NaBH4 reduction | 1.33 | visible: 300 W Xe lamp | 10 | 180 min: 98%, 0.0291 min-1 | [ | |
RB5 | H-TiO2 | H2-plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: ∼100%, 0.91 h-1 | 10 cycles | [ |
RB5 | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: >99% | - | [ |
RB5 | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 180 min: >90%, 2.12 h - 1 | - | [ |
RB5 | H-TiO2 | Annealing in H2 | 0.3 | solar: 150 W Xe lamp | 10 | 30 min: 0.0305 min-1 | - | [ |
OG | Black TiO2 | Solvothermal reaction | 1 | visible: 14 W visible light | 10 | 40 min: ∼100% | - | [ |
AO7 | Ti3+ self-doped TiO2 | Annealing in vacuum | 0.71 | visible: 500 W halogen lamp | 20 | 5 h: >60% | - | [ |
Color (From POME) | Colored TiO2 NPs | Glycerol-mediated solvothermal method | 0.8 | visible: 500 W halogen lamp | 2420 (PtCo) | 180 min: 62.18% | 3 cycles | [ |
Table 1. Photodegradation of dyes by single black TiO2.
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | InitialConcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
MB | Black TiO2 | Hydrogenation in 20.0 bar H2 at about 200 °C for 5 d | 0.005 | solar: ∼1 sun power | Optical density is ∼1.0 | 8 min: ∼100% | 8 cycles | [ |
MB | H-TiO2 | Hydrogenation in atmospheric purity H2 at 400 °C for 10 h | 1 | vis-UV: 250 W mercury lamp | 10 | 150 min: > 90% | - | [ |
MB | Ti3+ self-doped TiO2 | H2O2 oxidized TiH2 followed with calcination at 630 °C for 3 h in Ar | 1.67 | solar: Solar simulator | 10-5 M | 20 min: ∼100% | 6 cycles | [ |
MB | Ti3+ self-doped TiO2 | H2O2 oxidized TiH2 | 0.67 | visible: 300 W Xe lamp | 5 × 10-4 M | 40 min: ∼100% | 10 cycles | [ |
MB | H-TiO2 (M) | Hydrogenation in H2 at 300 °C for 3h | 0.5 | visible | - | 80 min: 0.6 h - 1 | - | [ |
MB | H-TiO2 | H2 plasma treatment | 0.25 | solar: 300 W Xe lamp | 3 × 10-5 M | 12 min: 100%, 0.291 min-1 | - | [ |
MB | H-TiO2-x | Water plasma | - | visible: 150 W Xe lamp | 5 | 180 min: 90%, 9.30 × 10-3 min-1 | 4 cycles | [ |
MB | Black TiO2 | Annealing in vacuum at 400 °C for 3 h | 0.5 | visible: 800 W Xe lamp | 4 × 10-5 M | 220 min: 66% | - | [ |
MB | Ar-TiO2 | Ar plasma treated | 0.5 | solar/visible: 300 W Xe lamp | 10 | 120 min: 3.78 h - 1/150 min: 1.05 h - 1 | - | [ |
RhB | Black TiO2 | Treating meatal Ti in an ionic liquid containing LiAc and HAc under mild ionothermal conditions | 1 | visible: 300 W Xe lamp | 10 | 4 h: >40% | 4 cycles | [ |
RhB | Black TiO2 | Pulsed laser irradiation | 0.33 | visible: green LED/Red LED | - | 5 h: 33% / 12% | - | [ |
RhB | Ti3+ self-doped TiO2 | Microwaving for 4 min and then rising the temperature to about 200 °C | 0.5 | visible: 500 W Xe lamp | 10-5 M | 120 min: 0.0957 min-1 | - | [ |
RhB | H-TiO2 | H2 plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: ∼100% | - | [ |
RhB | Ti3+ self-doped TiO2 | HF oxidized TiCl3 and TTIP | 2 | visible: 500 W halogen lamp | 10 | 120 min: 89.4%, 0.0166 min-1 | 5 cycles; No change in XRD, Raman, and EPR. | [ |
RhB | Reduced TiO2 | NaBH4 reduction assisted heat treatment | 1 | solar: Ultra vitalux 300W | 5 | 50 min: 100%, 0.125 min-1 | - | [ |
RhB | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: ∼100% | 7 cycles | [ |
RhB | Black TiO2 | UV irradiation followed by annealing at 300 °C for 3 h in N2 | 0.25 | visible: 800 W Xe lamp | 4 × 10-5 M | 160 min: 0.046 min-1 | - | [ |
RhB | Black TiO2 | Annealing in vacuum at 400 °C for 3 h | 0.25 | visible: 800 W Xe lamp | 4 × 10-5 M | 150 min: >90% | - | [ |
RhB | H-TiO2 | Plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 180 min: ∼80%, 1.42 h - 1 | - | [ |
RhB | Ar-TiO2 | Ar plasma treated | 0.5 | solar/visible: 300 W Xe lamp | 10 | 120 min: 4.10 h-1/150 min: 3.17 h - 1 | - | [ |
RhB | Ti3+ self-doped TiO2 | SMMW | 5 | visible: 500 W Xe lamp | 20 | 180 min: degrated ∼3.5 ppm | - | [ |
RhB | Ti3+ self-doped TiO2 | SMMW | - | visible: 200 W Xe lamp | 5 | 300 min: ∼60% | - | [ |
RhB | hollow-shell black TiO2 | NaBH4 reduction | 0.12 | visible: 300 W Xe lamp | 50 min: >90%, 0.038 min-1 | 5 cycles | [ | |
MO | black TiO2 | Sol-gel method to prepared TiO2 and subsequent heat treatment in H2/N2 | 0.13 | visible: visible lamp | 1 | 150 min: >60%, ∼0.026 min-1 | - | [ |
MO | Blue TiO2 | TiH2 reduction | 1 | solar: 300 W Xe lamp | - | 8 min: 100% | - | [ |
MO | Blue TiO2 | NaBH4 reduction with annealing in N2 | 0.8 | visible: 35 W Xe lamp | 15 | 90 minn: 100% | - | [ |
MO | Ar-TiO2 | Dielectric barrier discharge plasma treatment under Ar atmosphere | 0.5 | solar/visible: 300 W Xe lamp | 10 | 30 min: 5.38 h - 1/150 min: 2.14 h - 1 | - | [ |
MO | Ti3+ self-doped TiO2 | NaBH4 reduction | 1.33 | visible: 300 W Xe lamp | 10 | 180 min: 98%, 0.0291 min-1 | [ | |
RB5 | H-TiO2 | H2-plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: ∼100%, 0.91 h-1 | 10 cycles | [ |
RB5 | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 120 min: >99% | - | [ |
RB5 | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 3 | 180 min: >90%, 2.12 h - 1 | - | [ |
RB5 | H-TiO2 | Annealing in H2 | 0.3 | solar: 150 W Xe lamp | 10 | 30 min: 0.0305 min-1 | - | [ |
OG | Black TiO2 | Solvothermal reaction | 1 | visible: 14 W visible light | 10 | 40 min: ∼100% | - | [ |
AO7 | Ti3+ self-doped TiO2 | Annealing in vacuum | 0.71 | visible: 500 W halogen lamp | 20 | 5 h: >60% | - | [ |
Color (From POME) | Colored TiO2 NPs | Glycerol-mediated solvothermal method | 0.8 | visible: 500 W halogen lamp | 2420 (PtCo) | 180 min: 62.18% | 3 cycles | [ |
Fig. 3. ESI-MS of untreated MB solution (a), treated MB solution after 1 h solar radiation in the presence of Ti3+-doped TiO2 (b), untreated wastewater with no purification (c), photodegradated wastewater after 1 h of light irradiation (d), absence of photocatalyst in wastewater (e). And recycling test of MB photodegradation by the Ti3+-doped TiO2 (f). Reprinted with permission from Ref. [33].
Fig. 4. SEM image (a), and HRTEM image (b) of the as-prepared black Ti3+/TiO2. The inset is the SAED image. The scheme of the structure and density of states (DOS) for pristine TiO2 (left) and the Ti3+-doped TiO2 (right) (c). Photocatalytic activities of the Ti3+-doped TiO2 before and after calcination at elevated temperature (d). Recycling test of the fresh Ti3+-doped TiO2 for RhB degradation in aqueous solution under visible-light (e). Reprinted with permission from Ref. [75].
Fig. 5. Photocatalytic mechanism of the Ti3+ self-doped TiO2 (a). Photos of the fresh Ti3+ self-doped TiO2 (b) and that stored for three months (c). EPR spectra (d), XRD diffraction patterns (e), and Raman spectra (f) of the Ti3+ self-doped TiO2 measured before and after a photocatalytic reaction. Reprinted with permission from Ref. [34].
Target | Photocatalyst | Synthesis method of self-doped TiO2 | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
MB | b-TiO2@PCs | Solvothermal method | - | solar | 100 | 12 h: ∼100% | - | [ |
MB | RGO/TiO2-x | Solvothermal method | 1 | visible: 500 W Xe arc lamp | 40 | 120 min: 100% | 4 cycles | [ |
MB | N-Ti3+-TiO2/g-C3N4 | Solvothermal method | 0.3 | visible: Xe lamp | 5 | 100 min: 81.64%, 0.01284 min-1 | 3 cycles | [ |
MB | MIP-TiO2-x/CQDs | Solvothermal method | 0.5 | visible: 300 W Xe lamp | 10 | 120 min: 92.6%, 0.018 min-1 | 5 cycles | [ |
RhB | b-N-TiO2 | Solvothermal method | 0.2 | visible: Xe lamp | 3 | 160 min: 100% | - | [ |
RhB | Ti3+-TiO2/Ag2O | Solvothermal method | 0.125 | visible: 500 W Xe lamp | 10 | 150 min: >90% | - | [ |
RhB | b-Zr-TiO2 | Solvothermal method | 0.25 | visible: 300 W Xe lamp | 10 | 120 min: 95.25% | - | [ |
RhB | Ti3+-TiO2/O-g-C3N4 | Solvothermal method | - | visible: 30 W LED lamp | 10 | 100 min: ∼100%, 0.0356 min-1 | - | [ |
RhB | b-TiO2@carbon cloth | NaBH4 reduction | - | solar: Xe lamp (1 kW/m2) | 4 | 100 min: 95%, 0.02947 min-1 | 10 cycles | [ |
RhB | carbon dots/b-TiO2@Ti | NaBH4 reduction | - | solar: simulated solar light (121.5 mW/cm2) | 1.5 | 90 min: 0.8694 h - 1 | - | [ |
RhB | Cu-g-C3N4/b-TiO2 | NaBH4 reduction | - | solar: 150 W Xe lamp | 10 | 120 min: 86.2% | - | [ |
RhB | b-N-TiO2 | Solvothermal reaction | 0.25 | visible: 350 W Xe lamp | 20 | 120 min: 99.5%, 0.026 min-1 | 5 cycles | [ |
RhB | b-Ni-TiO2 | NaBH4 reduction | 1 | visible: 350 W Xe lamp | 10 | 150 min: 95.86%, 0.0215 min-1 | 6 cycles | [ |
RhB | b-N-TiO2 | NaBH4 reduction | 0.83 | visible: 350 W Xe lamp | 10 | 150 min: 93.64% | 6 cycles | [ |
RhB | N-Ti3+-TiO2/g-C3N4 | Solvothermal method | 0.3 | 10 | 2 h: >90% | - | [ | |
MO | b-TiO2-x/CNT | One-pot solvothermal reaction combined with a subsequent NaBH4 reduction under Ar atmosphere at 350 °C for 1 h | 1 | visible: 300 W Xe lamp | 10 | 150 min: 99.6% | - | [ |
MO | b-N-TiO2 | NaBH4 reduction | 0.71 | visible: 300 W Xe lamp | 10 | 160 min: 96%, 0.0185 min-1 | - | [ |
MO | b-N-TiO2 | NaBH4 reduction | 1.4 | visible: 300 W Xe lamp | 10 | 150 min: 95.2%, 0.0196 min-1 | - | [ |
MO | TiO2-x/g-C3N4 | Solvothermal method | 0.4 | visible: 300 W Xe lamp | 10 | 80 min: 96.8% | 3 cycles; Ti3+ signal for the stored sample | [ |
MO | M-Fe2O3/b-TiO2 | Solvothermal reaction | 0.5 | solar: 300 W Xe lamp | 10 | 40 min: 99.8% | - | [ |
MO | b-SnO2-TiO2 | Sol-gel method | 0.5 | solar: 500 W Xe lamp | 10 | 25 min: 94.7% | - | [ |
MO | b-Ni-TiO2 | NaBH4 reduction | 1 | visible: 350 W Xe lamp | 10 | 150 min: 95.38%, 0.0206 min-1 | 6 cycles | [ |
MO | b-N-TiO2 | NaBH4 reduction | 0.83 | visible: 350 W Xe lamp | 10 | 150 min: 93.27% | 6 cycles | [ |
Table 2. Photodegradation of dyes by heterojunction including black TiO2.
Target | Photocatalyst | Synthesis method of self-doped TiO2 | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
MB | b-TiO2@PCs | Solvothermal method | - | solar | 100 | 12 h: ∼100% | - | [ |
MB | RGO/TiO2-x | Solvothermal method | 1 | visible: 500 W Xe arc lamp | 40 | 120 min: 100% | 4 cycles | [ |
MB | N-Ti3+-TiO2/g-C3N4 | Solvothermal method | 0.3 | visible: Xe lamp | 5 | 100 min: 81.64%, 0.01284 min-1 | 3 cycles | [ |
MB | MIP-TiO2-x/CQDs | Solvothermal method | 0.5 | visible: 300 W Xe lamp | 10 | 120 min: 92.6%, 0.018 min-1 | 5 cycles | [ |
RhB | b-N-TiO2 | Solvothermal method | 0.2 | visible: Xe lamp | 3 | 160 min: 100% | - | [ |
RhB | Ti3+-TiO2/Ag2O | Solvothermal method | 0.125 | visible: 500 W Xe lamp | 10 | 150 min: >90% | - | [ |
RhB | b-Zr-TiO2 | Solvothermal method | 0.25 | visible: 300 W Xe lamp | 10 | 120 min: 95.25% | - | [ |
RhB | Ti3+-TiO2/O-g-C3N4 | Solvothermal method | - | visible: 30 W LED lamp | 10 | 100 min: ∼100%, 0.0356 min-1 | - | [ |
RhB | b-TiO2@carbon cloth | NaBH4 reduction | - | solar: Xe lamp (1 kW/m2) | 4 | 100 min: 95%, 0.02947 min-1 | 10 cycles | [ |
RhB | carbon dots/b-TiO2@Ti | NaBH4 reduction | - | solar: simulated solar light (121.5 mW/cm2) | 1.5 | 90 min: 0.8694 h - 1 | - | [ |
RhB | Cu-g-C3N4/b-TiO2 | NaBH4 reduction | - | solar: 150 W Xe lamp | 10 | 120 min: 86.2% | - | [ |
RhB | b-N-TiO2 | Solvothermal reaction | 0.25 | visible: 350 W Xe lamp | 20 | 120 min: 99.5%, 0.026 min-1 | 5 cycles | [ |
RhB | b-Ni-TiO2 | NaBH4 reduction | 1 | visible: 350 W Xe lamp | 10 | 150 min: 95.86%, 0.0215 min-1 | 6 cycles | [ |
RhB | b-N-TiO2 | NaBH4 reduction | 0.83 | visible: 350 W Xe lamp | 10 | 150 min: 93.64% | 6 cycles | [ |
RhB | N-Ti3+-TiO2/g-C3N4 | Solvothermal method | 0.3 | 10 | 2 h: >90% | - | [ | |
MO | b-TiO2-x/CNT | One-pot solvothermal reaction combined with a subsequent NaBH4 reduction under Ar atmosphere at 350 °C for 1 h | 1 | visible: 300 W Xe lamp | 10 | 150 min: 99.6% | - | [ |
MO | b-N-TiO2 | NaBH4 reduction | 0.71 | visible: 300 W Xe lamp | 10 | 160 min: 96%, 0.0185 min-1 | - | [ |
MO | b-N-TiO2 | NaBH4 reduction | 1.4 | visible: 300 W Xe lamp | 10 | 150 min: 95.2%, 0.0196 min-1 | - | [ |
MO | TiO2-x/g-C3N4 | Solvothermal method | 0.4 | visible: 300 W Xe lamp | 10 | 80 min: 96.8% | 3 cycles; Ti3+ signal for the stored sample | [ |
MO | M-Fe2O3/b-TiO2 | Solvothermal reaction | 0.5 | solar: 300 W Xe lamp | 10 | 40 min: 99.8% | - | [ |
MO | b-SnO2-TiO2 | Sol-gel method | 0.5 | solar: 500 W Xe lamp | 10 | 25 min: 94.7% | - | [ |
MO | b-Ni-TiO2 | NaBH4 reduction | 1 | visible: 350 W Xe lamp | 10 | 150 min: 95.38%, 0.0206 min-1 | 6 cycles | [ |
MO | b-N-TiO2 | NaBH4 reduction | 0.83 | visible: 350 W Xe lamp | 10 | 150 min: 93.27% | 6 cycles | [ |
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Phenol | Black TiO2 | Hydrogenation in 20.0 bar H2 at about 200 °C for 5 d | 0.33 | solar: 1 sun power | 10 | 40 min: ∼100% | - | [ |
Phenol | H-TiO2 | H2-plasma treatment | 0.5 | solar: 150 W Xe lamp | 1.88 | 180 min: > 80% | - | [ |
Phenol | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 1.88 | 120 min: ∼100% | - | [ |
Phenol | H-TiO2 | Plasma treatment | 0.5 | solar: 150 W Xe lamp | 1.88 | 180 min: ∼90% | - | [ |
Phenol | Black TiO2 | Solvothermal method | 0.2 | visible: 300 W Xe lamp | 10 | 6 h: 0.1316 h - 1 | - | [ |
Phenol | Ti3+ self-doped mixed-crystal TiO2 | NaBH4 reduction | 1.33 | visible: 300 W Xe lamp | 10 | 180 min: 97%, 0.0188 min-1 | - | [ |
Phenol | Black SnO2-TiO2 | Sol-gel method | 1 | solar: 500 W Xe lamp | 10 | 160 min: 82.3% | - | [ |
Phenol | RGO/TiO2-x | Solvothermal method | 1 | visible: 500 W Xe arc lamp | 10 | 150 min: 100% | - | [ |
Phenol | NTTC | Hydrothermal treatment | 0.3 | visible: Xe lamp | 50 | 3 h: >30% | - | [ |
Phenol | Black CNST | NaBH4 reduction | 0.67 | visible: 350 W Xe lamp | 10 | 180 min: 90.99%, 0.0192 min-1 | - | [ |
Phenol | Ag/N-TiO2-x | NaBH4 reduction | 1 | visible: 300 W Xe lamp | 10 | 150 min: 97.7%, 0.0227 min-1 | - | [ |
Phenol | Ag/S-TiO2-x | NaBH4 reduction | 0.5 | visible: 300 W Xe lamp | - | 150 min: 98.67%, 0.0291 min-1 | 5 cycles | [ |
Phenol | bm-TiO2/SiO2/g-C3N4 | Hydrogenation at 500 °C for 3 h | 1.4 | visible: 300 W Xe lamp | 10 | 210 min: 98.5% | 5 cycles | [ |
Phenol | Ag-MBTHs | UV irradiation | - | visible-NIR | - | 2 h: 100%, 1.09 h - 1 | - | [ |
Phenolic compounds (From POME) | Colored TiO2 NPs | Glycerol-mediated solvothermal method | 0.8 | visible: 500 W halogen lamp | 224.85 (GAE) | 180 min: 48.17% | - | [ |
2,4-dichlorophenol | Ag-TPBTPs | Hydrogenation in H2 at 400 °C | 1.67 | solar: 300 W Xe lamp | 5 | 2 h: ∼99% | 10 cycles | [ |
2,4,6-Trichlorophenol (2,4,6-TCP) | CSs/TiO2-x@g-C3N4 | Hydrothermal treatment used TiCl3 as precursor | visible: 1000 W Xe lamp | 10 | 150 min: >90% | - | [ | |
4-nitrophenol | Ag-MBTHs | UV irradiation | - | visible-NIR | - | 70 s: 100% | 10 cycles | [ |
Table 3. Photodegradation of phenolic compounds by black TiO2.
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Phenol | Black TiO2 | Hydrogenation in 20.0 bar H2 at about 200 °C for 5 d | 0.33 | solar: 1 sun power | 10 | 40 min: ∼100% | - | [ |
Phenol | H-TiO2 | H2-plasma treatment | 0.5 | solar: 150 W Xe lamp | 1.88 | 180 min: > 80% | - | [ |
Phenol | H-TiO2 | Underwater discharge plasma treatment | 0.5 | solar: 150 W Xe lamp | 1.88 | 120 min: ∼100% | - | [ |
Phenol | H-TiO2 | Plasma treatment | 0.5 | solar: 150 W Xe lamp | 1.88 | 180 min: ∼90% | - | [ |
Phenol | Black TiO2 | Solvothermal method | 0.2 | visible: 300 W Xe lamp | 10 | 6 h: 0.1316 h - 1 | - | [ |
Phenol | Ti3+ self-doped mixed-crystal TiO2 | NaBH4 reduction | 1.33 | visible: 300 W Xe lamp | 10 | 180 min: 97%, 0.0188 min-1 | - | [ |
Phenol | Black SnO2-TiO2 | Sol-gel method | 1 | solar: 500 W Xe lamp | 10 | 160 min: 82.3% | - | [ |
Phenol | RGO/TiO2-x | Solvothermal method | 1 | visible: 500 W Xe arc lamp | 10 | 150 min: 100% | - | [ |
Phenol | NTTC | Hydrothermal treatment | 0.3 | visible: Xe lamp | 50 | 3 h: >30% | - | [ |
Phenol | Black CNST | NaBH4 reduction | 0.67 | visible: 350 W Xe lamp | 10 | 180 min: 90.99%, 0.0192 min-1 | - | [ |
Phenol | Ag/N-TiO2-x | NaBH4 reduction | 1 | visible: 300 W Xe lamp | 10 | 150 min: 97.7%, 0.0227 min-1 | - | [ |
Phenol | Ag/S-TiO2-x | NaBH4 reduction | 0.5 | visible: 300 W Xe lamp | - | 150 min: 98.67%, 0.0291 min-1 | 5 cycles | [ |
Phenol | bm-TiO2/SiO2/g-C3N4 | Hydrogenation at 500 °C for 3 h | 1.4 | visible: 300 W Xe lamp | 10 | 210 min: 98.5% | 5 cycles | [ |
Phenol | Ag-MBTHs | UV irradiation | - | visible-NIR | - | 2 h: 100%, 1.09 h - 1 | - | [ |
Phenolic compounds (From POME) | Colored TiO2 NPs | Glycerol-mediated solvothermal method | 0.8 | visible: 500 W halogen lamp | 224.85 (GAE) | 180 min: 48.17% | - | [ |
2,4-dichlorophenol | Ag-TPBTPs | Hydrogenation in H2 at 400 °C | 1.67 | solar: 300 W Xe lamp | 5 | 2 h: ∼99% | 10 cycles | [ |
2,4,6-Trichlorophenol (2,4,6-TCP) | CSs/TiO2-x@g-C3N4 | Hydrothermal treatment used TiCl3 as precursor | visible: 1000 W Xe lamp | 10 | 150 min: >90% | - | [ | |
4-nitrophenol | Ag-MBTHs | UV irradiation | - | visible-NIR | - | 70 s: 100% | 10 cycles | [ |
Fig. 6. Photocatalytic degradation rate of phenol (a), variations of ln(C0/C) (b) versus irradiation time with three samples under visible light irradiation. Photocatalytic hydrogen evolution for N-TiO2, Ag/N-TiO2, and Ag/N-TiO2-x, respectively (c), and five cycling tests of H2 evolution of Ag/N-TiO2-x under AM 1.5 irradiation (d). Diagrammatic sketch for the synthetic process of 3D urchinlike Ag/N-TiO2-x (e). Schematic diagram of the visible-light-driven photocatalytic mechanism for Ag/N-TiO2-x (f). Reprinted with permission from Ref. [107].
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Industrial wastewater | Ti3+ self-doped TiO2 | H2O2 oxidized TiH2 followed with calcination at 630 °C for 3 h in Ar | 0.5l | solar: Solar simulator | - | 1 h: significant degradation | - | [ |
Aniline | Black TiO2 | Treating Ti in an ionic liquid containing LiAc and HAc under mild ionothermal conditions | 1 | visible: 300 W Xe lamp | 10 | 4 h: ∼60% | - | [ |
Formaldehyde | Reduced TiO2 | NaBH4 reduction | - | dark | 20 (1 L/min) | 60 min: ∼100% | - | [ |
Formaldehyde | Black TiO2 | Solvothermal reaction | - | visible: 8 W fluorescent lamps | - | 0.6351 min-1 | 3 cycles | [ |
Formaldehyde | H-TiO2 | Annealing in H2/Ar at 300 °C for 2 h | - | dark | 100 | 4 h: 53% | - | [ |
Formaldehyde | H—C-TiO2 | Annealing in H2/Ar at 300 °C for 2 h | - | dark | 100 | 4 h: 57% | - | [ |
Toluene | Black TiO2 | Solvothermal reaction | - | solar: 250 W Xe lamp | 100 (50 ml/min) | 89% | - | [ |
Toluene | Black TiO2 | Al reduction | 0.5 | solar/visible: 300 W Xe lamp | 50 | 3 h/6 h: >95% | 6 cycles; No change in EPR. | [ |
xylene | CuO-TiO2 | NaBH4 reduction | - | solar: ultraviolet-visible light lamps | 60 (200 mL/min) | 35.64% | 8 cycles | [ |
m-xylene | CNAgBT | Annealing in H2/Ar at 450 °C for 4 h | - | solar: 8 W daylight lamp | 1 ppm | 5 h: 79% | - | [ |
Ethylbenzene | CuCNBTNF | NaBH4 reduction | 0.39 mg cm-2 | solar: daylight fluorescent lamp | 1 (1 L/min) | 63.20% | - | [ |
Isopropanol (IPA) | Black TiO2 | Solvothermal reaction | - | solar: 250 W Xe lamp | 100 (50 ml/min) | 99% | - | [ |
benzyl alcohol | Pd-TiO2—OV | UV irradiation | 5.33 | visible: 300 W Xe lamp | 0.1 mmol | 2 h: ∼65% | 5 cycles | [ |
Ethyl acetate | Black TiO2 | Al reduction | 0.5 | solar: 300 W Xe lamp | 50 | 6 h: 90% | - | [ |
Formic acid | b-N-TiO2 | Solvothermal reaction | 0.2 | visible: Xe lamp | 5 | 180 min: >51% | 5 cycles; No change in EPR. | [ |
Salicylic acid (SA) | TiO2—NT's@Ag-HA | Annealing in Ar/H2 for 3 h. | - | solar: 100 W incandescent bulb | 0.2 mmol/dm3 | 240 min: ∼80%, 5.81×103 min-1 | 10 cycles | [ |
n-hexane | CNAgBT | Annealing in H2/Ar at 450 °C for 4 h | - | solar: 8 W daylight lamp | 1 | 5 h: 49% | - | [ |
Table 4. Photodegradation of common organic pollutants apart from dyes and phenolic compounds by black TiO2.
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Industrial wastewater | Ti3+ self-doped TiO2 | H2O2 oxidized TiH2 followed with calcination at 630 °C for 3 h in Ar | 0.5l | solar: Solar simulator | - | 1 h: significant degradation | - | [ |
Aniline | Black TiO2 | Treating Ti in an ionic liquid containing LiAc and HAc under mild ionothermal conditions | 1 | visible: 300 W Xe lamp | 10 | 4 h: ∼60% | - | [ |
Formaldehyde | Reduced TiO2 | NaBH4 reduction | - | dark | 20 (1 L/min) | 60 min: ∼100% | - | [ |
Formaldehyde | Black TiO2 | Solvothermal reaction | - | visible: 8 W fluorescent lamps | - | 0.6351 min-1 | 3 cycles | [ |
Formaldehyde | H-TiO2 | Annealing in H2/Ar at 300 °C for 2 h | - | dark | 100 | 4 h: 53% | - | [ |
Formaldehyde | H—C-TiO2 | Annealing in H2/Ar at 300 °C for 2 h | - | dark | 100 | 4 h: 57% | - | [ |
Toluene | Black TiO2 | Solvothermal reaction | - | solar: 250 W Xe lamp | 100 (50 ml/min) | 89% | - | [ |
Toluene | Black TiO2 | Al reduction | 0.5 | solar/visible: 300 W Xe lamp | 50 | 3 h/6 h: >95% | 6 cycles; No change in EPR. | [ |
xylene | CuO-TiO2 | NaBH4 reduction | - | solar: ultraviolet-visible light lamps | 60 (200 mL/min) | 35.64% | 8 cycles | [ |
m-xylene | CNAgBT | Annealing in H2/Ar at 450 °C for 4 h | - | solar: 8 W daylight lamp | 1 ppm | 5 h: 79% | - | [ |
Ethylbenzene | CuCNBTNF | NaBH4 reduction | 0.39 mg cm-2 | solar: daylight fluorescent lamp | 1 (1 L/min) | 63.20% | - | [ |
Isopropanol (IPA) | Black TiO2 | Solvothermal reaction | - | solar: 250 W Xe lamp | 100 (50 ml/min) | 99% | - | [ |
benzyl alcohol | Pd-TiO2—OV | UV irradiation | 5.33 | visible: 300 W Xe lamp | 0.1 mmol | 2 h: ∼65% | 5 cycles | [ |
Ethyl acetate | Black TiO2 | Al reduction | 0.5 | solar: 300 W Xe lamp | 50 | 6 h: 90% | - | [ |
Formic acid | b-N-TiO2 | Solvothermal reaction | 0.2 | visible: Xe lamp | 5 | 180 min: >51% | 5 cycles; No change in EPR. | [ |
Salicylic acid (SA) | TiO2—NT's@Ag-HA | Annealing in Ar/H2 for 3 h. | - | solar: 100 W incandescent bulb | 0.2 mmol/dm3 | 240 min: ∼80%, 5.81×103 min-1 | 10 cycles | [ |
n-hexane | CNAgBT | Annealing in H2/Ar at 450 °C for 4 h | - | solar: 8 W daylight lamp | 1 | 5 h: 49% | - | [ |
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Acetaminophen (ACE) | Black TiO2 | Annealing in vacuum | - | solar: 150 W Xe lamp | 1 | 3 h: ∼100%, 0.998 h - 1 | 5 cycles; Storing for 6 months. | [ |
Acetaminophen (ACE) | OVPTCN | Al reduction | 0.5 | visible: 300 W Xe lamp | 5 | 120 min: 96%, 0.025 min-1 | 4 cycles | [ |
Ibuprofen (IBP) | black N-TiO2 | NaBH4 reduction | 0.4 | visible: 5 W LED lamp | 2 | 75 min: 96%, 0.043 min-1 | 5 cycles | [ |
Tetracycline (TC) | black anatase-TiO2 | Annealing in H2 | 0.2 | visible: 1000 W Xe lamp | 10 | 240 min: 66.2%, 0.0045 min-1 | 4 cycles | [ |
Tetracycline (TC) | γ-Fe2O3/b-TiO2 | Annealing in H2 | 0.3 | solar: 300 W Xe lamp | 10 | 50 min: 99.3%, 0.0829 min-1 | 5 cycles; Storing for 6 months | [ |
Tetracycline (TC) | b/N-TDHG | NaBH4 reduction | - | visible: 150 W Xe lamp | 10 | 150 min: 92%, 0.0144 min-1 | 5 cycles | [ |
Tetracycline (TC) | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 90%, 0.00775 min-1 | 5 cycles; No change in major XRD peaks | [ |
Tetracycline (TC) | RGO@BT | NaBH4 reduction | 0.2 | solar | 40 | 120 min: 94.7% | 3 cycles; No change in major XRD peaks | [ |
Doxycycline hydrochloride | RGO/B-TiO2/2D-ZIF-8 | NaBH4 reduction | 0.1 | visible: 300 W Xe lamp | 25 | 120 min: 76%, 0.0118 min-1 | 3 cycles | [ |
Oxytetracycline | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 94% | - | [ |
Oxytetracycline hydrochloride | Dark brown TiO2 spheres | Solvothermal reaction | - | Natural sunlight | 0.5 | 80 min: > 80% | - | [ |
Ciprofloxacin (CIP) | CSs/TiO2-x@g-C3N4 | Hydrothermal treatment | 1 | visible: 1000 W Xe lamp | 10 | 140 min: > 90%, 0.01678 min-1 | 5 cycles | [ |
Ciprofloxacin (CIP) | b-N-TiO2 | NaBH4 reduction | 0.43 | visible: LED light | 0.5 | 70 min: 100% | 5 cycles | [ |
Ciproflocacin (CIP) | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 84% | - | [ |
Norfloxacin | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 45% | - | [ |
Levofloxacin (LVFX) | NTTC | Hydrothermal treatment | 0.3 | visible: Xe lamp | 20 | 2 h: ∼60% | - | [ |
Sulfisoxazole | C-doped TiO2-x | Solvothermal reaction | 0.4 | visible: CEL—HXF300 Xe lamp | 10 | 360 min: ∼70%, 0.00389 min-1 | 3 cycles | [ |
Sulfisoxazole | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 75% | - | [ |
Carbamazepine | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 63% | - | [ |
Table 5. Black TiO2 for the degradation of Photodegradation of pharmaceuticals and personal care products (PPCPs).
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Acetaminophen (ACE) | Black TiO2 | Annealing in vacuum | - | solar: 150 W Xe lamp | 1 | 3 h: ∼100%, 0.998 h - 1 | 5 cycles; Storing for 6 months. | [ |
Acetaminophen (ACE) | OVPTCN | Al reduction | 0.5 | visible: 300 W Xe lamp | 5 | 120 min: 96%, 0.025 min-1 | 4 cycles | [ |
Ibuprofen (IBP) | black N-TiO2 | NaBH4 reduction | 0.4 | visible: 5 W LED lamp | 2 | 75 min: 96%, 0.043 min-1 | 5 cycles | [ |
Tetracycline (TC) | black anatase-TiO2 | Annealing in H2 | 0.2 | visible: 1000 W Xe lamp | 10 | 240 min: 66.2%, 0.0045 min-1 | 4 cycles | [ |
Tetracycline (TC) | γ-Fe2O3/b-TiO2 | Annealing in H2 | 0.3 | solar: 300 W Xe lamp | 10 | 50 min: 99.3%, 0.0829 min-1 | 5 cycles; Storing for 6 months | [ |
Tetracycline (TC) | b/N-TDHG | NaBH4 reduction | - | visible: 150 W Xe lamp | 10 | 150 min: 92%, 0.0144 min-1 | 5 cycles | [ |
Tetracycline (TC) | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 90%, 0.00775 min-1 | 5 cycles; No change in major XRD peaks | [ |
Tetracycline (TC) | RGO@BT | NaBH4 reduction | 0.2 | solar | 40 | 120 min: 94.7% | 3 cycles; No change in major XRD peaks | [ |
Doxycycline hydrochloride | RGO/B-TiO2/2D-ZIF-8 | NaBH4 reduction | 0.1 | visible: 300 W Xe lamp | 25 | 120 min: 76%, 0.0118 min-1 | 3 cycles | [ |
Oxytetracycline | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 94% | - | [ |
Oxytetracycline hydrochloride | Dark brown TiO2 spheres | Solvothermal reaction | - | Natural sunlight | 0.5 | 80 min: > 80% | - | [ |
Ciprofloxacin (CIP) | CSs/TiO2-x@g-C3N4 | Hydrothermal treatment | 1 | visible: 1000 W Xe lamp | 10 | 140 min: > 90%, 0.01678 min-1 | 5 cycles | [ |
Ciprofloxacin (CIP) | b-N-TiO2 | NaBH4 reduction | 0.43 | visible: LED light | 0.5 | 70 min: 100% | 5 cycles | [ |
Ciproflocacin (CIP) | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 84% | - | [ |
Norfloxacin | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 45% | - | [ |
Levofloxacin (LVFX) | NTTC | Hydrothermal treatment | 0.3 | visible: Xe lamp | 20 | 2 h: ∼60% | - | [ |
Sulfisoxazole | C-doped TiO2-x | Solvothermal reaction | 0.4 | visible: CEL—HXF300 Xe lamp | 10 | 360 min: ∼70%, 0.00389 min-1 | 3 cycles | [ |
Sulfisoxazole | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 75% | - | [ |
Carbamazepine | BTN@PCs | Solvothermal method | 0.6 | visible: Xe lamp | 50 | 180 min: 63% | - | [ |
Fig. 7. Photos of the black TiO2 and initial TiO2 pellets (a). Photodegradation efficiency of ACE by different samples (b). Nyquist plots indicating electrochemical impedance spectroscopy (EIS) responses with real (Z’) and imaginary (Z’’) impedance components (c) and chronoamperometry tests (d) for P25, BT500, and PBT500 samples. Reprinted with permission from Ref. [132].
Fig. 8. Mechanism of photothermal catalytic degradation of tetracycline by the RGO@BT nanofluid under solar irradiation (a). Effect of temperature on the degradation of tetracycline (b). temperature and photothermal conversion efficiency of H2O, BT, GO, RGO, and the RGO@BT nanofluid at 200 mg/L (c). EPR spectra of DMPO-•OH (d) and DMPO-•O2- (e) under different conditions. Reprinted with permission from Ref. [141].
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
BPA | H-TiO2 | Annealing in H2 at 600 °C for 5 h | 0.1 | solar: solar simulator | 0.24 | 45 min: 100% | 5 cycles | [ |
BPA | Ag/MoS2/TiO2-x | NaBH4 reduction | 1.75 | visible: 500 W Xe lamp | 10 | 120 min: 96.7%, 0.0248 min-1 | 4 recycles; No change in XRD. | [ |
Atrazine | H-TiO2 | Annealing in H2 at 500 °C for 12 h | 0.5 | visible: 150 W light | 0.5 | 180 min: 0.007 min-1 | - | [ |
Atrazine | TTGN | Solvothermal reaction | 2 | visible: 150 W Xe lamp | 5 | 150 min: >90%, 0.014 min-1 | - | [ |
Atrazine | G@BTN | Annealing in H2 at 450 °C for 3 h | 0.5 | solar: 300 W Xe lamp | 1 | 5 h: 99%, 0.863 h - 1 | - | [ |
Metribuzin | M-Fe2O3/b-TiO2 | Annealing in H2 at 200 °C for 3 h | 0.5 | solar: 300 W Xe lamp | 10 | 60 min: 99%, 0.046 min-1 | 10 cycles; Storing for 6 months. | [ |
Table 6. Black TiO2 as photocatalysts for the degradation of endocrine disrupting chemicals (EDCs).
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
BPA | H-TiO2 | Annealing in H2 at 600 °C for 5 h | 0.1 | solar: solar simulator | 0.24 | 45 min: 100% | 5 cycles | [ |
BPA | Ag/MoS2/TiO2-x | NaBH4 reduction | 1.75 | visible: 500 W Xe lamp | 10 | 120 min: 96.7%, 0.0248 min-1 | 4 recycles; No change in XRD. | [ |
Atrazine | H-TiO2 | Annealing in H2 at 500 °C for 12 h | 0.5 | visible: 150 W light | 0.5 | 180 min: 0.007 min-1 | - | [ |
Atrazine | TTGN | Solvothermal reaction | 2 | visible: 150 W Xe lamp | 5 | 150 min: >90%, 0.014 min-1 | - | [ |
Atrazine | G@BTN | Annealing in H2 at 450 °C for 3 h | 0.5 | solar: 300 W Xe lamp | 1 | 5 h: 99%, 0.863 h - 1 | - | [ |
Metribuzin | M-Fe2O3/b-TiO2 | Annealing in H2 at 200 °C for 3 h | 0.5 | solar: 300 W Xe lamp | 10 | 60 min: 99%, 0.046 min-1 | 10 cycles; Storing for 6 months. | [ |
Fig. 9. Representative UV-vis diffuse reflectance spectra obtained for TiO2(T) (a) and H-TiO2(T) (b) samples treated at the indicated temperatures. The DR. spectrum of the parent TiO2 material is also shown, for comparison. Comparison of catalytic activity of H-TiO2(T) and TiO2(T) catalysts (100 mg/L) for the degradation of 240 g/L BPA in UPW and inherent pH. Concentration-time profiles under solar radiation (c); apparent rate constants under solar radiation (d); 360-min conversion under visible radiation (e). Photocatalytic degradation pathways of BPA in the presence of H-TiO2(600) (f). Reprinted with permission from Ref. [49].
Fig. 10. Scanning electron microscopy (SEM) of Microcystis aeruginosa cells with 0.6N—2(500 °C) after adsorption for 2 h (a) and after visible light irradiation for 12 h (b). Removal of chlorophy II-a in the presence of photocatalysts under visible light irradiation (c). Original and external microcystins (MCs) concentration change in the solution with 0.6N—N2(500 °C) under visible light irradiation for 12 h (d). Reprinted with permission from Ref. [164].
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration | Removal efficiency/ Degradation rate | Ref. |
---|---|---|---|---|---|---|---|
E. coli | H-TiO2 | Underwater discharge plasma treatment | 4 | solar: fluorescent light | 0.2 O.D. | 180 min: 82%-88% | [ |
E. coli | TiO2-x/Ag3PO4 | NaBH4 reduction | 0.2 | solar: Xenon lamplight | 107 CFU/ml | 20 min: 99.76% ± 0.15% | [ |
S. aureus | H-TiO2 | Underwater discharge plasma treatment | 4 | solar: fluorescent light | 0.2 O.D. | 180 min: 81%-90% | [ |
S. aureus | TiO2-x/Ag3PO4 | NaBH4 reduction | 0.2 | solar: Xenon lamplight | 107 CFU/ml | 20 min: 99.85% ± 0.09% | [ |
Chlamydomonas segnis | Reduced TiO2 | Li reduction | 0.4 | solar: Solar simulator | 7500±10 cells/ml | 2.5 h: 100% | [ |
Microcystis aeruginosa | N-doped black TiO2 | Annealing in N2 at 500 °C for 3 h | 0.2 | visible: 500 W Xe lamp | 0.2 O.D. (∼3.0 × 106 cells/ml) | 12 h: 99.09% chlorophyll-a | [ |
Table 7. Photocatalystic inactivation by black TiO2.
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration | Removal efficiency/ Degradation rate | Ref. |
---|---|---|---|---|---|---|---|
E. coli | H-TiO2 | Underwater discharge plasma treatment | 4 | solar: fluorescent light | 0.2 O.D. | 180 min: 82%-88% | [ |
E. coli | TiO2-x/Ag3PO4 | NaBH4 reduction | 0.2 | solar: Xenon lamplight | 107 CFU/ml | 20 min: 99.76% ± 0.15% | [ |
S. aureus | H-TiO2 | Underwater discharge plasma treatment | 4 | solar: fluorescent light | 0.2 O.D. | 180 min: 81%-90% | [ |
S. aureus | TiO2-x/Ag3PO4 | NaBH4 reduction | 0.2 | solar: Xenon lamplight | 107 CFU/ml | 20 min: 99.85% ± 0.09% | [ |
Chlamydomonas segnis | Reduced TiO2 | Li reduction | 0.4 | solar: Solar simulator | 7500±10 cells/ml | 2.5 h: 100% | [ |
Microcystis aeruginosa | N-doped black TiO2 | Annealing in N2 at 500 °C for 3 h | 0.2 | visible: 500 W Xe lamp | 0.2 O.D. (∼3.0 × 106 cells/ml) | 12 h: 99.09% chlorophyll-a | [ |
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Cr(Ⅵ) | hollow-shell black TiO2 | NaBH4 reduction | 1.67 | visible: 300 W Xe lamp | 20 | 60 min: 92.3%, 0.0356 min-1 | - | [ |
Cr(Ⅵ) | N-TiO2-x | NaBH4 reduction | 1.75 | visible: 300 W Xe lamp | 5 | 210 min: 96%, 0.01223 min-1 | 5 cycles | [ |
Cr(Ⅵ) | N2-b-TiO2 | Solvothermal method | 0.25 | visible: 350 W Xe lamp | 10 | 150 min: 96.2% | - | [ |
Cr(Ⅵ) | Black CNST | NaBH4 reduction | - | visible: 300 W Xe lamp | - | 180 min: 97%, 0.0135 min-1 | - | [ |
Cr(Ⅵ) | C-doped TiO2-x | Solvothermal method | 0.4 | visible: 300 W Xe lamp | 10 | 120 min: >80%, 0.01267 min-1 | - | [ |
Cr(Ⅵ) | Pd-TiO2—OV | UV irradiation | 0.5 | visible: 300 W Xe lamp | 10 | 30 min: ∼100%, 0.0998 min-1 | - | [ |
Cr(Ⅵ) | DTMCs/g-C3N4 NSs | Solvothermal method | 0.4 | visible: 300 W Xe lamp | 10 | 80 min: ∼100%, 0.063 min-1 | 3 cycles | [ |
Cr(Ⅵ) | bm-TiO2/SiO2/g-C3N4 | Annealing in H2 at 500 °C for 3 h | 1.4 | visible: 300 W Xe lamp | 10 | 210 min: 97% | 5 cycles | [ |
Table 8. Photocatalystic removal of pharmaceuticals by black TiO2.
Target | Photocatalyst | Synthesis method | Catalyst dosage (g/L) | Irradiation | Initialconcentration (10-3 g/L) | Removal efficiency/ Degradation rate | Stability | Ref. |
---|---|---|---|---|---|---|---|---|
Cr(Ⅵ) | hollow-shell black TiO2 | NaBH4 reduction | 1.67 | visible: 300 W Xe lamp | 20 | 60 min: 92.3%, 0.0356 min-1 | - | [ |
Cr(Ⅵ) | N-TiO2-x | NaBH4 reduction | 1.75 | visible: 300 W Xe lamp | 5 | 210 min: 96%, 0.01223 min-1 | 5 cycles | [ |
Cr(Ⅵ) | N2-b-TiO2 | Solvothermal method | 0.25 | visible: 350 W Xe lamp | 10 | 150 min: 96.2% | - | [ |
Cr(Ⅵ) | Black CNST | NaBH4 reduction | - | visible: 300 W Xe lamp | - | 180 min: 97%, 0.0135 min-1 | - | [ |
Cr(Ⅵ) | C-doped TiO2-x | Solvothermal method | 0.4 | visible: 300 W Xe lamp | 10 | 120 min: >80%, 0.01267 min-1 | - | [ |
Cr(Ⅵ) | Pd-TiO2—OV | UV irradiation | 0.5 | visible: 300 W Xe lamp | 10 | 30 min: ∼100%, 0.0998 min-1 | - | [ |
Cr(Ⅵ) | DTMCs/g-C3N4 NSs | Solvothermal method | 0.4 | visible: 300 W Xe lamp | 10 | 80 min: ∼100%, 0.063 min-1 | 3 cycles | [ |
Cr(Ⅵ) | bm-TiO2/SiO2/g-C3N4 | Annealing in H2 at 500 °C for 3 h | 1.4 | visible: 300 W Xe lamp | 10 | 210 min: 97% | 5 cycles | [ |
Fig. 11. Schematic diagram for the formation of bm-TiO2/SiO2/g-C3N4 sheets heterojunctions architecture (a). The photodegradation of phenol (b) and reduction of Cr6+ (c) under visible-light irradiation. The full-scale XPS spectra (d), Ti 2p (e), O 1 s (f), Si 2p (g), N 1 s (h), C 1 s (i) of bm-TiO2/SiO2/g-C3N4, respectively. Reprinted with permission from Ref. [110].
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