J. Mater. Sci. Technol. ›› 2021, Vol. 78: 1-19.DOI: 10.1016/j.jmst.2020.09.045
• Review Article • Next Articles
Jie Wang, Sijia Sun, Run Zhou, Yangzi Li, Zetian He, Hao Ding*(
), Daimei Chen, Weihua Ao
Received:2020-07-26
Revised:2020-09-25
Accepted:2020-09-29
Published:2021-07-10
Online:2020-11-14
Contact:
Hao Ding
About author:*E-mail address: dinghao113@126.com (H. Ding).Jie Wang, Sijia Sun, Run Zhou, Yangzi Li, Zetian He, Hao Ding, Daimei Chen, Weihua Ao. A review: Synthesis, modification and photocatalytic applications of ZnIn2S4[J]. J. Mater. Sci. Technol., 2021, 78: 1-19.
Fig. 1. Crystal structure of ZnIn2S4 (a) cubic, (b) hexagonal and (c) trigonal. (d) XRD patterns of different crystal polymorphs.
Fig. 2. Promoted strategy of ZnIn2S4 based photocatalytic system.
Fig. 3. Design special structure to improve performance of ZnIn2S4 based photocatalytic system.
Fig. 4. The chemical environment of doped Cu atoms. (a) Copper K-edge XANES spectra of Cu0.5-ZIS and Cu3.6-ZIS compared with Cu0 (Cu foil), Cu+ (Cu2S), and Cu2+ (CuS) standards. (b) Magnitude of the Fourier transforms of k3-weighted Cu K-edge EXAFS functions in Cu0.5-ZIS, Cu3.6-ZIS, CuS, and Cu2S. (c) Cu K-edge extended EXAFS oscillation function of CuS, Cu2S, Cu0.5-ZIS, and Cu3.6-ZIS. (d) Structure illustration and formation energy of atomic substitutional forms. (e) The corresponding EXAFS fitting results of Cu0.5-ZIS in r space. (f) The corresponding EXAFS fitting results of Cu3.6-ZIS in r space. Ref. [104] Copyright (2018) WILEY-VCH.
Fig. 5. Effect of N doping on ZnIn2S4. TA spectra of (a) ZnIn2S4 and (b) N-doped ZnIn2S4, (c) Mott-Schottky curves, (d) UPS spectra and (e) VB XPS spectra of ZnIn2S4 and N-doped ZnIn2S4. (f) Schematic illustration of the band structure of the pristine ZnIn2S4 and N-doped ZnIn2S4 samples. Ref. [111] Copyright (2019) Royal Society of Chemistry.
Fig. 6. The sulfur vacancy in ZnIn2S4. (a) false-color image of the HRTEM image of Vs-M- ZnIn2S4 nanosheets. (b) false-color image of the HRTEM image. (c) Side view structural model of Vs-M-ZnIn2S4 (the S atoms at the bottom are red, and the S atoms at the top are yellow), (d) corresponding of (c) charge density distributions of Vs-M- ZnIn2S4, and the distribution of charge density at the edge of conduction band of (e) perfect ZnIn2S4 structure and (f) Vs-M-ZnIn2S4. Reprinted with permission from Ref. [114] Copyright (2018) American Chemical Society.
Fig. 7. The main mechanism of CO2 reduction for the ZnIn2S4 with VZn. Ref. [97] Copyright (2019) WILEY-VCH.
Fig. 8. Effect of hydrogenation engineering on ZnIn2S4. (a) UV-vis DRS spectra and photographs (inset in a), (b) Tauc plots, (c) Photoluminescence (PL) spectra, (d) Electrochemical impedance spectra. Ref. [120] Copyright (2018) Elsevier.
Fig. 9. The transfer process of the photogenerated electrons (e-) and holes (h+) in the ZnIn2S4 with Co9S8 cocatalyst and the photocatalytic mechanism for Cr(VI) reduction and H2 evolution under visible-light irradiation. Ref. [136] Copyright (2020) WILEY-VCH.
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| H2O+ h+ → OH· + H+ | 2.38 |
| 2H2O +2h+ →H2O2+2H+ | 1.763 |
| H2O2 +h+→ •O2- + 2H+ | 1.72 |
| O2+e-→ •O2- | -0.33 |
| O2+ H2O+ e-→ H2O2+OH- | -0.134 |
| H2O2+ e- →OH·+OH- | 0.93 |
Table 1 Standard Redox Potentials for the Mentioned Reactions in Pollutants removal.
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| H2O+ h+ → OH· + H+ | 2.38 |
| 2H2O +2h+ →H2O2+2H+ | 1.763 |
| H2O2 +h+→ •O2- + 2H+ | 1.72 |
| O2+e-→ •O2- | -0.33 |
| O2+ H2O+ e-→ H2O2+OH- | -0.134 |
| H2O2+ e- →OH·+OH- | 0.93 |
| Photocatalyst | light source | photocatalyst concentration (g·L-1) | Pollutants | Photocatalytic degradation activity | Ref. |
|---|---|---|---|---|---|
| In2O3/ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.5 | 2,4-dichlorophenol (20 mg/L) | 0.0246 min-1 | [ |
| ZnIn2S4/In(OH)3 | 300 W Xe lamp, λ > 420 nm | 0.1 | methylene blue(5·10-5 M) | 95 % (3.5 h) | [ |
| BiVO4/ZnIn2S4 | LED lamp | 0.2 | methyl orange (15 mg/L) | 0.00997 min-1 | [ |
| p- ZnIn2S4/rGO/n-g-C3N4 | Visible light LED lamp (2 W) | Used as an electrode | Triclosan (50 mg/L) | 83 % (0.5 h) | [ |
| SiO2@TiO2@ZnIn2S4 | 00 W Xe lamp, λ > 420 nm | 0.4 | MB (30 mg/L) | 99.5 % (25 min) | [ |
| Bi2S3/BiOCl@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Cr (VI) (50 mg/L) | 21.7 mg L-1 (10 min) | [ |
| ZnIn2S4/MoS2 | LED white light (50 W YNL Model COB) | 0.5 | Cr (VI)(10 ppm) | 1.4 × 10-2 min-1 | [ |
| ZnIn2S4/SnS2 | 300 W Xe lamp, λ > 420 nm | 0.5 | Cr (VI) (50 mg/L) | 100 %(70 min) | [ |
| UiO-66-(COOH)2/ ZnIn2S4 | 500W Xe lamp | 0.4 | Cr (VI) (50 mg/L) | 98.4 %(60 min) | [ |
| ZnIn2S4@Fe3O4 | 300 W Xe lamp, λ > 400 nm | 0.2 | Rh B (20 mg/L) | 0.02008 min-1 | [ |
| ZnIn2S4@N-Doped Hollow Carbon | 300 W Xe lamp, λ > 420 nm | 1 | Cr (VI) (50 mg/L) | 100 % (50 min) | [ |
| WO2.72/ ZnIn2S4 | 300 W Xe lamp, λ > 400 nm | 1 | tetracycline (50 mg/L) | 97.3 % (60 min) | [ |
| ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Cr (VI) (50 mg L-1) | 39.3 mg L-1 (60 min) | [ |
| CQD/ZnIn2S4 | 250 W Xe lamp, λ > 420 nm | 0.25 | Tetracycline (10 mg L-1) | 0.01107 min-1 | [ |
| Fe-doped ZnIn2S4 | 100 W Tungsten-Halogen and the light intensity was 1925 mW/cm2 | 0.5 | 2,4,6-tribromophenol (0.12 mmol·L-1) | 0.436 min-1 | [ |
Table 2 Pollutants removal of ZnIn2S4 based composites.
| Photocatalyst | light source | photocatalyst concentration (g·L-1) | Pollutants | Photocatalytic degradation activity | Ref. |
|---|---|---|---|---|---|
| In2O3/ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.5 | 2,4-dichlorophenol (20 mg/L) | 0.0246 min-1 | [ |
| ZnIn2S4/In(OH)3 | 300 W Xe lamp, λ > 420 nm | 0.1 | methylene blue(5·10-5 M) | 95 % (3.5 h) | [ |
| BiVO4/ZnIn2S4 | LED lamp | 0.2 | methyl orange (15 mg/L) | 0.00997 min-1 | [ |
| p- ZnIn2S4/rGO/n-g-C3N4 | Visible light LED lamp (2 W) | Used as an electrode | Triclosan (50 mg/L) | 83 % (0.5 h) | [ |
| SiO2@TiO2@ZnIn2S4 | 00 W Xe lamp, λ > 420 nm | 0.4 | MB (30 mg/L) | 99.5 % (25 min) | [ |
| Bi2S3/BiOCl@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Cr (VI) (50 mg/L) | 21.7 mg L-1 (10 min) | [ |
| ZnIn2S4/MoS2 | LED white light (50 W YNL Model COB) | 0.5 | Cr (VI)(10 ppm) | 1.4 × 10-2 min-1 | [ |
| ZnIn2S4/SnS2 | 300 W Xe lamp, λ > 420 nm | 0.5 | Cr (VI) (50 mg/L) | 100 %(70 min) | [ |
| UiO-66-(COOH)2/ ZnIn2S4 | 500W Xe lamp | 0.4 | Cr (VI) (50 mg/L) | 98.4 %(60 min) | [ |
| ZnIn2S4@Fe3O4 | 300 W Xe lamp, λ > 400 nm | 0.2 | Rh B (20 mg/L) | 0.02008 min-1 | [ |
| ZnIn2S4@N-Doped Hollow Carbon | 300 W Xe lamp, λ > 420 nm | 1 | Cr (VI) (50 mg/L) | 100 % (50 min) | [ |
| WO2.72/ ZnIn2S4 | 300 W Xe lamp, λ > 400 nm | 1 | tetracycline (50 mg/L) | 97.3 % (60 min) | [ |
| ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Cr (VI) (50 mg L-1) | 39.3 mg L-1 (60 min) | [ |
| CQD/ZnIn2S4 | 250 W Xe lamp, λ > 420 nm | 0.25 | Tetracycline (10 mg L-1) | 0.01107 min-1 | [ |
| Fe-doped ZnIn2S4 | 100 W Tungsten-Halogen and the light intensity was 1925 mW/cm2 | 0.5 | 2,4,6-tribromophenol (0.12 mmol·L-1) | 0.436 min-1 | [ |
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| 2H+ + 2e- → H2 (g) | 0 |
| 2H2O (aq) + 4h+ → O2 (g) + 4H+ | 1.230 |
Table 3 Standard Redox Potentials for the Mentioned Reactions in Photocatalytic Hydrogen Evolution.
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| 2H+ + 2e- → H2 (g) | 0 |
| 2H2O (aq) + 4h+ → O2 (g) + 4H+ | 1.230 |
| Photocatalyst | Light source | Photocatalyst concentration (g·L-1) | Sacrificial agent | Co-catalyst | Performance (mmol h-1 g-1) | AQY | Ref. |
|---|---|---|---|---|---|---|---|
| ZnIn2S4/In(OH)3 | 350 W Xe lamp, λ > 420 nm | 1 | TEOA | Pt | 0.147 mmol h-1 | 38.3 % @420 nm | [ |
| Ti3C2TX@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.5 | TEOA | Pt | 3.475 | 11.14 %@420 nm | [ |
| BQ@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.2 | Na2S/Na2SO3 | Pt | 1.278 | 0.25 %@450nm | [ |
| CeO2@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.25 | Na2S/Na2SO3 | 0.847 | [ | ||
| Co9S8@ZnIn2S4 | 300 W Xe lamp, λ > 400 nm | 1 | TEOA | 9.039 | 5.61 %@405nm | [ | |
| ZnIn2S4@In(OH)3-NiS | 300 W Xe lamp, λ > 420 nm | 0.5 | lactic acid | 7.010 | 14.3 %@420 nm. | [ | |
| WS2/ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1.5 | lactic acid | 2.55 | 3.2 % at 420 nm | [ | |
| SiO2@TiO2@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.4 | MB, TEOA | 0.6183 | [ | ||
| ZnIn2S4/MoS2 | 150 Xe lamp | 1 | Na2S/Na2SO3 | 0.2 | 0.19 %@532nm | [ | |
| ZnIn2S4@NH2-MIL-53(Fe/Co0.75) | 300 W Xe lamp, λ > 420 nm | 0.25 | Na2S/Na2SO3 | Pt | 161724.8 μmol/g in 6 h. | [ | |
| ZnIn2S4@Co/N-Doped Graphitic Carbon | 300W Xe lamp, λ > 400 nm | 0.66 | TEOA | 11.27 | 5.07 %@420 | [ | |
| Cu-ZnIn2S4 | about 1 Sun power, | 1 | ascorbic acid | Pt | 26.2 | 4.76 %@420 nm. | [ |
| Zn(1-2x)(CuGa)xIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | Pt | 1.65 | [ | |
| ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | Pt/Pd | 1.582 | 3.57 % @40,518 nm. | [ |
| UiO-66@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.25 | TEOA | 1.86 | 1.4 %@420 nm | [ | |
| Ag0.2Au0.8/ZnIn2S4/TiO2 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | 0.986 | 1.47 % (whole visible light range) | [ | |
| rGO/TiO2/ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | 0.462 | 0.6888 % (whole visible light range) | [ |
Table 4 List of Photocatalytic Hydrogen Evolution Systems.
| Photocatalyst | Light source | Photocatalyst concentration (g·L-1) | Sacrificial agent | Co-catalyst | Performance (mmol h-1 g-1) | AQY | Ref. |
|---|---|---|---|---|---|---|---|
| ZnIn2S4/In(OH)3 | 350 W Xe lamp, λ > 420 nm | 1 | TEOA | Pt | 0.147 mmol h-1 | 38.3 % @420 nm | [ |
| Ti3C2TX@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.5 | TEOA | Pt | 3.475 | 11.14 %@420 nm | [ |
| BQ@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.2 | Na2S/Na2SO3 | Pt | 1.278 | 0.25 %@450nm | [ |
| CeO2@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.25 | Na2S/Na2SO3 | 0.847 | [ | ||
| Co9S8@ZnIn2S4 | 300 W Xe lamp, λ > 400 nm | 1 | TEOA | 9.039 | 5.61 %@405nm | [ | |
| ZnIn2S4@In(OH)3-NiS | 300 W Xe lamp, λ > 420 nm | 0.5 | lactic acid | 7.010 | 14.3 %@420 nm. | [ | |
| WS2/ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1.5 | lactic acid | 2.55 | 3.2 % at 420 nm | [ | |
| SiO2@TiO2@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.4 | MB, TEOA | 0.6183 | [ | ||
| ZnIn2S4/MoS2 | 150 Xe lamp | 1 | Na2S/Na2SO3 | 0.2 | 0.19 %@532nm | [ | |
| ZnIn2S4@NH2-MIL-53(Fe/Co0.75) | 300 W Xe lamp, λ > 420 nm | 0.25 | Na2S/Na2SO3 | Pt | 161724.8 μmol/g in 6 h. | [ | |
| ZnIn2S4@Co/N-Doped Graphitic Carbon | 300W Xe lamp, λ > 400 nm | 0.66 | TEOA | 11.27 | 5.07 %@420 | [ | |
| Cu-ZnIn2S4 | about 1 Sun power, | 1 | ascorbic acid | Pt | 26.2 | 4.76 %@420 nm. | [ |
| Zn(1-2x)(CuGa)xIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | Pt | 1.65 | [ | |
| ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | Pt/Pd | 1.582 | 3.57 % @40,518 nm. | [ |
| UiO-66@ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 0.25 | TEOA | 1.86 | 1.4 %@420 nm | [ | |
| Ag0.2Au0.8/ZnIn2S4/TiO2 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | 0.986 | 1.47 % (whole visible light range) | [ | |
| rGO/TiO2/ZnIn2S4 | 300 W Xe lamp, λ > 420 nm | 1 | Na2S/Na2SO3 | 0.462 | 0.6888 % (whole visible light range) | [ |
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| 2CO2 (g) + 2H+ + 2e- → HOOCCOOH (aq) | -0.481 |
| CO2 (g) + 2H+ + 2e- → HCOOH (aq) | -0.199 |
| CO2 (g) + 2H+ + 2e- → CO (g) + H2O | -0.117 |
| CO2 (g) + 4H+ + 4e- → HCHO (aq) + 2H2O | -0.07 |
| CO2 (g) + 8H+ + 8e- → CH4 (g) + 2H2O | 0.169 |
| CO2 (g) + 6H+ + 6e- → CH3OH (aq) + H2O | 0.03 |
| 2CO2 (g) + 8H++ 12e- → C2H4(g) + 12OH- | 0.07 |
| 2CO2 (g) + 9H2O+12e--→C2H5OH (aq) + 12OH- | 0.08 |
| 3CO2 (g) + 13H2O + 18e- → C3H7OH (aq) +18OH- | 0.09 |
Table 5 Standard Redox Potentials for the Mentioned Reactions in Photocatalytic Reduction of CO2.
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| 2CO2 (g) + 2H+ + 2e- → HOOCCOOH (aq) | -0.481 |
| CO2 (g) + 2H+ + 2e- → HCOOH (aq) | -0.199 |
| CO2 (g) + 2H+ + 2e- → CO (g) + H2O | -0.117 |
| CO2 (g) + 4H+ + 4e- → HCHO (aq) + 2H2O | -0.07 |
| CO2 (g) + 8H+ + 8e- → CH4 (g) + 2H2O | 0.169 |
| CO2 (g) + 6H+ + 6e- → CH3OH (aq) + H2O | 0.03 |
| 2CO2 (g) + 8H++ 12e- → C2H4(g) + 12OH- | 0.07 |
| 2CO2 (g) + 9H2O+12e--→C2H5OH (aq) + 12OH- | 0.08 |
| 3CO2 (g) + 13H2O + 18e- → C3H7OH (aq) +18OH- | 0.09 |
| Photocatalyst | Reaction system | Photocatalyst dosage (mg) | Reactor (mL) | Light source | Performance (μmol h-1 g-1) | Ref. |
|---|---|---|---|---|---|---|
| Pd/ ZnIn2S4 | 50 mL of a 0.08 M sodium bicarbonate solution in presence of 0.08 M HCl at 100 °C. | 50 mg | 30 cm × 15 cm × 5 cm | 300 W Xe lamp, λ > 420 nm | CH3OH:0.8 | [ |
| VZn-rich One-Unit-Cell ZnIn2S4 | CO2 (1 atm), deionized water(2 mL), 298 ± 0.2 K | 0.1 g | - | PLS-SXE300/300UV Xe lamp with a standard AM 1.5 filter, outputting the light density of about 100 mW/cm2 | CO:33.2 | [ |
| ZnIn2S4 nanosheets/TiO2 nanobelts | CO2 (1 atm), 0.4 mL of deionized water, | 0.1g | - | 500 W xenon lamp | CH4:1.135 | [ |
| ZnIn2S4-In2O3 | CO2 (1 atm), 2’2-bipyridine (15 mg), 2 μmol of CoCl2, 1 mL of triethanolamine, 2 mL H2O, 3 mL acetonitrile, ty. | 4mg | 80 mL | 300W Xe lamp, λ > 400 nm | CO:3075 | [ |
| Polymeric Carbon Nitride - ZnIn2S4 | CO2 (1 atm), bipyridine (20 mg), solvent (6 mL, acetonitrile: H2O = 2: 1), TEOA (1 mL) and CoCl2(1 μmol), | 50 mg | 80 mL | 300 W Xe lamp, λ > 420 nm | CO:44.6 | [ |
| 3D Hierarchical ZnIn2S4 Nanosheets with Rich Zn Vacancies | CO2 (0.04 MPa), acetonitrile (45 mL), TEOA (5 mL), reactor. | 20 mg | (110 mL) | 300 W Xe lamp with an AM 1.5 G filter | CO:255.8 | [ |
| CeOx-S/ZnIn2S4 | CO2 (1 atm), H2O (0.5 mL), CH3CN (0.5 mL), triethylamine (0.1 mL), 42 °C. | 10 mg | - | The 9 W LEDs centred at 455 nm | CO:180 | [ |
| ZnIn2S4@CNO | CO2 (1 atm), bipyridine (20 mg), solvent (6 mL, acetonitrile: H2O = 2:1), TEOA (1 mL), and CoCl2 (1 μmol), 40℃. | 50 mg | 200 mL | 300 W Xe lamp, λ > 400 nm | CO:12.67 CH4:0.98 | [ |
Table 6 List of Photocatalytic Reduction of CO2.
| Photocatalyst | Reaction system | Photocatalyst dosage (mg) | Reactor (mL) | Light source | Performance (μmol h-1 g-1) | Ref. |
|---|---|---|---|---|---|---|
| Pd/ ZnIn2S4 | 50 mL of a 0.08 M sodium bicarbonate solution in presence of 0.08 M HCl at 100 °C. | 50 mg | 30 cm × 15 cm × 5 cm | 300 W Xe lamp, λ > 420 nm | CH3OH:0.8 | [ |
| VZn-rich One-Unit-Cell ZnIn2S4 | CO2 (1 atm), deionized water(2 mL), 298 ± 0.2 K | 0.1 g | - | PLS-SXE300/300UV Xe lamp with a standard AM 1.5 filter, outputting the light density of about 100 mW/cm2 | CO:33.2 | [ |
| ZnIn2S4 nanosheets/TiO2 nanobelts | CO2 (1 atm), 0.4 mL of deionized water, | 0.1g | - | 500 W xenon lamp | CH4:1.135 | [ |
| ZnIn2S4-In2O3 | CO2 (1 atm), 2’2-bipyridine (15 mg), 2 μmol of CoCl2, 1 mL of triethanolamine, 2 mL H2O, 3 mL acetonitrile, ty. | 4mg | 80 mL | 300W Xe lamp, λ > 400 nm | CO:3075 | [ |
| Polymeric Carbon Nitride - ZnIn2S4 | CO2 (1 atm), bipyridine (20 mg), solvent (6 mL, acetonitrile: H2O = 2: 1), TEOA (1 mL) and CoCl2(1 μmol), | 50 mg | 80 mL | 300 W Xe lamp, λ > 420 nm | CO:44.6 | [ |
| 3D Hierarchical ZnIn2S4 Nanosheets with Rich Zn Vacancies | CO2 (0.04 MPa), acetonitrile (45 mL), TEOA (5 mL), reactor. | 20 mg | (110 mL) | 300 W Xe lamp with an AM 1.5 G filter | CO:255.8 | [ |
| CeOx-S/ZnIn2S4 | CO2 (1 atm), H2O (0.5 mL), CH3CN (0.5 mL), triethylamine (0.1 mL), 42 °C. | 10 mg | - | The 9 W LEDs centred at 455 nm | CO:180 | [ |
| ZnIn2S4@CNO | CO2 (1 atm), bipyridine (20 mg), solvent (6 mL, acetonitrile: H2O = 2:1), TEOA (1 mL), and CoCl2 (1 μmol), 40℃. | 50 mg | 200 mL | 300 W Xe lamp, λ > 400 nm | CO:12.67 CH4:0.98 | [ |
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| N2 + e- → N2- | -4.16 |
| N2 + H+ + e- → N2H | -3.20 |
| N2 + 2H+ + 2 e- → N2H2 | -1.32 |
| N2 + 4H+ + 4 e- → N2H4 | -0.36 |
| N2 + 5H+ + 4e-→ N2H5+ | -0.23 |
| N2 + 6H+ + 6e-→ 2NH3 | -0.137 |
| NO2 (g)+2H2O+3 h+→ NO3- + 4H+ | 0.957 |
| NO2 (g)+H2O + h+→ NO3- +2H+ | 0.80 |
| NH3+H2O→NH3·h2O⇋NH4++OH- | |
Table 7 Standard Redox Potentials for the Mentioned Reactions in Photocatalytic Nitrogen Fixation.
| Reaction | E (V) vs NHE (pH = 0) |
|---|---|
| N2 + e- → N2- | -4.16 |
| N2 + H+ + e- → N2H | -3.20 |
| N2 + 2H+ + 2 e- → N2H2 | -1.32 |
| N2 + 4H+ + 4 e- → N2H4 | -0.36 |
| N2 + 5H+ + 4e-→ N2H5+ | -0.23 |
| N2 + 6H+ + 6e-→ 2NH3 | -0.137 |
| NO2 (g)+2H2O+3 h+→ NO3- + 4H+ | 0.957 |
| NO2 (g)+H2O + h+→ NO3- +2H+ | 0.80 |
| NH3+H2O→NH3·h2O⇋NH4++OH- | |
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