Chinese Journal of Catalysis ›› 2022, Vol. 43 ›› Issue (9): 2273-2300.DOI: 10.1016/S1872-2067(21)63939-6
• Special column on renewable fuel synthesis by photocatalysis and photoelectrocatalysis • Previous Articles Next Articles
Wanjun Suna,c, Jiayu Zhua, Meiyu Zhanga, Xiangyu Menga, Mengxue Chena, Yu Fenga, Xinlong Chena, Yong Dinga,b,*(
)
Received:2021-07-14
Accepted:2021-09-07
Online:2022-09-18
Published:2022-08-05
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Yong Ding
About author:Yong Ding received his Ph.D. degree in Physical Chemistry from Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, in 2005. Then, he joined the College of Chemistry and Chemical Engineering of Lanzhou University. In 2009, he went to Emory University as a visiting scholar. When he returned back Lanzhou University in 2011, he was promoted to a full professor. He is now the director of the institute of physical chemistry of Lanzhou University and is Feitian scholar distinguished professor of Gansu Province. He joined the editorial board of Chinese Journal of Catalysis in 2020 and Chinese Chemical Letters in 2021. He has published about 130 peer-reviewed papers in primary SCI journals and gave about 50 invited lectures at various scientific conferences so far. Ding’s main research interests are as follows: 1) Artificial photosynthesis; 2) Water splitting by polyoxometalates, metal complexes and metal oxides; 3) Photocatalytic conversion of carbon dioxide; 4) Synthesis, characterization and catalytic applications of polyoxometalates.
Supported by:Wanjun Sun, Jiayu Zhu, Meiyu Zhang, Xiangyu Meng, Mengxue Chen, Yu Feng, Xinlong Chen, Yong Ding. Recent advances and perspectives in cobalt-based heterogeneous catalysts for photocatalytic water splitting, CO2 reduction, and N2 fixation[J]. Chinese Journal of Catalysis, 2022, 43(9): 2273-2300.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63939-6
Fig. 1. The cobalt-based catalysts discussed in this review.
Fig. 2. Schematic illustrations of water splitting, CO2 reduction and N2 fixation over semiconductor photocatalysts. (1) absorption of light irradiation and generation and separation of electrons and holes, (2) migration of electrons and holes to the surface and active sites, (3) surface redox reactions by the electrons and holes.
| Product | Reaction | E0 redox (V vs. NHE) |
|---|---|---|
| O2 | H2O → 1/2O2 + 2H+ + 2e- | +0.81 |
| H2 | 2H2 + 2e- → H2 | ‒0.42 |
| CO | CO2 + 2H+ + 2e- → CO + H2O | ‒0.53 |
| HCOOH | CO2 + 2H+ + 2e- → HCOOH | ‒0.61 |
| HCHO | CO2 + 4H+ + 4e- → HCHO + H2O | ‒0.48 |
| CH3OH | CO2 + 6H+ + 6e- → CH3OH + H2O | ‒0.38 |
| CH4 | CO2 + 8H+ + 8e- → CH4 + 2H2O | ‒0.24 |
| CH3CHO | 2CO2 + 10H+ + 10e- → CH3CHO + 3H2O | ‒0.36 |
| C2H4 | 2CO2 + 12H+ + 12e- → C2H4 + 4H2O | ‒0.34 |
| C2H5OH | 2CO2 + 12H+ + 12e- → C2H5OH + 3H2O | ‒0.33 |
| C2H6 | 2CO2 + 14H+ + 14e- → C2H6 + 4H2O | ‒0.27 |
| NH3 | N2 + 6H+ + 6e- → 2NH3 | +0.55 |
Table 1 Photocatalytic water splitting, CO2 reduction and N2 fixation reaction and corresponding redox potentials with reference to NHE.
| Product | Reaction | E0 redox (V vs. NHE) |
|---|---|---|
| O2 | H2O → 1/2O2 + 2H+ + 2e- | +0.81 |
| H2 | 2H2 + 2e- → H2 | ‒0.42 |
| CO | CO2 + 2H+ + 2e- → CO + H2O | ‒0.53 |
| HCOOH | CO2 + 2H+ + 2e- → HCOOH | ‒0.61 |
| HCHO | CO2 + 4H+ + 4e- → HCHO + H2O | ‒0.48 |
| CH3OH | CO2 + 6H+ + 6e- → CH3OH + H2O | ‒0.38 |
| CH4 | CO2 + 8H+ + 8e- → CH4 + 2H2O | ‒0.24 |
| CH3CHO | 2CO2 + 10H+ + 10e- → CH3CHO + 3H2O | ‒0.36 |
| C2H4 | 2CO2 + 12H+ + 12e- → C2H4 + 4H2O | ‒0.34 |
| C2H5OH | 2CO2 + 12H+ + 12e- → C2H5OH + 3H2O | ‒0.33 |
| C2H6 | 2CO2 + 14H+ + 14e- → C2H6 + 4H2O | ‒0.27 |
| NH3 | N2 + 6H+ + 6e- → 2NH3 | +0.55 |
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. | |
|---|---|---|---|---|
| Co-NCNT | A blue LED light (λ = 460 nm), 5 mg of catalysts in 15 mL of borate buffer solution (80 mmol L-1, pH 8.5), Ru[(bpy)3](ClO4)2 (1 mmol L-1) as photosensitizer and Na2S2O8 (5.0 mmol L-1) as electron acceptor | O2 yield of 51% | [ | |
| A blue LED light (λ = 460 nm), Eosin-Y as photosensitizer, 3.3 mg of catalysts in 10 mL TEOA (10 vol%) | H2 evolution rate of 14.7 mmol g-1 h-1 and oxygen yield of 51% | |||
| CoSAS@CD | 50 mg of photocatalyst in 100 mL of deionized water containing, 0.614 mmol La2O3 and 1 mmol NaIO3 (or AgNO3) | O2 evolution rate of 168 μmol g-1 h-1 | [ | |
| SBA-15/Co3O4 (4 %) | An Ar ion laser at 476 nm (240 mW), 200 mg of catalyst (8.4 mg Co3O4 in 40 mL of aqueous buffer (0.022‒0.028 mol L-1 Na2SiF6-NaHCO3, pH 5.8), 390 mg Na2SO4, 130 mg Na2S2O8 and 45 mg [Ru(bpy)3]Cl2·6H2O | TOF = 1.000 s-1 and QE of 18% for O2 evolution | [ | |
| 3.0 wt% CoAl2O4/g-C3N4 | 300 W xenon lamp with cutoff filter (L42), 50 mg of catalyst in an aqueous solution with 200 mg La2O3 and 10 mmol L-1 AgNO3 | O2 evolution rate of 2.7 ± 0.04 μmol h-1 | [ | |
| Co3O4 nanocrystals/CNF | 300 W xenon lamp (λ > 420 nm, 120 mW cm-2), 20 mg of catalyst in an aqueous solution with AgNO3 (0.01 mol L-1, 80 mL) and La2O3 (0.2 g) | O2 evolution rate of 24.9 μmol h-1 | [ | |
| CDs@CoOx-300 | LED lamp (λ = 460 nm, 33.8 mW cm-2), 2 mg of catalyst in 10 mL of borate buffer solution (80 mmol L-1, pH 9.0), 1 mmol L-1 [Ru(bpy)3](ClO4)2 as and 5 mmol L-1 Na2S2O8 | O2 yield of 40.4%, AQE of 58.6% at 460 nm | [ | |
| Co3O4 (112) | LED lamp (λ > 420, 16 mW), 5 mg of catalyst in 10 mL of borate buffer solution (80 mmol L-1, pH 9.0), 1 mmol L-1 Ru[(bpy)3]Cl2 and 2.5 mmol L-1 Na2S2O8 | O2 yield of 63.5%, AQEBET of 34.4% | [ | |
| CoS | LED lamp (λ = 460 ± 10 nm, 30 mW cm-2), 3 mg of catalyst in 10 mL of borate buffer solution (80 mmol L-1, pH 9.0), 1 mmol L-1 Ru[(bpy)3]Cl2 and 5 mmol L-1 Na2S2O8 | O2 yield of 63.5%, QE of 21% | [ | |
| 3W LED lamp (λ ≥ 420 nm), Eosin-Y as photosensitizer, 5 mg of catalysts in 10 mL 5 wt% Pt and 5% (v/v) TEOA/H2O (pH 7.0) | H2 evolution rate of 1196 μmol h-1 g-1 | |||
| R-CoPx/rGO | A blue LED light source (λ = 460 ± 10 nm, 30 mW cm-2), 2 mg of catalyst in a 10 mL solution, 1.0 mmol L-1 [Ru(bpy)3]Cl2 and Na2S2O8 (5.0 mmol L-1) in borate buffer solution (pH 9.0) | O2 yields of 34% | [ | |
| CoP/NC | LED light (λ = 460 nm), 4.5 mg of catalyst in 1.0 mmol L-1 [Ru(bpy)3]Cl2, 5.0 mmol L-1 Na2S2O8 borate buffer (80 mmol L-1, pH 8.0) | O2 evolution rate of 901.5 μmol h-1 g-1, O2 yield of 36.1%, QY of 61.5% | [ | |
| NiCoP@NiCo-Pi/g-C3N4 | 300 W Xe lamp, 50 mg of catalysts in 80 mL of 0.02 mol L-1 AgNO3 aqueous solution with 0.2 g of La2O3 | O2 evolution rate of 312 μmol h-1 g-1 | [ | |
| Co3.9/MIL-101 | 300 W xenon lamp (λ > 420 nm), 12.5 mg of catalyst, [Ru(bpy)3]Cl2 (0.05 mmol), Na2S2O8 (0.375 mmol), sodium borate buffer solution (10 mmol L-1), pH 9.0 | TOF of 0.012 s-1 per cobalt atom, O2 yield of 88% | [ | |
| Co-Fe LDHs | 300 W xenon lamp (400 nm < λ < 700 nm), LDH (50 mg) and AgNO3 (1 mmol) | 45 mmol O2 from water over 3 h | [ | |
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. | |
| Co/NGC@ZnIn2S4 | 300 W xenon lamp (λ > 400 nm), 4 mg of the photocatalyst, 1 mL of TEOA + 5 mL of H2O | H2 evolution rate of 11270 µmol h-1 g-1 | [ | |
| Co@NC/CdS | A 420 nm LED lamp (100 mW cm-2), 2.0 mg of the catalyst, Na2S (0.35 mol L-1)/Na2S2O3(0.25 mol L-1) | H2 evolution rate of 21.8 mmol g-1 h-1, AQE of 41.8% at 420 nm | [ | |
| Co-N-C(5.9wt%)/g-C3N4 | A LED light source (12 W, λ = 420 ± 10 nm), 2 mg of the samples in an aqueous solution with sacrifficial electron donors (5 mL, 10 vol%) | H2 evolution rate of 1180 μmol g-1 h-1 | [ | |
| Co1/PCN | 300 W Xe lamp, 50 mg of samples in an aqueous solution with TEOA (100 mL, 20 vol%) | H2 evolution rate of 10.8 μmol h-1 | [ | |
| Co9S8/CdS Hollow Cubes | 300 W Xenon lamp with an AM 1.5 filter, 20 mg catalyst in 100 mL of aqueous solution with Na2S and Na2SO3 | H2 evolution rate of 1061 µmol g-1 h-1 | [ | |
| Co9S8@ZnIn2S4 Cages | 300 W xenon lamp (λ > 400 nm), 4 mg of the catalyst, 1 mL of TEOA + 5 mL of H2O (80 mL in capacity) without the aid of any cocatalysts | H2 evolution rate of 6250 μmol h-1 g-1 | [ | |
| Co9S8/ZnIn2S4 tubular | 300 W Xenon commercial lamp, 10 mg of catalysts in aqueous solution with 10 mL TEOA and 90 mL H2O without the aid of any cocatalysts | H2 evolution rate of 9039 μmol h-1 g-1 | [ | |
| Co2P/CdS | White LEDs (30 × 3 W, λ ≥ 420 nm, 0.33 mg CdS NRs, 0.15 mg and DL-mandelic acid (0.5 mol L-1), pH 6.0 with 1 mol L-1 NaOH | H2 production rate of 19373 μmol g-1 h-1 | [ | |
| CoP3/Mn0.2Cd0.8S | 300W Xe lamp (λ > 400 nm), 50 mg of the samples in 100 mL of water containing 0.5 mmol L-1 Na2S and Na2SO3 | H2 evolution rate of 29.53 mmol g-1 h-1, AQE of 29.2% at 420 nm | [ | |
| CdS-Co-CoOx@C-450 | 300 W xenon lamp (λ > 420 nm), 100 mg of sample in 260 mL of 0.25 mol L-1/0.35 mol L-1 Na2S/Na2SO3 solution | H2 production rate of 1.997 mmol h-1, AQE of 43.7 % at 420 nm | [ | |
| NiCo-LDH/P-CdS | 300 W xenon lamp (λ > 400 nm), 50 mg of sample in 100 mL of 10 mL lactic acid and 90 mL H2O | H2 generation rate of 8.665 mmol·g-1 h-1, AQY of 14.0% at 420 nm | [ | |
| CdSe QDs/Co2C | λ = 450 nm, 87 μL Co2C solution were added to 5 mL CdSe QDs water solution, 400 μL TEA | H2 evolution rate of ∼18000 μmol g-1 h-1, AQY of 2.7% at 450 nm | [ | |
| Co3C/CdS | 300 W xenon lamp (λ > 420 nm), 2 mg of the photocatalyst, 20 mL H2O containing 1.05 mol L-1 Na2SO3 and 0.75 mol L-1 Na2S | H2 production rate of 315 μmol h-1, AQY of 19% at 420 nm | [ | |
| Co3N/CdS | 300 W Xenon lamp (λ > 420 nm), 1.0 mg of the sample in 20 mL of aqueous solution containing 0.75 mol L-1 Na2S and 1.05 mol L-1 Na2SO3 as sacrificial reagents | H2 production rate of 137.33 μmol g-1 h-1, AQY of 14.9% at 450 nm | [ | |
| Co3N/Zn0.5Cd0.5S | 300 W xenon lamp (λ > 420 nm), 1.0 mg of the sample in 200 mL of aqueous solution containing Na2S and Na2SO3 | H2 production rate of 218.8 mmol g-1 h-1, AQY of 30.2% at 420 nm | [ | |
| CoN/Mn0.2Cd0.8S | 5 W Xenon lamp, 10 mg of photocatalyst in 30 mL sacrificial reagents containing Na2S (0.25 mol L-1) and Na2SO3 (0.35 mol L-1) | H2 production rate of 14.6 mmol g-1 h-1 | [ | |
| Co1-phosphide/PCN | 300 W Xe lamp, 20 mg of photocatalysts in 100 mL pure water without any sacrificial agents or noble metal after sonication | H2 evolution rate of 410.3 μmol h-1 g-1, O2 evolution rate of 204.6 μmol h-1 g-1, QE of 2.2% at 500 nm | [ | |
| CoO nanoparticles | laser wavelength at 532 nm, 12 mg of photocatalysts in pure water without any co-catalysts or sacrificial reagents | STH efficiency of 5% for overall water splitting | [ | |
| CDots/CoO | white LED lamp (λ > 400 nm), 50 mg of photocatalyst in 20 mL of ultrapure water | overall water splitting into H2 (1.67 μmol h-1 and O2 0.91 μmol h-1) | [ | |
| 2D amorphous CoO | Xe lamp (HXF300) with an AM 1.5 filter, 20 mg photocatalys in 100 mL pure water without any scavengers or cocatalyst | overall water splitting into H2 (113.04 μmol h-1) and O2 (53.76 μmol h-1) | [ | |
| blende CoO atomic layers | 300 W Xe lamp with a standard AM 1.5 filter and UV cut-off filter, 50 mg samples in 200 mL deionized water | overall water splitting with H2 and O2 evolution rates of 4.43 and 2.63 μmol g-1 h-1 | [ | |
| L-NiCo | 300 W Xenon lamp with an AM 1.5 filter, 50 mg photocatalysts in 70 mL 1 mol L-1 KOH without any sacrificial agents or noble metal | overall water splitting into H2 and O2 evolution rates of 1.7 and 0.84 μmol h-1, AQE of 1.38 % at 380 nm | [ | |
Table 2 Photocatalytic water splitting of recently published cobalt based photocatalysts.
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. | |
|---|---|---|---|---|
| Co-NCNT | A blue LED light (λ = 460 nm), 5 mg of catalysts in 15 mL of borate buffer solution (80 mmol L-1, pH 8.5), Ru[(bpy)3](ClO4)2 (1 mmol L-1) as photosensitizer and Na2S2O8 (5.0 mmol L-1) as electron acceptor | O2 yield of 51% | [ | |
| A blue LED light (λ = 460 nm), Eosin-Y as photosensitizer, 3.3 mg of catalysts in 10 mL TEOA (10 vol%) | H2 evolution rate of 14.7 mmol g-1 h-1 and oxygen yield of 51% | |||
| CoSAS@CD | 50 mg of photocatalyst in 100 mL of deionized water containing, 0.614 mmol La2O3 and 1 mmol NaIO3 (or AgNO3) | O2 evolution rate of 168 μmol g-1 h-1 | [ | |
| SBA-15/Co3O4 (4 %) | An Ar ion laser at 476 nm (240 mW), 200 mg of catalyst (8.4 mg Co3O4 in 40 mL of aqueous buffer (0.022‒0.028 mol L-1 Na2SiF6-NaHCO3, pH 5.8), 390 mg Na2SO4, 130 mg Na2S2O8 and 45 mg [Ru(bpy)3]Cl2·6H2O | TOF = 1.000 s-1 and QE of 18% for O2 evolution | [ | |
| 3.0 wt% CoAl2O4/g-C3N4 | 300 W xenon lamp with cutoff filter (L42), 50 mg of catalyst in an aqueous solution with 200 mg La2O3 and 10 mmol L-1 AgNO3 | O2 evolution rate of 2.7 ± 0.04 μmol h-1 | [ | |
| Co3O4 nanocrystals/CNF | 300 W xenon lamp (λ > 420 nm, 120 mW cm-2), 20 mg of catalyst in an aqueous solution with AgNO3 (0.01 mol L-1, 80 mL) and La2O3 (0.2 g) | O2 evolution rate of 24.9 μmol h-1 | [ | |
| CDs@CoOx-300 | LED lamp (λ = 460 nm, 33.8 mW cm-2), 2 mg of catalyst in 10 mL of borate buffer solution (80 mmol L-1, pH 9.0), 1 mmol L-1 [Ru(bpy)3](ClO4)2 as and 5 mmol L-1 Na2S2O8 | O2 yield of 40.4%, AQE of 58.6% at 460 nm | [ | |
| Co3O4 (112) | LED lamp (λ > 420, 16 mW), 5 mg of catalyst in 10 mL of borate buffer solution (80 mmol L-1, pH 9.0), 1 mmol L-1 Ru[(bpy)3]Cl2 and 2.5 mmol L-1 Na2S2O8 | O2 yield of 63.5%, AQEBET of 34.4% | [ | |
| CoS | LED lamp (λ = 460 ± 10 nm, 30 mW cm-2), 3 mg of catalyst in 10 mL of borate buffer solution (80 mmol L-1, pH 9.0), 1 mmol L-1 Ru[(bpy)3]Cl2 and 5 mmol L-1 Na2S2O8 | O2 yield of 63.5%, QE of 21% | [ | |
| 3W LED lamp (λ ≥ 420 nm), Eosin-Y as photosensitizer, 5 mg of catalysts in 10 mL 5 wt% Pt and 5% (v/v) TEOA/H2O (pH 7.0) | H2 evolution rate of 1196 μmol h-1 g-1 | |||
| R-CoPx/rGO | A blue LED light source (λ = 460 ± 10 nm, 30 mW cm-2), 2 mg of catalyst in a 10 mL solution, 1.0 mmol L-1 [Ru(bpy)3]Cl2 and Na2S2O8 (5.0 mmol L-1) in borate buffer solution (pH 9.0) | O2 yields of 34% | [ | |
| CoP/NC | LED light (λ = 460 nm), 4.5 mg of catalyst in 1.0 mmol L-1 [Ru(bpy)3]Cl2, 5.0 mmol L-1 Na2S2O8 borate buffer (80 mmol L-1, pH 8.0) | O2 evolution rate of 901.5 μmol h-1 g-1, O2 yield of 36.1%, QY of 61.5% | [ | |
| NiCoP@NiCo-Pi/g-C3N4 | 300 W Xe lamp, 50 mg of catalysts in 80 mL of 0.02 mol L-1 AgNO3 aqueous solution with 0.2 g of La2O3 | O2 evolution rate of 312 μmol h-1 g-1 | [ | |
| Co3.9/MIL-101 | 300 W xenon lamp (λ > 420 nm), 12.5 mg of catalyst, [Ru(bpy)3]Cl2 (0.05 mmol), Na2S2O8 (0.375 mmol), sodium borate buffer solution (10 mmol L-1), pH 9.0 | TOF of 0.012 s-1 per cobalt atom, O2 yield of 88% | [ | |
| Co-Fe LDHs | 300 W xenon lamp (400 nm < λ < 700 nm), LDH (50 mg) and AgNO3 (1 mmol) | 45 mmol O2 from water over 3 h | [ | |
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. | |
| Co/NGC@ZnIn2S4 | 300 W xenon lamp (λ > 400 nm), 4 mg of the photocatalyst, 1 mL of TEOA + 5 mL of H2O | H2 evolution rate of 11270 µmol h-1 g-1 | [ | |
| Co@NC/CdS | A 420 nm LED lamp (100 mW cm-2), 2.0 mg of the catalyst, Na2S (0.35 mol L-1)/Na2S2O3(0.25 mol L-1) | H2 evolution rate of 21.8 mmol g-1 h-1, AQE of 41.8% at 420 nm | [ | |
| Co-N-C(5.9wt%)/g-C3N4 | A LED light source (12 W, λ = 420 ± 10 nm), 2 mg of the samples in an aqueous solution with sacrifficial electron donors (5 mL, 10 vol%) | H2 evolution rate of 1180 μmol g-1 h-1 | [ | |
| Co1/PCN | 300 W Xe lamp, 50 mg of samples in an aqueous solution with TEOA (100 mL, 20 vol%) | H2 evolution rate of 10.8 μmol h-1 | [ | |
| Co9S8/CdS Hollow Cubes | 300 W Xenon lamp with an AM 1.5 filter, 20 mg catalyst in 100 mL of aqueous solution with Na2S and Na2SO3 | H2 evolution rate of 1061 µmol g-1 h-1 | [ | |
| Co9S8@ZnIn2S4 Cages | 300 W xenon lamp (λ > 400 nm), 4 mg of the catalyst, 1 mL of TEOA + 5 mL of H2O (80 mL in capacity) without the aid of any cocatalysts | H2 evolution rate of 6250 μmol h-1 g-1 | [ | |
| Co9S8/ZnIn2S4 tubular | 300 W Xenon commercial lamp, 10 mg of catalysts in aqueous solution with 10 mL TEOA and 90 mL H2O without the aid of any cocatalysts | H2 evolution rate of 9039 μmol h-1 g-1 | [ | |
| Co2P/CdS | White LEDs (30 × 3 W, λ ≥ 420 nm, 0.33 mg CdS NRs, 0.15 mg and DL-mandelic acid (0.5 mol L-1), pH 6.0 with 1 mol L-1 NaOH | H2 production rate of 19373 μmol g-1 h-1 | [ | |
| CoP3/Mn0.2Cd0.8S | 300W Xe lamp (λ > 400 nm), 50 mg of the samples in 100 mL of water containing 0.5 mmol L-1 Na2S and Na2SO3 | H2 evolution rate of 29.53 mmol g-1 h-1, AQE of 29.2% at 420 nm | [ | |
| CdS-Co-CoOx@C-450 | 300 W xenon lamp (λ > 420 nm), 100 mg of sample in 260 mL of 0.25 mol L-1/0.35 mol L-1 Na2S/Na2SO3 solution | H2 production rate of 1.997 mmol h-1, AQE of 43.7 % at 420 nm | [ | |
| NiCo-LDH/P-CdS | 300 W xenon lamp (λ > 400 nm), 50 mg of sample in 100 mL of 10 mL lactic acid and 90 mL H2O | H2 generation rate of 8.665 mmol·g-1 h-1, AQY of 14.0% at 420 nm | [ | |
| CdSe QDs/Co2C | λ = 450 nm, 87 μL Co2C solution were added to 5 mL CdSe QDs water solution, 400 μL TEA | H2 evolution rate of ∼18000 μmol g-1 h-1, AQY of 2.7% at 450 nm | [ | |
| Co3C/CdS | 300 W xenon lamp (λ > 420 nm), 2 mg of the photocatalyst, 20 mL H2O containing 1.05 mol L-1 Na2SO3 and 0.75 mol L-1 Na2S | H2 production rate of 315 μmol h-1, AQY of 19% at 420 nm | [ | |
| Co3N/CdS | 300 W Xenon lamp (λ > 420 nm), 1.0 mg of the sample in 20 mL of aqueous solution containing 0.75 mol L-1 Na2S and 1.05 mol L-1 Na2SO3 as sacrificial reagents | H2 production rate of 137.33 μmol g-1 h-1, AQY of 14.9% at 450 nm | [ | |
| Co3N/Zn0.5Cd0.5S | 300 W xenon lamp (λ > 420 nm), 1.0 mg of the sample in 200 mL of aqueous solution containing Na2S and Na2SO3 | H2 production rate of 218.8 mmol g-1 h-1, AQY of 30.2% at 420 nm | [ | |
| CoN/Mn0.2Cd0.8S | 5 W Xenon lamp, 10 mg of photocatalyst in 30 mL sacrificial reagents containing Na2S (0.25 mol L-1) and Na2SO3 (0.35 mol L-1) | H2 production rate of 14.6 mmol g-1 h-1 | [ | |
| Co1-phosphide/PCN | 300 W Xe lamp, 20 mg of photocatalysts in 100 mL pure water without any sacrificial agents or noble metal after sonication | H2 evolution rate of 410.3 μmol h-1 g-1, O2 evolution rate of 204.6 μmol h-1 g-1, QE of 2.2% at 500 nm | [ | |
| CoO nanoparticles | laser wavelength at 532 nm, 12 mg of photocatalysts in pure water without any co-catalysts or sacrificial reagents | STH efficiency of 5% for overall water splitting | [ | |
| CDots/CoO | white LED lamp (λ > 400 nm), 50 mg of photocatalyst in 20 mL of ultrapure water | overall water splitting into H2 (1.67 μmol h-1 and O2 0.91 μmol h-1) | [ | |
| 2D amorphous CoO | Xe lamp (HXF300) with an AM 1.5 filter, 20 mg photocatalys in 100 mL pure water without any scavengers or cocatalyst | overall water splitting into H2 (113.04 μmol h-1) and O2 (53.76 μmol h-1) | [ | |
| blende CoO atomic layers | 300 W Xe lamp with a standard AM 1.5 filter and UV cut-off filter, 50 mg samples in 200 mL deionized water | overall water splitting with H2 and O2 evolution rates of 4.43 and 2.63 μmol g-1 h-1 | [ | |
| L-NiCo | 300 W Xenon lamp with an AM 1.5 filter, 50 mg photocatalysts in 70 mL 1 mol L-1 KOH without any sacrificial agents or noble metal | overall water splitting into H2 and O2 evolution rates of 1.7 and 0.84 μmol h-1, AQE of 1.38 % at 380 nm | [ | |
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. |
|---|---|---|---|
| W18O49@Co | 300 W xenon lamp (λ > 400 nm), 1 mg of catalyst, [Ru(bpy)3]Cl2·6H2O, 1.0 mL of TEOA + 2.0 mL of H2O + 3.0 mL of MeCN (80 mL in capacity) | CO generation rate of 21.18 mmol g-1 h-1 | [ |
| MOF-525-Co | 300 W xenon lamp (UV-cut filter), 2 mg of sample in 2 mL of solution (MeCN/TEOA = 4:1), 80 kPa of pure CO2 gas. | CO evolution rate of 200.6 μmol g-1 h-1, CH4 evolution rate of 36.76 μmol g-1 h-1 | [ |
| COF-367-CoIII | 300 W Xe lamp (λ > 380 nm), 10 mg of photocatalyst in 20 mL of CH3CN and 2 mL of TEA | 93.0 ± 4.63 μmol g-1 h-1 for HCOOH, 5.5 ± 0.88 and 10.1 ± 1.12 μmol g-1 h-1 for CO and CH4 | [ |
| Co2+@C3N4 | A halogen lamp (λ > 420 nm, 200 mW/cm2), 1 mg of catalyst in a 4.0 mL acetonitrile solution containing TEOA (acetonitrile : TEOA= 4:1 v/v) | TONCO > 200, QYCO = 0.4% | [ |
| 25-Co-C3N4 | 300 W Xe lamp (λ > 420 nm), 2.0 mg of photocatalyst in 4.0 mL CH3CN/H2O (v/v =3:1) and 1.0 mL TEOA, 2,2’-bipyridine (15.0 mg) | CO evolution rate of 394.4 μmol·g-1·h-1 | [ |
| Co1-G nanosheets | 300 W Xe lamp (λ > 420 nm, 264.25 mW/cm2), 15 mg [Ru(bpy)3]Cl2·6H2O, 3.0 mg of photocatalyst in 30 mL CH3CN/TEOA/H2O = 3:1:1 (v/v) | TONCO = 678, TOFCO = 3.77 min-1 | [ |
| Co-rGO/C3N4 | 300 W Xe lamp (λ > 420 nm, 260 mW cm-2), 20 mg of catalyst in 18 mL CH3CN, 6 mL TEOA and 6 mL H2O | the ratio of CO/H2 in produced syngas from 1:30 to 2:3, TONCO = 66 | [ |
| CoO-Mo8 UNWs | 300 W Xe lamp (λ > 400 nm, 92.1 mW·cm-2), 7 mg [Ru(bpy)3]Cl2·6H2O, 1 mg of catalyst in 4 mL CH3CN, 1 mL TEOA and 1 mL H2O | syngas: H2 and CO evolution rates of 11555 and 4165 μmol g-1 h-1 | [ |
| CDs@CoOx-300 | LED lamp (λ = 460 nm, 100 mW cm-2), 7.5 mg [Ru(bpy)3]Cl2·6H2O, 0.5 mg of catalyst in 3 mL CH3CN, 1 mL TEOA and 2 mL H2O | CO generation rate of 8.1 μmol h-1, CO selectivity of 89.3% | [ |
| Co3O4 HPs {112} | 300 W Xe lamp (λ > 420 nm, 293.61 mW cm-2), 10 mg [Ru(bpy)3]Cl2·6H2O, 10 mg of catalyst in 30 mL CH3CN/TEOA/H2O = 3:1:1 (v/v) | CO generation rate of 2003 μmol g-1 h-1, CO selectivity of 77.1% | [ |
| NC@NiCo2O4 nanoboxes | 300 W Xe lamp (λ > 420 nm), 10 μmol [Ru(bpy)3]Cl2·6H2O, 1 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO generation rate of 2.62×104 μmol g-1 h-1, AQY of 1.07% at 420 nm | [ |
| Co-Fe PBA CCs | 300 W Xe lamp (λ > 400 nm), 10 μmol [Ru(bpy)3]Cl2·6H2O, 1 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO generation rate of 14200 μmol g-1 h-1 | [ |
| Ni-CoS2 nanosheets | 300 W Xe lamp with a AM 1.5 filter and 800 nm cutoff filter to provide IR light, 5 mg of catalyst thin film in floated on 50 mL of water in a quartz boat | CH4 generation rate of 101.8 μmol g-1 h-1 | [ |
| FeCoS2-CoS2 double shelled nanotubes | 300 W Xe lamp (λ > 400 nm), 10 mg [Ru(bpy)3]Cl2·6H2O, 0.5 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO generating rate of 28.1 μmol h-1 | [ |
| Co@Co2P@NPC | 200 W white LED lamp, 5 mg [Ru(bpy)3]Cl2·6H2O and 1 mg of catalyst in 6.5 mL CH3CN /TEOA/H2O (v/v/v, 4:1.5:1) | CO generation rate of 35000 μmol g-1 h-1, CO selectivity of 79.1% | [ |
| NiCoOPNPs@MHCFs | 300 W Xe lamp (λ > 400 nm), 10 mg [Ru(bpy)3]Cl2·6H2O, 0.1 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO evolution rate of 16.6 μmol h-1 | [ |
| CoSn(OH)6 | 300 W Xe lamp (λ > 420 nm), 3.6 μmol of catalyst, 10 μmol [Ru(bpy)3]Cl2·6H2O in 6 mL TEOA/water/ CH3CN = 1:2:3 (v/v) | CO generation rate of 18.7 μmol h-1 | [ |
| CsPbBr3@ZIF-67 | 100 W Xe lamp with a AM 1.5G filter (150 mW cm-2), 4.5 mg of catalyst and 10 μL water to form a thin film within a 40 mL s ealed Pyrex bottle filled with CO2 and H2O vapor | 100% selectivity for CO2 reduction, CH4 and CO generation rate of 29.630 μmol g-1 h-1 | [ |
| MAF-X27-OH | λLED = 420 nm, 0.03 mmol of catalysts, 2 μmol [Ru(bpy)3]Cl2·6H2O, 0.3 mol L-1 TEOA and CH3CN/H2O (v/v = 4:1, 5 mL) | TOFCO = 28×10-3 s-1, CO selectivity of 97.2% under low CO2 concentration | [ |
| ZrPP-1-Co | 300 W Xe lamp (λ >420 nm), 20 mg photocatalyst, 5 mL mixed solvent (CH3CN and TEOA, v/v, 4/1) | CO (≈14 mmol g-1 h-1, selectivity of CH4 (>96.4%) | [ |
| Co3O4-NS | 5W LED lamp (400‒1000 nm ), 0.5 mg catalysts, [Ru(bpy)3]Cl2·6H2O (7.5 mg), CH3CN/H2O/TEOA (3 mL/2 mL/1 mL) | CO conversion rate of 4.52 μmol h-1, selectivity of 70.1% | [ |
| COF-367 NSs | 300 W Xenon lamp (λ ≥ 420 nm), 5 mg of catalysts, 19 mg of [Ru(bpy)3]Cl2·6H2O and ascorbic acid (2 mmol) in 0.1 mol L-1 KHCO3 aqueous solution (20 mL) | CO production rate as high as of 10162 μmol g-1 h-1, selectivity of ca. 78% | [ |
| DQTP COF-Co | 300W xenon lamp (λ ≥ 420 nm), 20 mg of the sample, 22.5 mg of Ru(bpy)3Cl2·H2O, a solvent mixture of 50 mL (MeCN/TEOA = 4:1, v/v) | CO production rate of 1.02 × 103 μmol h-1 g-1 | [ |
| Co-Co LDH/TNS | 5 W LED lamp (λ = 400‒1000 nm), 0.5 mg catalysts, 7.5 mg of [Ru(bpy)3]Cl2·6H2O, MeCN/H2O/TEOA (3mL/2 mL/1 mL) | CO evolving rate of 1.25×104 μmol h-1 g-1, AQE of 0.92% | [ |
| CoMgAl-LDH | 300W xenon lamp (λ ≥ 420 nm), [Ru(bpy)3]Cl2·6H2O (0.005 mmol), catalysts (1 mg) and solvent [10 mL in total, CH3CN/TEOA/H2O = 3:1:1 (volume ratio)] | CO evolution rate of 0.35 μmol·h-1 at 650 nm, QY of 0.86% | [ |
| Co2N/BiOBr | 300W xenon lamp, 30 mg sample in 50 mL H2O without other sacrificial reagent or extra photosensitizer. 80 KPa high-purity CO2 in the reactor | CO generation rate of 67.8 µmol g-1 h-1 | [ |
Table 3 Photocatalytic CO2 reduction of recently published cobalt based photocatalysts.
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. |
|---|---|---|---|
| W18O49@Co | 300 W xenon lamp (λ > 400 nm), 1 mg of catalyst, [Ru(bpy)3]Cl2·6H2O, 1.0 mL of TEOA + 2.0 mL of H2O + 3.0 mL of MeCN (80 mL in capacity) | CO generation rate of 21.18 mmol g-1 h-1 | [ |
| MOF-525-Co | 300 W xenon lamp (UV-cut filter), 2 mg of sample in 2 mL of solution (MeCN/TEOA = 4:1), 80 kPa of pure CO2 gas. | CO evolution rate of 200.6 μmol g-1 h-1, CH4 evolution rate of 36.76 μmol g-1 h-1 | [ |
| COF-367-CoIII | 300 W Xe lamp (λ > 380 nm), 10 mg of photocatalyst in 20 mL of CH3CN and 2 mL of TEA | 93.0 ± 4.63 μmol g-1 h-1 for HCOOH, 5.5 ± 0.88 and 10.1 ± 1.12 μmol g-1 h-1 for CO and CH4 | [ |
| Co2+@C3N4 | A halogen lamp (λ > 420 nm, 200 mW/cm2), 1 mg of catalyst in a 4.0 mL acetonitrile solution containing TEOA (acetonitrile : TEOA= 4:1 v/v) | TONCO > 200, QYCO = 0.4% | [ |
| 25-Co-C3N4 | 300 W Xe lamp (λ > 420 nm), 2.0 mg of photocatalyst in 4.0 mL CH3CN/H2O (v/v =3:1) and 1.0 mL TEOA, 2,2’-bipyridine (15.0 mg) | CO evolution rate of 394.4 μmol·g-1·h-1 | [ |
| Co1-G nanosheets | 300 W Xe lamp (λ > 420 nm, 264.25 mW/cm2), 15 mg [Ru(bpy)3]Cl2·6H2O, 3.0 mg of photocatalyst in 30 mL CH3CN/TEOA/H2O = 3:1:1 (v/v) | TONCO = 678, TOFCO = 3.77 min-1 | [ |
| Co-rGO/C3N4 | 300 W Xe lamp (λ > 420 nm, 260 mW cm-2), 20 mg of catalyst in 18 mL CH3CN, 6 mL TEOA and 6 mL H2O | the ratio of CO/H2 in produced syngas from 1:30 to 2:3, TONCO = 66 | [ |
| CoO-Mo8 UNWs | 300 W Xe lamp (λ > 400 nm, 92.1 mW·cm-2), 7 mg [Ru(bpy)3]Cl2·6H2O, 1 mg of catalyst in 4 mL CH3CN, 1 mL TEOA and 1 mL H2O | syngas: H2 and CO evolution rates of 11555 and 4165 μmol g-1 h-1 | [ |
| CDs@CoOx-300 | LED lamp (λ = 460 nm, 100 mW cm-2), 7.5 mg [Ru(bpy)3]Cl2·6H2O, 0.5 mg of catalyst in 3 mL CH3CN, 1 mL TEOA and 2 mL H2O | CO generation rate of 8.1 μmol h-1, CO selectivity of 89.3% | [ |
| Co3O4 HPs {112} | 300 W Xe lamp (λ > 420 nm, 293.61 mW cm-2), 10 mg [Ru(bpy)3]Cl2·6H2O, 10 mg of catalyst in 30 mL CH3CN/TEOA/H2O = 3:1:1 (v/v) | CO generation rate of 2003 μmol g-1 h-1, CO selectivity of 77.1% | [ |
| NC@NiCo2O4 nanoboxes | 300 W Xe lamp (λ > 420 nm), 10 μmol [Ru(bpy)3]Cl2·6H2O, 1 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO generation rate of 2.62×104 μmol g-1 h-1, AQY of 1.07% at 420 nm | [ |
| Co-Fe PBA CCs | 300 W Xe lamp (λ > 400 nm), 10 μmol [Ru(bpy)3]Cl2·6H2O, 1 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO generation rate of 14200 μmol g-1 h-1 | [ |
| Ni-CoS2 nanosheets | 300 W Xe lamp with a AM 1.5 filter and 800 nm cutoff filter to provide IR light, 5 mg of catalyst thin film in floated on 50 mL of water in a quartz boat | CH4 generation rate of 101.8 μmol g-1 h-1 | [ |
| FeCoS2-CoS2 double shelled nanotubes | 300 W Xe lamp (λ > 400 nm), 10 mg [Ru(bpy)3]Cl2·6H2O, 0.5 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO generating rate of 28.1 μmol h-1 | [ |
| Co@Co2P@NPC | 200 W white LED lamp, 5 mg [Ru(bpy)3]Cl2·6H2O and 1 mg of catalyst in 6.5 mL CH3CN /TEOA/H2O (v/v/v, 4:1.5:1) | CO generation rate of 35000 μmol g-1 h-1, CO selectivity of 79.1% | [ |
| NiCoOPNPs@MHCFs | 300 W Xe lamp (λ > 400 nm), 10 mg [Ru(bpy)3]Cl2·6H2O, 0.1 mg of catalyst in 6 mL CH3CN/TEOA/H2O = 3:1:2 (v/v) | CO evolution rate of 16.6 μmol h-1 | [ |
| CoSn(OH)6 | 300 W Xe lamp (λ > 420 nm), 3.6 μmol of catalyst, 10 μmol [Ru(bpy)3]Cl2·6H2O in 6 mL TEOA/water/ CH3CN = 1:2:3 (v/v) | CO generation rate of 18.7 μmol h-1 | [ |
| CsPbBr3@ZIF-67 | 100 W Xe lamp with a AM 1.5G filter (150 mW cm-2), 4.5 mg of catalyst and 10 μL water to form a thin film within a 40 mL s ealed Pyrex bottle filled with CO2 and H2O vapor | 100% selectivity for CO2 reduction, CH4 and CO generation rate of 29.630 μmol g-1 h-1 | [ |
| MAF-X27-OH | λLED = 420 nm, 0.03 mmol of catalysts, 2 μmol [Ru(bpy)3]Cl2·6H2O, 0.3 mol L-1 TEOA and CH3CN/H2O (v/v = 4:1, 5 mL) | TOFCO = 28×10-3 s-1, CO selectivity of 97.2% under low CO2 concentration | [ |
| ZrPP-1-Co | 300 W Xe lamp (λ >420 nm), 20 mg photocatalyst, 5 mL mixed solvent (CH3CN and TEOA, v/v, 4/1) | CO (≈14 mmol g-1 h-1, selectivity of CH4 (>96.4%) | [ |
| Co3O4-NS | 5W LED lamp (400‒1000 nm ), 0.5 mg catalysts, [Ru(bpy)3]Cl2·6H2O (7.5 mg), CH3CN/H2O/TEOA (3 mL/2 mL/1 mL) | CO conversion rate of 4.52 μmol h-1, selectivity of 70.1% | [ |
| COF-367 NSs | 300 W Xenon lamp (λ ≥ 420 nm), 5 mg of catalysts, 19 mg of [Ru(bpy)3]Cl2·6H2O and ascorbic acid (2 mmol) in 0.1 mol L-1 KHCO3 aqueous solution (20 mL) | CO production rate as high as of 10162 μmol g-1 h-1, selectivity of ca. 78% | [ |
| DQTP COF-Co | 300W xenon lamp (λ ≥ 420 nm), 20 mg of the sample, 22.5 mg of Ru(bpy)3Cl2·H2O, a solvent mixture of 50 mL (MeCN/TEOA = 4:1, v/v) | CO production rate of 1.02 × 103 μmol h-1 g-1 | [ |
| Co-Co LDH/TNS | 5 W LED lamp (λ = 400‒1000 nm), 0.5 mg catalysts, 7.5 mg of [Ru(bpy)3]Cl2·6H2O, MeCN/H2O/TEOA (3mL/2 mL/1 mL) | CO evolving rate of 1.25×104 μmol h-1 g-1, AQE of 0.92% | [ |
| CoMgAl-LDH | 300W xenon lamp (λ ≥ 420 nm), [Ru(bpy)3]Cl2·6H2O (0.005 mmol), catalysts (1 mg) and solvent [10 mL in total, CH3CN/TEOA/H2O = 3:1:1 (volume ratio)] | CO evolution rate of 0.35 μmol·h-1 at 650 nm, QY of 0.86% | [ |
| Co2N/BiOBr | 300W xenon lamp, 30 mg sample in 50 mL H2O without other sacrificial reagent or extra photosensitizer. 80 KPa high-purity CO2 in the reactor | CO generation rate of 67.8 µmol g-1 h-1 | [ |
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. |
|---|---|---|---|
| MXene/TiO2/Co-0.5% | 300 W Xenon lamp, 30 mg of photocatalyst dispersed in 100 mL of ultrapure water | NH3 evolution rate of 110 μmol g-1 h-1 | [ |
| WC-Co/NGC-2 | 50 mg of catalyst in 100 mL of an aqueous solution containing 1 mmol L-1 Na2SO3 | NH3 evolution rate of 142 μmol g-1 h-1 | [ |
| Co@g-C3N4 | 500 W Xe lamp, 20 mg of photocatalyst in 40 mL of an aqueous solution containing 4 wt% methanol | NH3 evolution rate of 50.2 µmol h-1 | [ |
| ZIF-67@PMo4V8 | 300 W Xenon lamp, 300 mg of photocatalyst, 80 mL of distilled water and 20 mL of ethyl alcohol | NH3 evolution rate of 149.0 μmol L-1 h-1, STA efficiency of 0.032% | [ |
| P2W17Co@V-g-C3N4 | 300 W Xenon lamp, 300 mg of photocatalyst, 80 mL of distilled water and 20 mL of ethyl alcohol | 214.6 μmol L-1 h-1, STA efficiency of 0.046% | [ |
Table 4 Photocatalytic N2 fixation of recently published cobalt based photocatalysts.
| Photocatalyst | Reaction conditions (light resource, amount of photocatalyst and sacrificial agent) | Photocatalytic activity | Ref. |
|---|---|---|---|
| MXene/TiO2/Co-0.5% | 300 W Xenon lamp, 30 mg of photocatalyst dispersed in 100 mL of ultrapure water | NH3 evolution rate of 110 μmol g-1 h-1 | [ |
| WC-Co/NGC-2 | 50 mg of catalyst in 100 mL of an aqueous solution containing 1 mmol L-1 Na2SO3 | NH3 evolution rate of 142 μmol g-1 h-1 | [ |
| Co@g-C3N4 | 500 W Xe lamp, 20 mg of photocatalyst in 40 mL of an aqueous solution containing 4 wt% methanol | NH3 evolution rate of 50.2 µmol h-1 | [ |
| ZIF-67@PMo4V8 | 300 W Xenon lamp, 300 mg of photocatalyst, 80 mL of distilled water and 20 mL of ethyl alcohol | NH3 evolution rate of 149.0 μmol L-1 h-1, STA efficiency of 0.032% | [ |
| P2W17Co@V-g-C3N4 | 300 W Xenon lamp, 300 mg of photocatalyst, 80 mL of distilled water and 20 mL of ethyl alcohol | 214.6 μmol L-1 h-1, STA efficiency of 0.046% | [ |
Fig. 3. (a) Schematic illustration for the synthetic process of hierarchical Co/NGC@ZIS cages; (b) Time yield plots of different samples; (c) H2 yield rates of Co/NGC@ZIS for five cycles. Adapted with permission from Ref. [62]. Copyright 2019, Wiley-VCH. (d) Schematic of CO2 reduction over W18O49@Co hybrid; (e) Gas generation rates of W18O49@Co and W18O49. Adapted with permission from Ref. [63]. Copyright 2021, American Chemical Society.
Fig. 4. Synthetic process (a), photocatalytic NH3 formation rate (b) and a schematic diagram (c) of the photocatalytic N2 fixation over WC-Co/NGC. Adapted with permission from Ref. [67]. Copyright 2019, Royal Society of Chemistry.
Fig. 5. (a) Schematic view of MOF-525-Co network incorporating active sites. (b) Production CO and CH4 evolution over different MOF-525. Adapted with permission from Ref. [79]. Copyright 2016, Wiley-VCH. Schematic of photogenerated charge transfer (c) and photocatalytic H2 evolution rate (d) for Co-N-C/g-C3N4 hybrid. Adapted with permission from Ref. [81]. Copyright 2019, Royal Society of Chemistry.
Fig. 6. (a) Schematic illustration of overall water splitting on the Co1-phosphide/PCN photocatalyst. (b) Representative HAADF-STEM image of Co1-phosphide/PCN (Isolated Co atoms are marked in white circles). (c) Typical time course of H2 and O2 productions over Co1-phosphide/PCN. Adapted with permission from Ref. [89]. Copyright 2017, Wiley-VCH.
Fig. 7. (a) Yield of NH3 for different samples. (b) Cycling measurements for photocatalytic N2 fixation over Co@g-C3N4-1 nanosheets. (c) N2 adsorption geometry on bare g-C3N4 and (d) Co@g-C3N4-1. Adapted with permission from Ref. [91]. Copyright 2020, Elsevier.
Fig. 8. (a) The main active species Co2+ in Co3O4 at tetrahedral sites. Adapted with permission from Ref. [113]. Copyright 2016, American Chemical Society. (b) Schematic of photocatalytic water oxidation over COCNF. Adapted with permission from Ref. [118]. Copyright 2020, American Chemical Society. (c) Schematic of photocatalytic overall water splitting over a sub-micrometer CoO octahedron photocatalyst. Typical time course (d) and cycle stability (e) of H2 and O2 production. (c-e) Adapted with permission from Ref. [121]. Copyright 2017, Royal Society of Chemistry. (f) Crystal structure of blende and rocksalt CoO. (g) O2 and H2 formation rates of CoO. (f,g) Adapted with permission from Ref. [123]. Copyright 2019, Wiley-VCH.
Fig. 9. (a) Synthetic procedures towards CoO UNWs and CoO-Mo8 UNWs. (b) Photochemical syngas production performance of CoO different materials. Adapted with permission from Ref. [134]. Copyright 2020, Wiley-VCH. (c) Time courses of O2 evolution measured by the Clark electrode. (d) Different facet effect of spinel Co3O4 in photocatalytic water oxidation. Adapted with permission from Ref. [141]. Copyright 2018, Elsevier.
Fig. 10. Average yields of CO and H2 (a) and Recycling tests (b). (c) Proposed mechanism for the photoreduction of CO2 to CO. (d) DFT calculation of adsorption and reduction of CO2 on Co3O4 surfaces. Adapted with permission from Ref. [142]. Copyright 2016, Wiley-VCH.
Fig. 11. (a) Polyhedral models of cubic Li2Co2O4 with a Co4O4 core. Adapted with permission from Ref. [153]. Copyright 2012, Wiley-VCH. (b) Schematic illustration of the synthetic process of hierarchical NC@NiCo2O4 nanoboxes. (c) Production of CO and H2 from the photocatalytic CO2 reduction (The percentage represents the selectivity of CO). (d) Generation of CO and H2 in stability tests. (b-d) Adapted with permission from Ref. [157]. Copyright 2018, Royal Society of Chemistry. Synthesis (e), TEM image (f) and cycling tests (g) of L-NiCo. (e-g) Adapted with permission from Ref. [162]. Copyright 2020, Wiley-VCH.
Fig. 12. (a) The preparative process for CdS/Co9S8 and its corresponding TEM images. (b) Illustration of multiple reflections within the CdS/Co9S8 hollow structure and the photoexcited charge-carrier distribution. Adapted with permission from Ref. [176]. Copyright 2017, Wiley-VCH.
Fig. 13. (a) Schematic of photocatalytic H2 generation over hierarchical Co9S8@ZnIn2S4. Adapted with permission from Ref. [177]. Copyright 2018, American Chemical Society. (b) Illustration of the fabrication process of hierarchical Co9S8/ZnIn2S4 tubular photocatalyst. Adapted with permission from Ref. [178]. Copyright 2020, Wiley-VCH.
Fig. 14. (a) TEM image of Ni-CoS2 nanosheets. (b) Generation rates of CH4 and CO under infrared light irradiation and 45?°C in the dark, respectively. CH4-TPD measurements (c) and In situ FTIR (d) for Ni-CoS2 nanosheets. Free energy diagrams of IR-light-driven CO2 reduction to CO and CH4 for Ni-CoS2 nanosheets (e) and CoS2 nanosheets (f). Adapted with permission from Ref. [182]. Copyright 2021, Wiley-VCH.
Fig. 15. (a) Schematic of photocatalytic H2 generation over Co2P/CdS. Adapted with permission from Ref. [200]. Copyright 2015, Royal Society of Chemistry. (b) Schematic diagram of the charge transfer and separation in Mn0.2Cd0.8S/CoP3 system and proposed mechanism for enhanced photocatalytic H2 evolution. Adapted with permission from Ref. [201]. Copyright 2018, Elsevier. (c) Schematic illustration for boosted photocatalytic H2 evolution over Co-Co2P@NPC. Adapted with permission from Ref. [202]. Copyright 2018, Wiley-VCH. (d) CO and H2 generation catalyzed by NiCoOP-NPs@MHCFs as a function of reaction time. (e) Schematic of photocatalytic CO2 reduction over NiCoOP-NPs@MHCFs. Adapted with permission from Ref. [203]. Copyright 2019, Wiley-VCH. (f) Schematic illustration for boosted photocatalytic water oxidation over R-CoPx/rGO. Adapted with permission from Ref. [204]. Copyright 2018, Royal Society of Chemistry. (g) Schematic illustration of the photo-induced charge transfer process, and photocatalytic process over NiCoP@NiCo-Pi/g-C3N4 for water splitting. Adapted with permission from Ref. [206]. Copyright 2017, Royal Society of Chemistry.
Fig. 16. (a) Schematic of photocatalytic water oxidation over Co3.9/MIL-101. (b) Photocatalytic O2 evolution over various samples under visible light irradiation. Adapted with permission from Ref. [213]. Copyright 2015, Royal Society of Chemistry.
Fig. 17. (a) Schematic illustration on charge carriers transfer and separation over CdS-Co-CoOx@C. (b) Comparison of the cocatalytic performance of different materials. Adapted with permission from Ref. [214]. Copyright 2021, Elsevier.
Fig. 18. (a) Schematic illustration of the fabrication process. (b) CO2 reduction over CsPbBr3/ZIFs. Adapted with permission from Ref. [218]. Copyright 2018, American Chemical Society.
Fig. 19. (a) High activity and selectivity over MAF-X27-OH under low CO2 pressure. (b) Comparison of the TOF values for the photocatalytic CO2 reduction under 1.0 atm (blue) and 0.1 atm (orange). Adapted with permission from Ref. [219]. Copyright 2018, American Chemical Society.
Fig. 20. (a) Schematic diagram of the photocatalytic N2 fixation of ZIF-67@PMo12?xVx. (b) NH3 yield of ZIF-67@PMo12?xVx. Adapted with permission from Ref. [222]. Copyright 2020, Wiley-VCH.
Fig. 21. (a) Schematic illustration of synthesis of the COF-367 NSs. (b) CO2 reduction performance under various reaction conditions. Stability tests (c) and proposed mechanism (d) of COF-367-Co NSs for the photocatalytic CO2 reduction. Adapted with permission from Ref. [230]. Copyright 2019, American Chemical Society.
Fig. 22. Synthesis and metallization of DQTP COF and DATP COF. Adapted with permission from Ref. [233]. Copyright 2019, Elsevier.
Fig. 23. Schematic illustration of a Co-Fe LDH structure (a) and its catalysis of water oxidation (b). (c) UV-Vis reflectance spectra of a CoFe LDH suspension. Adapted with permission from Ref. [242]. Copyright 2014, Royal Society of Chemistry. (d) Schematic illustration of charge transfer and H2 generation mechanism of NiCo-LDH/P-CdS. Adapted with permission from Ref. [243]. Copyright 2019, Elsevier. (e) Schematic diagram for Co-Co LDHs for CO2 reduction. Adapted with permission from Ref. [245]. Copyright 2020, Elsevier. Schematic diagram (f) and photocatalytic activity (g) of MgAl-LDH and CoMgAl-LDH for CO2 reduction. Adapted with permission from Ref. [249]. Copyright 2021, Elsevier.
Fig. 24. (a) TEM image of Co2C nanoflakes. (b) The calculated free-energy diagram of HER on the surfaces of the (101), (020), and (111) facet of the Co2C model, respectively. (c) Control experiments of H2 evolution. (d) H2 production with different QDs. Adapted with permission from Ref. [253]. Copyright 2018, American Chemical Society. (e) Schematic illustration of the Co3C/CdS based photocatalytic system. (f) Long-term H2 production. Adapted with permission from Ref. [254]. Copyright 2021, Royal Society of Chemistry. (g) Schematic illustration for H2 production over the Co3N/CdS. Adapted with permission from Ref. [256]. Copyright 2017, Royal Society of Chemistry. (h) H2 evolution mechanism diagram for CoN/Mn0.2Cd0.8S photocatalyst. Adapted with permission from Ref. [258]. Copyright 2021, Elsevier.
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