Chem. J. Chinese Universities ›› 2024, Vol. 45 ›› Issue (3): 20230527.doi: 10.7503/cjcu20230527
• Review • Previous Articles
ZHAO Xiaoguang1, WANG Yunlong1, YIN Haibo2, QU Yakun1, SU Haiwei2, FANG Wei1()
Received:
2023-12-30
Online:
2024-03-10
Published:
2024-02-21
Contact:
FANG Wei
E-mail:fangwei.ripp@sinopec.com
Supported by:
CLC Number:
TrendMD:
ZHAO Xiaoguang, WANG Yunlong, YIN Haibo, QU Yakun, SU Haiwei, FANG Wei. Research Progress of Electrocatalytic Ammonia Synthesis from Different Nitrogen Sources[J]. Chem. J. Chinese Universities, 2024, 45(3): 20230527.
Species | Electrocatalyst | Electrolyte | Potential/V (vs. RHE) | NH3 yield rate | NH3 Faradic efficiency(%) | Ref. |
---|---|---|---|---|---|---|
Noble metal catalyst | Ru/C | 2 mol/L KOH | -0.24 | 0.21 μg·h‒1·cm‒2 | 0.28 | [ |
Ru@ZrO2/NC | 0.1 mol/L HCl | -0.21 | 3.665 mg·h‒1·mg | 21 | [ | |
THH Au NR | 0.1 mol/L KOH | -0.2 | 1.648 µg·h‒1·cm‒2 | 4.02 | [ | |
Rh NNs | 0.1 mol/L KOH | -0.2 | 23.88 mg·h‒1·mg‒1 | 0.217 | [ | |
Pd/C | 0.1 mol/L PBS | 0.1 | 4.5 μg·mg‒1·h‒1 | 8.2 | [ | |
Non⁃noble metal catalyst | Fe/Fe3O4 | 0.1 mol/L PBS | -0.3 | 0.19 μg·h‒1·cm‒2 | 8.29 | [ |
Fe⁃CeO2 | 0.5 mol/L LiClO4 | -0.5 | 26.2 μg·mg‒1·h‒1 | 14.7 | [ | |
Mo⁃D⁃R⁃5h | 0.01 mol/L H2SO4 | -0.49 | 30.9 pmol·s‒1·cm‒2 | 0.71(-0.29 V) | [ | |
N@MoS2 | 0.1 mol/L Na2SO4 | -0.3 | 69.82 μg·h‒1·mg‒1 | 9.14 | [ | |
Mo0/GDY | 0.1 mol/L Na2SO4 | -0.96 | 145.4 μg·h‒1·mg‒1 | 21 | [ | |
MoO2/C700 | 1 mol/L KOH | -0.7 | 173.7 μg·h‒1·mg‒1 | 27.6 | [ | |
WO3⁃C3N4⁃R | 0.1 mol/L Li2SO4 | -0.3 | 43.5 μg·h‒1·mg‒1 | 11.2 | [ | |
Non⁃metallic catalyst | NPC | 0.05 mol/L H2SO4 | -0.9 | 1.40 mmol·g‒1·h‒1 | 1.42 | [ |
BG | 0.05 mol/L H2SO4 | -0.5 | 9.8 μg·h‒1·cm‒2 | 10.8 | [ | |
BNS | 0.1 mol/L Na2SO4 | -0.8 | 13.22 μg·h‒1·mg‒1 | 4.4 | [ |
Table 1 Summary of performance of electrocatalytic NH3 synthesis by NRR
Species | Electrocatalyst | Electrolyte | Potential/V (vs. RHE) | NH3 yield rate | NH3 Faradic efficiency(%) | Ref. |
---|---|---|---|---|---|---|
Noble metal catalyst | Ru/C | 2 mol/L KOH | -0.24 | 0.21 μg·h‒1·cm‒2 | 0.28 | [ |
Ru@ZrO2/NC | 0.1 mol/L HCl | -0.21 | 3.665 mg·h‒1·mg | 21 | [ | |
THH Au NR | 0.1 mol/L KOH | -0.2 | 1.648 µg·h‒1·cm‒2 | 4.02 | [ | |
Rh NNs | 0.1 mol/L KOH | -0.2 | 23.88 mg·h‒1·mg‒1 | 0.217 | [ | |
Pd/C | 0.1 mol/L PBS | 0.1 | 4.5 μg·mg‒1·h‒1 | 8.2 | [ | |
Non⁃noble metal catalyst | Fe/Fe3O4 | 0.1 mol/L PBS | -0.3 | 0.19 μg·h‒1·cm‒2 | 8.29 | [ |
Fe⁃CeO2 | 0.5 mol/L LiClO4 | -0.5 | 26.2 μg·mg‒1·h‒1 | 14.7 | [ | |
Mo⁃D⁃R⁃5h | 0.01 mol/L H2SO4 | -0.49 | 30.9 pmol·s‒1·cm‒2 | 0.71(-0.29 V) | [ | |
N@MoS2 | 0.1 mol/L Na2SO4 | -0.3 | 69.82 μg·h‒1·mg‒1 | 9.14 | [ | |
Mo0/GDY | 0.1 mol/L Na2SO4 | -0.96 | 145.4 μg·h‒1·mg‒1 | 21 | [ | |
MoO2/C700 | 1 mol/L KOH | -0.7 | 173.7 μg·h‒1·mg‒1 | 27.6 | [ | |
WO3⁃C3N4⁃R | 0.1 mol/L Li2SO4 | -0.3 | 43.5 μg·h‒1·mg‒1 | 11.2 | [ | |
Non⁃metallic catalyst | NPC | 0.05 mol/L H2SO4 | -0.9 | 1.40 mmol·g‒1·h‒1 | 1.42 | [ |
BG | 0.05 mol/L H2SO4 | -0.5 | 9.8 μg·h‒1·cm‒2 | 10.8 | [ | |
BNS | 0.1 mol/L Na2SO4 | -0.8 | 13.22 μg·h‒1·mg‒1 | 4.4 | [ |
Species | Electrocatalyst | Electrolyte | Potential/V (vs. RHE) | NH3 yield rate | NH3 Faradic efficiency(%) | Ref. |
---|---|---|---|---|---|---|
Vacancy engineering | TiO2-x | 0.5 mol/L Na2SO4+50 ppm | -1.36 | 0.045 mmol·h‒1·mg‒1 | 85 | [ |
P25⁃600 | 0.5 mol/L Na2SO4+100 ppm | -1.0 | 0.052 mmol·h‒1·mg‒1 | 78 | [ | |
Fe2TiO5 | PBS+0.1 mol/L | -1.0 | 0.77 mmol·h‒1·mg‒1 | 87.5 | [ | |
PCN⁃600 | 0.5 mol/L Na2SO4+100 ppm | -1.6 | 0.03262 mmol·h‒1·g‒1 | 89.96 | [ | |
Interface engineering | Ag/Cu2O | 0.5 mol/L Na2SO4+100 ppm | -0.8 | 0.225 mmol·h‒1·cm‒2 | 96.45 | [ |
Co/CoO NSAs | 0.1 mol/L Na2SO4+200 ppm | -1.06 | 194.46 μmol·h‒1·cm‒2 | 93.8 | [ | |
CuCl_BEF | 0.5 mol/L Na2SO4+100 ppm | -1.0 | 1.82 mg·h‒1·cm‒2 | 98.6 | [ | |
Alloy engineering | CuCo alloy | 1 mol/L KOH+100 mmol/L | -0.2 | 960 mmol·h‒1·g‒1 | 100±1 | [ |
RuFe NFs | 0.5 mol/L Na2SO4+0.1 mol/L | -0.65 | 8.68 mg·h‒1·mg‒1 | 74.4(-0.3 V) | [ | |
PdCu/Cu2O | 0.5 mol/L Na2SO4+100 ppm | -0.8 | 0.19 mmol·h‒1·cm‒2 | 94.32 | [ | |
PA⁃RhCu cNCs | 0.1 mol/L HClO4+0.05 mol/L KNO3 | 0.05 | 2.4 mg·h‒1·mg‒1 | 93.7 | [ | |
meso⁃PdN NCs | 0.1 mol/L Na2SO4+5 mmol/L | -0.7 | 3760 μg·h‒1·mg‒1 | 96.1 | [ | |
Single⁃atom catalyst | Fe SACs | 0.1 mol/L K2SO4+0.5 mol/L | -0.66 | 20 mg·h‒1·mg‒1 | 75 | [ |
Cu/Ni⁃NC | 0.5 mol/L Na2SO4+100 ppm | -0.7 | 0.324 mmol·h‒1·cm‒2 | 97.28 | [ | |
Au/Cu SAA | 0.5 mol/L Na2SO4+100 ppm | -0.8 | 0.193 mmol·h‒1·cm‒2 | 99.69 | [ | |
VCu⁃Au1Cu SAAs | 0.1 mol/L KOH+7.14 mmol/L | -0.2 | 555 μg·h‒1·cm‒2 | 98.7 | [ | |
Doped engineering | Zn/Cu⁃2.3 | 0.5 mol/L K2SO4+0.1 mol/L | -0.55 | 5.8 mol·h‒1·g‒1 | 98.4 | [ |
Co⁃Fe@Fe2O3 | 0.1 mol/L Na2SO4+50 ppm | -0.645 | 1,505.9 μg·h‒1·cm‒2 | 85.2±0.6 | [ | |
Ru/β⁃Co(OH)2 | 1 mol/L KOH+0.1 mol/L | 0.071 | 0.38 mmol·h‒1·cm‒2 | 98.78 | [ | |
N⁃C⁃1000 | 0.1 mol/L KOH+0.1 mol/L | -0.7 | 78.2 μmol·h‒1·cm‒2 | 95.0 | [ | |
Morphological and | ox⁃LIG | 1 mol/L | -0.93 | 2859 µg·h‒1·cm‒2 | ca. 100 | [ |
structural control | Cu nanosheets | 1 mol/L KOH+0.2 mol/L | -0.59 | 1.41 mmol·h‒1·cm‒2 | 88 | [ |
Cu@C | 1 mol/L KOH+1 mmol/L | -0.3 | 469.5 µg·h‒1·cm‒2 | 72 | [ |
Table 2 Summary of performance of electrocatalytic NH3 synthesis by NO3RR
Species | Electrocatalyst | Electrolyte | Potential/V (vs. RHE) | NH3 yield rate | NH3 Faradic efficiency(%) | Ref. |
---|---|---|---|---|---|---|
Vacancy engineering | TiO2-x | 0.5 mol/L Na2SO4+50 ppm | -1.36 | 0.045 mmol·h‒1·mg‒1 | 85 | [ |
P25⁃600 | 0.5 mol/L Na2SO4+100 ppm | -1.0 | 0.052 mmol·h‒1·mg‒1 | 78 | [ | |
Fe2TiO5 | PBS+0.1 mol/L | -1.0 | 0.77 mmol·h‒1·mg‒1 | 87.5 | [ | |
PCN⁃600 | 0.5 mol/L Na2SO4+100 ppm | -1.6 | 0.03262 mmol·h‒1·g‒1 | 89.96 | [ | |
Interface engineering | Ag/Cu2O | 0.5 mol/L Na2SO4+100 ppm | -0.8 | 0.225 mmol·h‒1·cm‒2 | 96.45 | [ |
Co/CoO NSAs | 0.1 mol/L Na2SO4+200 ppm | -1.06 | 194.46 μmol·h‒1·cm‒2 | 93.8 | [ | |
CuCl_BEF | 0.5 mol/L Na2SO4+100 ppm | -1.0 | 1.82 mg·h‒1·cm‒2 | 98.6 | [ | |
Alloy engineering | CuCo alloy | 1 mol/L KOH+100 mmol/L | -0.2 | 960 mmol·h‒1·g‒1 | 100±1 | [ |
RuFe NFs | 0.5 mol/L Na2SO4+0.1 mol/L | -0.65 | 8.68 mg·h‒1·mg‒1 | 74.4(-0.3 V) | [ | |
PdCu/Cu2O | 0.5 mol/L Na2SO4+100 ppm | -0.8 | 0.19 mmol·h‒1·cm‒2 | 94.32 | [ | |
PA⁃RhCu cNCs | 0.1 mol/L HClO4+0.05 mol/L KNO3 | 0.05 | 2.4 mg·h‒1·mg‒1 | 93.7 | [ | |
meso⁃PdN NCs | 0.1 mol/L Na2SO4+5 mmol/L | -0.7 | 3760 μg·h‒1·mg‒1 | 96.1 | [ | |
Single⁃atom catalyst | Fe SACs | 0.1 mol/L K2SO4+0.5 mol/L | -0.66 | 20 mg·h‒1·mg‒1 | 75 | [ |
Cu/Ni⁃NC | 0.5 mol/L Na2SO4+100 ppm | -0.7 | 0.324 mmol·h‒1·cm‒2 | 97.28 | [ | |
Au/Cu SAA | 0.5 mol/L Na2SO4+100 ppm | -0.8 | 0.193 mmol·h‒1·cm‒2 | 99.69 | [ | |
VCu⁃Au1Cu SAAs | 0.1 mol/L KOH+7.14 mmol/L | -0.2 | 555 μg·h‒1·cm‒2 | 98.7 | [ | |
Doped engineering | Zn/Cu⁃2.3 | 0.5 mol/L K2SO4+0.1 mol/L | -0.55 | 5.8 mol·h‒1·g‒1 | 98.4 | [ |
Co⁃Fe@Fe2O3 | 0.1 mol/L Na2SO4+50 ppm | -0.645 | 1,505.9 μg·h‒1·cm‒2 | 85.2±0.6 | [ | |
Ru/β⁃Co(OH)2 | 1 mol/L KOH+0.1 mol/L | 0.071 | 0.38 mmol·h‒1·cm‒2 | 98.78 | [ | |
N⁃C⁃1000 | 0.1 mol/L KOH+0.1 mol/L | -0.7 | 78.2 μmol·h‒1·cm‒2 | 95.0 | [ | |
Morphological and | ox⁃LIG | 1 mol/L | -0.93 | 2859 µg·h‒1·cm‒2 | ca. 100 | [ |
structural control | Cu nanosheets | 1 mol/L KOH+0.2 mol/L | -0.59 | 1.41 mmol·h‒1·cm‒2 | 88 | [ |
Cu@C | 1 mol/L KOH+1 mmol/L | -0.3 | 469.5 µg·h‒1·cm‒2 | 72 | [ |
Electrocatalyst | Electrolyte | Potential/V (vs. RHE) | NH3 Yield rate | NH3 Faradicefficiency(%) | Reactor | Ref. |
---|---|---|---|---|---|---|
Cu Foam | 3 mol/L KCl | -0.9 | 517.1 μmol·cm‒2·h‒1 | 93.5 | H⁃type cell | [ |
Cu nanoparticle | 0.1 mol/L NaOH+ | 0.03 | 1806 μmol·cm‒2·h‒1 | 78(0.1 V) | Flow cell | [ |
0.9 mol/L NaClO4 | ||||||
Cu1/MoS2 | 0.5 mol/L Na2SO4 | -0.6 | 337.5 μmol·cm‒2·h‒1 | 90.6 | H⁃type cell | [ |
Ni⁃NCNR700 | 0.1 mol/L HCl | 0.61 | (23.8±2.6) μmol·cm‒2·h‒1 | 85.5±0.8 | H⁃type cell | [ |
Ni(210) | 0.5 mol/L K2SO4 | -0.68 | 544 μmol·cm‒2·h‒1 | 85 | Flow cell | [ |
Sb1/a⁃MoO3 | 0.5 mol/L Na2SO4 | -0.6 | 273.5 μmol·cm‒2·h‒1 | 91.7 | H⁃type cell | [ |
NiNC@CF | 0.5 mol/L PBS | -0.5 | 94 μmol·cm‒2·h‒1 | 87 | H⁃type cell | [ |
Ru⁃LCN | 0.5 mol/L Na2SO4 | -0.2 | 45.02 μmol·h‒1·mg‒1 | 65.9 | Flow cell | [ |
Fe/C | 0.5 mol/L H2SO4 | -0.4 | 1239 μmol·cm‒2·h‒1 | 50.4 | Flow cell | [ |
MoS2/GF | 0.1 mol/L HCl+ | 0.1 | 99.6 μmol·cm‒2·h‒1 | 76.6 | H⁃type cell | [ |
0.5 mmol/L Fe(II)SB | ||||||
hcp⁃Co | 0.1 mol/L Na2SO4 | 0.6 | 439.50 μmol·cm‒2·h‒1 | 72.58 | H⁃type cell | [ |
Single atom Nb | 0.1 mol/L HCl | -0.6 | 295.2 μmol·cm‒2·h‒1 | 77.1 | H⁃type cell | [ |
TiO2-x/TP | 0.2 mol/L PBS | -0.7 | 1233.3 μg·h‒1·cm‒2 | 92.5(-0.4 V) | H⁃type cell | [ |
a⁃B2.6C@TiO2/Ti | 0.1 mol/L Na2SO4+ | -0.9 | 3678.6 μg·h‒1·cm‒2 | 87.6 | H⁃type cell | [ |
0.5 mmol/L Fe2+⁃EDTA | ||||||
Cu6Sn5 | 1 mol/L KOH | -0.23 | 10 mmol·cm‒2·h‒1 | > 96 | Flow cell | [ |
Table 3 Summary of performance of electrocatalytic NH3 synthesis by NORR
Electrocatalyst | Electrolyte | Potential/V (vs. RHE) | NH3 Yield rate | NH3 Faradicefficiency(%) | Reactor | Ref. |
---|---|---|---|---|---|---|
Cu Foam | 3 mol/L KCl | -0.9 | 517.1 μmol·cm‒2·h‒1 | 93.5 | H⁃type cell | [ |
Cu nanoparticle | 0.1 mol/L NaOH+ | 0.03 | 1806 μmol·cm‒2·h‒1 | 78(0.1 V) | Flow cell | [ |
0.9 mol/L NaClO4 | ||||||
Cu1/MoS2 | 0.5 mol/L Na2SO4 | -0.6 | 337.5 μmol·cm‒2·h‒1 | 90.6 | H⁃type cell | [ |
Ni⁃NCNR700 | 0.1 mol/L HCl | 0.61 | (23.8±2.6) μmol·cm‒2·h‒1 | 85.5±0.8 | H⁃type cell | [ |
Ni(210) | 0.5 mol/L K2SO4 | -0.68 | 544 μmol·cm‒2·h‒1 | 85 | Flow cell | [ |
Sb1/a⁃MoO3 | 0.5 mol/L Na2SO4 | -0.6 | 273.5 μmol·cm‒2·h‒1 | 91.7 | H⁃type cell | [ |
NiNC@CF | 0.5 mol/L PBS | -0.5 | 94 μmol·cm‒2·h‒1 | 87 | H⁃type cell | [ |
Ru⁃LCN | 0.5 mol/L Na2SO4 | -0.2 | 45.02 μmol·h‒1·mg‒1 | 65.9 | Flow cell | [ |
Fe/C | 0.5 mol/L H2SO4 | -0.4 | 1239 μmol·cm‒2·h‒1 | 50.4 | Flow cell | [ |
MoS2/GF | 0.1 mol/L HCl+ | 0.1 | 99.6 μmol·cm‒2·h‒1 | 76.6 | H⁃type cell | [ |
0.5 mmol/L Fe(II)SB | ||||||
hcp⁃Co | 0.1 mol/L Na2SO4 | 0.6 | 439.50 μmol·cm‒2·h‒1 | 72.58 | H⁃type cell | [ |
Single atom Nb | 0.1 mol/L HCl | -0.6 | 295.2 μmol·cm‒2·h‒1 | 77.1 | H⁃type cell | [ |
TiO2-x/TP | 0.2 mol/L PBS | -0.7 | 1233.3 μg·h‒1·cm‒2 | 92.5(-0.4 V) | H⁃type cell | [ |
a⁃B2.6C@TiO2/Ti | 0.1 mol/L Na2SO4+ | -0.9 | 3678.6 μg·h‒1·cm‒2 | 87.6 | H⁃type cell | [ |
0.5 mmol/L Fe2+⁃EDTA | ||||||
Cu6Sn5 | 1 mol/L KOH | -0.23 | 10 mmol·cm‒2·h‒1 | > 96 | Flow cell | [ |
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