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Table 1 A brief summary of the representative experimental studies on NRR using various electrocatalytic heterogeneous catalysts

From: Photocatalytic and electrocatalytic approaches towards atmospheric nitrogen reduction to ammonia under ambient conditions

Catalyst Electrolyte Condition NH3 formation rate Unit Potential Reference electrode Faradaic efficiency Year
Fe-phthalocyanine 1.0 M KOH 25 °C 7.0E+05 mol s−1 cm−2 − 47.8 mA cm−2 Current density 0.34% 1989 [59]
ZnS 1.0 M KOH 25 °C 7.1E+06 mol s−1 cm−2 − 0.1 V vs RHE 0.964% 1990 [60]
ZnSe 1.0 M KOH 25 °C 8.1E+06 mol s−1 cm−2 − 0.1 V vs RHE 1.29% 1990 [60]
Ti 0.2 M LiClO4/0.18 M ethanol in THF 25 °C    2.0 V Cell Voltage 8.20% 1994 [60]
Cu 0.2 M LiClO4/0.18 M ethanol in THF 25 °C    2.0 V Cell Voltage 5.30% 1994 [61]
Ru/C 2.0 M KOH 20 °C 3.43137E−12 mol s−1 cm−2 − 1.10 V vs Ag/AgCl 0.28% 2000 [62]
90 °C 4.08497E−12 mol s−1 cm−2 − 0.96 V vs Ag/AgCl 0.92% 2000 [62]
Polyaniline methanol/LiCiO4/H2SO4 25 °C 0.000,000,014 mol−1 ml−1 − 0.12 V vs RHE 2.00% 2005 [63]
30 wt % Pt/C 0.50 M H2SO4 RT 1.14E−09 mol s−1 cm−2 1.6 V Cell Voltage 0.50% 2013 [64]
H+/Li+/NH4+ mixed electrolyte 80 °C 9.37E−10 mol s−1 cm−2 1.2 V Cell Voltage 0.83% 2013 [65]
Ru/Ti 0.50 M H2SO4 30 °C 1.2E−10 mol s−1 cm−2 − 0.15 V vs NHE N/A 2014 [66]
Rh/Ti 1.5E−11 mol s−1 cm−2 − 0.171 V
Ni wire 0.050 M H2SO4/0.1 M LiCl, EDA RT 3.58E−11 mol s−1 cm−2 1.8 V Cell Voltage 17.20% 2016 [58]
Porous Ni 2-propanol/H2SO4 RT 1.54E−11 mol s−1 cm−2 0.5 mA cm−2 Current Density 0.89% 2016 [67]
Mo nanofilm 0.010 M H2SO4 RT 3.09E−11 mol s−1 cm−2 − 0.49 V vs RHE 0.72%(at − 0.29 V vs RHE) 2017 [54]
γ-Fe2O3 0.10 M KOH 65 °C 1.21528E−11 mol s−1 cm−2 0 V vs RHE 1.96% 2017 [68]
Au nanorods 0.10 M KOH RT 2.69281E−11 mol s−1 cm−2 − 0.2 V vs RHE 4.00% 2017 [55]
Au/TiO2 0.10 M HCl RT 3.49673E−10 mol s−1 mg −1cat − 0.2 V vs RHE 8.11% 2017 [56]
Au-CeOx/RGO 0.10 M KOH RT 1.35621E−10 mol s−1 mg −1cat − 0.2 V vs RHE 10.10% 2017 [57]
30 wt % Fe2O3-CNT 0.50 M KOH RT 6.74E−12 mol s−1 cm−2 − 2.0 V vs Ag/AgCl 0.16% 2017 [69]
PEBCD (poly N-ethyl-benzene-1,2,4,5-tetracarboxylic diimide)/C 0.50 M Li2SO4 25 °C 2.5817E−11 mol s−1 cm−2 − 0.5 V vs RHE 2.85% 2017 [70]
40 °C 7.07516E−11 mol s−1 cm−2 − 0.5 V 4.87%
MOF(Fe)(metal–organic-frameworks) 2.0 M KOH 90 °C 2.12E−09 mol s−1 cm−2 1.2 V Cell Voltage 1.43% 2017 [71]
Fe2O3-CNT 2.0 M NaHCO3 RT 3.59477E−12 mol s−1 cm−2 − 2.0 V vs Ag/AgCl 0.15%(at − 1.0 V vs Ag/AgCl) 2017 [72]
Fe on stainless steel mesh Ionic liquid RT 3.88889E−10 mol s−1 cm−2 − 0.8 V vs NHE 30% 2017 [73]
N-doped carbon 0.05 M H2SO4 RT 3.88889E−16 mol s−1 mg−1 − 0.9 V vs RHE 1.42% 2018 [32]
Ru nanosheets 0.10 M KOH RT 3.90196E−10 mol s−1 mg −1cat − 0.2 V vs RHE 0.217% 2018 [74]
Mo2N nanorod 0.1 M HCl 25 °C 1.28105E−09 mol s−1 mg −1cat − 0.3 V vs RHE 4.50% 2018 [75]
VN nanowire array 0.1 M HCl 25 °C 2.48E−10 mol s−1 cm−2 − 0.3 V vs RHE 3.58% 2018 [76]
Pt 6 M KOH/polymer gel 30 °C 4.049E−11 mol s−1 cm−2 0.5 V Cell Voltage 0.0108% 2018 [77]
Ir 60 °C 2.763E−11 mol s−1 cm−2 0.25 V Cell Voltage 0.108%
Bi4V2O11/CeOx HCl, PH = 1 RT 3.79248E−10 mol s−1 mg −1cat − 0.2 V vs RHE 10.16% 2018 [78]
Pore-size-controlled hollow gold nanocatalysts 0.1 M LiOH RT 6.11111E−11 mol s−1 cm−2 − 0.4 V vs RHE 35.90% 2018 [37]
Hollow gold nanocages 0.5 M LiClO4 RT 6.37255E−11 mol s−1 cm−2 at − 0.5 V − 0.4 V vs RHE 30.20% 2018 [79]
MoN Nanosheets 0.1 M HCl RT 3.01 mol s−1 cm−2 − 0.3 V vs RHE 1.15% 2018 [34]
N-doped carbon nanospikes 0.25 M LiClO4 RT 1.58791E−09 mol s−1 cm−2 − 1.19 V vs RHE 11.56 ± 0.85% 2018 [36]
Vanadium Nitride Nanoparticles 3 M KOH RT 3.31E−10 mol s−1 cm−2   vs RHE 5.95% 2018 [35]
Chromium Oxynitride nanoparticles Nafion Solution(5% wt) RT 8.9E−11 mol s−1 cm−2 2.0 V Cell Voltage 6.70% 2018 [38]
MoS2 0.1 M Na2SO4 RT 8.08E−11 mol s−1 cm−2 − 0.5 V vs RHE 1.17% 2018 [33]