Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (8): 1297-1326.DOI: 10.1016/S1872-2067(20)63736-6
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Junwei Chen, Zuqiao Ou, Haixin Chen, Shuqin Song, Kun Wang, Yi Wang*()
Received:
2020-10-05
Accepted:
2020-11-29
Online:
2021-08-18
Published:
2020-12-10
Supported by:
Junwei Chen, Zuqiao Ou, Haixin Chen, Shuqin Song, Kun Wang, Yi Wang. Recent developments of nanocarbon based supports for PEMFCs electrocatalysts[J]. Chinese Journal of Catalysis, 2021, 42(8): 1297-1326.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63736-6
Nano carbon- based materials | Preparation methods | Material characteristics | Application fields | Problems to be solved as a catalyst support | Solutions | |||
---|---|---|---|---|---|---|---|---|
CNTs | 1. Arc discharge method 2. Laser ablation 3. Solid phase pyrolysis 4. Ion or laser sputtering 5. Catalytic cracking | 1. Hexagonal arrangement of carbon atom layers 2. One-dimensional nanostructure 3. Low impedance 4. Good conductivity and stability 5. Excellent resistance to electrochemical corrosion | 1. Composite materials 2. Electronic devices 3. Fluorescent labels | 1. Small active specific surface area 2. Surface inertness 3. High price | 1. Form hybrid materials with other carbon materials; 2. Dope metal or nonmetal to form composite materials | |||
Graphene (GP) | 1. Mechanical peeling 2. Redox method 3. Chemical vapor deposition (CVD) 4. Oriented epiphysis | 1. Two-dimensional planar structure 2. Large theoretical specific surface area (2630 m2 g-1) 3. High electrical conductivity (106 S cm-1) 4. Good resistance to electrochemical corrosion | 1. Physics 2. Materials 3. Electronic information 4. Computers | 1. Metal nanoparticles are easily reunited 2. Surface is chemically inert | 1. Structured into 3D material 2. Heteroatom doping 3. Surface defect engineering | |||
Ordered mesoporous carbon (OMC) | 1. Hard template method 2. Soft template method | 1. Uniformly adjustable pore diameter 2. Good conductivity 3. Good stability 4. Large specific surface area 5. Large pore volume | 1. Adsorption 2. Electrochemistry 3. Biology 4. Catalysis | 1. Complex manufacturing process 2. Orderly structure is easily broken | Surface functionalization with acid | |||
Carbon aerogel (CA) | 1. Organogel formation 2. Super-critical drying 3. Carbonization process | 1. Amorphous carbon materials 2. Controllable nanoporous 3D network structure 3. High specific surface area (600-1100 m2 g-1) 4. High porosity (80%-98%) 5. High stability | 1. Catalyst 2. Electrochemistry 3. Hydrogen storage 4. Template | 1. Low graphitization degree 2. Poor electrochemical corrosion resistance | 1. Surface modification 2. Improving the graphitization degree | |||
Carbon nanofiber (CNF) | 1. CVD 2. Solid phase synthesis 3. Electrospinning | 1. Large specific surface area 2. Good electrical conductivity 3. Good chemical stability 4. High single strength 5. Low cost | 1. Chemical engineering 2. Medicine 3. Sewage prevention | 1. Difficult to control shape 2. Uneven performance | 1. Surface stabilization 2. Element doping | |||
CB | 1. Spray method 2. Lamp smoke method 3. Drum method 4. Plasma method | 1. Good electrochemical performance 2. BET specific surface area is approximately 250 m2 g-1 3. The proportion of mesopores and macropores exceeds 54% 4. Electrical conductivity is approximately 2.77 S cm-1 | 1. Chemical engineering 2. Transportation 3. Textile | 1. Poor resistance to electrochemical corrosion 2. The proportion of micropores is still very high | 1. Improve the degree of graphitization 2. Doping heteroatoms |
Table 1 Nanocarbons as the support for PEMFC electrocatalysts.
Nano carbon- based materials | Preparation methods | Material characteristics | Application fields | Problems to be solved as a catalyst support | Solutions | |||
---|---|---|---|---|---|---|---|---|
CNTs | 1. Arc discharge method 2. Laser ablation 3. Solid phase pyrolysis 4. Ion or laser sputtering 5. Catalytic cracking | 1. Hexagonal arrangement of carbon atom layers 2. One-dimensional nanostructure 3. Low impedance 4. Good conductivity and stability 5. Excellent resistance to electrochemical corrosion | 1. Composite materials 2. Electronic devices 3. Fluorescent labels | 1. Small active specific surface area 2. Surface inertness 3. High price | 1. Form hybrid materials with other carbon materials; 2. Dope metal or nonmetal to form composite materials | |||
Graphene (GP) | 1. Mechanical peeling 2. Redox method 3. Chemical vapor deposition (CVD) 4. Oriented epiphysis | 1. Two-dimensional planar structure 2. Large theoretical specific surface area (2630 m2 g-1) 3. High electrical conductivity (106 S cm-1) 4. Good resistance to electrochemical corrosion | 1. Physics 2. Materials 3. Electronic information 4. Computers | 1. Metal nanoparticles are easily reunited 2. Surface is chemically inert | 1. Structured into 3D material 2. Heteroatom doping 3. Surface defect engineering | |||
Ordered mesoporous carbon (OMC) | 1. Hard template method 2. Soft template method | 1. Uniformly adjustable pore diameter 2. Good conductivity 3. Good stability 4. Large specific surface area 5. Large pore volume | 1. Adsorption 2. Electrochemistry 3. Biology 4. Catalysis | 1. Complex manufacturing process 2. Orderly structure is easily broken | Surface functionalization with acid | |||
Carbon aerogel (CA) | 1. Organogel formation 2. Super-critical drying 3. Carbonization process | 1. Amorphous carbon materials 2. Controllable nanoporous 3D network structure 3. High specific surface area (600-1100 m2 g-1) 4. High porosity (80%-98%) 5. High stability | 1. Catalyst 2. Electrochemistry 3. Hydrogen storage 4. Template | 1. Low graphitization degree 2. Poor electrochemical corrosion resistance | 1. Surface modification 2. Improving the graphitization degree | |||
Carbon nanofiber (CNF) | 1. CVD 2. Solid phase synthesis 3. Electrospinning | 1. Large specific surface area 2. Good electrical conductivity 3. Good chemical stability 4. High single strength 5. Low cost | 1. Chemical engineering 2. Medicine 3. Sewage prevention | 1. Difficult to control shape 2. Uneven performance | 1. Surface stabilization 2. Element doping | |||
CB | 1. Spray method 2. Lamp smoke method 3. Drum method 4. Plasma method | 1. Good electrochemical performance 2. BET specific surface area is approximately 250 m2 g-1 3. The proportion of mesopores and macropores exceeds 54% 4. Electrical conductivity is approximately 2.77 S cm-1 | 1. Chemical engineering 2. Transportation 3. Textile | 1. Poor resistance to electrochemical corrosion 2. The proportion of micropores is still very high | 1. Improve the degree of graphitization 2. Doping heteroatoms |
Fig. 4. (a) Schematic illustration for the effect of the structural regularity of the carbon support on the activity of Pt and (b) cyclic voltagrammograms of ethanol oxidation on Pt/WMCs and Pt/CMK-3. Reproduced with permission from Ref. [57], Copyright 2010 Elsevier. (c) Cyclic voltammetry curves of the as-prepared Pt/WMCs and Pt/CMK-3; (d) schematic diagram of highly OMC (CMK-3 and FDU-15) with different nanopore arrays and (e) comparison of electrochemical performance of Pt/CMK-3 and Pt/FDU-15. Reproduced with permission from Ref. [59], Copyright 2011 Royal Society of Chemistry.
Fig. 5. SEM (a), TEM (b), and HAADF-STEM (c,d) images of Fe/N-GPC; (e) Schematic diagram of molecular diffusion in an hierarchical pore structure. Reproduced with permission from Ref. [74], Copyright 2017 American Chemical Society.
Fig. 6. CV curve (a) and polarization curve (b) of Pt/WMC-F0 and Pt/WMC-F4; (c) Schematic of the effect of pore diameter of WMCs on the accessibility of Pt nanoparticles; (d) Comparison of the peak current density for EOR of mesoporous carbon with different pore diameters under different temperatures. Reproduced with permission from Ref. [78], Copyright 2010 Elsevier.
Fig. 8. (a) Schematic diagram of four types of N species in NCs, namely, pyridinic nitrogen (A), pyrrolic nitrogen (B), quaternary nitrogen (C), and pyridine-N-X (D); (b) Comparison of polarization curves; (c) Electrochemical performance of Pd/C, Pd@N-C NFs, and N-C NFs. Reproduced with permission from Ref. [97], Copyright 2019 Royal Society of Chemistry; (d) CV curves of Pt/NMC-1 and Pt/NMC-2 in an acid electrolyte. Reproduced with permission from Ref. [93], Copyright 2018 Elsevier.
Introduction method | Nanostructured morphology | N-precursor /method | T/°C | NAa /at% | N6b /% | N5c /% | NQd /% | NXe /% | ABET /m2 g-1 | ORR | R啊啊啊ef. | ||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
pH | Onset potential (V) | Limiting current density (mA cm-2) | |||||||||||
In situ process | N-CNTi | CCVDj | 1000 | 1.0 | 38.0 | 25.0 | √ | √ | 911.0 | 13.0 | — | — | [ |
N-Carbon nanocapsule | Gd-DTPAk carbonization | 700 | 7.1 | 27.6 | 61.8 | 8.4 | 2.2 | — | 13.0 | ~-0.95f,g | 20.1 | [ | |
900 | 3.2 | 19.8 | 63.3 | 7.2 | 5.3 | — | 13.0 | ~-0.95f,g | 17.6 | [ | |||
N-OMCl | Modified nanocasting | 800 | 5.07 | 31.9 | √ | √ | 9.0 | 470.0 | 13.0 | ~0.71h | 4.0 | [ | |
900 | 3.13 | 26.4 | √ | √ | 14.0 | 569.0 | 13.0 | ~0.75h | 4.3 | [ | |||
1000 | 2.20 | 20.9 | √ | √ | 18.5 | 629.0 | 13.0 | ~0.78h | 4.5 | [ | |||
1100 | 1.25 | 17.9 | √ | √ | 17.4 | 517.0 | 13.0 | ~0.73h | 4.0 | [ | |||
N-Nanoporous carbon | NaCl-assisted pyrolysis | 900 | 6.7 | 72.0 | 13.4 | 10.5 | 4.1 | 733.0 | 13.0 | 0.98g | 33.8 | [ | |
N-ZIFl derived carbon | N2+ carbonization | 700 | — | 52.0 | 32.0 | 11.0 | 5.0 | 74.47 | 1.0 | — | — | [ | |
750 | — | 46.0 | 27.0 | 16.0 | 11.0 | 75.81 | 1.0 | — | — | [ | |||
800 | — | 45.0 | 21.0 | 18.0 | 16.00 | 77.74 | 1.0 | — | — | [ | |||
850 | — | 42.0 | 21.0 | 19.0 | 17.0 | 79.43 | 1.0 | 0.58h | 4.75 | [ | |||
900 | — | 37.0 | 21.0 | 21.0 | 21.0 | 83.50 | 1.0 | — | — | [ | |||
N-mesoporous carbon | SiO2-assisted sol-gel method | 800 | 11.0 | 18.0 | 58.0 | — | 24.0 | 609.0 | 2.0 | ~0.80h | 1.44 | [ | |
800 | 6.0 | 12.0 | 61.0 | — | 27.0 | 736.0 | 2.0 | ~0.75h | 1.18 | [ | |||
Post treatment | N-GP | Flake graphite + NH3 heat treatment | 800 | 2.8 | 55.4 | 33.2 | 11.4 | — | — | 13.0 | 0.184g | ~2.7 | [ |
900 | 2.8 | 55.7 | 30.4 | 13.9 | — | — | 13.0 | 0.308g | ~2.9 | [ | |||
1000 | 2.0 | 51.0 | 33.0 | 16.0 | — | — | 13.0 | 0.204g | ~3.0 | [ | |||
N-OMC | NH3 heat treatment | 950 | 6.0 | 44.0 | — | 8.6 | — | 690.0 | 2.0 | 0.67h | ~3.7 | [ | |
1000 | 3.6 | 45.2 | — | 9.0 | — | 482.0 | 2.0 | 0.7h | ~4.0 | [ | |||
1050 | 4.6 | 46.9 | — | 10.0 | — | 229.0 | 2 | 0.72h | ~4.2 | [ | |||
N-MWCNTm | N2 plasma sputtering | — | 4.0 | 9.99 | 58.6 | 18.28 | 13.13 | — | 2.0 | 0.90h | 6.0 | [ | |
N-CNTi | CCVDj + NH3 heat treatment | 670 | 1.0 | 45.0 | 43.0 | 12.0 | — | 160.0 | 2.0 | 0.77h | 2.88 | [ |
Table 2 Metal free NC as electrocatalysts.
Introduction method | Nanostructured morphology | N-precursor /method | T/°C | NAa /at% | N6b /% | N5c /% | NQd /% | NXe /% | ABET /m2 g-1 | ORR | R啊啊啊ef. | ||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
pH | Onset potential (V) | Limiting current density (mA cm-2) | |||||||||||
In situ process | N-CNTi | CCVDj | 1000 | 1.0 | 38.0 | 25.0 | √ | √ | 911.0 | 13.0 | — | — | [ |
N-Carbon nanocapsule | Gd-DTPAk carbonization | 700 | 7.1 | 27.6 | 61.8 | 8.4 | 2.2 | — | 13.0 | ~-0.95f,g | 20.1 | [ | |
900 | 3.2 | 19.8 | 63.3 | 7.2 | 5.3 | — | 13.0 | ~-0.95f,g | 17.6 | [ | |||
N-OMCl | Modified nanocasting | 800 | 5.07 | 31.9 | √ | √ | 9.0 | 470.0 | 13.0 | ~0.71h | 4.0 | [ | |
900 | 3.13 | 26.4 | √ | √ | 14.0 | 569.0 | 13.0 | ~0.75h | 4.3 | [ | |||
1000 | 2.20 | 20.9 | √ | √ | 18.5 | 629.0 | 13.0 | ~0.78h | 4.5 | [ | |||
1100 | 1.25 | 17.9 | √ | √ | 17.4 | 517.0 | 13.0 | ~0.73h | 4.0 | [ | |||
N-Nanoporous carbon | NaCl-assisted pyrolysis | 900 | 6.7 | 72.0 | 13.4 | 10.5 | 4.1 | 733.0 | 13.0 | 0.98g | 33.8 | [ | |
N-ZIFl derived carbon | N2+ carbonization | 700 | — | 52.0 | 32.0 | 11.0 | 5.0 | 74.47 | 1.0 | — | — | [ | |
750 | — | 46.0 | 27.0 | 16.0 | 11.0 | 75.81 | 1.0 | — | — | [ | |||
800 | — | 45.0 | 21.0 | 18.0 | 16.00 | 77.74 | 1.0 | — | — | [ | |||
850 | — | 42.0 | 21.0 | 19.0 | 17.0 | 79.43 | 1.0 | 0.58h | 4.75 | [ | |||
900 | — | 37.0 | 21.0 | 21.0 | 21.0 | 83.50 | 1.0 | — | — | [ | |||
N-mesoporous carbon | SiO2-assisted sol-gel method | 800 | 11.0 | 18.0 | 58.0 | — | 24.0 | 609.0 | 2.0 | ~0.80h | 1.44 | [ | |
800 | 6.0 | 12.0 | 61.0 | — | 27.0 | 736.0 | 2.0 | ~0.75h | 1.18 | [ | |||
Post treatment | N-GP | Flake graphite + NH3 heat treatment | 800 | 2.8 | 55.4 | 33.2 | 11.4 | — | — | 13.0 | 0.184g | ~2.7 | [ |
900 | 2.8 | 55.7 | 30.4 | 13.9 | — | — | 13.0 | 0.308g | ~2.9 | [ | |||
1000 | 2.0 | 51.0 | 33.0 | 16.0 | — | — | 13.0 | 0.204g | ~3.0 | [ | |||
N-OMC | NH3 heat treatment | 950 | 6.0 | 44.0 | — | 8.6 | — | 690.0 | 2.0 | 0.67h | ~3.7 | [ | |
1000 | 3.6 | 45.2 | — | 9.0 | — | 482.0 | 2.0 | 0.7h | ~4.0 | [ | |||
1050 | 4.6 | 46.9 | — | 10.0 | — | 229.0 | 2 | 0.72h | ~4.2 | [ | |||
N-MWCNTm | N2 plasma sputtering | — | 4.0 | 9.99 | 58.6 | 18.28 | 13.13 | — | 2.0 | 0.90h | 6.0 | [ | |
N-CNTi | CCVDj + NH3 heat treatment | 670 | 1.0 | 45.0 | 43.0 | 12.0 | — | 160.0 | 2.0 | 0.77h | 2.88 | [ |
Fig. 9. Comparison of the relative potential surface energy of different types of N in nitrogen-doping graphitic carbon materials as calculated by DFT. Reproduced with permission from Ref. [104], Copyright 2020 American Chemical Society.
Fig. 10. Comparison of specific activity (a) and mass activity (b) of Pt/C and Pt@CNx/CNT before and after ADT. Reproduced with permission from Ref. [121], Copyright 2015 American Chemical Society.
Type of group | Name | Species released | Peak temperature (K) | |
---|---|---|---|---|
| Carboxylic | CO2 | ca. 510 | |
| Lactone | CO2 | ca. 940 | |
| Anhydride | CO + CO2 | ca. 820 | |
| Phenol | CO | ca. 905 | |
| Carbonyl | CO | ca. 1080 | |
| Ether | CO | ca. 973 | |
| Quinone | CO | ca. 1080 |
Table 3 Type of groups and their decomposition temperatures in the TPD test [147].
Type of group | Name | Species released | Peak temperature (K) | |
---|---|---|---|---|
| Carboxylic | CO2 | ca. 510 | |
| Lactone | CO2 | ca. 940 | |
| Anhydride | CO + CO2 | ca. 820 | |
| Phenol | CO | ca. 905 | |
| Carbonyl | CO | ca. 1080 | |
| Ether | CO | ca. 973 | |
| Quinone | CO | ca. 1080 |
Carbon materials | Oxidative treatment | Catalyst synthesis method | Untreated Pt particle (nm) | Treated Pt particle (nm) | Untreated electrochemical surface area (m2 g-1) | Treated electrochemical surface Area (m2 g-1) | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
OMC | H2SO4:HNO3 (1:1) | Acid + refluxing + AEPTMSa | 4.3 | 2.9 | — | — | [ |
CB | HNO3:HCl (2:1) | Impregnation + H2 reduction | 2.7e | 3.5e | 63.0d 36.0e | 77.0b 34.9c | [ |
CS | Ozone | Heat treatment + 25 °C d | — | — | 24.4 | 2.9 | [ |
Heat treatment + 90 °C d | — | — | 24.4 | 11.1 | [ | ||
Heat treatment + 160 °C d | — | — | 24.4 | 87.1 | [ | ||
Heat treatment + 200 °C d | — | — | 24.4 | 18.7 | [ | ||
MWCNTe | KOH + calcination | EGf + microwave | 3.2 | 2.9 | 20.0 | 60.0 | [ |
H2SO4:HNO3 (3:1) | Plasma sputtering | 3.2d | 4.9d | 61.4 | 90.4 | [ | |
OH‒ | H2(PtCl6) + heat treatment | — | 2.4 | 79.0 | 58.0 | [ | |
COOH‒ | — | 2.6 | 79.0 | 73.0 | [ | ||
R-GOg | Ozone | High temperature adsorption | 2.0 | 3.0 | 48.0 | 51.0 | [ |
Fluorine | Soaking + freezing | 2.0 | 5.9 | 48.0 | 20.0 | [ |
Table 4 The effect of carbon support oxidative treatment on the electrocatalyst activity.
Carbon materials | Oxidative treatment | Catalyst synthesis method | Untreated Pt particle (nm) | Treated Pt particle (nm) | Untreated electrochemical surface area (m2 g-1) | Treated electrochemical surface Area (m2 g-1) | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
OMC | H2SO4:HNO3 (1:1) | Acid + refluxing + AEPTMSa | 4.3 | 2.9 | — | — | [ |
CB | HNO3:HCl (2:1) | Impregnation + H2 reduction | 2.7e | 3.5e | 63.0d 36.0e | 77.0b 34.9c | [ |
CS | Ozone | Heat treatment + 25 °C d | — | — | 24.4 | 2.9 | [ |
Heat treatment + 90 °C d | — | — | 24.4 | 11.1 | [ | ||
Heat treatment + 160 °C d | — | — | 24.4 | 87.1 | [ | ||
Heat treatment + 200 °C d | — | — | 24.4 | 18.7 | [ | ||
MWCNTe | KOH + calcination | EGf + microwave | 3.2 | 2.9 | 20.0 | 60.0 | [ |
H2SO4:HNO3 (3:1) | Plasma sputtering | 3.2d | 4.9d | 61.4 | 90.4 | [ | |
OH‒ | H2(PtCl6) + heat treatment | — | 2.4 | 79.0 | 58.0 | [ | |
COOH‒ | — | 2.6 | 79.0 | 73.0 | [ | ||
R-GOg | Ozone | High temperature adsorption | 2.0 | 3.0 | 48.0 | 51.0 | [ |
Fluorine | Soaking + freezing | 2.0 | 5.9 | 48.0 | 20.0 | [ |
Fig. 11. Schematic diagram of H2SO4/HNO3, AEPTMS, and H2O2 oxidatively modifying the OMC surface. Reproduced with permission from Ref. [150], Copyright 2012 Elsevier.
Fig. 12. (a) Mass activity comparison of Pt/CB and Pt/CB_O before and after the ADT test; (b) Schematic diagram of the particle size changes of Pt/CB and Pt/CB_O during ADT. Reproduced with permission from Ref. [155], Copyright 2016 Elsevier.
Fig. 13. Schematic diagram of the structure and performance of the Pt/S-C catalyst. Reproduced with permission from Ref. [162], Copyright 2020 Elsevier.
Introduction method | Materials | Preparation methods | Particles size (nm) | pH value | Electrocatalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | S-carbon shell | Sodium dodecyl sulfate (SDS) + ethyleneglycol (EG)-stirring + pyrolysis | 8.39 | 13.0 | 0.99 c (vs. RHE) | [ |
S-nanocarbon spheres | Thioanisole (TOAS) + benzene-(solution plasma synthesis) | 3.00 | 13.0 | 490 d | [ | |
Post-treatment | S-graphene | GO + diethylene glycol methyl ether-refluxing | — | 13.0 | 0.02 c (vs. Hg/HgO) -0.105 e (vs. Hg/HgO) | [ |
GP + phenyl disulfide (PDS) + annealing | 4.00 | 2.0 | 182 d | [ | ||
S-CNTa | Functionalized CNTa + PDS-heating | 6.20 | 2.0 | 272 d 17.2f 1.61g | [ | |
S-MWCNTb | MWCNTs + SDS-ultrasonication 3,4-ethylenedioxythiophene + (NH4)2S2O8-annealing | 2.37 | 1.0 | 161.4f 0.16c | [ |
Table 5 Sulfur-doped carbon as the PEMFC electrocatalyst support.
Introduction method | Materials | Preparation methods | Particles size (nm) | pH value | Electrocatalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | S-carbon shell | Sodium dodecyl sulfate (SDS) + ethyleneglycol (EG)-stirring + pyrolysis | 8.39 | 13.0 | 0.99 c (vs. RHE) | [ |
S-nanocarbon spheres | Thioanisole (TOAS) + benzene-(solution plasma synthesis) | 3.00 | 13.0 | 490 d | [ | |
Post-treatment | S-graphene | GO + diethylene glycol methyl ether-refluxing | — | 13.0 | 0.02 c (vs. Hg/HgO) -0.105 e (vs. Hg/HgO) | [ |
GP + phenyl disulfide (PDS) + annealing | 4.00 | 2.0 | 182 d | [ | ||
S-CNTa | Functionalized CNTa + PDS-heating | 6.20 | 2.0 | 272 d 17.2f 1.61g | [ | |
S-MWCNTb | MWCNTs + SDS-ultrasonication 3,4-ethylenedioxythiophene + (NH4)2S2O8-annealing | 2.37 | 1.0 | 161.4f 0.16c | [ |
Fig. 14. (a) Schematic diagram for the preparation of the Pt/S-MWCNTs catalyst and (b,c) CV and current-time curves of Pt/S-MWCNT (A), Pt/AO-MWCNT (B), and commercial Pt/C (C) catalysts. Reproduced with permission from Ref. [166], Copyright 2017 Royal Society of Chemistry.
Introduction method | Material | Method | Metal particle size (nm) | pH | Catalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | N/S co-doped honeycomb-ordered carbon | 1. SiO2 template + fluidic ANTc cladding 2. Carbonization 3. HF etching | 2.6 | 1 | 100i (for ORR) 0.99j (for ORR) | [ |
N/S co-doped porous carbon | 1. Salt template method | 4.59 | 13 | 528k (for ORR) 112.34l (for ORR) ~0.8j (for ORR) | [ | |
Post treatment | N/P co-doped GP | 1. Phosphoric acid + GP -hydrothermal synthesis 2. NH4OH + P-GOd hydrothermal synthesis | 2-4 | 13 | 108.6m (for MOR) 133.5l (for MOR) | [ |
N/B co-doped SWCNHa | 1. B4C + melamine composites + carbon rod-DCe arc-vaporization | 5 | 1 | 100i (for ORR) | [ | |
S/P co-doped GP | 1. Phosphoric acid + GO (ultrasonication-calcination) 2. Sulfuric acid + P-GOd (ultrasonication-calcination) | 4.5 | 13 | 0.93i (for ORR) | [ | |
N-S-P co-doped HCSb | 1. HCCPf + BPSg + TEAh pyrolysis 2. Etching | 4-6 | 1 | 1127n (for EOR) 1.61o (for EOR) | [ |
Table 6 Multi-atom co-doped carbon as the PEMFC electrocatalyst support.
Introduction method | Material | Method | Metal particle size (nm) | pH | Catalytic performance | R啊啊啊ef. |
---|---|---|---|---|---|---|
In situ | N/S co-doped honeycomb-ordered carbon | 1. SiO2 template + fluidic ANTc cladding 2. Carbonization 3. HF etching | 2.6 | 1 | 100i (for ORR) 0.99j (for ORR) | [ |
N/S co-doped porous carbon | 1. Salt template method | 4.59 | 13 | 528k (for ORR) 112.34l (for ORR) ~0.8j (for ORR) | [ | |
Post treatment | N/P co-doped GP | 1. Phosphoric acid + GP -hydrothermal synthesis 2. NH4OH + P-GOd hydrothermal synthesis | 2-4 | 13 | 108.6m (for MOR) 133.5l (for MOR) | [ |
N/B co-doped SWCNHa | 1. B4C + melamine composites + carbon rod-DCe arc-vaporization | 5 | 1 | 100i (for ORR) | [ | |
S/P co-doped GP | 1. Phosphoric acid + GO (ultrasonication-calcination) 2. Sulfuric acid + P-GOd (ultrasonication-calcination) | 4.5 | 13 | 0.93i (for ORR) | [ | |
N-S-P co-doped HCSb | 1. HCCPf + BPSg + TEAh pyrolysis 2. Etching | 4-6 | 1 | 1127n (for EOR) 1.61o (for EOR) | [ |
Fig. 15. (a) Schematic diagram for the preparation of the Pd/N-P-G catalyst; (b) Comparison of CV curves of different catalysts in 1 M KOH; (c) Comparison chart of the ECSA values of different catalysts. Reproduced with permission from Ref. [170], Copyright 2019 Elsevier.
Introduction method | Synthesis product | Synthesis procedure | Nanostructured morphology | Surface area (m2 g-1) | Particle sizea (nm) | Electrocatalyst ratio for electrochemical reaction | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
In situ process | WC-C | Hydrothermal carbonization | Microspheres | 256.0 | — | 1.4 for ESA 1.6 for ORRb,c | [ |
Hydrothermal carbonization | Mesoporous nanochain | 113.0 | — | 1.3 for ESA 1.6 for MORb | [ | ||
Hydrothermal carbonization | Hollow morphology | 433 | 3.6 | 1.96 for MORb | [ | ||
738 | — | 2.4 for MORb | |||||
Hydrothermal carbonization | Spherical morphology | 89 | 5.0 | 1.5 for ORRb | [ | ||
Soft templating carbonization | Ordered mesoporosity | 538.0 | 7.2 | 2.4 for MORd | [ | ||
WC-OMC | Hydrothermal and hard-templating carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.1 for MORd | [ | |
Pulse microwave-assisted polyol carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.0 for MORb | [ | ||
Hydrothermal carbonization | Ordered mesoporosity | 344.0 | 3.86 | — | [ | ||
Post-treatment | WC-C | Carbothermal H2 reduction | Bamboo-like morphology | — | — | 1.56 for MORb | [ |
Carbothermal N2 calcination | Macroporosity | 82.1 | 3.4 | 2.9 for ORRb | [ | ||
Carbothermal H2 reduction | Spherical morphology | 89.0 | 50.0-100.0 | — | [ | ||
WC-Ge | Microwave assisted carburization | Hexagonal prism shape | — | 5 | 2.29 for ESA | [ | |
WC-MWCNTf | Microwave carburization | Nanotube structure | — | — | 1.1 for MORb | [ | |
WC-GCg | Indirect carbonization | 3D Spheris | — | 50.0-200.0 | 3.7 for ORRa | [ | |
WC-HMGh | Microwave irradiation | Hemisphere-shaped macroporosity | 58.7 | 3.0 | 2.4 for ORRb | [ | |
WC-NCi | Indirect carbonization | Macroporosity | — | — | 2.5 for ORRb | [ |
Table 7 WC as electrocatalyst material supports.
Introduction method | Synthesis product | Synthesis procedure | Nanostructured morphology | Surface area (m2 g-1) | Particle sizea (nm) | Electrocatalyst ratio for electrochemical reaction | R啊啊啊ef. |
---|---|---|---|---|---|---|---|
In situ process | WC-C | Hydrothermal carbonization | Microspheres | 256.0 | — | 1.4 for ESA 1.6 for ORRb,c | [ |
Hydrothermal carbonization | Mesoporous nanochain | 113.0 | — | 1.3 for ESA 1.6 for MORb | [ | ||
Hydrothermal carbonization | Hollow morphology | 433 | 3.6 | 1.96 for MORb | [ | ||
738 | — | 2.4 for MORb | |||||
Hydrothermal carbonization | Spherical morphology | 89 | 5.0 | 1.5 for ORRb | [ | ||
Soft templating carbonization | Ordered mesoporosity | 538.0 | 7.2 | 2.4 for MORd | [ | ||
WC-OMC | Hydrothermal and hard-templating carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.1 for MORd | [ | |
Pulse microwave-assisted polyol carbonization | Ordered mesoporosity | 409.0 | 5.0 | 1.0 for MORb | [ | ||
Hydrothermal carbonization | Ordered mesoporosity | 344.0 | 3.86 | — | [ | ||
Post-treatment | WC-C | Carbothermal H2 reduction | Bamboo-like morphology | — | — | 1.56 for MORb | [ |
Carbothermal N2 calcination | Macroporosity | 82.1 | 3.4 | 2.9 for ORRb | [ | ||
Carbothermal H2 reduction | Spherical morphology | 89.0 | 50.0-100.0 | — | [ | ||
WC-Ge | Microwave assisted carburization | Hexagonal prism shape | — | 5 | 2.29 for ESA | [ | |
WC-MWCNTf | Microwave carburization | Nanotube structure | — | — | 1.1 for MORb | [ | |
WC-GCg | Indirect carbonization | 3D Spheris | — | 50.0-200.0 | 3.7 for ORRa | [ | |
WC-HMGh | Microwave irradiation | Hemisphere-shaped macroporosity | 58.7 | 3.0 | 2.4 for ORRb | [ | |
WC-NCi | Indirect carbonization | Macroporosity | — | — | 2.5 for ORRb | [ |
Fig. 17. (a) Schematic description for adsorbed CO on Pt and surface hydroxyls formed on WC with Pt/WC-C as the catalyst; (b) Schematic diagram of the preparation of the Pt@WC/OMC nanocomposite catalyst. Reproduced with permission from Ref. [200], Copyright 2015 Elsevier. (c) The MOR activity ratio between Pt/WC-C electrocatalysts with different surface areas and the commercial Pt/C.
Fig. 18. (a) ORR test curves of HMG/WC/Pt and Pt/C (1st and 2000th cycles); (b) Mass activity diagrams of HMG/WC/Pt and Pt/C; the CV curve of Pt/C (c) and HMG/WC/Pt (d) before and after 2000 cycles. Reproduced with permission from Ref. [191], Copyright 2016, Elsevier. a electrochemical surface area (m2 g-1), b limiting diffusion current (%), c mass activity (mA mgPt-1).
Fig. 19. (a) Comparison chart of the ECSA and current density of Pt/SiC and Pt/C single cells and (b) interface structure diagram of Pt/SiC and Pt/C electrodes before and after the AST test. Reproduced with permission from Ref. [223], Copyright 2017 Elsevier.
Functional carbide support | Catalyst synthesis method | T/oC | Pt particle size (nm) | ORR | Ref. | |
---|---|---|---|---|---|---|
pH | ECSAc/m2 gPt-1 | |||||
SiC | 1. Wood pyrolysis 2. Si and SiO2 calcination 3. Unreacted carbon separation 4. Acid washing | 1450 | — | 2.0 | 34d ; >80%e | [ |
TiC | — | — | 3.8 | 2.0 | 75d ; — | [ |
NbC | 1. ANOa + PVPb electrospinning 2. Calcination | 1100 | 3.1 | 13.0 | 43d ; 31%f | [ |
Table 9 Other functional carbides as the support for PEMFC electrocatalysts.
Functional carbide support | Catalyst synthesis method | T/oC | Pt particle size (nm) | ORR | Ref. | |
---|---|---|---|---|---|---|
pH | ECSAc/m2 gPt-1 | |||||
SiC | 1. Wood pyrolysis 2. Si and SiO2 calcination 3. Unreacted carbon separation 4. Acid washing | 1450 | — | 2.0 | 34d ; >80%e | [ |
TiC | — | — | 3.8 | 2.0 | 75d ; — | [ |
NbC | 1. ANOa + PVPb electrospinning 2. Calcination | 1100 | 3.1 | 13.0 | 43d ; 31%f | [ |
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