CN114855206A - Preparation of 3D printing monolithic electrocatalyst and application thereof in electrocatalytic reaction - Google Patents
Preparation of 3D printing monolithic electrocatalyst and application thereof in electrocatalytic reaction Download PDFInfo
- Publication number
- CN114855206A CN114855206A CN202210410619.4A CN202210410619A CN114855206A CN 114855206 A CN114855206 A CN 114855206A CN 202210410619 A CN202210410619 A CN 202210410619A CN 114855206 A CN114855206 A CN 114855206A
- Authority
- CN
- China
- Prior art keywords
- monolithic
- carbon
- electrocatalyst
- reaction
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 51
- 238000010146 3D printing Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000007547 defect Effects 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000012360 testing method Methods 0.000 claims description 25
- 238000004070 electrodeposition Methods 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 15
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 8
- -1 transition metal salt Chemical class 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000007639 printing Methods 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000009286 beneficial effect Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 239000002149 hierarchical pore Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229920006158 high molecular weight polymer Polymers 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 30
- 239000000976 ink Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 241000080590 Niso Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QXYRRCOJHNZVDJ-UHFFFAOYSA-N 4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(CCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 QXYRRCOJHNZVDJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
Preparation of 3D printing monolithic electrocatalyst and application in electrocatalysis reaction, relating to the field of electrochemical conversion and energy storage. The preparation method comprises the following steps: mixing a carbon material with good electric and heat conduction performance and an amino-containing high molecular polymer to prepare a non-Newtonian fluid with proper viscoelasticity, manufacturing and molding the non-Newtonian fluid by using a 3D printer in a DIW mode, roasting the non-Newtonian fluid in an inert atmosphere to obtain an integral carbon carrier, and finally electrodepositing a transition metal to improve the cathode electro-catalytic performance. The method has simple process, and the integral electrocatalyst structure can be designed according to the requirements of the electrocatalysis reaction; the prepared monolithic electrocatalyst has high specific surface area, periodically ordered multi-stage pore structure, excellent conducting capacity, adjustable carbon defect sites and excellent activity and stability in cathode electrocatalytic reaction.
Description
Technical Field
The invention relates to the field of electrochemical conversion and energy storage, in particular to preparation of a 3D printing monolithic electrocatalyst and application thereof in electrocatalysis reaction.
Background
Threat of exhaustion of traditional fossil energy and CO generated by the same in the face of petroleum crisis 2 The problems of global warming, environmental deterioration and the like caused by excessive emission are solved, and clean and efficient alternative energy sources and various catalytic conversion methods are actively sought by extensive research workers. Wherein the cathode electrocatalytic reduction reaction such as Hydrogen Evolution Reaction (HER), CO 2 Electroreduction reaction (CO) 2 RR), there have been many research results in recent years in terms of energy conversion and utilization.
The prepared electrocatalyst is often in the form of powder, and before use, the electrocatalyst is often mixed with a conductive agent (such as carbon black), a binder (such as Nafion) and a solvent such as ethanol or isopropanol to prepare an ink to be coated on a glassy carbon electrode or a self-supporting material such as carbon paper, carbon cloth and foamed nickel, which affects the exposure of active components and even results in low response current. In this regard, there are many reports in the literature on the use of self-supporting materials such as nickel foam, carbon paper and carbon cloth to grow catalysts in situ and achieve better activity. Such as Li et al (w.li, y.jiang, y.li, q.gao, w.shen, y.jiang,r.he, m.li, chem.eng.j.2021, 130651) constructed 3D free-standing Cr-doped CoP nanoarrays (Cr-CoP/CP) to facilitate water electrolysis. The results show that Cr-CoP/CP exhibits excellent activity for full pH universal hydrogen evolution reactions. Chinese patent CN 108677179A discloses modification of copper foil electrode and electrocatalytic reduction of CO 2 Investigation of the reaction, the invention uses KHCO 3 The copper foil is subjected to hydrothermal modification for 4 hours at 140 ℃ by using the aqueous solution. The modified copper foil is more beneficial to the high-yield high-added-value ethylene in the process of catalyzing carbon dioxide electroreduction.
However, the traditional self-supporting carrier has an irregular and disordered appearance and has no effectively communicated pore channel structure, so that great resistance exists for the timely transmission and release of gas products, and effective diffusion of gas reactants is not facilitated, so that the self-supporting carrier is only a loaded medium, the function of the carrier is not correspondingly exerted, and therefore, the 3D porous electrode with the ordered pore channel structure which is favorable for conducting and separating bubbles is indispensable.
The 3D printing technology is also called additive manufacturing technology, and a 3D porous electrode with an ordered pore channel structure can be designed and constructed according to actual reaction needs. Chinese patent CN107759986A discloses a carbon fiber composite material suitable for 3D printing, which is composed of polylactic acid (PLA), carbon fibers, a toughening agent, a compatilizer and an auxiliary agent. One-dimensional carbon nanotubes and two-dimensional graphene are widely used in the field of electrocatalysis due to their high surface area and excellent electrical conductivity. Many researches have been reported on 3D printing monolithic materials constructed by using graphene and carbon nanotubes as substrates. Peng et al (m.peng, d.shi, y.sun, j.cheng, b.zhao, y.xie, j.zhang, w.guo, z.jia, z.liang, l.jiang, adv.mater.2020,1908201) reported 3D printed bioelectrodes of one-dimensional carbon nanotube-reinforced graphene with high bending strength and hierarchical porous structure by 3D printing strategies. In 3D printing of graphene-based materials, no additional additives are usually added, but the viscoelasticity of such materials is less than ideal depending on the limited forces between the molecules. Mechanical modeling revealed a key role for one-dimensional CNTs in enhanced flexural strength by increasing the friction and adhesion between 2D graphene nanoplatelets. Xue et al (y.xue, l.hui, h.yu, y.liu, y.fang, b.huang, y.zhao, z.li, y.li, nat.commun.2019,2282) have demonstrated by theoretical calculations a reasonable surface conditioning strategy in terms of structural and electronic properties, enabling a significant improvement in the hydrogen evolution reactivity of electrocatalysts. The amidation modified catalyst surface will significantly promote more electron transfer to C ═ O, and this metal-free electrode has excellent hydrogen evolution reactivity and long-term stability in both acidic and basic media, even exceeding the commercial 20 wt% Pt/C catalyst. In addition, the doping of the nitrogen element can effectively regulate and control the electronic property of the carrier and improve the electrocatalytic activity of the carrier. Therefore, it is a very important research to explore a research of improving the performance of the 3D printing electrocatalysis carrier by reacting and crosslinking the amino-containing high molecular polymer and the graphene-based carbon material into 3D printing ink with proper viscoelasticity and doping nitrogen elements on the carrier.
Disclosure of Invention
The invention aims to provide preparation of a 3D printing monolithic electrocatalyst and application thereof in electrocatalysis reaction, the preparation method has simple process, and the monolithic electrocatalyst structure can be designed according to the electrocatalysis reaction requirement; the prepared monolithic carbon carrier has high specific surface area, a periodically ordered hierarchical pore structure, excellent conductivity and abundant carbon defect sites, and has better activity and stability when applied to cathode electrocatalytic reaction. The simple electrodeposition method is adopted to deposit transition metal on the monolithic carbon carrier, so that the cathode electro-catalysis of the electrode, such as hydrogen evolution reaction and CO, can be greatly improved 2 Activity and stability of electroreduction.
The invention provides a 3D printing monolithic electrocatalyst, which is obtained by electrodepositing and reducing metal on a monolithic carbon carrier prepared by 3D printing, and is named 3DPC-T @ M, wherein 3DP represents 3D printing preparation, T represents roasting temperature, @ represents load, and M represents deposited metal, and can be one metal or alloy of a plurality of metals.
The elemental composition of the carrier is C, N, O; the deposited metal includes at least one of Ni, Cu, Co, Fe, Mn, etc.
The invention provides a preparation method of a 3D printing monolithic electrocatalyst, mainly relating to 3D printing and electrodeposition, and specifically comprising the following steps:
1) refluxing the carbon material by using a strong acid oil bath, filtering, washing and drying to obtain an oxidized carbon material;
2) dissolving and dispersing the amino-containing high-molecular polymer in a solvent, adding the oxidized carbon material into the solvent for uniform dispersion, mixing, stirring, heating for reaction, and removing excessive solvent to prepare gel ink;
3) filling the gel ink into a needle cylinder, installing a needle nozzle with a proper size, extruding and molding the gel ink by using a modified 3D printer with a DIW mode according to a designed model, and then placing the gel ink into an oven for drying;
4) placing the dried printing material in a tubular furnace for roasting to obtain an integral carbon carrier;
5) and (3) taking the monolithic carbon carrier obtained by roasting as a working electrode, taking silver/silver chloride as a reference electrode and a graphite rod as a counter electrode, and carrying out cathodic electrodeposition in a solution containing transition metal salt and an additive to obtain the monolithic electrocatalyst.
In step 1), the strong acid is a mixture of concentrated sulfuric acid (98%) and concentrated nitric acid (68%); the carbon material can adopt graphene, carbon nano tubes, activated carbon or carbon fibers; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid can be 1: 1-4: 1; preferably, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3-3: 1; the oil bath temperature is 60-100 ℃; the reflux time is 2-12 h; preferably, the oil bath temperature is 60-80 ℃; the reflux time is 2-6 h.
In the step 2), the amine group-containing high molecular polymer can adopt polyethyleneimine or polydopamine; the solvent is water, acetic acid and ethanol; the mass ratio of the amino group-containing high molecular polymer to the carbon material can be 0.5: 1-5: 1, and preferably the mass ratio of the amino group-containing high molecular polymer to the carbon material is 1: 1-4: 1; the dosage of the solvent is 5-20 mL; preferably, the dosage of the solvent is 10-15 mL; the mixing and stirring time is 10-60 min; the heating temperature is 50-100 ℃; preferably, the mixing and stirring time is 20-40 min; the heating temperature is 50-80 ℃; the amino-containing high molecular polymer contains abundant amino functional groups, can form bonds with carboxyl functional groups on an oxidized carbon material, is used as a cross-linking agent to connect a carbon nano tube to form a three-dimensional network, and is also used as a nitrogen source to be doped with nitrogen elements after being roasted.
In the step 3), the modified 3D printer with the DIW mode is a 3D printer modified from a fused deposition type 3D printer into a needle cylinder pneumatic extrusion 3D printer, and the specific method is that a heating extrusion device of the original printer is replaced by a clamping seat capable of fixing the needle cylinder, one end of the needle cylinder is connected with a glue machine controller through a gas transmission pipeline, and the controller is connected with an air compressor through the gas transmission pipeline; the inner diameter of the needle nozzle can be 0.08-1.55 mm; the designed model is a periodic hole electrode model.
In the step 4), the roasting is performed at the constant temperature of 300-800 ℃ for 1-4 h in the inert atmosphere, preferably at the constant temperature of 450-750 ℃ for 1h in the inert atmosphere; the inert atmosphere is nitrogen, the amino-containing high molecular polymer has thermal instability and can be gradually decomposed along with the rise of temperature, a small amount of nitrogen atoms are doped into the carbon material and exist in the form of pyrrole nitrogen, pyridine nitrogen or graphite nitrogen, and the introduction of the nitrogen atoms is also beneficial to improving the electronic structure of the material and improving the conductive capability of the material; the monolithic carbon carrier mainly comprises C, N and O elements, and the material has high specific surface area, a periodically ordered hierarchical pore structure, excellent conductivity, abundant carbon defect sites and nitrogen heteroatom sites.
In step 5), the transition metal salt may be selected from a cobalt salt, a nickel salt, an iron salt or a copper salt; the concentration of the transition metal salt is 0.1-2 mol/L; the additive can adopt boric acid, sulfuric acid or sodium hydroxide; the concentration of the additive is 0.25-2 mol/L; in order to further improve the catalytic capability of the prepared monolithic carbon carrier applied to cathode electrocatalysis reaction and embody the application value of materials, active metal is deposited on the monolithic carbon carrier by adopting a simple electrodeposition method; the electrodeposition method comprises cyclic voltammetry, potentiostatic deposition, galvanostatic deposition or square-wave electrodeposition and the like.
When the electrodeposition method is cyclic voltammetry, the cycle time is 1-10 times, and the scanning rate is 1-100 mV/s.
When the electrodeposition method is constant potential deposition, the deposition potential is 0-minus 0.6V (relative to a silver/silver chloride electrode), and the deposition time is 200-1000 s.
The invention provides an application of a monolithic electrocatalyst for depositing active metal on a monolithic carbon carrier in cathode electrocatalytic reaction.
The specific conditions of the application may be: applied to the cathodic hydrogen evolution reaction, and the electrolyte is 1.0M KOH or 0.5M H 2 SO 4 (ii) a Application to cathode CO 2 Reduction reaction with electrolyte of 0.1M KHCO 3 (ii) a The test was carried out using a three-electrode system, CHI660E electrochemical workstation.
Compared with the traditional self-supporting material, the monolithic electrocatalyst has better electrocatalytic hydrogen evolution activity and stability, and the transmission of bubbles is faster; application to CO 2 The electroreduction can effectively convert CO 2 Is a multi-carbon product.
The invention prints and shapes the gel ink made of the graphene carbon material and the amino-containing high molecular polymer according to a designed model in a 3D printing mode, then removes the polymer by high-temperature roasting in an inert atmosphere, and then deposits the transition metal by adopting a simple electrodeposition method to obtain the integral electrocatalyst, and the method has the following advantages:
(1) the 3D printing preparation process is simple, less in time consumption and free of environmental pollution, the personalized product design can be met, the electrode structure is controllable and easy to adjust, and the method is suitable for large-scale production;
(2) the electrodeposition of the active metal is simple and easy to operate, can quickly obtain the material with high catalytic performance, does not involve dangerous hydrothermal reaction of heating and pressurizing and complex operation, and is suitable for batch production.
The prepared monolithic electrocatalyst shows the following 5 distinct advantages over the traditional self-supporting material electrocatalyst:
(1) the thermal decomposition of the amino-containing high molecular polymer dopes nitrogen elements in the carrier, improves the conductive capability of the material and increases active sites, and the oxidation and roasting treatment increases abundant carbon defects and improves the reaction active sites of the material;
(2) the obtained integral carbon carrier has high specific surface area and rich micropore and mesoporous structures, and is communicated with a macroscopic pore canal with controllable design to form a developed pore canal structure;
(3) the obtained integral carbon carrier has extremely strong hydrophilic performance, which is beneficial to the infiltration of electrolyte;
(4) the obtained integral carbon carrier has good gas-dredging performance, is weak in restraining small bubbles generated in the material from the material, can leave the surface of the material in time and quickly, and is beneficial to the reaction;
(5) the electro-deposition of the active metal on the monolithic carbon carrier does not reduce the conductivity, the hydrophilic property and the gas-dredging property of the material, the monolithic electrocatalyst still has a pore passage with the communication and the cooperation of macro macropores and micro mesopores, and the catalytic activity of the monolithic electrocatalyst is obviously stronger than that of the traditional catalytic material for electro-deposition of the active metal on the self-supporting material.
Drawings
FIG. 1 is a rheological characterization of a gel ink provided in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a monolithic carbon support according to example 1 of the present invention;
FIG. 3 shows the IR and Raman spectra, XRD pattern and N of monolithic carbon support according to example 1 of the present invention 2 Physical adsorption-desorption curves;
FIG. 4 is an X-ray photoelectron spectrum of a monolithic carbon support provided in example 1 of the present invention;
FIG. 5 shows the results of electrochemical tests of monolithic carbon supports in 1.0M KOH according to examples 1 to 4 of the present invention;
fig. 6 is a continuous dynamic contact angle and a high-speed camera captured image of the monolithic carbon support provided in example 1 of the present invention;
FIG. 7 is a scanning electron micrograph of a monolithic carbon nickel-plated electrode provided in example 5 of the present invention;
FIG. 8 shows the IR, Raman spectrum and XRD patterns of the monolithic carbon-nickel-plated electrode provided in example 5 of the present inventionSpectrum and N 2 Physical adsorption-desorption curves;
FIG. 9 is an X-ray photoelectron spectrum of a monolithic carbon nickel-plated electrode provided in example 5 of the present invention;
FIG. 10 shows the results of electrochemical measurements of monolithic electrocatalysts provided in example 5 of the present invention and comparative examples 1 to 3 in 1.0M KOH;
FIG. 11 shows the results of continuous dynamic contact angles of monolithic electrocatalysts provided in example 5 of the present invention and comparative examples 1 to 3 in 1.0M KOH;
FIG. 12 shows high-speed camera-captured images of monolithic electrocatalysts provided in example 5 of the present invention and comparative examples 1-3 in 1.0M KOH;
FIG. 13 is a scanning electron micrograph of a monolithic electrocatalyst according to example 6 of the present invention;
figure 14 is an XRD spectrum of the monolithic electrocatalyst provided in example 6 of the present invention;
FIG. 15 shows CO in the monolithic electrocatalyst according to example 6 of the present invention 2 And (5) electroreduction test results.
Detailed Description
To describe the present invention more specifically, the following detailed description of the embodiments of the present invention is provided with reference to the accompanying drawings and the detailed description, and the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The 3D printer used in the following examples was commercially available from a model 3Drag K8200 fused deposition printer from Valleman corporation; the dispenser controller may be a dispenser controller manufactured by Advanced Ele Eqiop corporation. The modified 3D printer with the DIW mode can be obtained by replacing a heating extrusion device of the fused deposition type 3D printer with a clamping seat capable of fixing a needle cylinder, connecting one end of the needle cylinder with a glue machine controller through a gas transmission pipeline, and connecting the controller with an air compressor through the gas transmission pipeline.
Example 1
Refluxing carbon nanotube with concentrated sulfuric acid and concentrated nitric acid (volume ratio 1: 3) at 80 deg.C for 3h, washing with deionized water, and drying. 2.08g of polyethyleneimine is weighed and dissolved in 15ml of acetic acid solution, 1.06g of prepared carbon oxide nanotube is weighed and dissolved in the solution while stirring, the solution is stirred for 30min, and then the gel ink is obtained by heating and stirring at 70 ℃ to remove excessive solvent.
The prepared ink is filled into a syringe, a 0.62mm needle nozzle is selected as an extrusion caliber, a modified DIW mode 3D printer is used for printing an electrode model with 5 layers, and then drying is carried out in an oven.
The rheological properties of the gel ink prepared in this example are shown in fig. 1, and as can be seen from a in fig. 1, the gel ink has shear thinning property, that is, the apparent viscosity decreases rapidly with the increase of the shear rate. As can be seen from graph b in fig. 1, the gel inks each have a linear viscoelastic region independent of shear stress at low shear stress, and a yield point exists. As can be seen from graph c in fig. 1, in the frequency range of the scanning, the change of modulus with frequency is not large, and the storage modulus G' is greater than the loss modulus G ″, which indicates that the ink exhibits the behavior characteristic of gel, has high elasticity, and the polyethyleneimine and the carbon nanotubes are crosslinked into a three-dimensional network structure, so that the extruded line can keep the structure stable for a long time and is not easy to collapse and deform.
And (3) placing the dried printing material in a tubular furnace, introducing nitrogen as a roasting atmosphere, and keeping the temperature at 650 ℃ for 1 h.
Adopting a three-electrode system to carry out a cathodic hydrogen evolution reaction, taking an integral carbon carrier obtained by roasting as a working electrode, a mercury/mercury oxide electrode as a reference electrode, and a carbon rod as a counter electrode; measuring 60mL of potassium hydroxide solution (with the concentration of 1.0M) as electrolyte;
on a CHI660E electrochemical workstation, activity evaluation adopts a linear scanning voltammetry, and the scanning speed is 5 mV/s; the electrochemical impedance test has the test frequency of 100k to-0.01 Hz and the amplitude of 5mV under the voltage of-1.224V (relative to a mercury/mercury oxide electrode); the electrochemical active area test is carried out in a non-faradaic range with the amplification of 1.0 to 5.0 and 0.5mVs -1 Performing cyclic voltammetry scanning at the scanning speed; the stability test adopts a potentiostatic method, and 50mAcm is taken -2 The corresponding current is the control condition.
FIG. 2 is a scanning electron micrograph of the monolith carbon support prepared in example 1. As can be seen from electron micrographs, the support prepared under the high-temperature calcination condition is essentially composed of carbon nanotubes, no significant polyethyleneimine remains, and a large number of stacked pore structures are generated.
Fig. 3 a is an infrared spectrum of the monolith carbon support prepared in example 1. The infrared spectrum shows that the material is 1580cm -1 The contraction vibration peak is the C ═ C double bond contraction vibration mode of the multi-wall carbon nanotube wall, which indicates the existence of the carbon nanotube graphite structure. 1640cm -1 Has a strong absorption peak which is attributed to the characteristic peak of amide group (-CO-NH-) peculiar to the interfacial polymerization reaction, 1060cm -1 The absorption peak corresponds to the characteristic peak of C-N stretching vibration, which shows that the monolithic carbon carrier is formed into a cross-linked structure by the carbon oxide nano tube and the polyethyleneimine through polymerization reaction.
Fig. 3 b is a raman spectrum of the monolith carbon support prepared in example 1. The material is 1583cm in length according to Raman spectrum -1 The G peak of the carbon nanotube appears at 1325cm -1 The Raman peak of (A) is a characteristic peak D induced by the defect, and the ratio I of the two peaks D /I G 2.13, much higher than the oxidized carbon nanotubes, indicating that the material has more defective carbon structure.
Fig. 3c is a graph showing the X-ray diffraction results of the monolithic carbon support prepared in example 1. Compared with a standard card (PDF #65-6212) of carbon, the diffraction peak of the material at 26.5 degrees and 42.3 degrees is corresponding to the (002), (100) crystal face of the CNT.
FIGS. d-e in FIG. 3 are N for the monolithic carbon support prepared in example 1 2 Physical adsorption-desorption test results. As can be seen from the figure, the adsorption-desorption isotherm of the material conforms to the characteristics of the IV-type isotherm, a large number of microporous structures exist, and the P/P ratio is higher 0 Capillary condensation occurs in the zone, desorption isotherms and adsorption isotherms are not coincident, adsorption hysteresis is generated, and a hysteresis loop appears, which indicates that a mesoporous pore structure exists, and the specific surface area of the material is 138.32m 2 ·g -1 Pore volume of 0.214cm 3 ·g -1 。
Fig. 4 is a result of X-ray photoelectron spectroscopy of the monolith carbon support prepared in example 1. As can be seen from the graph a in fig. 4, C, N and O elements were detected in the material, and the peaks at 398.0eV and 400.2eV correspond to pyridine nitrogen (pyridine N) and graphite nitrogen (graphite N), respectively. As can be seen from panel b of fig. 4, the pyridine nitrogen and graphite nitrogen are in similar proportions, and the area fit shows that the pyridine nitrogen and graphite nitrogen are in proportions of 45.86% and 54.14%, respectively.
FIG. 5, panel a, shows the results of electrochemical polarization curve tests on monolithic carbon supports prepared in examples 1-4. With the increase of the roasting temperature, the hydrogen evolution reaction activity of the carrier is increased firstly and then reduced; the optimum calcination temperature is 650 deg.C, when the current density is 50mA cm -2 When the hydrogen evolution overpotential is 315mV in a 1M KOH solution; panel b of FIG. 5 shows that 3DPC-650 was at 50mA cm -2 Has good stability of more than 16h at the current density of (2). FIG. 5, panel c, is an electrochemical impedance test of monolithic carbon supports prepared in examples 1-4. With the increase of the roasting temperature, the charge transfer resistance of the material is basically stable after being reduced; the charge transfer resistance Rct of the carrier with the roasting temperature of 650 ℃ is 0.48 omega, and the carrier shows good conductive performance. FIG. 5, panel d, is an electrochemical active area test of monolithic carbon supports prepared in examples 1-4. Electric double layer capacitance C of the carrier with increasing baking temperature dl Decreasing first and then increasing; double electric layer capacitance C of carrier with roasting temperature of 650 DEG C dl Is 276mF cm -2 Taking the electrochemical active area of the carbon material calculated by the general standard to be 6003cm 2 。
Fig. 6, panel a, shows the contact angle test results of the monolith carbon support prepared in example 1. The continuous dynamic contact angle image showed that the droplets were completely penetrated into the material in a very short time of only 80ms, showing a very strong wetting property, indicating the good hydrophilic properties of the material prepared in example 1.
Fig. 6, panel b, is a high speed camera observation of the monolith carbon support prepared in example 1 in a hydrogen evolution reaction. The image showed that the carrier generated fine and numerous bubbles (bubble diameter not more than 200 μm) and no bubbles adhered to the surface of the material, and the release behavior of the bubbles was in accordance with the internal growth and department model (Joule 5, 1-14, April 21,2021). The characteristic of this mode is that the generated bubbles are small and much and usually do not adhere to the surface of the material to influence the reaction, which indicates that the carrier has better gas-permeable performance.
Example 2
The roasting temperature of the example 1 is changed to 450 ℃ and kept for 1h, and other steps are carried out by adopting the method of the example 1, so as to obtain the carrier provided by the invention.
Example 3
The roasting temperature of the example 1 is changed to 550 ℃ and kept for 1h, and other steps are carried out by adopting the method of the example 1, so as to obtain the carrier provided by the invention.
Example 4
The calcination temperature of example 1 was changed to 750 ℃ and maintained for 1h, and the other steps were performed by the method of example 1, to obtain the carrier of the present invention.
Example 5
The monolithic carbon carrier obtained by the calcination treatment in example 1 was used as a working electrode, silver/silver chloride as a reference electrode, a graphite rod as a counter electrode, and the electrode was doped with 0.5M NiSO 4 And 0.25M H 3 BO 3 The monolithic electrocatalyst is obtained by cathodic electrochemical deposition in the solution of (a).
Adopting a three-electrode system to carry out cathode hydrogen evolution reaction, taking an integral electrocatalyst as a working electrode, a mercury/mercury oxide electrode as a reference electrode, and a carbon rod as a counter electrode; measuring 60mL of potassium hydroxide solution (with the concentration of 1.0M) as electrolyte;
on a CHI660E electrochemical workstation, activity evaluation adopts linear sweep voltammetry, and the sweep rate is 5 mV/s; the electrochemical impedance test has the test frequency of 100k to-0.01 Hz and the amplitude of 5mV under the voltage of-1.224V (relative to a mercury/mercury oxide electrode); the electrochemical active area test is carried out in a non-faradaic range with the amplification of 1.0 to 5.0 and 0.5mVs -1 Performing cyclic voltammetry scanning at the scanning speed of (1); the stability test adopts a potentiostatic method, and 50mAcm is taken -2 The corresponding current is the control condition.
The scanning electron micrograph of the monolithic electrocatalyst prepared in this example is shown in fig. 7, and it can be seen from the electron micrograph that Ni nanoparticles are formed on the support, the particle size is in the range of 100 nm or more, and the distribution is relatively uniform.
The IR spectrum of the monolithic electrocatalyst prepared in this example is shown in FIG. 8, panel a, where the material is at 1580cm -1 The contraction vibration peak is the C ═ C double bond contraction vibration mode of the multi-wall carbon nanotube wall, which indicates the existence of the carbon nanotube graphite structure. 1640cm -1 Has a strong absorption peak which is attributed to the characteristic peak of amide group (-CO-NH-) peculiar to the interfacial polymerization reaction, 1060cm -1 The absorption peak corresponds to the characteristic peak of C-N stretching vibration, which shows that the monolithic electrocatalyst is formed by the carbon oxide nanotubes and the polyethyleneimine into a cross-linked structure through polymerization reaction.
The Raman spectrum of the monolithic electrocatalyst prepared in this example is shown in FIG. 8, panel b, and it can be seen from the Raman spectrum that the material is at 526cm -1 Has a Raman peak due to beta-Ni (OH) 2 The overlap of the A1g and 2nd peaks formed by the species indicates that there are multiple chemical states for Ni.
The monolithic electrocatalyst prepared in this example had the X-ray diffraction results shown in FIG. 8, panel c, with diffraction peaks at 19.26, 33.06, 38.54 corresponding to Ni (OH) 2 The (001), (100), (101) planes (PDF # 14-0117); the diffraction peaks at 44.35 ° and 51.67 ° correspond to the (111) and (200) crystallographic planes of Ni (PDF # 65-0380). These diffraction peak signals are relatively weak, indicating that less Ni is deposited on the monolithic electrocatalyst.
The monolithic electrocatalyst prepared in this example was subjected to N 2 The results of the physisorption-desorption tests are shown in fig. 8, panels d-e. The adsorption-desorption isotherm of the material conforms to the characteristics of the IV-type isotherm, and due to the deposition of Ni on the carrier, part of micropores are blocked, a pore channel structure mainly comprising mesopores is generated, and the specific surface area of the material is 93.27m 2 ·g -1 Pore volume of 0.293cm 3 ·g -1 。
The monolithic electrocatalyst prepared in this example was subjected to X-ray photoelectron spectroscopyThe results of the tests are shown in FIG. 9. The full spectrum shows that Ni element is detected in the material, and the peaks at 855.7eV and 873.3eV respectively correspond to Ni 2+ 2p of 3/2 And 2p 1/2 . With Ar + After etching, peaks 852.8eV, 871.2eV appeared, corresponding to Ni 0 2p of 3/2 And 2p 1/2 Indicating that the deposited Ni exists in 0-valent and + 2-valent forms.
FIG. 10, panel a, shows the results of electrochemical polarization curve tests performed on the monolithic electrocatalysts prepared in example 5 and comparative examples 1 to 3. Compared with the traditional nickel-plated electrocatalyst on carriers (carbon paper, carbon cloth and foamed nickel), the monolithic electrocatalyst prepared by the invention has the current density of 50 mA-cm in 1M KOH solution -2 When the activity is higher, the hydrogen evolution overpotential is 160mV, which shows that the activity is better. Panel b of FIG. 10 shows the monolithic electrocatalyst at 50mA cm -2 Has good stability of over 120h at the current density of (2).
FIG. 10, panel c, shows the results of electrochemical impedance testing of monolithic electrocatalysts prepared in example 5 and comparative examples 1 to 3. Compared with the traditional nickel-plated electrocatalyst on a carrier (carbon paper, carbon cloth and foamed nickel), the monolithic electrocatalyst prepared by the invention has smaller charge transfer resistance Rct of 0.52 omega in 1M KOH solution, and the monolithic electrocatalyst prepared by the embodiment has good conductivity.
FIG. 10, panel d, shows the results of electrochemical active area tests performed on the monolithic electrocatalysts prepared in example 5 and comparative examples 1 to 3. Compared with the traditional nickel-plated electrocatalyst on a carrier (carbon paper, carbon cloth and foamed nickel), the monolithic electrocatalyst prepared by the invention has larger double electric layer capacitance C in 1M KOH solution dl (344.2mF cm -2 ) The electrochemical active area calculated by taking the general standard of the carbon material is 7486.35cm 2 。
FIG. 11 shows the results of contact angle measurements performed on the monolithic electrocatalysts prepared in example 5 and comparative examples 1 to 3. The continuous dynamic contact angle image shows that compared with the traditional carrier nickel-plated electrocatalyst, the liquid drops can completely permeate into the monolithic electrocatalyst within a very short time of 80ms, and the strong wettability is shown, which indicates that the material prepared by the embodiment has good hydrophilic performance.
FIG. 12 shows the results of high-speed camera observation of monolithic electrocatalysts prepared in example 5 and comparative examples 1 to 3 in a hydrogen evolution reaction. It can be found that the bubbles generated on the monolithic electrocatalyst are fine and numerous (the diameter of the bubbles is not more than 200 μm), no bubbles are attached to the surface of the material, and the release behavior of the bubbles conforms to the internal growth and recovery model. This mode is characterized by the generation of small and numerous bubbles and generally no adhesion to the surface of the material to affect the reaction, which also indicates that the monolithic electrocatalyst has better gas-phobic properties.
Example 6
The monolithic carbon carrier obtained by the calcination treatment in example 2 was used as a working electrode, silver/silver chloride as a reference electrode, a graphite rod as a counter electrode, and the working electrode was doped with 0.5M CuSO 4 And 1.5M H 3 SO 4 The monolithic electrocatalyst is obtained by cathodic electrochemical deposition in the solution of (a).
Cathodic CO with three-electrode system 2 Performing electroreduction reaction, namely taking an integral type electrocatalyst as a working electrode, a silver/silver chloride electrode as a reference electrode, and a platinum sheet as a counter electrode; measuring 36mL of potassium bicarbonate solution (with the concentration of 0.1M) as electrolyte;
on CHI660E electrochemical workstation, activity evaluation adopts linear sweep voltammetry, and sweep rate is 5 mV/s; the selectivity of the product is evaluated by Faraday efficiency, the method is to select proper potential to carry out constant current test for 1h, the gas phase product is analyzed on line by the gas chromatography which is used in the period, and the liquid phase product is subjected to nuclear magnetic resonance analysis by taking the electrolyte after the reaction.
The scanning electron micrograph of the monolithic electrocatalyst prepared in this example is shown in fig. 13, and it can be seen from the electron micrograph that the material prepared under this condition generates particles of Cu on the monolithic carbon support, which are distributed more uniformly.
The monolithic electrocatalyst prepared in this example showed X-ray diffraction results in fig. 14, having diffraction peaks at 43.34 ° and 50.48 ° corresponding to the (111), (200) crystal plane (PDF #65-9026) of Cu; diffraction peaks at 36.50 °, 42.40 °, 61.52 ° correspond to Cu 2 (111), (200) and (2) of O(220) Crystal plane (PDF # 65-3288). This indicates that Cu is deposited on the bulk electrocatalyst, accompanied by Cu 2 O。
The monolithic electrocatalyst prepared in this example was subjected to CO 2 The results of the electroreduction test are shown in FIG. 15. As can be seen from the polarization curve of graph a in FIG. 15, the reduction current in the potential range of 0 to-1.3V is attributed to CO 2 Whereas a larger reduction current after-1.3V is that a vigorous hydrogen evolution reaction takes place. A constant current stability test was performed at a potential of-1.6V, as shown in panel b of FIG. 15. The material is seen to be relatively stable during the reaction process. The results of on-line gas chromatography during the stability test and liquid-phase nmr analysis after the reaction are shown in fig. 15, panels c, d. Liquid phase nuclear magnetic analysis indicated the presence of ethanol, acetic acid and formic acid. The gas phase product is mainly H 2 And CO, H due to a relatively violent hydrogen evolution reaction 2 The selectivity of (A) is higher.
Example 7
0.64g of 1-pyrenebutanoic acid-1, 4-butanediamine compound (AP-DSS), 0.114g, was weighed out and dissolved in 2.374g of water of polyethyleneimine containing 50% aqueous solution, and stirred for 1 hour with a magnetic stirrer. 0.543g of graphene is weighed, dissolved in the above solution while stirring, stirred for 15min, and then heated at 70 ℃ to promote the amine-aldehyde condensation reaction and pi-pi stacking. Adding distilled water with a certain mass to restore the mass of the mixture before drying, and stirring for 15min to obtain homogeneous gel ink. The ink is filled into a syringe, a 0.62mm needle head is selected as an extrusion nozzle, and a modified 3D printer with a DIW mode is used for printing a model. Then drying in a vacuum oven for 30min, placing in a tube furnace for roasting, wherein the roasting temperature is increased from 30 ℃ to 250 ℃ for 110min, the roasting temperature is kept at 250 ℃ for 30min, the roasting temperature is increased from 250 ℃ to 600 ℃ for 175min, the roasting temperature is kept at the highest temperature of 600 ℃ for 60min, and then slowly cooling.
The monolithic carbon support prepared in this example was subjected to electrochemical impedance testing at 0.5M H 2 SO 4 The solution impedance Rs in the solution is 8.239 Ω, the charge transfer impedance Rct is 0.1776 Ω, and the interface impedance Rh is 1.944 Ω.
Example 8
50% aqueous solution of polyethyleneimine 0.6664g were weighed out and dissolved in 2.3403g of water, and stirred with a magnetic stirrer for 1 h. 0.543g of graphene was weighed into the above solution, stirred for 15min, and then heated at 70 ℃ to promote the amine-aldehyde condensation reaction and Π - Π stacking. Adding 1717mg of water and 100mg of 1-pyrenebutanoic acid-1, 4-butanediamine compound (AP-DSS) to recover the mass of the mixture before drying, and stirring for 15min to obtain homogeneous gel ink. The ink is filled into a syringe, a 0.62mm needle head is selected as an extrusion nozzle, and a modified 3D printer with a DIW mode is used for printing a model. Then drying in a vacuum oven for 30min, placing in a tube furnace for roasting, wherein the roasting temperature is increased from 30 ℃ to 250 ℃ for 110min, the roasting temperature is kept at 250 ℃ for 30min, the roasting temperature is increased from 250 ℃ to 600 ℃ for 175min, the roasting temperature is kept at the highest temperature of 600 ℃ for 60min, and then slowly cooling.
The monolithic carbon support prepared in this example was subjected to electrochemical impedance testing at 0.5M H 2 SO 4 The solution resistance Rs in the solution was 2.736 Ω, the charge transfer resistance Rct was 0.9031 Ω, and the interface resistance Rh was 1.963 Ω.
Example 9
19.3mg of 1, 4-butanediamine and 63.3mg of 1-pyrenebutanoic acid were weighed and dissolved in 36.5ml of N, N-dimethylformamide to prepare a mixed solution.
0.65g of a 50% aqueous polyethyleneimine solution was dissolved in 2.237ml of water, and 136mg of the above mixed solution was added to the solution. 0.54g of graphene is weighed and added into the solution, the mixture is stirred for 15min to be uniformly mixed, and then the homogeneous gel ink is obtained at 70 ℃. And (3) filling the ink into a needle cylinder, selecting a 0.62mm needle head as an extrusion nozzle, printing a model by using a modified 3D printer in a DIW mode, drying in a 70 ℃ oven, and roasting at 600 ℃ for 1h to obtain the integral carbon carrier.
0.0756g of iron acetylacetonate and 0.0951g of nickel acetylacetonate were weighed and dissolved in a mixed solution of 20ml of water and 10ml of ethanol, and then the monolithic carbon support was added to the solution. 0.504g of sodium borohydride and 0.059g of sodium hydroxide are weighed and dissolved in 4ml of water, and the solution is dropped into the solution of the integral carbon carrier and placed in an ultrasonic dispersion instrument for reaction for 2 hours. After the reaction, the catalyst was washed with deionized water and then dried in an oven at 70 ℃ to obtain the monolithic electrocatalyst prepared in this example.
The monolithic electrocatalyst prepared in this example was subjected to a polarization curve test. When the current density is 50mA cm -2 At 0.5M H 2 SO 4 The overpotential for hydrogen evolution in the solution is 672 mV. The monolithic electrocatalyst has good stability in acidic solutions as tested.
The monolithic electrocatalyst prepared in this example was subjected to electrochemical impedance testing. The current density of the electrocatalytic hydrogen evolution reaction is 50mA cm -2 Is 0.5M H with respect to the overpotential of (2) 2 SO 4 The solution resistance Rs in the solution was 2.71 Ω, the charge transfer resistance Rct was 1.54 Ω, and the interface resistance Rh was 5.71 Ω.
Comparative example 1
Taking cleaned fresh carbon paper as a working electrode, silver/silver chloride as a reference electrode, a graphite rod as a counter electrode, and adding 0.5M NiSO 4 And 0.25M H 3 BO 3 And carrying out cathodic electrochemical deposition in the solution to obtain the nickel plating electrocatalyst. Other test procedures were carried out using the method of example 5.
Comparative example 2
Taking clean fresh carbon cloth as a working electrode, silver/silver chloride as a reference electrode, a graphite rod as a counter electrode, and adding 0.5M NiSO 4 And 0.25M H 3 BO 3 And carrying out cathodic electrochemical deposition in the solution to obtain the nickel plating electrocatalyst. Other test procedures were carried out using the method of example 5.
Comparative example 3
Taking cleaned fresh foam nickel as a working electrode, silver/silver chloride as a reference electrode, a graphite rod as a counter electrode, and adding 0.5M NiSO 4 And 0.25M H 3 BO 3 And carrying out cathodic electrochemical deposition in the solution to obtain the nickel plating electrocatalyst. Other test procedures were carried out using the method of example 5.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a 3D printing monolithic electrocatalyst is characterized by comprising the following steps:
1) refluxing the carbon material by using a strong acid oil bath, filtering, washing and drying to obtain an oxidized carbon material;
2) dissolving and dispersing the amino-containing high molecular polymer in a solvent, adding the oxidized carbon material into the solvent for uniform dispersion, mixing, stirring, heating for reaction, and removing the excessive solvent to obtain gel ink;
3) filling the gel ink into a needle cylinder, installing a needle nozzle with a proper size, extruding and molding the gel ink by using a modified 3D printer with a DIW mode according to a designed model, and then placing the gel ink into an oven for drying;
4) placing the dried printing material in a tubular furnace for roasting to obtain an integral carbon carrier;
5) and (3) taking the monolithic carbon carrier obtained by roasting as a working electrode, taking silver/silver chloride as a reference electrode and a graphite rod as a counter electrode, and carrying out cathodic electrodeposition in a solution containing transition metal salt and an additive to obtain the monolithic electrocatalyst.
2. The method for preparing a 3D printing monolithic electrocatalyst according to claim 1, characterized in that in step 1), the strong acid is a mixture of concentrated nitric acid and concentrated sulfuric acid; the carbon material can adopt graphene, carbon nano tubes, activated carbon or carbon fibers; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid can be 1: 1-4: 1; preferably, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3-3: 1; the oil bath temperature is 60-100 ℃; the reflux time is 2-12 h; preferably, the oil bath temperature is 60-80 ℃; the reflux time is 2-6 h.
3. The method for preparing a 3D printing monolithic electrocatalyst according to claim 1, wherein in step 2), the amine group containing high molecular weight polymer can be selected from polyethyleneimine, polydopamine; the solvent is water, acetic acid and ethanol; the mass ratio of the amino group-containing high molecular polymer to the carbon material can be 0.5: 1-5: 1, and preferably the mass ratio of the amino group-containing high molecular polymer to the carbon material is 1: 1-4: 1; the dosage of the solvent is 5-20 mL; preferably, the dosage of the solvent is 10-15 mL; the mixing and stirring time is 10-60 min; the heating temperature is 50-100 ℃; preferably, the mixing and stirring time is 20-40 min; the heating temperature is 50-80 ℃; the amino-containing high molecular polymer contains abundant amino functional groups, can form bonds with carboxyl functional groups on an oxidized carbon material, is used as a cross-linking agent to connect a carbon nano tube to form a three-dimensional network, and is also used as a nitrogen source to be doped with nitrogen elements after being roasted.
4. The preparation method of the 3D printing monolithic electrocatalyst according to claim 1, wherein in step 3), the modified 3D printer with DIW mode is obtained by modifying a fused deposition type 3D printer into a syringe pneumatic extrusion 3D printer, and the specific method comprises replacing a heating extrusion device of an original printer with a clamping seat capable of fixing the syringe, wherein one end of the syringe is connected with a glue machine controller through a gas transmission pipeline, and the controller is connected with an air compressor through the gas transmission pipeline; the inner diameter of the needle nozzle can be 0.08-1.55 mm; the designed model is a periodic hole electrode model.
5. The preparation method of the 3D printing monolithic electrocatalyst according to claim 1, wherein in step 4), the calcination can be performed at 300-800 ℃ for 1-4 h under inert atmosphere, preferably at 450-750 ℃ for 1h under inert atmosphere; the inert atmosphere is nitrogen, argon or helium, the amino-containing high polymer has thermal instability and can be gradually decomposed along with the rise of temperature, a small amount of nitrogen atoms are doped into the carbon material and exist in the form of pyrrole nitrogen, pyridine nitrogen or graphite nitrogen, and the introduction of the nitrogen atoms is also beneficial to improving the electronic structure of the material and improving the conductive capability of the material; the monolithic carbon carrier mainly comprises C, N and O elements, and the material has high specific surface area, a periodically ordered hierarchical pore structure, excellent conductivity, abundant carbon defect sites and nitrogen heteroatom sites.
6. The method for preparing a 3D-printed monolithic electrocatalyst according to claim 1, wherein in step 5) the transition metal salt is selected from cobalt, nickel, iron or copper salts; the concentration of the transition metal salt is 0.1-2 mol/L; the additive can adopt boric acid, sulfuric acid or sodium hydroxide; the concentration of the additive is 0.25-2 mol/L; in order to further improve the catalytic capability of the prepared monolithic carbon carrier applied to cathode electrocatalysis reaction and embody the application value of materials, active metal is deposited on the monolithic carbon carrier by adopting a simple electrodeposition method; the electrodeposition method comprises cyclic voltammetry and potentiostatic deposition.
7. The method for preparing a 3D printing monolithic electrocatalyst according to claim 6, characterized in that when the electrodeposition method is cyclic voltammetry, the number of cycles is 1-10, and the scan rate is 1-100 mV/s; when the electrodeposition method is constant potential deposition, the deposition potential is 0-minus 0.6V, and the deposition time is 200-1000 s.
8. The monolithic electrocatalyst prepared by the preparation method of the 3D printing monolithic electrocatalyst according to any one of claims 1 to 7, wherein the monolithic electrocatalyst is prepared by electrodepositing a reduced metal on a monolithic carbon support prepared by 3D printing, and is named 3DPC-T @ M, wherein 3DP represents the preparation of 3D printing, T represents the calcination temperature, @ represents the load, and M represents the deposited metal.
9. Use of a monolithic electrocatalyst according to claim 8 in a cathodic electrocatalytic reaction; the cathode electro-catalytic reactions include, but are not limited to, cathode hydrogen evolution reaction and cathode CO 2 And (4) carrying out reduction reaction.
10. Use according to claim 9, characterized in that the specific conditions are: when the catalyst is applied to the cathodic hydrogen evolution reaction, the reaction temperature is 1.0M KOH or 0.5M H 2 SO 4 Testing the hydrogen evolution reaction activity in the electrolyte; application to cathode CO 2 Reduction reaction at 0.1M KHCO 3 The reaction activity was tested in the electrolyte of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210410619.4A CN114855206B (en) | 2022-04-19 | 2022-04-19 | Preparation of 3D printing integral electrocatalyst and application thereof in electrocatalytic reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210410619.4A CN114855206B (en) | 2022-04-19 | 2022-04-19 | Preparation of 3D printing integral electrocatalyst and application thereof in electrocatalytic reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114855206A true CN114855206A (en) | 2022-08-05 |
| CN114855206B CN114855206B (en) | 2023-12-12 |
Family
ID=82631783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210410619.4A Active CN114855206B (en) | 2022-04-19 | 2022-04-19 | Preparation of 3D printing integral electrocatalyst and application thereof in electrocatalytic reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114855206B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659394A (en) * | 2020-06-24 | 2020-09-15 | 浙江大学 | Copper-based catalyst and preparation method and application thereof |
-
2022
- 2022-04-19 CN CN202210410619.4A patent/CN114855206B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659394A (en) * | 2020-06-24 | 2020-09-15 | 浙江大学 | Copper-based catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114855206B (en) | 2023-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | N-doped hierarchically porous carbon derived from grape marcs for high-performance supercapacitors | |
| Sk et al. | Review on advances in porous nanostructured nickel oxides and their composite electrodes for high-performance supercapacitors | |
| CN108940285A (en) | A kind of preparation method and application of flexibility electrolysis water catalysis material | |
| Rezaee et al. | 3D ternary Ni x Co 2− x P/C nanoflower/nanourchin arrays grown on HCNs: a highly efficient bi-functional electrocatalyst for boosting hydrogen production via the urea electro-oxidation reaction | |
| CN108103517B (en) | A kind of metal nanoparticle of self-supporting/porous nitrogen carbon dope film and its preparation method and application | |
| CN111659401A (en) | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof | |
| CN110767914B (en) | Co-N doped porous carbon-coated carbon nanotube core-shell structure catalyst and preparation method and application thereof | |
| EP3022785A1 (en) | Microtubes made of carbon nanotubes | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN105271217A (en) | Method for preparing nitrogen-doped three-dimensional graphene | |
| CN110117009B (en) | Preparation method of iron-nitrogen co-doped magnetic porous graphitized nano carbon aerogel | |
| CN112194818B (en) | Copper/silver-based electrode with conductive bacterial cellulose composite membrane as substrate | |
| CN109244484A (en) | A kind of preparation method of porous graphene/carbon nano tube flexible self-supported membrane material | |
| CN112354550A (en) | Composite modified catalyst with through hole structure | |
| CN111468162A (en) | CO of porous carbon-graphene loaded nano cobalt2Reduction catalyst and process for producing the same | |
| Venkateshalu et al. | Heterogeneous 3D graphene derivatives for supercapacitors | |
| CN111185201B (en) | Rhenium-doped molybdenum sulfide nanosheet/carbon cloth composite material, preparation method thereof and application thereof in hydrogen production by electrocatalysis of water | |
| Tang et al. | Hemispherical flower-like N-doped porous carbon/NiCo2O4 hybrid electrode for supercapacitors | |
| Lin et al. | Hierarchical monolithic carbon with high transfer performance for hydrogen evolution reaction | |
| Tong et al. | Spontaneous synthesis of Ag nanoparticles on ultrathin Co (OH) 2 nanosheets@ nitrogen-doped carbon nanoflake arrays for high-efficient water oxidation | |
| CN111804313B (en) | Fe 2 O 3 @Co 9 S 8 Preparation method and application of double-hollow core-shell structure nano composite material | |
| CN111389430B (en) | Catalyst CoP for hydrogen production by water electrolysis x S y MWCNTs and preparation method thereof | |
| CN106521598B (en) | A kind of nanometer sheet self assembly ferro-cobalt hydroxide and preparation method thereof | |
| CN113083272A (en) | FeNxPreparation method of nano-particle doped bamboo-like carbon nano-tube | |
| CN114855206B (en) | Preparation of 3D printing integral electrocatalyst and application thereof in electrocatalytic reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |