CN112138664A - Carbon-based electrocatalyst and preparation method thereof - Google Patents
Carbon-based electrocatalyst and preparation method thereof Download PDFInfo
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- CN112138664A CN112138664A CN202010946443.5A CN202010946443A CN112138664A CN 112138664 A CN112138664 A CN 112138664A CN 202010946443 A CN202010946443 A CN 202010946443A CN 112138664 A CN112138664 A CN 112138664A
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- carbon
- plant shell
- based electrocatalyst
- shell particles
- plant
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010420 shell particle Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 20
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 12
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 235000015497 potassium bicarbonate Nutrition 0.000 claims abstract description 12
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 239000011736 potassium bicarbonate Substances 0.000 claims abstract description 12
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002019 doping agent Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 53
- 241000196324 Embryophyta Species 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 22
- 244000183278 Nephelium litchi Species 0.000 claims description 19
- 238000007873 sieving Methods 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010298 pulverizing process Methods 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 8
- 244000105624 Arachis hypogaea Species 0.000 claims description 8
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 8
- 235000018262 Arachis monticola Nutrition 0.000 claims description 8
- 240000001008 Dimocarpus longan Species 0.000 claims description 8
- 235000000235 Euphoria longan Nutrition 0.000 claims description 8
- 240000006053 Garcinia mangostana Species 0.000 claims description 8
- 235000017048 Garcinia mangostana Nutrition 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 235000020232 peanut Nutrition 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 235000015742 Nephelium litchi Nutrition 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 108700004121 sarkosyl Proteins 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 claims description 3
- 229940045885 sodium lauroyl sarcosinate Drugs 0.000 claims description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004475 Arginine Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000001593 sorbitan monooleate Substances 0.000 claims description 2
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 2
- 235000020238 sunflower seed Nutrition 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 description 55
- 239000000047 product Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000967 suction filtration Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical group [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/08—Heat treatment
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- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
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- 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
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- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a carbon-based electrocatalyst and a preparation method thereof. The preparation method of the carbon-based electrocatalyst comprises the following steps of: 1) crushing plant shells to obtain plant shell particles; 2) mixing the plant shell particles, sodium chlorite, a surfactant and water, and then carrying out hydrothermal reaction to obtain hydrothermal activated plant shell particles; 3) mixing the hydrothermally activated plant shell particles, potassium bicarbonate, basic copper carbonate, calcium carbonate and a solvent, then carrying out ball milling, then placing in a carbon dioxide atmosphere for carbonization, and then soaking in an acid solution to obtain a plant shell derived carbon material; 4) immersing the plant shell derived carbon material in a metal salt solution for soaking, and then carbonizing in an atmosphere containing a heteroatom dopant. The carbon-based electrocatalyst has large specific surface area and different levels of pore structures, and can be matched with different types of electrocatalytic reactions by doping different heteroatoms.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a carbon-based electrocatalyst and a preparation method thereof.
Background
A large number of shells exist in nature and can be divided into animal and plant shells. Animal shells have a high calcium carbonate or chitin content and are generally used for the production of calcium carbonate or chitosan. The plant shell contains a large amount of carbohydrate, a small amount of amino acid and other plant components, namely a large amount of carbon, hydrogen and oxygen elements, and a small amount of nitrogen, sulfur, phosphorus and other elements.
The shells of the fruits and the seeds of the plants are often not eaten and utilized by people, and for the shells of the fruits and the seeds which are relatively hard, the existing treatment means is generally landfill or incineration, so that the potential application value is not effectively developed, and the resources are wasted. In recent years, plant hulls have been used to produce carbon-based materials in view of their advantages of high yield, wide sources, renewability, low price, and the like, and their high content of carbon and heteroatoms. However, since the components and structures of plant shells are unique, the plant shells often show hard physical properties and have small specific surface areas, carbon materials or electrocatalysts obtained by direct carbonization through traditional technical means also have small specific surface areas and poor electrocatalysis effects, actual requirements are difficult to meet, and the application is greatly limited. Therefore, it is required to prepare the plant shells into the carbon-based electrocatalyst with larger specific surface area and better electrocatalytic effect.
Disclosure of Invention
One of the objects of the present invention is to provide a carbon-based electrocatalyst.
The second object of the present invention is to provide a method for preparing the carbon-based electrocatalyst.
The technical scheme adopted by the invention is as follows:
the preparation method of the carbon-based electrocatalyst comprises the following steps of:
1) crushing plant shells to obtain plant shell particles;
2) mixing the plant shell particles, sodium chlorite, a surfactant and water, and then carrying out hydrothermal reaction to obtain hydrothermal activated plant shell particles;
3) mixing the hydrothermally activated plant shell particles, potassium bicarbonate, basic copper carbonate, calcium carbonate and a solvent, then carrying out ball milling, then placing in a carbon dioxide atmosphere for carbonization, and then soaking in an acid solution to obtain a plant shell derived carbon material;
4) immersing the plant shell derived carbon material in a metal salt solution for soaking, and then carbonizing in an atmosphere containing a heteroatom dopant to obtain the carbon-based electrocatalyst.
Preferably, the preparation method of the carbon-based electrocatalyst comprises the following steps:
1) cleaning plant shell, drying, pulverizing and sieving to obtain plant shell granule;
2) mixing the plant shell particles, sodium chlorite, a surfactant and water, heating to 150-250 ℃ for hydrothermal reaction, separating out a solid product, washing with water, drying, crushing and sieving to obtain the hydrothermal activated plant shell particles;
3) mixing the hydrothermally activated plant shell particles, potassium bicarbonate, basic copper carbonate, calcium carbonate and a solvent, then carrying out ball milling, drying, then placing in a carbon dioxide atmosphere, heating to 700-1000 ℃ at a speed of 10-20 ℃/min, carrying out carbonization, cooling to room temperature, then soaking in an acid solution, separating out a solid product, washing with water and drying to obtain a plant shell derived carbon material;
4) immersing the plant shell derived carbon material in a metal salt solution for soaking, separating out a solid product, drying and grinding, then placing in an atmosphere containing a heteroatom dopant, heating to 600-900 ℃ for carbonization, cooling to room temperature, washing with ethanol and water, and drying to obtain the carbon-based electrocatalyst.
Preferably, the plant shells in the step 1) are at least one of lychee shells, longan shells, mangosteen shells, sunflower seed shells and peanut shells.
Preferably, the sieving in step 1) is 100 mesh sieving.
Preferably, the mass ratio of the plant shell particles, the sodium chlorite and the surfactant in the step 2) is (3-8): (0.7-1.5): (0.4-1.5).
Preferably, the surfactant in step 2) is at least one of polyvinylpyrrolidone, sodium dodecylbenzene sulfonate, cetyl trimethyl ammonium bromide, sorbitan monooleate and sodium lauroyl sarcosinate.
Preferably, the hydrothermal reaction time in the step 2) is 8-24 h.
Preferably, the sieving in step 2) is 100 mesh sieving.
Preferably, the mass ratio of the hydrothermally activated plant shell particles, the potassium bicarbonate, the basic copper carbonate and the calcium carbonate in the step 3) is (15-25): (2-5): (1-4): (0.4-2).
Preferably, the revolution speed of the ball mill is 30rpm to 100rpm and the rotation speed of the ball mill is 50rpm to 300rpm when the ball milling is performed in the step 3).
More preferably, the revolution speed of the ball mill is 50rpm to 80rpm and the rotation speed of the ball mill is 120rpm to 250rpm when the ball milling is performed in the step 3).
Preferably, the carbonization time in the step 3) is 1-4 h.
Preferably, the mass ratio of the plant shell derived carbon material, the metal salt and the heteroatom dopant in the step 4) is (3-5): (5-12): (0 to 20).
Preferably, the metal salt in step 4) is at least one of ferric nitrate, nickel nitrate, cobalt nitrate, copper nitrate, indium nitrate, bismuth nitrate, manganese chloride and ammonium molybdate.
Preferably, the heteroatom dopant in step 4) is at least one of oxalic acid, urea, arginine, thiourea, sulfur powder and sodium hypophosphite.
Preferably, the carbonization time in the step 4) is 1 to 2 hours.
The invention has the beneficial effects that: the carbon-based electrocatalyst has large specific surface area and different levels of pore structures, and the electronic structure of the carbon-based electrocatalyst can be adjusted by doping different heteroatoms, so that the electrocatalyst can be endowed with catalytic performance matched with different types of electrocatalytic reactions.
Specifically, the method comprises the following steps:
1) the invention can prepare the plant shells into the carbon-based electrocatalyst with large specific surface area and high catalytic activity, excavates the application value of the plant shells in the aspect of the electrocatalyst, and changes waste into valuable;
2) according to the invention, the plant shell particles are activated by hydrothermal, so that part of lignin and other components in the plant shell can be removed, the tissue structure in the plant shell particles is changed, the microstructure of the plant shell particles can be primarily changed, the specific surface area of the particles is increased, the particle size is further reduced by mixing and ball milling with potassium bicarbonate, basic copper carbonate and calcium carbonate, the carbon skeleton is further etched in high-temperature calcination, holes are constructed, the specific surface area of the carbon material is greatly increased, and finally the carbon-based electrocatalyst with holes in different layers is obtained;
3) according to the invention, through doping of different heteroatoms, the electronic structure of the carbon-based electrocatalyst can be adjusted, the performance of the carbon-based electrocatalyst is favorably improved, the inorganic salt and the heteroatoms can form an electrocatalytic active substance under high-temperature calcination, and the carbon-based electrocatalyst can be endowed with catalytic performance suitable for different electrocatalytic reactions.
Drawings
Fig. 1 is a scanning electron micrograph of the carbon-based electrocatalyst according to example 1.
Fig. 2 is a scanning electron micrograph of the carbon-based electrocatalyst according to example 2.
Fig. 3 is a scanning electron micrograph of the carbon-based electrocatalyst according to example 3.
Fig. 4 is a scanning electron micrograph of the carbon-based electrocatalyst according to example 4.
Fig. 5 is a scanning electron microscope image of the carbon-based electrocatalyst according to comparative example 2.
Fig. 6 is a scanning electron microscope image of the carbon-based electrocatalyst according to comparative example 3.
Fig. 7 is a linear sweep voltammogram of the oxygen evolution reaction of the carbon-based electrocatalysts of example 1, example 2, and comparative example 1.
Fig. 8 is a linear sweep voltammogram of electrocatalytic urea oxidation for the carbon-based electrocatalysts of example 3 and comparative example 1.
Fig. 9 is a cyclic voltammogram of electrocatalytic ethanol oxidation of the carbon-based electrocatalysts of example 4, comparative example 1, comparative example 2, and comparative example 3.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a carbon-based electrocatalyst is prepared by the following steps:
1) cleaning longan shell, drying at 100 deg.C for 4 days in drying oven, adding into high speed pulverizer, pulverizing for 2min, and sieving with 100 mesh sieve to obtain longan shell granule;
2) mixing and stirring 3 parts by mass of longan shell particles, 0.7 part by mass of sodium chlorite, 0.4 part by mass of hexadecyl trimethyl ammonium bromide and 40 parts by mass of distilled water for 5min, adding the mixture into a hydrothermal reaction kettle, heating to 180 ℃, reacting for 12h, carrying out suction filtration, washing the filtered solid with water, placing the solid in a drying oven at 100 ℃, drying for 24h, adding the dried solid into a high-speed crusher, crushing for 2min, and sieving with a 100-mesh sieve to obtain hydrothermal activated longan shell particles;
3) mixing 12 parts by mass of hydrothermally activated longan shell particles, 2 parts by mass of potassium bicarbonate, 2 parts by mass of basic copper carbonate, 1 part by mass of calcium carbonate and 6 parts by mass of absolute ethyl alcohol, adding the mixture into a ball mill for ball milling for 15min, wherein the revolution speed of the ball mill is 40rpm, the rotation speed of the ball mill is 120rpm, drying the ball-milled product, placing the ball-milled product into a tube furnace, heating the ball-milled product to 700 ℃ at the speed of 15 ℃/min under the carbon dioxide airflow with the flow rate of 60mL/min, carbonizing the ball-milled product for 2h, cooling the ball-milled product to room temperature, soaking the carbonized product in 120 parts by mass of 2mol/L hydrochloric acid solution, ultrasonically stirring the product for 4h, performing suction filtration, washing the filtered solid with;
4) mixing 2 parts by mass of longan shell derived carbon material, 3 parts by mass of manganese chloride, 3 parts by mass of ferric nitrate and 50 parts by mass of absolute ethyl alcohol, performing ultrasonic treatment for 15min, performing suction filtration, drying the filtered solid, grinding the dried solid for 5min by using a mortar, placing the ground solid at the downstream of a tubular furnace, placing 5 parts by mass of sodium hypophosphite at the upstream of the tubular furnace, carbonizing the ground solid for 2h under nitrogen flow at the flow rate of 15mL/min, wherein the carbonization temperature is 700 ℃, cooling the ground solid to room temperature, washing the ground solid alternately by using absolute ethyl alcohol and distilled water, and drying the ground solid to obtain the carbon-based electrocatalyst (a scanning electron microscope image is shown in figure 1).
Example 2:
a carbon-based electrocatalyst is prepared by the following steps:
1) cleaning peanut shells, placing in a drying oven, drying at 100 deg.C for 6 days, adding into a high-speed pulverizer, pulverizing for 5min, and sieving with 100 mesh sieve to obtain peanut shell particles;
2) mixing and stirring 5 parts by mass of peanut shell particles, 1 part by mass of sodium chlorite, 0.8 part by mass of sodium lauroyl sarcosinate and 50 parts by mass of distilled water for 5min, adding the mixture into a hydrothermal reaction kettle, heating to 200 ℃, reacting for 16h, performing suction filtration, washing the filtered solid with water, placing the solid in a drying oven at 100 ℃, drying for 24h, adding the dried solid into a high-speed pulverizer, pulverizing for 2min, and sieving with a 100-mesh sieve to obtain hydrothermal activated peanut shell particles;
3) mixing 20 parts by mass of hydrothermally activated peanut shell particles, 3 parts by mass of potassium bicarbonate, 2 parts by mass of basic copper carbonate, 2 parts by mass of calcium carbonate and 8 parts by mass of absolute ethyl alcohol, adding the mixture into a ball mill for ball milling for 30min, wherein the revolution speed of the ball mill is 60rpm, the rotation speed of the ball mill is 180rpm, drying the ball milled product, placing the ball milled product into a tube furnace, heating the ball milled product to 900 ℃ at the speed of 10 ℃/min under the carbon dioxide airflow at the flow rate of 70mL/min, carbonizing the ball milled product for 3h, cooling the ball milled product to room temperature, soaking the carbonized product in 180 parts by mass of 2mol/L hydrochloric acid solution, ultrasonically stirring the product for 6h, performing suction filtration, washing the filtered solid with water for 7 times;
4) mixing 4 parts by mass of peanut shell derived carbon material, 13 parts by mass of cobalt nitrate and 50 parts by mass of absolute ethyl alcohol, performing ultrasonic treatment for 15min, performing suction filtration, drying the filtered solid, grinding for 5min by using a mortar, placing the ground solid at the downstream of a tubular furnace, placing 10 parts by mass of urea at the upstream of the tubular furnace, carbonizing for 1h under nitrogen flow at the flow rate of 30mL/min, wherein the carbonization temperature is 900 ℃, cooling to room temperature, alternately washing with absolute ethyl alcohol and distilled water, and drying to obtain the carbon-based electrocatalyst (a scanning electron microscope image is shown in figure 2).
Example 3:
a carbon-based electrocatalyst is prepared by the following steps:
1) cleaning mangosteen shell, drying in a drying oven at 100 deg.C for 9 days, adding into a high-speed pulverizer, pulverizing for 3min, and sieving with 100 mesh sieve to obtain mangosteen shell particles;
2) mixing and stirring 10 parts by mass of mangosteen shell particles, 2 parts by mass of sodium chlorite, 2 parts by mass of polyvinylpyrrolidone and 80 parts by mass of distilled water for 5min, adding the mixture into a hydrothermal reaction kettle, heating to 160 ℃, reacting for 24h, performing suction filtration, washing the filtered solid with water, placing the solid in a drying oven for drying for 24h at 100 ℃, adding the solid into a high-speed pulverizer for pulverizing for 1min, and sieving with a 100-mesh sieve to obtain hydrothermal activated mangosteen shell particles;
3) mixing 28 parts by mass of hydrothermally activated mangosteen shell particles, 4 parts by mass of potassium bicarbonate, 5 parts by mass of basic copper carbonate, 0.5 part by mass of calcium carbonate and 10 parts by mass of absolute ethyl alcohol, adding the mixture into a ball mill for ball milling for 15min, wherein the revolution speed of the ball mill is 80rpm, the rotation speed of the ball mill is 250rpm, drying the ball milled product, placing the ball milled product into a tube furnace, heating the ball milled product to 1000 ℃ at the speed of 20 ℃/min under carbon dioxide airflow at the flow rate of 90mL/min, carbonizing the ball milled product for 1h, cooling the product to room temperature, soaking the carbonized product with 150 parts by mass of 2mol/L hydrochloric acid solution, ultrasonically stirring the product for 7h, performing suction filtration, washing the filtered solid with water for 8 times, and drying the;
4) mixing 5 parts by mass of mangosteen shell derived carbon material, 6 parts by mass of ammonium molybdate, 8 parts by mass of nickel nitrate and 50 parts by mass of absolute ethyl alcohol, performing ultrasonic treatment for 15min, performing suction filtration, drying the filtered solid, grinding the dried solid for 5min by using a mortar, placing the ground solid on the downstream of a tubular furnace, placing 16 parts by mass of thiourea on the upstream of the tubular furnace, carbonizing the solid for 2h under nitrogen flow at the flow rate of 40mL/min, wherein the carbonization temperature is 800 ℃, cooling the solid to room temperature, alternately washing the solid with absolute ethyl alcohol and distilled water, and drying the solid to obtain the carbon-based electrocatalyst (a scanning electron microscope image is shown in figure 3).
Example 4:
a carbon-based electrocatalyst is prepared by the following steps:
1) cleaning litchi shells, placing in a drying oven, drying at 100 deg.C for 5 days, adding into a high-speed pulverizer, pulverizing for 4min, and sieving with 100 mesh sieve to obtain litchi shell particles;
2) mixing 7 parts by mass of litchi shell particles, 1.2 parts by mass of sodium chlorite, 1 part by mass of hexadecyl trimethyl ammonium bromide and 40 parts by mass of distilled water, stirring for 5min, adding the mixture into a hydrothermal reaction kettle, heating to 230 ℃ to react for 10h, carrying out suction filtration, washing the filtered solid with water, placing the solid in a drying oven at 100 ℃ for drying for 24h, adding the dried solid into a high-speed pulverizer for pulverizing for 2min, and sieving the pulverized solid with a 100-mesh sieve to obtain hydrothermal activated litchi shell particles;
3) mixing 16 parts by mass of hydrothermal activated litchi shell particles, 3 parts by mass of potassium bicarbonate, 4 parts by mass of basic copper carbonate, 1 part by mass of calcium carbonate and 7 parts by mass of absolute ethyl alcohol, adding the mixture into a ball mill for ball milling for 25min, wherein the revolution speed of the ball mill is 50rpm, the rotation speed of the ball mill is 230rpm, drying the ball milled product, placing the ball milled product into a tube furnace, heating the ball milled product to 800 ℃ at the speed of 15 ℃/min under the carbon dioxide flow of 80mL/min, carbonizing the ball milled product for 3h, cooling the product to room temperature, soaking the carbonized product in 180 parts by mass of 2mol/L hydrochloric acid solution, ultrasonically stirring the product for 5h, performing suction filtration, washing the filtered solid with water for 6 times, and drying the solid to obtain a litchi shell derived;
4) mixing 5 parts by mass of litchi shell derived carbon material, 3 parts by mass of indium nitrate, 9 parts by mass of nickel nitrate and 50 parts by mass of absolute ethyl alcohol, performing ultrasonic treatment for 15min, performing suction filtration, drying the filtered solid, grinding the dried solid for 5min by using a mortar, placing the ground solid on the downstream of a tubular furnace, placing 12 parts by mass of oxalic acid on the upstream of the tubular furnace, carbonizing the solid for 2h under nitrogen flow at the flow rate of 25mL/min, wherein the carbonization temperature is 900 ℃, cooling the solid to room temperature, alternately washing the solid with absolute ethyl alcohol and distilled water, and drying the solid to obtain the carbon-based electrocatalyst (a scanning electron microscope image is shown in figure 4).
Comparative example 1:
a carbon-based electrocatalyst is a platinum-carbon catalyst of Shanghai Michelin Biotechnology, Inc., wherein the mass percent of platinum is 20%.
Comparative example 2:
a carbon-based electrocatalyst is prepared by the following steps:
1) cleaning litchi shells, placing in a drying oven, drying at 100 deg.C for 5 days, adding into a high-speed pulverizer, pulverizing for 4min, and sieving with 100 mesh sieve to obtain litchi shell particles;
2) placing 16 parts by mass of lychee shell particles in a tubular furnace, heating to 800 ℃ at the speed of 15 ℃/min under the carbon dioxide airflow with the flow rate of 80mL/min, carbonizing for 3h, cooling to room temperature, soaking the carbonized product in 180 parts by mass of hydrochloric acid solution with the concentration of 2mol/L, ultrasonically stirring for 5h, carrying out suction filtration, washing the filtered solid with water for 6 times, and drying to obtain the lychee shell derived carbon material;
3) mixing 5 parts by mass of litchi shell derived carbon material, 3 parts by mass of indium nitrate, 9 parts by mass of nickel nitrate and 50 parts by mass of absolute ethyl alcohol, performing ultrasonic treatment for 15min, performing suction filtration, drying the filtered solid, grinding the dried solid for 5min by using a mortar, placing the ground solid on the downstream of a tubular furnace, placing 12 parts by mass of oxalic acid on the upstream of the tubular furnace, carbonizing the solid for 2h under nitrogen flow at the flow rate of 25mL/min, wherein the carbonization temperature is 900 ℃, cooling the solid to room temperature, alternately washing the solid with absolute ethyl alcohol and distilled water, and drying the solid to obtain the carbon-based electrocatalyst (a scanning electron microscope image is shown in figure 5).
Comparative example 3:
a carbon-based electrocatalyst is prepared by the following steps:
1) cleaning litchi shells, placing in a drying oven, drying at 100 deg.C for 5 days, adding into a high-speed pulverizer, pulverizing for 4min, and sieving with 100 mesh sieve to obtain litchi shell particles;
2) mixing 7 parts by mass of litchi shell particles, 1.2 parts by mass of sodium chlorite, 1 part by mass of hexadecyl trimethyl ammonium bromide and 40 parts by mass of distilled water, stirring for 5min, adding the mixture into a hydrothermal reaction kettle, heating to 230 ℃ to react for 10h, carrying out suction filtration, washing the filtered solid with water, placing the solid in a drying oven at 100 ℃ for drying for 24h, adding the dried solid into a high-speed pulverizer for pulverizing for 2min, and sieving the pulverized solid with a 100-mesh sieve to obtain hydrothermal activated litchi shell particles;
3) mixing 16 parts by mass of hydrothermal activated litchi shell particles, 3 parts by mass of potassium bicarbonate, 4 parts by mass of basic copper carbonate, 1 part by mass of calcium carbonate and 7 parts by mass of absolute ethyl alcohol, adding the mixture into a ball mill for ball milling for 25min, wherein the revolution speed of the ball mill is 50rpm, the rotation speed of the ball mill is 230rpm, drying the ball milled product, placing the ball milled product into a tube furnace, heating the ball milled product to 800 ℃ at the speed of 15 ℃/min under the carbon dioxide flow of 80mL/min, carbonizing the ball milled product for 3h, cooling the ball milled product to room temperature, soaking the carbonized product in 180 parts by mass of 2mol/L hydrochloric acid solution, ultrasonically stirring the product for 5h, performing suction filtration, washing the filtered solid with water for 6 times, and drying the solid to obtain the carbon-based electrocatalyst (a scanning.
And (3) performance testing:
1) the specific surface area and the average pore diameter of the carbon-based electrocatalysts of examples 1 to 4 and comparative examples 1 to 3 were tested by a multi-station full-automatic specific surface area and pore diameter test system, and the test results are shown in the following table:
TABLE 1 test results of specific surface area and average pore diameter of carbon-based electrocatalysts of examples 1 to 4 and comparative examples 1 to 3
As can be seen from FIGS. 1 to 6 and Table 1:
a) the carbon-based electrocatalysts of examples 1 to 4 have pore structures of different levels and a large specific surface area, and inorganic salts and heteroatoms can form electrocatalytic active substances of various shapes under high-temperature calcination, for example: the pellet form of example 1, the ribbon form of example 3, and the pellet form of examples 2 and 4 contribute to further improvement in catalytic activity;
b) the carbon-based electrocatalyst of comparative example 2 has no holes as shown in the carbon-based electrocatalyst of example 4 due to no hydrothermal activation and etching treatment, and the agglomeration of metal active substances is not beneficial to the improvement of catalytic performance;
c) the carbon-based electrocatalyst of comparative example 3 retains the pore structure of the carbon-based electrocatalyst of example 4, but does not have good catalytic performance due to the absence of metal active species.
2) Respectively dispersing the carbon-based electrocatalysts of examples 1 to 4 and comparative examples 1 to 3 in a mixed solution composed of ethanol, water and nafion solution with the mass fraction of 5% according to the mass ratio of 7:3:0.1, uniformly mixing by ultrasonic waves to prepare catalyst ink, and loading the catalyst ink on the surface of an electrode, wherein the catalyst loading is 0.1mg/cm2Further testing the linear sweep voltammograms of the carbon-based electrocatalysts of example 1, example 2 and comparative example 1, which performed oxygen evolution reactions in a solution system (0.1mol/L KOH solution) at a sweep rate of 5mV/s, the test results are shown in FIG. 7, the linear sweep voltammograms of the carbon-based electrocatalysts of example 3 and comparative example 1, which performed electrocatalytic urea oxidation in a solution system (containing 1mol/L KOH and 1mol/L urea) at a sweep rate of 50mV/s, the test results are shown in FIG. 8, test example 4, the cyclic voltammograms of the carbon-based electrocatalysts of comparative examples 1, 2 and 3, which were subjected to electrocatalytic ethanol oxidation in a solution system (containing 1mol/L KOH and 1mol/L ethanol) at a sweep rate of 50mV/s, are shown in FIG. 9.
As can be seen from FIGS. 7 to 9: the carbon-based electrocatalysts of examples 1 to 4 all show higher current density than commercial platinum-carbon catalysts in corresponding catalytic reactions, are expected to replace commercial platinum-carbon catalysts, and become cheap, environment-friendly and high-performance electrocatalysts.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-based electrocatalyst is characterized by comprising the following steps:
1) crushing plant shells to obtain plant shell particles;
2) mixing the plant shell particles, sodium chlorite, a surfactant and water, and then carrying out hydrothermal reaction to obtain hydrothermal activated plant shell particles;
3) mixing the hydrothermally activated plant shell particles, potassium bicarbonate, basic copper carbonate, calcium carbonate and a solvent, then carrying out ball milling, then placing in a carbon dioxide atmosphere for carbonization, and then soaking in an acid solution to obtain a plant shell derived carbon material;
4) immersing the plant shell derived carbon material in a metal salt solution for soaking, and then carbonizing in an atmosphere containing a heteroatom dopant to obtain the carbon-based electrocatalyst.
2. The method of preparing a carbon-based electrocatalyst according to claim 1, comprising the steps of:
1) cleaning plant shell, drying, pulverizing and sieving to obtain plant shell granule;
2) mixing the plant shell particles, sodium chlorite, a surfactant and water, heating to 150-250 ℃ for hydrothermal reaction, separating out a solid product, washing with water, drying, crushing and sieving to obtain the hydrothermal activated plant shell particles;
3) mixing the hydrothermally activated plant shell particles, potassium bicarbonate, basic copper carbonate, calcium carbonate and a solvent, then carrying out ball milling, drying, then placing in a carbon dioxide atmosphere, heating to 700-1000 ℃ at a speed of 10-20 ℃/min, carrying out carbonization, cooling to room temperature, then soaking in an acid solution, separating out a solid product, washing with water and drying to obtain a plant shell derived carbon material;
4) immersing the plant shell derived carbon material in a metal salt solution for soaking, separating out a solid product, drying and grinding, then placing in an atmosphere containing a heteroatom dopant, heating to 600-900 ℃ for carbonization, cooling to room temperature, washing with ethanol and water, and drying to obtain the carbon-based electrocatalyst.
3. A method of preparing a carbon-based electrocatalyst according to claim 1 or 2, wherein: the plant shells in the step 1) are at least one of lychee shells, longan shells, mangosteen shells, sunflower seed shells and peanut shells.
4. A method of preparing a carbon-based electrocatalyst according to claim 1 or 2, wherein: and 2) the surfactant is at least one of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, sorbitan monooleate and sodium lauroyl sarcosinate.
5. A method of preparing a carbon-based electrocatalyst according to claim 1 or 2, wherein: and 4) the metal salt is at least one of ferric nitrate, nickel nitrate, cobalt nitrate, copper nitrate, indium nitrate, bismuth nitrate, manganese chloride and ammonium molybdate.
6. A method of preparing a carbon-based electrocatalyst according to claim 1 or 2, wherein: and 4) the heteroatom dopant is at least one of oxalic acid, urea, arginine, thiourea, sulfur powder and sodium hypophosphite.
7. A method of preparing a carbon-based electrocatalyst according to claim 1 or 2, wherein: the time of the hydrothermal reaction in the step 2) is 8-24 h; the carbonization time in the step 3) is 1-4 h; the carbonization time in the step 4) is 1-2 h.
8. A carbon-based electrocatalyst, characterized by: prepared by the method of any one of claims 1 to 7.
9. Use of the carbon-based electrocatalyst according to claim 8 in electrocatalytic oxidation reactions.
10. Use according to claim 9, characterized in that: the electrocatalytic oxidation reaction is one of an electrocatalytic oxidation reaction of methanol, an electrocatalytic oxidation reaction of ethanol, an electrocatalytic oxidation reaction of glycerol, an electrocatalytic oxidation reaction of urea, an electrocatalytic oxygen evolution reaction and an electrocatalytic hydrogen evolution reaction.
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