CN112080757A - Boron-doped nano g-C3N 4-coated nano Co electro-catalytic hydrogen production material and preparation method thereof - Google Patents
Boron-doped nano g-C3N 4-coated nano Co electro-catalytic hydrogen production material and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229960000892 attapulgite Drugs 0.000 claims abstract description 88
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 88
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 28
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims abstract description 14
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 238000010438 heat treatment Methods 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 51
- 239000012153 distilled water Substances 0.000 claims description 42
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 24
- BPGLMKMMPBQINX-UHFFFAOYSA-N C(#N)N1C(=O)NC=2NC(=O)NC2C1=O.N1=C(N)N=C(N)N=C1N Chemical compound C(#N)N1C(=O)NC=2NC(=O)NC2C1=O.N1=C(N)N=C(N)N=C1N BPGLMKMMPBQINX-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 239000000523 sample Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 15
- 229910052796 boron Inorganic materials 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000004227 thermal cracking Methods 0.000 abstract description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 12
- 238000004821 distillation Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- 229920000557 Nafion® Polymers 0.000 description 7
- 229910021397 glassy carbon Inorganic materials 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of electrocatalytic hydrogen production materials, and discloses a boron-doped nano g-C3N 4-coated nano Co electrocatalytic hydrogen production material, which comprises the following formula raw materials and components: attapulgite, silane coupling agent, melamine, cyanuric chloride, Co (NO)3)3Triisopropyl borate. The boron-doped nano g-C3N4The electrocatalytic hydrogen production material coated with the nano Co, 3-glycidyl ether oxypropyl triethoxysilane graft modification attapulgite, so that melamine is evenly loaded on the surface of the attapulgite, and the trichloro chlorideCyanogen is used for adjusting carbon-nitrogen ratio, triisopropyl borate is used as a boron source, and boron-doped nano g-C with developed specific surface area and pore structure is prepared by a hydrothermal synthesis method and a thermal cracking method3N4Nanosheets, enlarged by nano-g-C3N4Specific surface area and conductivity of (2), nano g-C3N4Uniformly dispersed and attached on the surface of attapulgite, and relieve g-C3N4Agglomeration of Co nanoparticles in the g-C range3N4The coating of (2) prevents the electrolyte from being dissolved by direct contact.
Description
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen production materials, in particular to an electrocatalytic hydrogen production material with boron doped nano g-C3N4 coated with nano Co and a preparation method thereof.
Background
With the decreasing of fossil fuel reserves and the increasing severity of environmental pollution caused by the combustion of fossil energy, the development of green and efficient energy becomes urgent, hydrogen appears on the earth mainly in a combined state and is the most widely distributed substance in the universe, and the hydrogen energy has the advantages of good combustion performance, high combustion heat value, no water pollution of combustion products and the like, is an efficient and clean energy with rich resources and sustainable development, and has wide application in the aspects of hydrogen power automobiles, hydrogen energy power generation, phosphate fuel cells, solid oxide cells and the like.
The current industrial hydrogen preparation method mainly comprises a water gas conversion method, a hydrocarbon cracking method, a hydrocarbon steam conversion method and the like, the hydrogen preparation by water electrolysis is a very potential hydrogen preparation method, direct current is introduced into electrolyte, water molecules are subjected to electrochemical reaction on an electrode and are decomposed into hydrogen and oxygen, the most important thing in the hydrogen preparation method by water electrolysis is an electrode catalytic material, and the current hydrogen production catalyst by water electrolysis mainly comprises noble metal catalysts such as platinum, ruthenium and the like, but the yield is rare, the price is high, and the wide commercial application of the noble metal catalysts is limited.
Fe. Transition metals such as Co, Ni and the like are the electrocatalytic hydrogen production catalytic materials with development prospect at present, but the catalytic activity of the transition metal catalyst is unsatisfactory, and the transition metal catalyst is easily corroded in electrolyte or directly reacts with the electrolyte to cause the loss and even decomposition of a catalyst matrix, and graphite-phase carbon nitride g-C3N4Has the advantages of stable structure, conductive performance and the like, has wide research and application in the fields of light, electricity, catalysis and the like, but has the nanometer g-C3N4Aggregation and agglomeration easily occur in the electrolyte, and the active sites are greatly reduced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides boron-doped nano g-C3N4Electrocatalysis of coated nano CoThe hydrogen-producing material and the preparation method thereof solve the problems of low electromagnetic shielding and wave-absorbing performance of polyurethane coating, and solve the problem of poor dispersibility and compatibility of carbon-series and iron-series wave-absorbing materials in polyurethane (II)
In order to achieve the purpose, the invention provides the following technical scheme: boron-doped nano g-C3N4The electrocatalytic hydrogen production material coated with the nano Co comprises the following formula raw materials in parts by weight: 14-18 parts of attapulgite, 11-15 parts of silane coupling agent, 33-48 parts of melamine, 22-26 parts of cyanuric chloride and 4-8 parts of Co (NO)3)3And 1-3 parts of triisopropyl borate.
Preferably, the silane coupling agent is 3-glycidyl ether oxypropyl triethoxysilane.
Preferably, the boron is doped with nanog-C3N4The preparation method of the electrocatalytic hydrogen production material coated with the nano Co comprises the following steps:
(1) putting attapulgite in a planetary ball mill, ball-milling until the attapulgite passes through an 1800 plus 2000-mesh sieve, adding a toluene solvent and 14-18 parts of attapulgite into a reaction bottle, putting the reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 30-50min at the ultrasonic frequency of 20-30KHz, adding 11-15 parts of silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane, putting the reaction bottle in a constant-temperature water bath, heating to 65-85 ℃, stirring at a constant speed for reaction for 6-8h, carrying out reduced pressure concentration on the solution to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the silane coupling agent grafted modified attapulgite.
(2) Adding distilled water and modified attapulgite into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h at the ultrasonic frequency of 25-35KHz, then adding 38-53 parts of melamine and 15-21 parts of cyanuric chloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 85-95 ℃, uniformly stirring for reaction for 3-5h, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material.
(3) Adding distilled water into a reaction bottle,Melamine-cyanuric chloride-attapulgite composite material, 1-3 parts of triisopropyl borate and 4-8 parts of Co (NO)3)3Placing the reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2-3h at an ultrasonic frequency of 25-35KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing in a reaction kettle heating box, heating to 190-, introducing nitrogen, heating to 520-550 ℃ at the heating rate of 2-4 ℃/min, calcining for 2-3h, heating to 740-760 ℃ and keeping the temperature for 3-4h, placing the calcined product in a sulfuric acid solution with the mass concentration of 0.4-0.8mol/L, stirring at a constant speed for 2-5h, filtering to obtain a solid product, and washing the solid product with distilled water to prepare the boron-doped nano g-C.3N4An electrocatalytic hydrogen production material coated with nano Co.
Preferably, the ultrasonic treatment appearance includes the host computer, host computer top fixedly connected with support, install ultrasonic generrator on the support, ultrasonic probe and adjusting device are installed to ultrasonic generrator's bottom, the reaction flask has been placed at the top of host computer, it has agitating unit to peg graft in the inside of reaction flask, agitating unit passes through positioner fixed mounting on the host computer, install fastening components on the longitude and latitude device, fastening components includes the main tributary seat, the top activity of main tributary seat is pegged graft and is had the regulation pole, fixed plate and fly leaf that are connected with agitating unit and positioner respectively are installed in the outside of main tributary seat, adjust through connecting rod swing joint between pole and the fly leaf.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the boron-doped nano g-C3N4The attapulgite which is a natural nano material has larger specific surface area and rich hydroxyl matrixes on the surface, the attapulgite is grafted and modified by using a silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane, and an epoxy group in the silane coupling agent and an amino group in melamine undergo a ring opening reaction to ensure that the melamine is uniformThe boron-doped nano g-C with developed specific surface area and pore structure is prepared by using cyanuric chloride to adjust carbon-nitrogen ratio and using triisopropyl borate as a boron source through a hydrothermal synthesis method and a thermal cracking method3N4Nanosheets, doping of boron atoms, substituted g-C3N4Carbon atoms in the grid structure form a pi-bonded planar layered structure, so that the nano g-C is increased3N4Expose more electrochemically active sites, and enhance g-C3N4The electric conductivity of (2) shortens the transmission path of electric charges, promotes the diffusion and migration of electric charges, and the nano g-C3N4Uniformly dispersed and attached on the surface of attapulgite, effectively relieving the nano g-C3N4Agglomeration and caking phenomena avoid covering active sites, and greatly enhance the hydrogen evolution activity of the catalyst.
The boron-doped nano g-C3N4The boron-doped nano g-C is prepared from the electro-catalytic hydrogen production material coated with nano Co by a high-temperature thermal reduction method3N4Coating nanometer Co, wherein Co nanometer particles can provide electron transfer in acid electrolyte to promote hydrogen production reaction by electrolysis, and the Co nanometer particles are in nanometer g-C3N4The catalyst is prevented from being dissolved by direct contact with the electrolyte or generating side reaction with the electrolyte under the coating, so that the catalyst matrix is prevented from being lost or even decomposed.
Drawings
FIG. 1 is a schematic front view of the present invention;
fig. 2 is a schematic view of a fastening assembly of the present invention.
In the figure: 1. a host; 2. a support; 3. an ultrasonic generator; 4. an ultrasonic probe; 5. an adjustment device; 6. a reaction bottle; 7. a stirring device; 8. a positioning device; 9. a fastening assembly; 901. a main base; 902. adjusting a rod; 903. a movable plate; 904. and (7) fixing the plate.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: boron-doped nano g-C3N4The electrocatalytic hydrogen production material coated with the nano Co comprises the following formula raw materials in parts by weight: 14-18 parts of attapulgite, 11-15 parts of silane coupling agent, 33-48 parts of melamine, 22-26 parts of cyanuric chloride and 4-8 parts of Co (NO)3)31-3 parts of triisopropyl borate, and the silane coupling agent is 3-glycidyl ether oxypropyl triethoxysilane.
Boron doped nano g-C3N4The preparation method of the electrocatalytic hydrogen production material coated with the nano Co comprises the following steps:
(1) placing attapulgite in a planetary ball mill, ball-milling until the attapulgite passes through a 1800-plus-2000-mesh sieve, adding toluene solvent and 14-18 parts of attapulgite into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument, wherein the reaction bottle comprises a host machine, the top of the host machine is fixedly connected with a bracket, an ultrasonic generator is installed on the bracket, an ultrasonic probe and an adjusting device are installed at the bottom of the ultrasonic generator, the top of the host machine is placed with the reaction bottle, a stirring device is inserted in the reaction bottle, the stirring device is fixedly installed on the host machine through a positioning device, a fastening assembly is installed on a longitude and latitude device, the fastening assembly comprises a main seat, an adjusting rod is movably inserted in the top of the main seat, a fixed plate and a movable plate which are respectively connected with the stirring device and the positioning device are installed on the outer side of the main seat, the adjusting rod is movably connected with the movable, and (2) adding 11-15 parts of silane coupling agent 3-glycidyl ether oxypropyltriethoxysilane at the ultrasonic frequency of 20-30KHz, placing the reaction bottle in a constant-temperature water bath, heating to 65-85 ℃, uniformly stirring for reaction for 6-8 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the silane coupling agent grafted modified attapulgite.
(2) Adding distilled water and modified attapulgite into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1-2h at the ultrasonic frequency of 25-35KHz, then adding 38-53 parts of melamine and 15-21 parts of cyanuric chloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 85-95 ℃, uniformly stirring for reaction for 3-5h, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material.
(3) Adding distilled water, melamine-cyanuric chloride-attapulgite composite material, 1-3 parts of triisopropyl borate and 4-8 parts of Co (NO) into a reaction bottle3)3Placing the reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2-3h at an ultrasonic frequency of 25-35KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing in a reaction kettle heating box, heating to 190-, introducing nitrogen, heating to 520-550 ℃ at the heating rate of 2-4 ℃/min, calcining for 2-3h, heating to 740-760 ℃ and keeping the temperature for 3-4h, placing the calcined product in a sulfuric acid solution with the mass concentration of 0.4-0.8mol/L, stirring at a constant speed for 2-5h, filtering to obtain a solid product, and washing the solid product with distilled water to prepare the boron-doped nano g-C.3N4An electrocatalytic hydrogen production material coated with nano Co.
(4) Doping boron with nano-g-C3N4And uniformly mixing the electro-catalytic hydrogen production material coated with the nano Co, the conductive carbon black and the Nafion solution, coating the mixture on a glassy carbon electrode, and drying to prepare the electro-catalytic working electrode material.
Example 1
(1) Preparing a modified attapulgite component 1: putting attapulgite into a planetary ball mill, ball-milling until the attapulgite passes through a 1800-mesh sieve, adding toluene solvent and 14 parts of attapulgite into a reaction bottle, putting the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a host machine, the top of the host machine is fixedly connected with a bracket, an ultrasonic generator is installed on the bracket, an ultrasonic probe and an adjusting device are installed at the bottom of the ultrasonic generator, the reaction bottle is placed at the top of the host machine, a stirring device is inserted into the reaction bottle, the stirring device is fixedly installed on the host machine through a positioning device, a fastening assembly is installed on a longitude and latitude device, the fastening assembly comprises a main seat, an adjusting rod is movably inserted into the top of the main seat, a fixed plate and a movable plate which are respectively connected with the stirring device and the positioning device are installed on the outer side of the main seat, the adjusting rod is movably connected with the, the ultrasonic frequency is 20KHz, 11 parts of silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane is added, a reaction bottle is placed in a constant-temperature water bath kettle, the temperature is increased to 65 ℃, the reaction is carried out for 6 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing the solid product, and the solid product is fully dried to prepare the silane coupling agent grafted modified attapulgite component 1.
(2) Preparing a melamine-cyanuric chloride-attapulgite composite material 1: adding distilled water and the modified attapulgite component 1 into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1h at the ultrasonic frequency of 25KHz, then adding 53 parts of melamine and 15 parts of cyanuric chloride, placing the reaction bottle into a constant-temperature water bath, heating to 85 ℃, uniformly stirring for reaction for 3h, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material 1.
(3) Preparation of boron-doped Nano g-C3N4Electrocatalytic hydrogen production material 1 coated with nano Co: distilled water, 1 part of melamine-cyanuric chloride-attapulgite composite material, 1 part of triisopropyl borate and 4 parts of Co (NO) are added into a reaction bottle3)3Placing a reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours at the ultrasonic frequency of 25KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the solution into a reaction kettle heating box, heating to 190 ℃, reacting for 15 hours, cooling the solution to room temperature, performing reduced pressure concentration to remove a solvent, placing a concentrated product in an atmosphere resistance furnace, introducing nitrogen, heating to 520 ℃ at the heating rate of 2 ℃/min, calcining for 2 hours, heating to 740 ℃, performing heat preservation and calcination for 3 hours, placing the calcined product in a sulfuric acid solution with the mass concentration of 0.4mol/L, uniformly stirring for 2 hours, filtering to obtain a solid product, washing the solid product with distilled water, and preparing to obtain boron-doped nano g-C3N4An electrocatalytic hydrogen production material 1 coated with nano Co.
(4) Doping boron with nano-g-C3N4The electrocatalytic hydrogen production material 1 coated with the nano Co, the conductive carbon black and the Nafion solution are uniformly mixed and coatedCovering the glassy carbon electrode and drying to prepare the electrocatalytic working electrode material 1.
Example 2
(1) Preparing a modified attapulgite component 2: putting attapulgite into a planetary ball mill, ball-milling until the attapulgite passes through a 1800-mesh sieve, adding toluene solvent and 15 parts of attapulgite into a reaction bottle, putting the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a host machine, the top of the host machine is fixedly connected with a bracket, an ultrasonic generator is installed on the bracket, an ultrasonic probe and an adjusting device are installed at the bottom of the ultrasonic generator, the reaction bottle is placed at the top of the host machine, a stirring device is inserted into the reaction bottle, the stirring device is fixedly installed on the host machine through a positioning device, a fastening assembly is installed on a longitude and latitude device, the fastening assembly comprises a main seat, an adjusting rod is movably inserted into the top of the main seat, a fixed plate and a movable plate which are respectively connected with the stirring device and the positioning device are installed on the outer side of the main seat, the adjusting rod is movably connected with the, the ultrasonic frequency is 30KHz, 12 parts of silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane is added, the reaction bottle is placed in a constant temperature water bath, the temperature is increased to 65 ℃, the reaction is carried out for 6 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing the solid product, and the solid product is fully dried to prepare the silane coupling agent grafted modified attapulgite component 2.
(2) Preparing a melamine-cyanuric chloride-attapulgite composite material 2: adding distilled water and the modified attapulgite component 2 into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1h at the ultrasonic frequency of 35KHz, then adding 48 parts of melamine and 16.5 parts of cyanuric chloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 85 ℃, uniformly stirring for reaction for 5h, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material 2.
(3) Preparation of boron-doped Nano g-C3N4Electrocatalytic hydrogen production material coated with nano Co 2: distilled water and 1.5 parts of melamine-cyanuric chloride-attapulgite composite material are added into a reaction bottleTriisopropyl borate and 5 parts Co (NO)3)3Placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 3 hours with the ultrasonic frequency of 35KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a reaction kettle heating box, heating to 190 ℃, reacting for 20 hours, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, placing the concentrated product in an atmosphere resistance furnace, introducing nitrogen, heating to 520 ℃ at the heating rate of 4 ℃/min, calcining for 3 hours, heating to 740 ℃, carrying out heat preservation and calcination for 3 hours, placing the calcined product in a sulfuric acid solution with the mass concentration of 0.8mol/L, carrying out uniform stirring for 2 hours, filtering to obtain a solid product, washing the solid product with distilled water, and preparing to obtain boron-doped nano g-C3N4An electrocatalytic hydrogen production material 2 coated with nano Co.
(4) Doping boron with nano-g-C3N4The electrocatalytic hydrogen production material 2 coated with the nano Co, the conductive carbon black and the Nafion solution are uniformly mixed, coated on a glassy carbon electrode and dried to prepare the electrocatalytic working electrode material 2.
Example 3
(1) Preparing a modified attapulgite component 3: putting attapulgite into a planetary ball mill, ball-milling until the attapulgite passes through a 2000-mesh sieve, adding toluene solvent and 16 parts of attapulgite into a reaction bottle, putting the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a host machine, the top of the host machine is fixedly connected with a bracket, an ultrasonic generator is installed on the bracket, an ultrasonic probe and an adjusting device are installed at the bottom of the ultrasonic generator, the reaction bottle is placed at the top of the host machine, a stirring device is inserted into the reaction bottle, the stirring device is fixedly installed on the host machine through a positioning device, a fastening assembly is installed on a longitude and latitude device, the fastening assembly comprises a main seat, an adjusting rod is movably inserted into the top of the main seat, a fixed plate and a movable plate which are respectively connected with the stirring device and the positioning device are installed on the outer side of the main seat, the adjusting rod is movably connected with the, and (2) adding 13 parts of silane coupling agent 3-glycidyl ether oxypropyltriethoxysilane at the ultrasonic frequency of 25KHz, placing a reaction bottle in a constant-temperature water bath, heating to 75 ℃, uniformly stirring for reaction for 7 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the silane coupling agent grafted modified attapulgite component 3.
(2) Preparing a melamine-cyanuric chloride-attapulgite composite material 3: adding distilled water and the modified attapulgite component 3 into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1.5h at the ultrasonic frequency of 30KHz, then adding 43 parts of melamine and 18 parts of cyanuric chloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring for reaction for 4h, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material 3.
(3) Preparation of boron-doped Nano g-C3N4Electrocatalytic hydrogen production material coated with nano Co 3: distilled water, 3 parts of melamine-cyanuric chloride-attapulgite composite material, 2 parts of triisopropyl borate and 6 parts of Co (NO) are added into a reaction bottle3)3Placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 2.5h with the ultrasonic frequency of 30KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the solution into a reaction kettle heating box, heating to 195 ℃, reacting for 18h, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, placing the concentrated product into an atmosphere resistance furnace, introducing nitrogen, heating to 535 ℃, calcining for 2.5h, heating to 750 ℃, carrying out heat preservation calcination for 3.5h, placing the calcined product into a sulfuric acid solution with the mass concentration of 0.6mol/L, uniformly stirring for 3h, filtering to obtain a solid product, washing the solid product with distilled water, and preparing to obtain boron-doped nano g-C3N4An electrocatalytic hydrogen production material 3 coated with nano Co.
(4) Doping boron with nano-g-C3N4The electrocatalytic hydrogen production material 3 coated with the nano Co, the conductive carbon black and the Nafion solution are uniformly mixed, coated on a glassy carbon electrode and dried to prepare the electrocatalytic working electrode material 3.
Example 4
(1) Preparing a modified attapulgite component 4: putting attapulgite into a planetary ball mill, ball-milling until the attapulgite passes through a 2000-mesh sieve, adding toluene solvent and 18 parts of attapulgite into a reaction bottle, putting the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a host machine, the top of the host machine is fixedly connected with a bracket, an ultrasonic generator is installed on the bracket, an ultrasonic probe and an adjusting device are installed at the bottom of the ultrasonic generator, the reaction bottle is placed at the top of the host machine, a stirring device is inserted into the reaction bottle, the stirring device is fixedly installed on the host machine through a positioning device, a fastening assembly is installed on a longitude and latitude device, the fastening assembly comprises a main seat, an adjusting rod is movably inserted into the top of the main seat, a fixed plate and a movable plate which are respectively connected with the stirring device and the positioning device are installed on the outer side of the main seat, the adjusting rod is movably connected with the, the ultrasonic frequency is 30KHz, 15 parts of silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane is added, the reaction bottle is placed in a constant temperature water bath, the temperature is increased to 85 ℃, the reaction is carried out for 8 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing the solid product, and the solid product is fully dried to prepare the silane coupling agent grafted modified attapulgite component 4.
(2) Preparing a melamine-cyanuric chloride-attapulgite composite material 4: adding distilled water and the modified attapulgite component 4 into a reaction bottle, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours at the ultrasonic frequency of 35KHz, then adding 38 parts of melamine and 21 parts of cyanuric chloride, placing the reaction bottle into a constant-temperature water bath, heating to 95 ℃, uniformly stirring for reaction for 5 hours, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material 4.
(3) Preparation of boron-doped Nano g-C3N4Electrocatalytic hydrogen production material coated with nano Co 4: distilled water, melamine-cyanuric chloride- attapulgite composite material 4, 3 parts of triisopropyl borate and 8 parts of Co (NO) are added into a reaction bottle3)3Placing the reaction bottle in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 3h, wherein the ultrasonic frequency is 35KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a heating box of the reaction kettle, and heating the solution until the solution is heatedReacting for 20 hours at 200 ℃, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, placing the concentrated product in an atmosphere resistance furnace, introducing nitrogen, heating to 550 ℃ at the heating rate of 4 ℃/min, calcining for 3 hours, heating to 760 ℃, keeping the temperature and calcining for 4 hours, placing the calcined product in a sulfuric acid solution with the mass concentration of 0.8mol/L, stirring at a constant speed for 5 hours, filtering to obtain a solid product, washing the solid product with distilled water, and preparing to obtain boron-doped nano g-C3N4An electrocatalytic hydrogen production material 4 coated with nano Co.
(4) Doping boron with nano-g-C3N4The electrocatalytic hydrogen production material 4 coated with the nano Co, the conductive carbon black and the Nafion solution are uniformly mixed, coated on a glassy carbon electrode and dried to prepare the electrocatalytic working electrode material 4.
Comparative example 1
(1) Preparing a modified attapulgite component 1: putting attapulgite into a planetary ball mill, ball-milling until the attapulgite passes through a 2000-mesh sieve, adding toluene solvent and 13 parts of attapulgite into a reaction bottle, putting the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a host machine, the top of the host machine is fixedly connected with a bracket, an ultrasonic generator is installed on the bracket, an ultrasonic probe and an adjusting device are installed at the bottom of the ultrasonic generator, the reaction bottle is placed at the top of the host machine, a stirring device is inserted into the reaction bottle, the stirring device is fixedly installed on the host machine through a positioning device, a fastening assembly is installed on a longitude and latitude device, the fastening assembly comprises a main seat, an adjusting rod is movably inserted into the top of the main seat, a fixed plate and a movable plate which are respectively connected with the stirring device and the positioning device are installed on the outer side of the main seat, the adjusting rod is movably connected with the, the ultrasonic frequency is 30KHz, 10 parts of silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane is added, the reaction bottle is placed in a constant temperature water bath, the temperature is increased to 65 ℃, the reaction is carried out for 6 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing the solid product, and the solid product is fully dried to prepare the silane coupling agent grafted modified attapulgite component 1.
(2) Preparing a melamine-cyanuric chloride-attapulgite composite material 1: adding distilled water and the modified attapulgite component 1 into a reaction flask, placing the reaction flask into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 2 hours at the ultrasonic frequency of 35KHz, then adding 58 parts of melamine and 14 parts of cyanuric chloride, placing the reaction flask into a constant-temperature water bath, heating to 95 ℃, uniformly stirring for reaction for 3 hours, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material 1.
(3) Preparation of boron-doped Nano g-C3N4Electrocatalytic hydrogen production material 1 coated with nano Co: distilled water, 1 part of melamine-cyanuric chloride-attapulgite composite material, 0.5 part of triisopropyl borate and 2.5 parts of Co (NO) are added into a reaction bottle3)3Placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment for 3 hours with the ultrasonic frequency of 35KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a reaction kettle heating box, heating to 190 ℃, reacting for 20 hours, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, placing the concentrated product in an atmosphere resistance furnace, introducing nitrogen, heating to 520 ℃ at the heating rate of 2 ℃/min, calcining for 2 hours, heating to 740 ℃, carrying out heat preservation calcination for 3 hours, placing the calcined product in a sulfuric acid solution with the mass concentration of 0.8mol/L, carrying out uniform stirring for 5 hours, filtering to obtain a solid product, washing the solid product with distilled water, and preparing to obtain boron-doped nano g-C3N4An electrocatalytic hydrogen production material 1 coated with nano Co.
(4) Doping boron with nano-g-C3N4The electrocatalytic hydrogen production material 1 coated with the nano Co, the conductive carbon black and the Nafion solution are uniformly mixed, coated on a glassy carbon electrode and dried to prepare the electrocatalytic working electrode material 1.
Comparative example 2
(1) Preparing a modified attapulgite component 2: putting attapulgite into a planetary ball mill, ball-milling until the attapulgite passes through a 2000-mesh sieve, adding toluene solvent and 19 parts of attapulgite into a reaction bottle, putting the reaction bottle into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a host machine, the top of the host machine is fixedly connected with a bracket, an ultrasonic generator is installed on the bracket, an ultrasonic probe and an adjusting device are installed at the bottom of the ultrasonic generator, the reaction bottle is placed at the top of the host machine, a stirring device is inserted into the reaction bottle, the stirring device is fixedly installed on the host machine through a positioning device, a fastening assembly is installed on a longitude and latitude device, the fastening assembly comprises a main seat, an adjusting rod is movably inserted into the top of the main seat, a fixed plate and a movable plate which are respectively connected with the stirring device and the positioning device are installed on the outer side of the main seat, the adjusting rod is movably connected with the, the ultrasonic frequency is 30KHz, 11 parts of silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane is added, the reaction bottle is placed in a constant temperature water bath, the temperature is increased to 65 ℃, the reaction is carried out for 8 hours under uniform stirring, the solution is decompressed and concentrated to remove the solvent, distilled water and ethanol are used for washing the solid product, and the solid product is fully dried to prepare the silane coupling agent grafted modified attapulgite component 2.
(2) Preparing a melamine-cyanuric chloride-attapulgite composite material 2: adding distilled water and the modified attapulgite component 2 into a reaction flask, placing the reaction flask into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 1h at the ultrasonic frequency of 35KHz, then adding 32 parts of melamine and 22 parts of cyanuric chloride, placing the reaction flask into a constant-temperature water bath, heating to 85 ℃, uniformly stirring for reaction for 5h, performing reduced pressure distillation to remove the solvent, washing the solid product with distilled water, and preparing to obtain the melamine-cyanuric chloride-attapulgite composite material 2.
(3) Preparation of boron-doped Nano g-C3N4Electrocatalytic hydrogen production material coated with nano Co 2: distilled water, 2 parts of melamine-cyanuric chloride-attapulgite composite material, 4 parts of triisopropyl borate and 9 parts of Co (NO) are added into a reaction bottle3)3Placing a reaction bottle in an ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 3h, wherein the ultrasonic frequency is 25KHz, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in a reaction kettle heating box, heating to 200 ℃, reacting for 15h, cooling the solution to room temperature, performing reduced pressure concentration to remove the solvent, placing the concentrated product in an atmosphere resistance furnace, introducing nitrogen, heating to 550 ℃, calcining for 3h, heating to 740 ℃, and keeping the temperatureCalcining for 4h, placing the calcined product into a sulfuric acid solution with the mass concentration of 0.4mol/L, stirring at a constant speed for 2h, filtering to obtain a solid product, washing the solid product with distilled water to prepare the boron-doped nano g-C3N4An electrocatalytic hydrogen production material 2 coated with nano Co.
(4) Doping boron with nano-g-C3N4The electrocatalytic hydrogen production material 2 coated with the nano Co, the conductive carbon black and the Nafion solution are uniformly mixed, coated on a glassy carbon electrode and dried to prepare the electrocatalytic working electrode material 2.
Electrochemical performance and hydrogen evolution initiation potential of the electrocatalytic working electrode materials in examples and comparative examples were tested in CHI660D electrochemical workstation using a platinum electrode as a counter electrode, a saturated calomel electrode as a reference electrode, and a 0.5mol/L sulfuric acid solution as an electrolyte, EvsRHE＝EvsSCE+ESCE+0.059pH, test standard GB/T19774-.
In summary, the boron-doped nano g-C3N4An electrically catalytic hydrogen-generating nano Co-coated attapulgite as a natural nano material has a large specific surface area and rich hydroxyl radicals on its surface, which is grafted and modified by 3-glycidoxypropyltriethoxysilane as silane coupling agent, whose epoxy radicals react with the amino radicals in melamine to make the melamine uniformly loaded on the surface of attapulgite, and the cyanuric chloride is used to regulate C/N ratio, and triisopropyl borate is used as boron source, and through hydrothermal synthesis and thermal cracking, the boron-doped nano g-C with developed specific surface area and pore structure is prepared3N4Nanosheets, doping of boron atoms, substituted g-C3N4Carbon atoms in the grid structure form a pi-bonded planar layered structure, so that the nano g-C is increased3N4Expose more electrochemically active sites, and enhance g-C3N4The electric conductivity of (2) shortens the transmission path of electric charges, promotes the diffusion and migration of electric charges, and the nano g-C3N4Uniformly dispersed and attached on the surface of attapulgite, effectively relieving the nano g-C3N4Agglomeration and caking phenomena avoid covering active sites, and greatly enhance the hydrogen evolution activity of the catalyst.
Boron doped nano g-C prepared by high temperature thermal reduction method3N4Coating nanometer Co, wherein Co nanometer particles can provide electron transfer in acid electrolyte to promote hydrogen production reaction by electrolysis, and the Co nanometer particles are in nanometer g-C3N4The catalyst is prevented from being dissolved by direct contact with the electrolyte or generating side reaction with the electrolyte under the coating, so that the catalyst matrix is prevented from being lost or even decomposed.
Claims (4)
1. Boron-doped nano g-C3N4The electrocatalytic hydrogen production material coated with the nano Co comprises the following formula raw materials and components in parts by weight, and is characterized in that: 14-18 parts of attapulgite, 11-15 parts of silane coupling agent, 33-48 parts of melamine, 22-26 parts of cyanuric chloride and 4-8 parts of Co (NO)3)3And 1-3 parts of triisopropyl borate.
2. The boron-doped nanog-C as claimed in claim 13N4The electrocatalytic hydrogen production material coated with the nano Co is characterized in that: the silane coupling agent is 3-glycidyl ether oxypropyl triethoxysilane.
3. The boron-doped nanog-C as claimed in claim 13N4The electrocatalytic hydrogen production material coated with the nano Co is characterized in that: the boron-doped nano g-C3N4The preparation method of the electrocatalytic hydrogen production material coated with the nano Co comprises the following steps:
(1) ball milling attapulgite until the attapulgite passes through a 1800-plus 2000-mesh sieve, adding 14-18 parts of attapulgite into a toluene solvent, placing the solution into an ultrasonic treatment instrument for ultrasonic dispersion treatment for 30-50min at the ultrasonic frequency of 20-30KHz, adding 11-15 parts of silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane, heating the solution to 65-85 ℃, reacting for 6-8h, removing the solvent from the solution, washing a solid product, and drying to prepare the silane coupling agent grafted modified attapulgite.
(2) Adding modified attapulgite into a distilled water solvent, performing ultrasonic dispersion treatment on the solution for 1-2h at the ultrasonic frequency of 25-35KHz, then adding 38-53 parts of melamine and 15-21 parts of cyanuric chloride, heating the solution to 85-95 ℃, stirring at a constant speed for reaction for 3-5h, removing the solvent from the solution, washing a solid product, and drying to prepare the melamine-cyanuric chloride-attapulgite composite material.
(3) Adding melamine-cyanuric chloride-attapulgite composite material, 1-3 parts of triisopropyl borate and 4-8 parts of Co (NO) into distilled water solvent3)3Carrying out ultrasonic dispersion treatment on the inverse solution for 2-3h, wherein the ultrasonic frequency is 25-35KHz, transferring the solution into a reaction kettle, heating to 190-200 ℃, reacting for 15-20h, removing the solvent from the solution, placing the concentrated product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 2-4 ℃/min to 520-550 ℃, calcining for 2-3h, heating to 740-760 ℃, carrying out heat preservation and calcination for 3-4h, placing the calcined product into a sulfuric acid solution with the mass concentration of 0.4-0.8mol/L, stirring at a constant speed for 2-5h, filtering and washing the solid product to prepare the boron-doped nano g-C3N4An electrocatalytic hydrogen production material coated with nano Co.
4. The boron-doped nanog-C as claimed in claim 33N4The electro-catalysis hydrogen production material coated with the nano Co, the ultrasonic treatment instrument comprises a host (1), and is characterized in that: the top of the main machine (1) is fixedly connected with a support (2), the support (2) is provided with an ultrasonic generator (3), the bottom of the ultrasonic generator (3) is provided with an ultrasonic probe (4) and an adjusting device (5), the top of the main machine (1) is provided with a reaction bottle (6), the reaction bottle (6) is internally inserted with a stirring device (7), the stirring device (7) is fixedly arranged on the main machine (1) through a positioning device (8), a fastening component (9) is arranged on the longitude and latitude device (8),the fastening assembly (9) comprises a main seat (901), an adjusting rod (902) is movably inserted into the top of the main seat (901), a fixed plate (904) and a movable plate (903) which are respectively connected with the stirring device (7) and the positioning device (8) are installed on the outer side of the main seat (901), and the adjusting rod (902) is movably connected with the movable plate (903) through a connecting rod.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789592A (en) * | 2021-11-15 | 2021-12-14 | 因达孚先进材料(苏州)有限公司 | Method for improving carbonization yield of viscose-based carbon felt |
| CN115318323A (en) * | 2022-07-27 | 2022-11-11 | 天津大学（青岛）海洋工程研究院有限公司 | Cobalt phosphide-phosphorus loaded boron doped carbon nitride photocatalyst and preparation method and application thereof |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789592A (en) * | 2021-11-15 | 2021-12-14 | 因达孚先进材料(苏州)有限公司 | Method for improving carbonization yield of viscose-based carbon felt |
| CN113789592B (en) * | 2021-11-15 | 2022-02-08 | 因达孚先进材料(苏州)有限公司 | Method for improving carbonization yield of viscose-based carbon felt |
| CN115318323A (en) * | 2022-07-27 | 2022-11-11 | 天津大学（青岛）海洋工程研究院有限公司 | Cobalt phosphide-phosphorus loaded boron doped carbon nitride photocatalyst and preparation method and application thereof |
| CN115318323B (en) * | 2022-07-27 | 2023-11-21 | 天津大学（青岛）海洋工程研究院有限公司 | Cobalt phosphide-phosphorus loaded boron doped carbon nitride photocatalyst, preparation method and application |
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