CN111905767A - Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof - Google Patents
Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111905767A CN111905767A CN202010744305.9A CN202010744305A CN111905767A CN 111905767 A CN111905767 A CN 111905767A CN 202010744305 A CN202010744305 A CN 202010744305A CN 111905767 A CN111905767 A CN 111905767A
- Authority
- CN
- China
- Prior art keywords
- molybdenum sulfide
- nano
- wood
- electrode material
- porous electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002023 wood Substances 0.000 title claims abstract description 140
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 241000219071 Malvaceae Species 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 244000166124 Eucalyptus globulus Species 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 241001388119 Anisotremus surinamensis Species 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000009210 therapy by ultrasound Methods 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 210000002816 gill Anatomy 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nano napped molybdenum sulfide/wood-based carbon porous electrode material and a preparation method and application thereof. The porous electrode material consists of a porous carbonized wood chip and nano fuzzy ball-shaped molybdenum sulfide uniformly grown on the surface of the porous carbonized wood chip, the diameter of the nano fuzzy ball-shaped molybdenum sulfide is 0.1-3 mu m, and the nano fuzzy ball-shaped molybdenum sulfide consists of molybdenum sulfide nanosheets. According to the invention, nano flaky molybdenum sulfide is accumulated into nano pompon shape and is uniformly loaded on the surface of the carbonized wood chip, so that the defects of the traditional powdery catalyst are effectively overcome; meanwhile, the fluffy spherical molybdenum sulfide enables the flaky molybdenum sulfide edge to be fully exposed outside, the exposure proportion of the active edge is improved, and the prepared three-dimensional self-supporting electrolytic water hydrogen evolution catalyst has good catalytic performance; meanwhile, the carbonized wood material with good conductivity well improves the conductivity of the molybdenum sulfide as a catalyst material.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a nano pompon molybdenum sulfide/wood-based carbon porous electrode material as well as a preparation method and application thereof.
Background
With the over consumption of global energy and the environmental pollution caused by the consumption of traditional energy, the search for alternative energy with low environmental pollution and high energy density becomes the focus of global attention. Hydrogen continues to be of interest as a new energy source with high energy density and zero carbon emissions. However, the conventional hydrogen production process is generally coal gasification, natural gas and steam reforming, which all cause carbide emission and still cause certain environmental pollution. The hydrogen evolution by water electrolysis is regarded as one of the most promising hydrogen production technologies as an environment-friendly and efficient hydrogen production way. From the chemical thermodynamic point of view, electrolysis of water is a non-spontaneous reaction requiring energy (electrical energy) input, and therefore an efficient catalyst is required to reduce energy consumption. Noble metal (platinum-based) catalysts are currently the most active catalysts recognized, but cost and stability limit their further development. Therefore, the development of a non-noble metal catalyst with economy, good performance and good stability is the key problem of sustainable development of the hydrogen production industry by water electrolysis.
Most of the traditional electrocatalysts are powdery, a binder is often needed in the preparation process of the electrode, and the biggest defect of the traditional electrocatalysts is that the mutual overlapping of the powder inevitably causes the existence of the resistance among catalyst particles and the covering of active sites, thereby greatly influencing the exertion of the intrinsic performance of the catalyst, reducing the efficiency of materials and increasing the hydrogen production cost. With the intensive research, people grow the catalyst on a conductive substrate (such as foamed nickel, foamed copper, carbon cloth … and the like) with high specific surface area, and then the catalyst is directly used as an electrode, so that the defects of the traditional powder catalyst are well overcome. However, the manufacturing process of the conductive substrate such as the foamed nickel is complex and high in cost, so that the replaceable cheap conductive substrate is a problem in front of people.
Molybdenum sulfide, as a highly active catalyst for the electrohydrolization of hydrogen, has been developed into catalyst materials with different chemical ratios and different morphologies due to its ideal free energy of Gilles. But the disadvantage is that the powder particles seriously limit the full exertion of intrinsic catalytic activity in practical application. Through a large amount of researches, the microscopic molybdenum sulfide nanosheets are catalytically active for the flaky molybdenum sulfide edges, but are catalytically inactive on the basal plane, so that the key for improving the activity of the catalyst is to improve the exposed number and proportion of the molybdenum sulfide edges. Furthermore, molybdenum sulfide has poor conductivity, and the improvement of the conductivity is also the key to the improvement of the catalytic performance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a nano-napped molybdenum sulfide/wood-based carbon porous electrode material.
The invention also aims to provide a preparation method of the nano napped molybdenum sulfide/wood-based carbon porous electrode material. The invention uses wood abundant in nature as raw material, and the porous carbon material is obtained by high-temperature calcination under the protection of inert gas, thereby solving the problems of high cost and complex process of foam metal as a substrate, and the foam metal has higher specific surface area and higher conductivity when used as a conductive substrate.
The invention further aims to provide application of the nano napped molybdenum sulfide/wood-based carbon porous electrode material.
The purpose of the invention is realized by the following scheme:
a nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material is composed of a porous carbonized wood sheet and nano pompon-shaped molybdenum sulfide uniformly grown on the surface of the porous carbonized wood sheet, wherein the diameter of the nano pompon-shaped molybdenum sulfide is 0.1-3 mu m, and the nano pompon-shaped molybdenum sulfide is composed of molybdenum sulfide nanosheets.
According to the nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material, molybdenum sulfide grows uniformly on the surface of a porous carbonized wood chip, the molybdenum sulfide is flaky, and the flaky molybdenum sulfide is clustered together to form a regular sphere. The nano size exposes the active surface area more fully, the spherical accumulation of the nano sheets enables more active edges to be exposed, and the problem that the catalyst is not exerted to the maximum extent due to the overlapping of active sites is solved.
The preparation method of the nano napped spherical molybdenum sulfide/wood-based carbon porous electrode material comprises the following steps:
(1) pretreating wood: placing the dried wood in a tubular furnace, calcining at high temperature under the protection of nitrogen or inert gas, naturally cooling and taking out, cutting the wood into carbonized wood chips with the thickness of 0.1-5mm along the direction vertical to the growth direction of the wood, respectively washing the carbonized wood chips with water, ethanol and acetone until the liquid is in a clear state, and finally drying the carbonized wood chips for later use;
(2) preparing a mixed aqueous solution containing 0.005-1mol/L sodium molybdate dihydrate and 0.01-1mol/L thiourea, soaking the carbonized wood chips dried for standby in the step (1) in the mixed solution, standing for 0-60min under a vacuum condition to ensure that the mixed solution fully enters the porous carbonized wood chips, then placing the mixed solution and the carbonized wood chips in a high-pressure reaction kettle for closed reaction, and purifying the carbonized wood chips after the reaction is finished to obtain the nano velvet spherical molybdenum sulfide/wood-based carbon porous electrode material.
The wood in the step (1) refers to at least one of natural basswood, poplar and eucalyptus;
the dried wood in the step (1) means that the wood is dried in a drying oven at 60-120 ℃ for 0.5-12 hours.
The high-temperature calcination in the step (1) refers to calcination at the temperature of 500-1500 ℃ for 1-12h, and the heating rate is 1-25 ℃/min; the calcination is preferably carried out at 1000 ℃ for 6 hours at a rate of 5 ℃/min.
The washing described in step (1) is preferably washing under ultrasonic conditions.
The drying for standby in the step (1) refers to the standby after vacuum drying for 1-24 hours at the temperature of 60-100 ℃.
The concentration of the sodium molybdate dihydrate in the mixed water solution in the step (2) is preferably 0.0214-0.0414 mol/L, and the concentration of the thiourea is preferably 0.13-0.17 mol/L.
The carbonized wood chips in the step (2) also comprise a purification step before being dipped into the mixed solution, and the specific purification step is as follows: ultrasonically treating the carbonized wood chips in concentrated nitric acid (40-86 wt%) for 0-10h to remove surface impurities and improve the surface hydrophilicity so as to facilitate the back generation of pompon-shaped molybdenum sulfide for paving; then ultrasonic treating with water and low boiling point organic solvent for 1-60min, and vacuum drying at 60-100 deg.C for 1-24 hr for use, wherein the low boiling point organic solvent is at least one of ethanol, acetone, diethyl ether, chloroform, etc.
And (3) standing for 0-60min under a vacuum condition in the step (2) to ensure that the mixed solution fully enters the porous carbonized wood chips, so that the problems of catalyst aggregation and uneven growth in the traditional high-temperature environment are solved.
The closed reaction in the step (2) is a reaction at 50-300 ℃ for 1-24 h; preferably at 200 ℃ for 12 h.
And (2) the purification in the step (2) is to take out the carbonized wood chips after the reaction is finished, fully wash the carbonized wood chips with water and ethanol to remove redundant residues on the surface, and then dry the carbonized wood chips in vacuum at 60-100 ℃ for 1-24 hours to obtain the nano napped molybdenum sulfide/wood-based carbon porous electrode material.
The nano napped spherical molybdenum sulfide/wood-based carbon porous electrode material is applied to a catalyst for hydrogen evolution by water electrolysis.
The mechanism of the invention is as follows:
according to the invention, nano flaky molybdenum sulfide is accumulated into nano pompon shape and is uniformly loaded on the surface of carbonized wood, so that the defects of the traditional powdery catalyst are effectively overcome; meanwhile, the fluffy spherical molybdenum sulfide enables the flaky molybdenum sulfide edge to be fully exposed outside, and the exposure proportion of the active edge is improved; the carbonized wood is used as a substrate, so that the specific surface area is large, the exposed number of active sites is increased, and meanwhile, the conductivity of the carbonized wood material with good conductivity is well increased by using molybdenum sulfide as a catalyst material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention discloses a three-dimensional self-supporting electrolytic water evolution hydrogen catalyst material prepared by taking a carbonized wood chip as a carrier, and relates to the carbonized wood chip obtained by taking natural wood as a raw material and carbonizing at high temperature and a preparation method thereof, and the three-dimensional self-supporting electrolytic water evolution hydrogen catalyst material prepared by taking the carbonized wood chip as the carrier and sodium molybdate dihydrate and thiourea as raw materials and growing molybdenum sulfide in situ on the inner and outer walls of the carbonized wood in a high-pressure reaction kettle by a hydrothermal method. The electrolyzed water hydrogen evolution catalyst prepared by the invention has the advantages of high catalytic performance, rich raw materials, high specific surface area, good conductivity, no addition of a bonding agent, simple preparation method, low cost, energy conservation and environmental protection, and the raw materials are from biomass wood-based materials. The carbonized wood chips obtained by high-temperature carbonization are used as carriers, so that the raw materials are rich, the manufacturing is simple, the electrical properties are excellent, and carriers such as commercial foam nickel, foam copper, carbon cloth … … and the like are replaced; meanwhile, the molybdenum sulfide grown in situ is of a nano structure, has a high specific surface area, exposes more active sites for hydrogen evolution by electrolysis, enables the prepared three-dimensional self-supporting catalyst for hydrogen evolution by electrolysis to have good catalytic performance, and provides a good route for the preparation of the three-dimensional self-supporting catalyst for hydrogen evolution by electrolysis.
Drawings
Fig. 1 is a scanning electron micrograph (500 times) of a blank carbonized wood chip after the concentrated nitric acid treatment in step (2) of example 1.
Fig. 2 is an SEM image (1000 x) of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode prepared in example 1.
Fig. 3 is SEM images (2000 x and 5000 x) of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode prepared in example 1.
Fig. 4 is SEM images (2000 x and 5000 x) of the nano-pompon-like molybdenum sulfide/wood-based carbon porous electrode prepared in example 2.
FIG. 5 is a linear sweep voltammogram of the porous electrode material prepared in examples 1-5 of the present invention.
Fig. 6 is an SEM image (500 times) of the electrode prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Natural basswood is used as a raw material, and the basswood needs to be pretreated for 12 hours in a drying oven at 103 ℃ before being calcined. Then, under the protection of nitrogen gas, the temperature rising speed is 5 ℃/min, the mixture is calcined in a tube furnace at 1000 ℃ for 6 hours, and the mixture is naturally cooled at room temperature. Then cut into carbonized wood chips with a thickness of 1mm in a direction perpendicular to the growth direction of the wood with a small table saw, followed by ultrasonic treatment with deionized water, ethanol and acetone, respectively, until the ultrasonic-treated solution is in a clear state, followed by vacuum drying at 75 ℃ for 12 hours for standby.
(2) The prepared carbonized wood chips are firstly treated by ultrasonic treatment for 2 hours by concentrated nitric acid (63wt percent), then treated by ultrasonic treatment for 15 minutes by deionized water, ethanol and acetone respectively, and dried for standby. A mixed aqueous solution containing 0.0214mol/L of sodium molybdate dihydrate and 0.13mol/L of thiourea was prepared. Mixing the treated carbonized wood chips with the mixed solution, vacuumizing to realize vacuum impregnation for 5 minutes to ensure that the mixed solution fully enters the porous carbonized wood chips, transferring the mixed solution and the carbonized wood chips into a high-pressure reaction kettle together, and keeping the temperature of the reaction kettle at 200 ℃ for 12 hours. Naturally cooling at room temperature, taking out the carbonized wood chips, fully washing with deionized water, removing redundant residues on the surfaces, and carrying out vacuum drying at 75 ℃ for 12 hours to obtain the composite material (the nano pompon molybdenum sulfide/wood-based carbon porous electrode material) with the pompon molybdenum sulfide loaded on the surfaces of the carbonized wood chips.
Scanning electron micrographs (500 times) of blank carbonized wood chips after concentrated nitric acid treatment in step (2) of example 1 are shown in fig. 1, and it can be seen from fig. 1 that carbonized wood has many holes which provide many attachment points for active substances and naturally increase the active sites.
SEM images (1000 times, 2000 times and 5000 times) of the composite material of pompon-shaped molybdenum sulfide loaded on the surface of the carbonized wood chip obtained in the step (2) are respectively shown in fig. 2 and fig. 3, and as can be seen from fig. 2 and fig. 3, molybdenum sulfide spheres are uniformly loaded on the inner surface and the outer surface, and the spheres continuously grow outwards, and the connecting area between the spheres is small, and some spheres are even in point connection, so that more sphere surfaces are exposed, more active sites are exposed, and the number of the active sites is increased to a certain extent.
Example 2
(1) Natural basswood is used as a raw material, and the basswood needs to be pretreated for 12 hours in a drying oven at 103 ℃ before being calcined. Then, under the protection of nitrogen gas, the temperature rising speed is 5 ℃/min, the mixture is calcined in a tube furnace at 1000 ℃ for 6 hours, and the mixture is naturally cooled at room temperature. Then cut into carbonized wood chips with a thickness of 1mm in a direction perpendicular to the growth direction of the wood with a small table saw, followed by ultrasonic treatment with deionized water, ethanol and acetone, respectively, until the ultrasonic-treated solution is in a clear state, followed by vacuum drying at 75 ℃ for 12 hours for standby.
(2) The prepared carbonized wood chips are firstly treated by ultrasonic treatment for 2 hours by concentrated nitric acid (63wt percent), then treated by ultrasonic treatment for 15 minutes by deionized water, ethanol and acetone respectively, and dried for standby. A mixed aqueous solution containing 0.0214mol/L of sodium molybdate dihydrate and 0.15mol/L of thiourea was prepared. Mixing the treated carbonized wood chips with the mixed solution, vacuumizing to realize vacuum impregnation for 5 minutes to ensure that the mixed solution fully enters the porous carbonized wood chips, transferring the mixed solution and the carbonized wood chips into a high-pressure reaction kettle together, and keeping the temperature of the reaction kettle at 200 ℃ for 12 hours. Naturally cooling at room temperature, taking out the carbonized wood chips, fully washing with deionized water, removing redundant residues on the surfaces, and carrying out vacuum drying at 75 ℃ for 12 hours to obtain the composite material (the nano pompon molybdenum sulfide/wood-based carbon porous electrode material) with the pompon molybdenum sulfide loaded on the surfaces of the carbonized wood chips.
SEM images (2000 x and 5000 x) of the nano-pompon-like molybdenum sulfide/wood-based carbon porous electrode prepared in example 2 are shown in fig. 4.
Example 3
(1) Natural basswood is used as a raw material, and the basswood needs to be pretreated for 12 hours in a drying oven at 103 ℃ before being calcined. Then, under the protection of nitrogen gas, the temperature rising speed is 5 ℃/min, the mixture is calcined in a tube furnace at 1000 ℃ for 6 hours, and the mixture is naturally cooled at room temperature. Then cut into carbonized wood chips with a thickness of 1mm in a direction perpendicular to the growth direction of the wood with a small table saw, followed by ultrasonic treatment with deionized water, ethanol and acetone, respectively, until the ultrasonic-treated solution is in a clear state, followed by vacuum drying at 75 ℃ for 12 hours for standby.
(2) The prepared carbonized wood chips are firstly treated by ultrasonic treatment for 2 hours by concentrated nitric acid (63wt percent), then treated by ultrasonic treatment for 15 minutes by deionized water, ethanol and acetone respectively, and dried for standby. A mixed aqueous solution containing 0.0214mol/L of sodium molybdate dihydrate and 0.17mol/L of thiourea was prepared. Mixing the treated carbonized wood chips with the mixed solution, vacuumizing to realize vacuum impregnation for 5 minutes to ensure that the mixed solution fully enters the porous carbonized wood chips, transferring the mixed solution and the carbonized wood chips into a high-pressure reaction kettle together, and keeping the temperature of the reaction kettle at 200 ℃ for 12 hours. Naturally cooling at room temperature, taking out the carbonized wood chips, fully washing with deionized water, removing redundant residues on the surfaces, and carrying out vacuum drying at 75 ℃ for 12 hours to obtain the composite material (the nano pompon molybdenum sulfide/wood-based carbon porous electrode material) with the pompon molybdenum sulfide loaded on the surfaces of the carbonized wood chips. The production of nano-sized molybdenum sulfide in the ball can also be seen on the SEM image of the composite material.
Example 4
(1) Natural basswood is used as a raw material, and the basswood needs to be pretreated for 12 hours in a drying oven at 103 ℃ before being calcined. Then, under the protection of nitrogen gas, the temperature rising speed is 5 ℃/min, the mixture is calcined in a tube furnace at 1000 ℃ for 6 hours, and the mixture is naturally cooled at room temperature. Then cut into carbonized wood chips with a thickness of 1mm in a direction perpendicular to the growth direction of the wood with a small table saw, followed by ultrasonic treatment with deionized water, ethanol and acetone, respectively, until the ultrasonic-treated solution is in a clear state, followed by vacuum drying at 75 ℃ for 12 hours for standby.
(2) The prepared carbonized wood chips are firstly treated by ultrasonic treatment for 2 hours by concentrated nitric acid (63wt percent), then treated by ultrasonic treatment for 15 minutes by deionized water, ethanol and acetone respectively, and dried for standby. A mixed aqueous solution containing 0.0314mol/L of sodium molybdate dihydrate and 0.15mol/L of thiourea was prepared. Mixing the treated carbonized wood chips with the mixed solution, vacuumizing to realize vacuum impregnation for 5 minutes to ensure that the mixed solution fully enters the porous carbonized wood chips, transferring the mixed solution and the carbonized wood chips into a high-pressure reaction kettle together, and keeping the temperature of the reaction kettle at 200 ℃ for 12 hours. Naturally cooling at room temperature, taking out the carbonized wood chips, fully washing with deionized water, removing redundant residues on the surfaces, and carrying out vacuum drying at 75 ℃ for 12 hours to obtain the composite material (the nano pompon molybdenum sulfide/wood-based carbon porous electrode material) with the pompon molybdenum sulfide loaded on the surfaces of the carbonized wood chips. The production of nano-sized molybdenum sulfide in the ball can also be seen on the SEM image of the composite material.
Example 5
(1) Natural basswood is used as a raw material, and the basswood needs to be pretreated for 12 hours in a drying oven at 103 ℃ before being calcined. Then, under the protection of nitrogen gas, the temperature rising speed is 5 ℃/min, the mixture is calcined in a tube furnace at 1000 ℃ for 6 hours, and the mixture is naturally cooled at room temperature. Then cut into carbonized wood chips with a thickness of 1mm in a direction perpendicular to the growth direction of the wood with a small table saw, followed by ultrasonic treatment with deionized water, ethanol and acetone, respectively, until the ultrasonic-treated solution is in a clear state, followed by vacuum drying at 75 ℃ for 12 hours for standby.
(2) The prepared carbonized wood chips are firstly treated by ultrasonic treatment for 2 hours by concentrated nitric acid (63wt percent), then treated by ultrasonic treatment for 15 minutes by deionized water, ethanol and acetone respectively, and dried for standby. A mixed aqueous solution containing 0.0414mol/L of sodium molybdate dihydrate and 0.15mol/L of thiourea was prepared. Mixing the treated carbonized wood chips with the mixed solution, vacuumizing to realize vacuum impregnation for 5 minutes to ensure that the mixed solution fully enters the porous carbonized wood chips, transferring the mixed solution and the carbonized wood chips into a high-pressure reaction kettle together, and keeping the temperature of the reaction kettle at 200 ℃ for 12 hours. Naturally cooling at room temperature, taking out the carbonized wood chips, fully washing with deionized water, removing redundant residues on the surfaces, and carrying out vacuum drying at 75 ℃ for 12 hours to obtain the composite material (the nano pompon molybdenum sulfide/wood-based carbon porous electrode material) with the pompon molybdenum sulfide loaded on the surfaces of the carbonized wood chips. The production of nano-sized molybdenum sulfide in the ball can also be seen on the SEM image of the composite material.
The linear sweep voltammetry curve of the nano napped spherical molybdenum sulfide/wood-based carbon porous electrode materials obtained in examples 1-5 is shown in fig. 5, and it can be seen from fig. 5 that the nano napped spherical molybdenum sulfide/wood-based carbon porous electrode materials prepared in examples 1-5 of the present invention all have good hydrogen evolution performance.
Comparative example 1
Step (1) in example 1 was deleted, and "treated carbonized wood chips" in "mixing treated carbonized wood chips and mixed solution together" in step (2) were replaced with "nickel foam", and the rest was the same as in example 1.
The SEM image of the product obtained in comparative example 1 is shown in fig. 6, and it can be seen from fig. 6 that even in the same experimental method, when the carriers are different, the morphology of the molybdenum sulfide obtained is completely different.
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. The nano velvet spherical molybdenum sulfide/wood-based carbon porous electrode material is characterized by consisting of a porous carbonized wood chip and nano velvet spherical molybdenum sulfide uniformly grown on the surface of the porous carbonized wood chip, wherein the diameter of the nano velvet spherical molybdenum sulfide is 0.1-3 mu m, and the nano velvet spherical molybdenum sulfide consists of molybdenum sulfide nanosheets.
2. The preparation method of the nano-fluff spherical molybdenum sulfide/wood-based carbon porous electrode material according to claim 1, characterized by comprising the following steps:
(1) pretreating wood: placing the dried wood in a tubular furnace, calcining at high temperature under the protection of nitrogen or inert gas, naturally cooling and taking out, cutting the wood into carbonized wood chips with the thickness of 0.1-5mm along the direction vertical to the growth direction of the wood, respectively washing the carbonized wood chips with water, ethanol and acetone until the liquid is in a clear state, and finally drying the carbonized wood chips for later use;
(2) preparing a mixed aqueous solution containing 0.005-1mol/L sodium molybdate dihydrate and 0.01-1mol/L thiourea, soaking the carbonized wood chips dried for standby in the step (1) in the mixed solution, standing for 0-60min under a vacuum condition to ensure that the mixed solution fully enters the porous carbonized wood chips, then placing the mixed solution and the carbonized wood chips in a high-pressure reaction kettle for closed reaction, and purifying the carbonized wood chips after the reaction is finished to obtain the nano velvet spherical molybdenum sulfide/wood-based carbon porous electrode material.
3. The preparation method of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material according to claim 2, characterized by comprising the following steps:
the high-temperature calcination in the step (1) refers to calcination at the temperature of 500-1500 ℃ for 1-12h, and the heating rate is 1-25 ℃/min.
4. The preparation method of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material according to claim 2, characterized by comprising the following steps:
the wood in the step (1) is at least one of natural basswood, poplar and eucalyptus.
5. The preparation method of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material according to claim 2, characterized by comprising the following steps:
the dried wood in the step (1) is dried in a drying oven at 60-120 ℃ for 0.5-12 hours;
the drying for standby in the step (1) refers to the standby after vacuum drying for 1-24 hours at the temperature of 60-100 ℃.
6. The preparation method of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material according to claim 2, characterized by comprising the following steps:
the concentration of the sodium molybdate dihydrate in the mixed water solution in the step (2) is 0.0214-0.0414 mol/L, and the concentration of the thiourea is 0.13-0.17 mol/L.
7. The preparation method of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material according to claim 2, characterized by comprising the following steps:
the carbonized wood chips in the step (2) also comprise a purification step before being dipped into the mixed solution, and the specific purification step is as follows: ultrasonically treating carbonized wood chips in concentrated nitric acid for 0-10h to remove surface impurities, then respectively ultrasonically treating with water and a low-boiling-point organic solvent for 1-60min, and vacuum drying at 60-100 ℃ for 1-24h for later use, wherein the low-boiling-point organic solvent is at least one of ethanol, acetone, diethyl ether and chloroform.
8. The preparation method of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material according to claim 2, characterized by comprising the following steps:
the closed reaction in the step (2) refers to a reaction at 50-300 ℃ for 1-24 h.
9. The preparation method of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material according to claim 2, characterized by comprising the following steps:
and (2) the purification in the step (2) is to take out the carbonized wood chips after the reaction is finished, fully wash the carbonized wood chips with water and ethanol to remove redundant residues on the surface, and then dry the carbonized wood chips in vacuum at 60-100 ℃ for 1-24 hours to obtain the nano napped molybdenum sulfide/wood-based carbon porous electrode material.
10. The use of the nano-fluff-ball-shaped molybdenum sulfide/wood-based carbon porous electrode material as claimed in claim 1 as a catalyst for hydrogen evolution by electrolysis of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010744305.9A CN111905767B (en) | 2020-07-29 | 2020-07-29 | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010744305.9A CN111905767B (en) | 2020-07-29 | 2020-07-29 | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111905767A true CN111905767A (en) | 2020-11-10 |
| CN111905767B CN111905767B (en) | 2021-11-26 |
Family
ID=73286751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010744305.9A Active CN111905767B (en) | 2020-07-29 | 2020-07-29 | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111905767B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113130930A (en) * | 2021-04-19 | 2021-07-16 | 北京化工大学 | Gas diffusion layer material, electrode comprising same, preparation and application |
| CN113215594A (en) * | 2021-04-07 | 2021-08-06 | 中南林业科技大学 | Nickel-iron hydroxide/nickel-iron alloy loaded wood-based electrocatalyst, preparation method thereof and catalyst for hydrogen production by electrolyzing water |
| CN113235106A (en) * | 2021-04-07 | 2021-08-10 | 中南林业科技大学 | Preparation method of molybdenum carbide-loaded wood-based electrocatalyst and catalyst for hydrogen production by water electrolysis |
| CN115354346A (en) * | 2022-08-26 | 2022-11-18 | 华南农业大学 | P-induced doped CoFe-LDH/porous carbon electrolysis water hydrogen evolution electrode material and preparation and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3737517A (en) * | 1971-02-08 | 1973-06-05 | Universal Oil Prod Co | Method for reducing oxysulfur compounds |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107829106A (en) * | 2017-11-01 | 2018-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of molybdenum sulfide/nitridation carbon composite and products thereof and application |
| CN108642517A (en) * | 2018-04-16 | 2018-10-12 | 肇庆市华师大光电产业研究院 | A method of utilizing Chinese photinia wood growing high density boundary molybdenum disulfide nano material |
| CN109482200A (en) * | 2018-11-20 | 2019-03-19 | 华南理工大学 | Porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind and preparation method thereof |
| CN110124699A (en) * | 2019-05-30 | 2019-08-16 | 河北科技大学 | Biomass carbon pipe assists MoS2The preparation method and applications of liberation of hydrogen catalyst |
| CN110255524A (en) * | 2019-05-09 | 2019-09-20 | 华南师范大学 | A kind of preparation method for the self-supporting porous carbon electrodes loading two-dimensional material |
-
2020
- 2020-07-29 CN CN202010744305.9A patent/CN111905767B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3737517A (en) * | 1971-02-08 | 1973-06-05 | Universal Oil Prod Co | Method for reducing oxysulfur compounds |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107829106A (en) * | 2017-11-01 | 2018-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of molybdenum sulfide/nitridation carbon composite and products thereof and application |
| CN108642517A (en) * | 2018-04-16 | 2018-10-12 | 肇庆市华师大光电产业研究院 | A method of utilizing Chinese photinia wood growing high density boundary molybdenum disulfide nano material |
| CN109482200A (en) * | 2018-11-20 | 2019-03-19 | 华南理工大学 | Porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind and preparation method thereof |
| CN110255524A (en) * | 2019-05-09 | 2019-09-20 | 华南师范大学 | A kind of preparation method for the self-supporting porous carbon electrodes loading two-dimensional material |
| CN110124699A (en) * | 2019-05-30 | 2019-08-16 | 河北科技大学 | Biomass carbon pipe assists MoS2The preparation method and applications of liberation of hydrogen catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 许冰洁等: ""基于二硫化钼 /多孔石墨烯复合材料的木犀草素电化学传感器"", 《分析化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113215594A (en) * | 2021-04-07 | 2021-08-06 | 中南林业科技大学 | Nickel-iron hydroxide/nickel-iron alloy loaded wood-based electrocatalyst, preparation method thereof and catalyst for hydrogen production by electrolyzing water |
| CN113235106A (en) * | 2021-04-07 | 2021-08-10 | 中南林业科技大学 | Preparation method of molybdenum carbide-loaded wood-based electrocatalyst and catalyst for hydrogen production by water electrolysis |
| CN113235106B (en) * | 2021-04-07 | 2022-07-15 | 中南林业科技大学 | Preparation method of molybdenum carbide-loaded wood-based electrocatalyst and catalyst for hydrogen production by electrolyzing water |
| CN113130930A (en) * | 2021-04-19 | 2021-07-16 | 北京化工大学 | Gas diffusion layer material, electrode comprising same, preparation and application |
| CN115354346A (en) * | 2022-08-26 | 2022-11-18 | 华南农业大学 | P-induced doped CoFe-LDH/porous carbon electrolysis water hydrogen evolution electrode material and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111905767B (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111905767B (en) | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof | |
| Wang et al. | Emerging nanostructured carbon-based non-precious metal electrocatalysts for selective electrochemical CO 2 reduction to CO | |
| CN109267092B (en) | Molybdenum disulfide composite material and preparation method and application thereof | |
| CN105712303B (en) | A kind of selenizing molybdenum nanometer sheet/fiber base carbon aerogel composite material and preparation method thereof | |
| CN109433228B (en) | Angular Ni with hierarchical structure3S2/VS4Electrode material and preparation method thereof | |
| CN114164448B (en) | Heterogeneous nickel phosphide material and preparation method thereof | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| CN113149115B (en) | Multistage heterostructure membrane for photo-thermal seawater desalination and preparation method | |
| CN114182287A (en) | Nickel-molybdenum nickel nitride composite catalyst and preparation method and application thereof | |
| CN108565469B (en) | Cobalt-nitrogen doped carbon composite material and preparation method thereof | |
| CN111068717B (en) | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof | |
| CN114538408A (en) | Method for preparing high electrocatalytic activity biochar through micro-aerobic pyrolysis | |
| CN114023980A (en) | Preparation method of nitrogen-doped porous carbon material based on furfural residues and electrocatalytic oxygen reduction performance of nitrogen-doped porous carbon material | |
| CN115323400A (en) | Three-dimensional porous Mo 2 C/NC @ Ni composite hydrogen production material and preparation method and application thereof | |
| CN111777102A (en) | Metal oxide-based bifunctional water decomposition nano material and preparation method thereof | |
| CN113737218B (en) | Copper-based graphene aerogel composite catalyst, gas diffusion electrode and application | |
| CN114892206A (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN114214640B (en) | Biomass carbon-based nano molybdenum carbide-molybdenum nitride heterojunction composite catalyst and method | |
| CN114534744B (en) | Preparation method of solid acid catalyst based on aluminous ash-green carbon-based double-carrier | |
| CN113355692B (en) | Preparation method of molybdenum disulfide nanosheet@cobalt sulfide nanoparticle composite electrocatalyst | |
| CN114774983A (en) | Ultra-small Ru nanocluster loaded on MoO3-xDouble-function composite material of nanobelt and preparation method and application thereof | |
| CN110272115B (en) | Cu-Ce-Y spherical cavity composite material and preparation method and application thereof | |
| CN110642239B (en) | Preparation method and application of eggshell membrane derived carbon/graphene/copper sulfide composite material | |
| CN113061928A (en) | Preparation method of molybdenum disulfide nanosheet @ cobalt sulfide nanoparticle array electrode | |
| CN113089014A (en) | Super-hydrophilic super-gas-dredging efficient hydrogen evolution catalyst with core-shell structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |