CN111111731A - Preparation method of graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst - Google Patents
Preparation method of graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst Download PDFInfo
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- CN111111731A CN111111731A CN201911327124.XA CN201911327124A CN111111731A CN 111111731 A CN111111731 A CN 111111731A CN 201911327124 A CN201911327124 A CN 201911327124A CN 111111731 A CN111111731 A CN 111111731A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 3
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract 6
- 239000000376 reactant Substances 0.000 claims abstract 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 abstract 1
- 238000000137 annealing Methods 0.000 abstract 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- -1 transition metal nitrides Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 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
-
- 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
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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 Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a preparation method of a graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst, belonging to the technical field of preparation of novel inorganic nano functional materials. The method takes B-NiO/graphene nano-sheets as precursors to prepare N, B-Ni through annealing under the protection of gas2P/graphene composite catalysts. The method comprises the following specific steps: firstly, preparing B-NiO/graphene as a precursor by using nickel nitrate, graphene oxide and sodium borohydride as reactants through a gas-phase synthesis method; further using sodium hypophosphite to heat the precursor under the protection of gas for phosphorization to obtain N, B-Ni2P/graphene composite electrolytic water catalyst.
Description
Technical Field
The invention relates to a preparation method of a graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst, belonging to the technical field of novel inorganic nano functional materials.
Background
Hydrogen (H)2) Are considered as clean energy carriers to replace fossil fuels due to their high energy density and environmental friendliness. Currently, large-scale high-purity Hydrogen (HER) produced by cathodic hydrogen evolution reactions through water electrolysis is considered a cost-effective and viable process. So far, electrocatalysts with high catalytic hydrogen production catalytic efficiency have been limited to expensive and scarce noble metal catalysts (e.g., platinum), which severely hamper their practical application. For this reason, many non-noble metal-based electrocatalysts have been developed with high efficiency in acidic and alkaline electrolytes, including transition metal nitrides, sulfides, selenides, carbides, phosphides, and the like. However, most of the catalysts having excellent hydrogen evolution activity in acidic or basic media have unsatisfactory catalytic activity in neutral media due to their low conductivity, low intrinsic catalytic activity, and the like. In addition, in an acidic or alkaline medium, the strong acid and the strong base are easy to corrode an electrolysis instrument and a catalyst, so that the method is low in environmental and economic friendliness. In contrast, electrochemical water splitting in neutral media can effectively reduce the overall cost of an electrolyzed water system because expensive proton exchange membranes are not required. Therefore, the development of efficient and stable neutral HER electrocatalysts is an important basis and key link for the development of hydrogen production technology by water electrolysis, but still faces greater challenges.
So far, Transition Metal Phosphide (TMP), including Ni2P，Ni12P5，CoP，Co2P, NiCoP, FeP and MoP, etc. are widely used as substitutes for Pt-based catalysts due to their non-metallic characteristics, high electrocatalytic properties and significant soil abundance. However, the monotonic morphology, small specific surface area, and low conductivity and low stability severely limit their practical applications. In order to solve the above problems and further improve the electrochemical activity, several strategies to solve the above key problems have been proposed, and some progress has been made so far. For example, increasing the specific surface area of TMP nanostructures by surface roughening or porous structures can not only create more exposed active sites, but can also enhance water moleculesDiffusion and rapid release of gaseous products. Based on earlier stage research, the invention develops a preparation method of the full-pH electrolyzed water hydrogen evolution catalyst with low cost, simplicity, convenience, practicability and low energy consumption, and Ni is regulated and controlled by doping boron and nitrogen2P-electron structure, enhancement of Ni by graphene loading2P conductivity, successfully synthesizes the graphene loaded nitrogen boron doped nickel phosphide (N, B-Ni)2P/graphene) nanoplatelets and for stable HER catalysis. N, B-Ni obtained by synergistic regulation of water and hydrogen binding energy2P/graphene shows significant HER activity in acidic, basic and neutral electrolytes.
Disclosure of Invention
The invention develops the N, B-Ni full-pH electrolyzed water hydrogen evolution with low cost, simple and easy operation and low energy consumption2A preparation method of a P/graphene catalyst. The preparation method provided by the invention has the advantages of simple process and low cost, and the prepared N, B-Ni2The P/graphene water electrolysis catalyst has excellent performance, has good catalytic performance in acidic, alkaline and neutral environments, and has high practical application value.
The invention aims to realize the preparation method of the graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst by adopting the following technical scheme, which comprises the following steps of:
1) weighing 1-3 mmol of Ni (NO)3)2 .6H2Dissolving O in water, preparing 1.5-3 mg/L graphene oxide aqueous solution, mixing and stirring in a beaker, stirring for a period of time, and adding 0.5 mol/L NaBH4Continuously stirring for a period of time and then centrifugally drying;
2) grinding the substance obtained in the step 1 into powder, placing the powder in a quartz boat, and adding N2Heating under the protection of (1) to obtain B-NiO/graphene;
3) grinding the B-NiO/graphene obtained in the step 2, and weighing 150-300 mg NaH2PO2Mixing B-NiO/graphene with weighed NaH2PO2Put together in a quartz boat and in NH3Heating under the protection of/Ar mixed gas to obtain N, B-Ni2P/graphene；
4) AsIn comparison, the B-NiO/graphene obtained in step 2 is ground and weighed as 150-300 mg NaH2PO2Mixing B-NiO/graphene with weighed NaH2PO2Are placed together in a quartz boat and are in N2Heating under the protection of (2) to obtain B-Ni2P/graphene。
The invention has the beneficial effects that:
(1) the invention provides N, B-Ni with excellent performance under full pH2The preparation method of the P/graphene electrolytic water catalyst comprises the steps of firstly preparing B-NiO/graphene through a simple gas phase synthesis method, and then continuing to prepare NH3Heating under the protection of/Ar mixed gas to obtain N, B-Ni2P/graphene. The preparation method is simple and easy to operate, does not need special equipment, has low cost, is suitable for large-scale preparation, and can meet the requirements of practical application;
(2) the product prepared by the invention is N, B-Ni2The product of the P/graphene nano-sheet has uniform shape and size, and the active component is loaded by graphene and is easy to use;
(3) n, B-Ni prepared by the invention2The P/graphene composite water electrolysis catalyst has excellent water electrolysis hydrogen production performance and good stability in a full pH environment;
(4) the preparation of the invention only needs common equipment in a laboratory, does not need special equipment, and has simple and easy technical process.
Drawings
FIG. 1 (a) is a Transmission Electron Microscope (TEM) photograph of B-NiO/graphene prepared in step 2 of the present invention taken after observation with a transmission electron microscope;
(b) is N, B-Ni prepared in step 32A Transmission Electron Microscope (TEM) photograph of the P/graphene taken after observation with a transmission electron microscope;
(c) B-Ni prepared in step 42A Transmission Electron Microscope (TEM) photograph of the P/graphene taken after observation with a transmission electron microscope.
FIG. 2 (a) is an X-ray diffraction (XRD) pattern of B-NiO/graphene prepared in step 2 of the present invention;
(b) is N, B-Ni prepared in step 32X-ray of P/grapheneDiffraction (XRD) pattern;
(c) B-Ni prepared for step 42X-ray diffraction (XRD) pattern of P/graphene.
FIG. 3 shows the final N, B-Ni produced by the present invention using energy dispersive spectrometer2And (4) carrying out element analysis on the P/graphene to obtain an energy spectrum.
FIG. 4 shows N, B-Ni2The P/graphene is used as a working electrode for water electrolysis hydrogen production reaction, and water electrolysis hydrogen production experiments are carried out under (a) acidic, (b) alkaline and (c) neutral environments, so that a polarization curve graph is obtained.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are not intended to limit the scope of the present invention.
Example 1
Firstly, nickel nitrate with the concentration of 0.01 mol per liter and graphene oxide aqueous solution with the concentration of 3 mg per milliliter are mixed and stirred for 30 minutes, and then NaBH with the concentration of 0.5 mol per liter is added4The solution was stirred for an additional 40 minutes and then dried by centrifugation. Grinding the obtained material into powder, placing the powder in a quartz boat, and placing the quartz boat in a reactor under N2Heating to 300 ℃ for 2 hours under the protection of gas to obtain B-NiO/graphene. 150mg of NaH is weighed2PO2Mixing the obtained B-NiO/graphene and the weighed NaH2PO2Put together in a quartz boat and in NH3Heating to 320 ℃ for 1 hour under the protection of/Ar mixed gas to obtain N, B-Ni2P/graphene, N, B-Ni after naturally cooling to room temperature2P/graphene composite electrolytic water catalyst.
Example 2
Firstly, nickel nitrate with the concentration of 0.02 mol/L and graphene oxide aqueous solution with the concentration of 6 mg/mL are mixed and stirred for 60 minutes, and then NaBH with the concentration of 0.5 mol/L is added4The solution was stirred for 60 minutes and then dried by centrifugation. Grinding the obtained material into powder, placing the powder in a quartz boat, and placing the quartz boat in a reactor under N2Heating to 350 ℃ for 2 hours under the protection of the above to obtain B-NiO/graphene. Weighing 300 mg of NaH2PO2Mixing the obtained B-NiO/graphene with the weighed B-NiO/grapheneNaH2PO2Are placed together in a quartz boat and are in N2Heating to 350 ℃ for 1 hour under the protection of (1) and naturally cooling to room temperature to obtain the B-Ni2P/graphene composite electrolytic water catalyst.
Example 3
Using Chenhua 760D electrochemical workstation to pair N, B-Ni2The activity and stability of hydrogen production by water electrolysis of the P/graphene composite water electrolysis catalyst are tested. Taking a platinum wire as a counter electrode, silver/silver chloride as a reference electrode, and N, B-Ni2P/graphene is a working electrode, 1.0 mol of KOH aqueous solution per liter and 0.5 mol of H per liter2SO4The electrolyte solution is aqueous solution, 1 mol/L PBS aqueous solution. And performing linear volt-ampere scanning at a scanning speed of 5 milliamperes per second within a voltage range of-0.8 to-1.5V to obtain a polarization curve of hydrogen production by catalytic electrolysis of water.
Claims (3)
1. A preparation method of a graphene-loaded nitrogen-boron-doped nickel phosphide electrolysis water catalyst is characterized by comprising the following steps:
1) preparing B-NiO/graphene as a precursor by a gas-phase synthesis method by taking nickel nitrate, graphene oxide and sodium borohydride as reactants;
2) drying the B-NiO/graphene obtained in the step 1, and weighing a certain amount of NaH2PO2Mixing B-NiO/graphene with weighed NaH2PO2Put together in a quartz boat and in NH3Heating under the protection of/Ar mixed gas to obtain N, B-Ni2P/graphene。
2. N, B-Ni as claimed in claim 12The preparation method of the P/graphene composite electrolytic water catalyst is characterized in that the preparation of the precursor of the composite catalyst is carried out by a gas phase synthesis method.
3. N, B-Ni as claimed in claim 12The preparation method of the P/graphene composite electrolytic water catalyst is characterized in that the products are all synthesized by precursors under the condition of gas protection and no solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911327124.XA CN111111731A (en) | 2019-12-20 | 2019-12-20 | Preparation method of graphene-loaded nitrogen-boron-doped nickel phosphide electrolyzed water catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113289650A (en) * | 2021-06-08 | 2021-08-24 | 华东师范大学 | Bimetallic phosphide-carbon electrocatalytic hydrogen evolution material and preparation method thereof |
| CN114921809A (en) * | 2022-04-24 | 2022-08-19 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
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| CN104437572A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Preparation method of graphene-loaded nano nickel phosphate hydrogenation catalyst |
| CN106238060A (en) * | 2016-09-29 | 2016-12-21 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene/nickel composite |
| CN108620106A (en) * | 2018-05-21 | 2018-10-09 | 燕山大学 | A kind of preparation method of nickel phosphide/boron-doping reduction-oxidation graphite liberation of hydrogen composite material |
| CN109759066A (en) * | 2019-01-29 | 2019-05-17 | 济南大学 | A kind of preparation method for the cobalt nickel bimetal oxide oxygen-separating catalyst that boron doping is graphene-supported |
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2019
- 2019-12-20 CN CN201911327124.XA patent/CN111111731A/en active Pending
Patent Citations (5)
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|---|---|---|---|---|
| CN103611555A (en) * | 2013-11-20 | 2014-03-05 | 东华大学 | Nitrogen-doped graphene catalyst and preparation method and application thereof |
| CN104437572A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Preparation method of graphene-loaded nano nickel phosphate hydrogenation catalyst |
| CN106238060A (en) * | 2016-09-29 | 2016-12-21 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene/nickel composite |
| CN108620106A (en) * | 2018-05-21 | 2018-10-09 | 燕山大学 | A kind of preparation method of nickel phosphide/boron-doping reduction-oxidation graphite liberation of hydrogen composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113289650A (en) * | 2021-06-08 | 2021-08-24 | 华东师范大学 | Bimetallic phosphide-carbon electrocatalytic hydrogen evolution material and preparation method thereof |
| CN113289650B (en) * | 2021-06-08 | 2023-02-03 | 华东师范大学 | Bimetallic phosphide-carbon electrocatalytic hydrogen evolution material and preparation method thereof |
| CN114921809A (en) * | 2022-04-24 | 2022-08-19 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
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