CN113584517A - Preparation method of non-noble metal Ni-Mo-P-B efficient electro-catalytic hydrogen evolution electrode - Google Patents
Preparation method of non-noble metal Ni-Mo-P-B efficient electro-catalytic hydrogen evolution electrode Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 55
- 239000010439 graphite Substances 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000009713 electroplating Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 15
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000012634 fragment Substances 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25D3/00—Electroplating: Baths therefor
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- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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Abstract
The invention discloses a preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electro-catalysis hydrogen evolution electrode, which comprises the following steps: selecting a carbon material including a polycrystalline graphite rod as a substrate electrode; sequentially polishing and ultrasonically treating a substrateWashing, absolute ethyl alcohol washing, washing and drying, and finally sealing the obtained sample for later use; adding nickel nitrate hexahydrate, phosphomolybdic acid, sodium citrate dihydrate and boric acid into deionized water, and fully stirring until the nickel nitrate hexahydrate, the phosphomolybdic acid, the sodium citrate dihydrate and the boric acid are completely dissolved to obtain electroplating solution; at 25-60 deg.C, the treated graphite rod substrate is placed as cathode, high-purity graphite rod is used as anode, and the temp. is controlled at 30-75 mA.cm‑2And (3) carrying out cathodic electrodeposition under the condition, wherein the deposition time is 60-120 min, taking out the working electrode after electroplating, washing with deionized water, and airing to obtain the non-noble metal Ni-Mo-P-B efficient electro-catalytic hydrogen evolution electrode. The invention reduces the production cost, and the prepared high-efficiency electrocatalytic hydrogen evolution electrode has ultrahigh electrocatalytic hydrogen evolution performance and high stability.
Description
Technical Field
The invention relates to the field of materials and hydrogen energy, in particular to a preparation method of a non-noble metal Ni-Mo-P-B efficient electrocatalytic hydrogen evolution electrode.
Background
Hydrogen energy is an efficient, clean and ideal secondary energy, and is increasingly paid more attention from various countries. The hydrogen production by electrolyzing water has the advantages of reproducibility, high product purity, no pollution in the preparation process and the like, and is an effective way for storing renewable energy sources. However, the current cathode material for hydrogen production by water electrolysis still has the problems of high cost, high energy consumption caused by high overpotential and the like, so that the research on the hydrogen evolution electrode for promoting the development of the hydrogen energy technology has important significance. Platinum group noble metals are considered as the best electrocatalysts for cathodic hydrogen production, however, the low natural reserves thereof bring high cost problems, thereby limiting the large-scale industrial application thereof. In order to solve the problems, Ni-Mo-B-P is loaded on a cheap high-purity polycrystalline graphite electrode by a simple electrochemical deposition method, and the ultrahigh electrocatalytic hydrogen evolution performance and high stability of a platinum-based catalyst which can be compared with those of a platinum-based catalyst are ensured. Meanwhile, the characteristics of simple preparation method, low cost and environment-friendly and pollution-free preparation process lead the preparation method to be hopeful to be applied to industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electro-catalysis hydrogen evolution electrode, which reduces the production cost, and the prepared high-efficiency electro-catalysis hydrogen evolution electrode has ultrahigh electro-catalysis hydrogen evolution performance and high stability.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electrocatalytic hydrogen evolution electrode comprises the following steps:
(1) selecting carbon material substrate including polycrystalline graphite rod
Selecting a carbon material including a polycrystalline graphite rod as a substrate electrode;
(2) substrate pretreatment
Sequentially carrying out polishing, ultrasonic washing, absolute ethyl alcohol washing, washing and drying on a substrate, and finally sealing the obtained sample for later use;
(3) electroplating solution preparation
Adding nickel nitrate hexahydrate, phosphomolybdic acid, sodium citrate dihydrate and boric acid into deionized water, and fully stirring until the nickel nitrate hexahydrate, the phosphomolybdic acid, the sodium citrate dihydrate and the boric acid are completely dissolved to obtain electroplating solution;
(4) plating of
At 25-60 deg.C, the treated graphite rod substrate is placed as cathode, high-purity graphite rod is used as anode, and the temp. is controlled at 30-75 mA.cm-2And (3) carrying out cathodic electrodeposition under the condition, wherein the deposition time is 60-120 min, taking out the working electrode after electroplating, washing with deionized water, and airing to obtain the non-noble metal Ni-Mo-P-B efficient electro-catalytic hydrogen evolution electrode.
Preferably, the substrate pretreatment method in the step (2) is specifically that after the cross section of the grinding rod is ground on 800-mesh sand paper, the grinding rod is further ground on 3000-mesh sand paper to be smooth, then the grinding rod is subjected to ultrasonic treatment in deionized water for 2min to remove the ground debris on the surface, and then the grinding rod is washed with absolute ethyl alcohol and water and then dried for standby.
Preferably, the electrolyte preparation method in the step (3) is as follows: adding nickel nitrate hexahydrate, phosphomolybdic acid, sodium citrate dihydrate and boric acid into 20mL of deionized water, stirring at room temperature of 25 ℃ until the nickel nitrate hexahydrate, the phosphomolybdic acid and the boric acid are completely dissolved, and adding ionized water until the volume is up to 40mL to obtain the electroplating solution, wherein the nickel nitrate hexahydrate is 0.05-0.2 mol/L, the sodium citrate dihydrate is 0.1-0.3 mol/L, and the boric acid is 0-0.2 mol/L.
Compared with the prior art, the invention has the beneficial effects that:
the invention is firstly atAnd (3) carrying out electrodeposition on a carbon material substrate to prepare the Ni-Mo-P-B composite material. The electrode of the invention is 1.0 mol/LH2SO4Has very small hydrogen evolution overpotential in 1.0mol/L KOH when the current density is 10mA/cm2The overpotential is 56mV and 47mV, which can compare favourably with commercial Pt-C electrode in performance, but the preparation cost is far less than that of Pt-C electrode. And the preparation process of the electrode is simple, the binding force between the electroplated layer and the substrate of the graphite grinding rod is good, the stability is strong, and the performance is almost unchanged after the cyclic voltammetry scanning is carried out for 1000 circles. And the used electroplating solution has little corrosivity and does not contain heavy metal, and the whole electroplating process has no pollution to the environment. In conclusion, the electrode disclosed by the invention has the advantages of high performance, low price, strong stability, simplicity in preparation and environmental friendliness in an acid-base environment, so that the requirement of large-scale industrial production can be met.
Drawings
FIG. 1a is a surface SEM photograph of a Ni-Mo-P-B electrode in example 1 of the present invention; FIG. 1B is a surface SEM photograph of a Ni-Mo-P-B electrode in example 2 of the present invention;
FIG. 2 is an XPS plot of Ni-Mo-P-B material of example 3 of the present invention;
FIG. 3 shows the results of examples 1, 2 and 3 of the present invention at 1.0mol/L H2SO4Comparing the linear voltammetry scanning curves of the test in (1);
FIG. 4 is a graph comparing the linear voltammetry sweep curves tested in 1.0mol/L KOH for examples 1, 2, and 3 of the present invention;
FIG. 5 shows that the molecular weight of the polymer is 1.0mol/L H in example 4 of the present invention2SO4Comparing the linear voltammetry scanning curves of the test in (1);
FIG. 6 is a graph comparing the linear voltammetry sweep curves tested in 1.0mol/L KOH for example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electro-catalysis hydrogen evolution electrode comprises the following steps:
(1) selecting carbon material substrate including polycrystalline graphite rod
Selecting a high-purity polycrystalline graphite rod as a substrate electrode;
(2) graphite rod substrate pretreatment
Polishing the cross section of a graphite rod substrate on 800-mesh abrasive paper, then polishing the cross section of the graphite rod substrate on 3000-mesh abrasive paper to be smooth, then performing ultrasonic treatment in deionized water for 2min to remove fragments polished on the surface, and then washing the graphite rod substrate with absolute ethyl alcohol and water, and airing the graphite rod substrate for later use;
(3) electroplating solution preparation
Adding 0.1mol/L nickel nitrate hexahydrate, 0.0833mol/L phosphomolybdic acid, 0.3mol/L sodium citrate dihydrate and 0.05mol/L boric acid into 40ml deionized water, and fully stirring until the mixture is completely dissolved to prepare electroplating solution;
(4) plating of
Insulating the side surface of a treated graphite rod electrode at room temperature of 25 ℃, taking a graphite rod substrate as an example, exposing the cross section of the electrode as the electrode surface, putting the electrode into an electrolyte as a cathode, taking a high-purity graphite rod as an anode, and carrying out the treatment at the temperature of 60 mA.cm-2And (3) carrying out cathodic electrodeposition under the condition, wherein the deposition time is 90min, taking out the working electrode after the deposition is finished, washing with deionized water, and airing for later use.
Electrochemical testing:
linear voltammetric sweep test: in a three-electrode system, at room temperature of 25 ℃, the concentration is respectively 1.0mol/L H2SO4The test was performed in 1.0mol/L KOH with Ni-Mo-P-B electrode as the working electrode and 0.5 x 0.5cm platinum electrode as the counter electrode at 1.0mol/L H2SO4In Hg/Hg2SO4As a reference electrode, a linear voltammetric sweep test was carried out in the range-0.3 to 0.1V vs RHE at a sweep rate of 10mV/s in 1.0mol/L KOH with Hg/HgO as a reference electrode.
Example 2
A preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electro-catalysis hydrogen evolution electrode comprises the following steps:
(1) selecting carbon material substrate including polycrystalline graphite rod
Selecting a high-purity polycrystalline graphite rod as a substrate electrode;
(2) graphite rod substrate pretreatment
Polishing the cross section of a graphite rod substrate on 800-mesh abrasive paper, then polishing the cross section of the graphite rod substrate on 3000-mesh abrasive paper to be smooth, then performing ultrasonic treatment in deionized water for 2min to remove fragments polished on the surface, and then washing the graphite rod substrate with absolute ethyl alcohol and water, and airing the graphite rod substrate for later use;
(3) electroplating solution preparation
Adding 0.1mol/L nickel nitrate hexahydrate, 0.0833mol/L phosphomolybdic acid, 0.3mol/L sodium citrate dihydrate and 0.1mol/L boric acid into 40ml deionized water, and fully stirring until the mixture is completely dissolved to prepare electroplating solution;
(4) plating of
Insulating the side surface of a treated graphite rod electrode at room temperature of 25 ℃, taking a graphite rod substrate as an example, exposing the cross section of the electrode as the electrode surface, putting the electrode into an electrolyte as a cathode, taking a high-purity graphite rod as an anode, and carrying out the treatment at the temperature of 60 mA.cm-2Performing cathodic electrodeposition for 90min under the condition, taking out the working electrode after the electrodeposition, washing with deionized water, and airing for later use;
electrochemical testing was the same as in example 1.
Example 3
A preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electro-catalysis hydrogen evolution electrode comprises the following steps:
(1) selecting carbon material substrate including polycrystalline graphite rod
Selecting a high-purity polycrystalline graphite rod as a substrate electrode;
(2) graphite rod substrate pretreatment
Polishing the cross section of a graphite rod substrate on 800-mesh abrasive paper, then polishing the cross section of the graphite rod substrate on 3000-mesh abrasive paper to be smooth, then performing ultrasonic treatment in deionized water for 2min to remove fragments polished on the surface, and then washing the graphite rod substrate with absolute ethyl alcohol and water, and airing the graphite rod substrate for later use;
(3) electroplating solution preparation
Adding 0.1mol/L nickel nitrate hexahydrate, 0.0833mol/L phosphomolybdic acid, 0.3mol/L sodium citrate dihydrate and 0.15 mol/L boric acid into 40ml deionized water, and fully stirring until the mixture is completely dissolved to prepare electroplating solution;
(4) plating of
Insulating the side surface of a treated graphite rod electrode at room temperature of 25 ℃, taking a graphite rod substrate as an example, exposing the cross section of the electrode as the electrode surface, putting the electrode into an electrolyte as a cathode, taking a high-purity graphite rod as an anode, and carrying out the treatment at the temperature of 60 mA.cm-2Performing cathodic electrodeposition for 90min under the condition, taking out the working electrode after the electrodeposition, washing with deionized water, and airing for later use;
electrochemical testing was the same as in example 1.
Example 4
A preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electro-catalysis hydrogen evolution electrode comprises the following steps:
(1) selecting carbon material substrate including polycrystalline graphite rod
Selecting a high-purity polycrystalline graphite rod as a substrate electrode;
(2) graphite rod substrate pretreatment
Polishing the cross section of a graphite rod substrate on 800-mesh abrasive paper, then polishing the cross section of the graphite rod substrate on 3000-mesh abrasive paper to be smooth, then performing ultrasonic treatment in deionized water for 2min to remove fragments polished on the surface, and then washing the graphite rod substrate with absolute ethyl alcohol and water, and airing the graphite rod substrate for later use;
(3) electroplating solution preparation
Adding 0.1mol/L nickel nitrate hexahydrate, 0.0833mol/L phosphomolybdic acid, 0.3mol/L sodium citrate dihydrate and 0.15 mol/L boric acid into 40ml deionized water, and fully stirring until the mixture is completely dissolved to prepare electroplating solution;
(4) plating of
Insulating the side surface of a treated graphite rod electrode by taking a graphite rod substrate as an example at room temperature of 25 ℃, only exposing the cross section of the graphite rod electrode as the surface of the electrode, putting the electrode into an electrolyte as a cathode, taking a high-purity graphite rod as an anode, and performing the treatment at the temperature of 60mAcm-2Performing cathodic electrodeposition for 90min under the condition, taking out the working electrode after the electrodeposition, washing with deionized water, and airing for later use;
electrochemical testing: and (3) performing electrochemical test after the prepared electrode is scanned for 1000 circles in cyclic voltammetry within a certain potential range, wherein the test method is the same as that of the example 1.
The invention discovers that the prepared Ni-Mo-P-B quaternary alloy has certain difference in microstructure under the conditions of different boric acid concentrations, such as figure 1a (example 1) and figure 1B (example 2). In example 1, the concentration of boric acid is 0.05mol/L, and it can be seen from FIG. 1a that the surface has many nano-particle compositions. The boric acid concentration in example 2 was 0.1mol/L, and it can be seen from FIG. 1b that the deposited layer on the surface was more dense. FIG. 2 is an X-ray photoelectron spectroscopy (XPS) of the Ni-Mo-B-P material of example 3, from which we can see that it contains a part of oxygen element, and carbon element of graphite substrate, in addition to the four elements of Ni, Mo, B, and P. In addition, the peak position comparison of each element on XPS shows that the element is not in a zero valence state, which also indicates that the Ni-Mo-B-P material is not purely physically mixed, and electron transfer occurs, so that a certain degree of synergistic effect exists. FIG. 3 shows (examples 1, 2 and 3) the molecular weight at 1.0mol/L H2SO4FIG. 4 is a graph (examples 1, 2 and 3) showing the performance of electrocatalytic hydrogen evolution in 1.0mol/L KOH in which linear voltammetric sweep curves were measured by an electrochemical workstation in comparison with 10mA cm-2Overpotential at the time, it can be seen that the performance of the Ni-Mo-B-P electrode prepared by example 3 is optimal in both acidic and alkaline conditions. FIG. 5 shows the results of cyclic voltammetry scans at 1.0mol/L H for the Ni-Mo-B-P electrodes of examples 3 and 4 after 1000 cycles2SO4The graph in fig. 6 is a graph of the performance of the Ni-Mo-B-P electrode in examples 3 and 4 in 1.0mol/L KOH after 1000 cycles of cyclic voltammetric scan, and it can be seen from the graph that the hydrogen evolution potential value of the Ni-Mo-B-P electrode is not changed after 1000 cycles of cyclic voltammetric scan, indicating that the stability of the electrocatalytic hydrogen evolution is very strong.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (3)
1. A preparation method of a non-noble metal Ni-Mo-P-B high-efficiency electrocatalytic hydrogen evolution electrode is characterized by comprising the following steps:
(1) selecting carbon material substrate including polycrystalline graphite rod
Selecting a carbon material including a polycrystalline graphite rod as a substrate electrode;
(2) substrate pretreatment
Sequentially carrying out polishing, ultrasonic washing, absolute ethyl alcohol washing, washing and drying on a substrate, and finally sealing the obtained sample for later use;
(3) electroplating solution preparation
Adding nickel nitrate hexahydrate, phosphomolybdic acid, sodium citrate dihydrate and boric acid into deionized water, and fully stirring until the nickel nitrate hexahydrate, the phosphomolybdic acid, the sodium citrate dihydrate and the boric acid are completely dissolved to obtain electroplating solution;
(4) plating of
At 25-60 deg.C, the treated graphite rod substrate is placed as cathode, high-purity graphite rod is used as anode, and the temp. is controlled at 30-75 mA.cm-2And (3) carrying out cathodic electrodeposition under the condition, wherein the deposition time is 60-120 min, taking out the working electrode after electroplating, washing with deionized water, and airing to obtain the non-noble metal Ni-Mo-P-B efficient electro-catalytic hydrogen evolution electrode.
2. The method for preparing the non-noble metal Ni-Mo-P-B high-efficiency electro-catalytic hydrogen evolution electrode as claimed in claim 1, wherein the method comprises the following steps: the substrate pretreatment method in the step (2) is specifically as follows, the cross section of a stone grinding rod is ground on 800-mesh abrasive paper, then is ground on 3000-mesh abrasive paper to be smooth, then is subjected to ultrasonic treatment in deionized water for 2min to remove fragments ground on the surface, and then is washed with absolute ethyl alcohol and water, and then is dried for standby.
3. The method for preparing the non-noble metal Ni-Mo-P-B high-efficiency electro-catalytic hydrogen evolution electrode as claimed in claim 1, wherein the method comprises the following steps: the electrolyte preparation method in the step (3) is that nickel nitrate hexahydrate, phosphomolybdic acid, sodium citrate dihydrate and boric acid are added into 20mL of deionized water, then the mixture is stirred at room temperature of 25 ℃ until the mixture is completely dissolved, and then ionized water is added until the volume is up to 40mL to prepare the electroplating solution, wherein the nickel nitrate hexahydrate is 0.05-0.2 mol/L, the phosphomolybdic acid is 0.05-0.2 mol/L, the sodium citrate dihydrate is 0.1-0.3 mol/L, and the boric acid is 0-0.2 mol/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114000176A (en) * | 2021-12-02 | 2022-02-01 | 合肥工业大学 | Preparation method of bifunctional electrolytic water catalyst coating |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787329A (en) * | 2012-08-31 | 2012-11-21 | 重庆大学 | Preparation method of efficient Ni-Mo-P/Ni hydrogen evolution electrode |
| CN105483751A (en) * | 2015-12-08 | 2016-04-13 | 天津市大陆制氢设备有限公司 | Efficient Ni-S-Mo hydrogen evolution electrode and preparation method thereof |
| CN105839131A (en) * | 2016-06-13 | 2016-08-10 | 成都玖奇新材料科技有限公司 | Water electrolytic hydrogen production catalytic electrode of self-supporting metal-doped cobalt phosphide nano structure |
| CN107988617A (en) * | 2017-11-24 | 2018-05-04 | 复旦大学 | Water electrolysis efficiently, double-function catalyzing electrode and preparation method thereof |
| CN108400346A (en) * | 2018-03-11 | 2018-08-14 | 浙江大学 | A kind of preparation method of the overmolded carbon material of cuprous oxide |
| CN109136983A (en) * | 2018-09-26 | 2019-01-04 | 太原理工大学 | A kind of Mo/Ni/Co/P/C composite material and preparation method and application |
| CN111790415A (en) * | 2020-06-28 | 2020-10-20 | 江苏师范大学 | B-P co-doped double-transition metal catalyst and preparation method and application thereof |
| CN112151341A (en) * | 2020-09-10 | 2020-12-29 | 湘潭大学 | Preparation method for in-situ growth of boron carbide photocathode material on carbon substrate |
| CN112264047A (en) * | 2020-11-13 | 2021-01-26 | 中国科学技术大学 | Noble metal monoatomic catalyst for electrolyzing water to generate oxygen and preparation method and application thereof |
| CN112626552A (en) * | 2021-01-07 | 2021-04-09 | 兰州大学 | Method for electrodepositing Ni-Fe-Sn-P alloy on surface of foamed nickel |
-
2021
- 2021-06-30 CN CN202110733830.5A patent/CN113584517A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787329A (en) * | 2012-08-31 | 2012-11-21 | 重庆大学 | Preparation method of efficient Ni-Mo-P/Ni hydrogen evolution electrode |
| CN105483751A (en) * | 2015-12-08 | 2016-04-13 | 天津市大陆制氢设备有限公司 | Efficient Ni-S-Mo hydrogen evolution electrode and preparation method thereof |
| CN105839131A (en) * | 2016-06-13 | 2016-08-10 | 成都玖奇新材料科技有限公司 | Water electrolytic hydrogen production catalytic electrode of self-supporting metal-doped cobalt phosphide nano structure |
| CN107988617A (en) * | 2017-11-24 | 2018-05-04 | 复旦大学 | Water electrolysis efficiently, double-function catalyzing electrode and preparation method thereof |
| CN108400346A (en) * | 2018-03-11 | 2018-08-14 | 浙江大学 | A kind of preparation method of the overmolded carbon material of cuprous oxide |
| CN109136983A (en) * | 2018-09-26 | 2019-01-04 | 太原理工大学 | A kind of Mo/Ni/Co/P/C composite material and preparation method and application |
| CN111790415A (en) * | 2020-06-28 | 2020-10-20 | 江苏师范大学 | B-P co-doped double-transition metal catalyst and preparation method and application thereof |
| CN112151341A (en) * | 2020-09-10 | 2020-12-29 | 湘潭大学 | Preparation method for in-situ growth of boron carbide photocathode material on carbon substrate |
| CN112264047A (en) * | 2020-11-13 | 2021-01-26 | 中国科学技术大学 | Noble metal monoatomic catalyst for electrolyzing water to generate oxygen and preparation method and application thereof |
| CN112626552A (en) * | 2021-01-07 | 2021-04-09 | 兰州大学 | Method for electrodepositing Ni-Fe-Sn-P alloy on surface of foamed nickel |
Non-Patent Citations (2)
| Title |
|---|
| XIAOFANYANG: "Graphite defect network constitutes a robust and polishable matrix: Ultralow catalyst loading and excellent electrocatalytic performance", 《ELECTROCHIMICAACTA》 * |
| XIAOFANYANG: "Graphite defect network constitutes a robust and polishable matrix: Ultralow catalyst loading and excellent electrocatalytic performance", 《ELECTROCHIMICAACTA》, 28 April 2020 (2020-04-28), pages 136333 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114000176A (en) * | 2021-12-02 | 2022-02-01 | 合肥工业大学 | Preparation method of bifunctional electrolytic water catalyst coating |
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Application publication date: 20211102 |