CN110961102A - Cluster platinum-manganese alloy nanofiber material, preparation method and application thereof in hydrogen evolution reaction - Google Patents
Cluster platinum-manganese alloy nanofiber material, preparation method and application thereof in hydrogen evolution reaction Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 61
- IGOJMROYPFZEOR-UHFFFAOYSA-N manganese platinum Chemical compound [Mn].[Pt] IGOJMROYPFZEOR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 113
- 239000000243 solution Substances 0.000 claims abstract description 59
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 65
- 239000011572 manganese Substances 0.000 description 29
- 229910052697 platinum Inorganic materials 0.000 description 25
- 229910052748 manganese Inorganic materials 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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Abstract
The invention discloses a cluster platinum-manganese alloy nanofiber material and a preparation method and application thereof in hydrogen evolution reaction, wherein a chloroplatinic acid solution and a manganese salt solution are added into a mixed solution of triethylene glycol and N, N-dimethylformamide, and are stirred and mixed uniformly; then adding potassium hydroxide into the solution, and stirring until the potassium hydroxide is completely dissolved and the solution is changed from light yellow to red; transferring the precursor solution into a reaction kettle, reacting for 4-8 h at 160-190 ℃, cooling the solution, washing and centrifuging to obtain the clustered platinum-manganese alloy one-dimensional nanofiber material; the method has the advantages of simple preparation, mild reaction conditions, and one-step synthesis of the nano-fiber, the synthesized platinum-manganese alloy nano-fiber has high yield and stable synthesis, the morphology of the obtained nano-fiber can be controlled by adjusting the amount of potassium hydroxide, the nano-fiber is gradually formed, and meanwhile, the hydrogen production by water electrolysis under acid-base conditions has good performance.
Description
Technical Field
The invention belongs to the field of inorganic nano materials and the field of catalyst preparation research, and particularly relates to a clustered platinum-manganese alloy nano fiber material, a preparation method and application thereof in hydrogen evolution reaction.
Background
Platinum-based materials are considered to be the most effective catalysts for hydrogen evolution reactions among all pure metals due to their lower overpotentials and higher current exchange densities. But the cost is high, the reserves are small, the electrocatalysis durability is poor, and the large-scale application of industrialization is limited. Therefore, it becomes important to reduce the cost of hydrogen production by water electrolysis, reduce the load of the platinum catalyst, and further improve the utilization efficiency of the platinum catalyst.
Therefore, the search for suitable catalysts with high electrochemical performance and low cost is the key to performing the hydrogen evolution reaction. For this reason, there is a typical solution: reduction of the platinum content is generally achieved by alloying with transition metal elements such as copper, nickel, cobalt and iron.
Disclosure of Invention
The invention aims to provide a clustered platinum-manganese alloy one-dimensional nanofiber material, which introduces manganese ions into a platinum-based system so as to achieve the purposes of reducing the cost of noble metals and improving the catalytic efficiency.
The invention also aims to provide a preparation method of the clustered platinum-manganese alloy one-dimensional nanofiber material, which is prepared by one-step reaction, and has the advantages of simple preparation and mild reaction conditions.
The invention also aims to provide the application of the clustered platinum-manganese alloy one-dimensional nanofiber material in hydrogen evolution reaction, and the performance of hydrogen production by water electrolysis with response under acid-base conditions.
The specific technical scheme of the invention is as follows:
a preparation method of a clustered platinum-manganese alloy one-dimensional nanofiber material comprises the following steps:
(1) preparing a precursor solution: adding a chloroplatinic acid solution and a manganese salt solution into a mixed solution of triethylene glycol and N, N-dimethylformamide, and uniformly stirring and mixing; then adding potassium hydroxide to adjust the pH value of the system, and stirring until the potassium hydroxide is completely dissolved and the solution is changed from light yellow to red;
(2) solvent thermal reaction: and (2) transferring the precursor solution prepared in the step (1) into a reaction kettle, reacting for 4-8 h at 160-190 ℃, cooling the solution, washing, and centrifuging to obtain the clustered platinum-manganese alloy one-dimensional nanofiber material.
Further, in the step (1), the chloroplatinic acid solution is prepared by dissolving chloroplatinic acid in triethylene glycol; the manganese salt solution is prepared by dissolving manganese chloride in triethylene glycol.
In the step (1), the volume ratio of the triethylene glycol to the N, N-dimethylformamide to the chloroplatinic acid solution to the manganese salt solution is (5-10): (1-5): (0.05-0.15): (0.05 to 0.3), preferably 5: (0.1-0.15): (0.05-0.3).
In the step (1), the concentrations of the chloroplatinic acid solution and the manganese salt solution are both 0.02-0.1M, and preferably 0.05-0.1M.
Further, the mass ratio of chloroplatinic acid to manganese salt is 1 (0.3-3), preferably 1: 1.
In the step (1), the mass-to-volume ratio of the potassium hydroxide to the chloroplatinic acid solution is (0.1-0.6) g: (0.05-0.15) mL, preferably 0.4 g: (0.1-0.15) mL.
In the step (2), the washing is carried out by using ethanol and water for three times respectively.
The cluster platinum-manganese alloy one-dimensional nanofiber material prepared by the preparation method is a cluster one-dimensional nanowire.
The invention also provides application of the cluster platinum manganese alloy one-dimensional nanofiber material in hydrogen evolution reaction, and the cluster platinum manganese alloy one-dimensional nanofiber material can realize hydrogen preparation by electrolyzing water under acidic or alkaline conditions.
According to the preparation method of the clustered platinum-manganese alloy one-dimensional nanofiber material, triethylene glycol is used as a surfactant and a solvent, DMF is used as a reducing agent, the triethylene glycol induces platinum in a precursor solution to grow into nano particles, and the addition of potassium hydroxide is adjusted to promote the platinum to grow into the nanofibers from the nano particles. Meanwhile, manganese ions deposited on the surface are mixed with platinum atoms through mutual diffusion under the drive of high temperature, and simultaneously, a platinum precursor is directly reduced, so that the clustered platinum-manganese alloy one-dimensional nanofiber material is finally formed.
Compared with the prior art, the invention has the following advantages:
(1) the method has simple preparation and mild reaction conditions, and adopts a one-step method to synthesize the nano-fibers;
(2) the synthesized platinum-manganese nano fiber has high yield of 80-85%, and the synthesized product is relatively stable;
(3) the obtained nano-fiber can control the morphology thereof by adjusting the amount of potassium hydroxide, from the particle aggregation morphology to the small short line and finally to the nano-fiber;
(4) the obtained nano-fiber has better performance under the acid-base condition in the hydrogen production by water electrolysis.
Drawings
FIG. 1 is a scanning electron microscope image of a clustered Pt-Mn alloy one-dimensional nanofiber material prepared in example 1;
FIG. 2 is a transmission electron microscope image of the clustered Pt-Mn alloy one-dimensional nanofiber material prepared in example 1;
FIG. 3 is an XRD spectrum of the clustered Pt-Mn alloy one-dimensional nanofiber material prepared in example 1;
FIG. 4 is a transmission electron microscope image of the clustered Pt-Mn alloy one-dimensional nanofiber material prepared in example 2;
FIG. 5 is a transmission electron microscope image of the clustered Pt-Mn alloy one-dimensional nanofiber material prepared in example 3;
FIG. 6 is a transmission electron microscope image of a Pt-Mn alloy material prepared in comparative example 1;
FIG. 7 is a transmission electron microscope image of a platinum manganese alloy material prepared in comparative example 2;
FIG. 8 is a plot of linear sweep voltammetry and Tafel slope for different samples of example 4 under alkaline hydrogen evolution;
FIG. 9 is a plot of linear sweep voltammetry and Tafel slope for different samples of example 5 under alkaline hydrogen evolution;
FIG. 10 is a graph of hydrogen evolution lsv under alkaline conditions for platinum manganese alloy materials prepared at a platinum to manganese molar ratio of 1:1 with different potassium hydroxide additions;
FIG. 11 is a graph of hydrogen evolution lsv under acidic conditions for platinum manganese alloy materials prepared at a platinum to manganese molar ratio of 1:1 with different potassium hydroxide additions.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
A preparation method of a clustered platinum-manganese alloy one-dimensional nanofiber material comprises the following steps:
(1) preparing a precursor solution: mixing 5mL of triethylene glycol and 5mL of N, N-dimethylformamide, adding 100 mu L of 0.1M of triethylene glycol solution of chloroplatinic acid and 100 mu L of 0.1M of triethylene glycol solution of manganese chloride into the mixed solution, uniformly stirring, adding 0.4g of potassium hydroxide into the mixed solution, stirring and dissolving for 2 hours until the potassium hydroxide is completely dissolved and the color of the solution is changed into red from light yellow;
(2) and (2) transferring the precursor solution prepared in the step (1) into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 4 hours at 170 ℃, cooling the solution, washing with ethanol and water for three times respectively, and performing centrifugal separation to obtain the clustered platinum-manganese nano fiber.
According to the one-dimensional clustered platinum-manganese nanofiber prepared by the preparation method, the molar quantity ratio of platinum to manganese is adjusted to be 1:1, the morphology of the one-dimensional clustered platinum-manganese nanofiber is observed through a scanning electron microscope and a transmission electron microscope, as shown in figures 1 and 2, the one-dimensional clustered platinum-manganese nanofiber material can be seen from the figures, and through an X-ray diffraction test, as shown in figure 3, the substance of the one-dimensional clustered platinum-manganese nanofiber material is further proved to be platinum-manganese alloy.
Example 2
A preparation method of a clustered platinum-manganese alloy one-dimensional nanofiber material comprises the following steps:
(1) preparing a precursor solution: mixing 5mL of triethylene glycol and 5mL of N, N-dimethylformamide, adding 150 mu L of 0.1M triethylene glycol solution of chloroplatinic acid and 50 mu L of 0.1M triethylene glycol solution of manganese chloride into the mixed solution, uniformly stirring, adding 0.4g of potassium hydroxide, stirring and dissolving for 2 hours until the potassium hydroxide is completely dissolved and the color of the solution is changed from light yellow to red;
(2) and (2) transferring the precursor solution prepared in the step (1) into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 4 hours at 170 ℃, cooling the solution, washing with ethanol and water for three times respectively, and performing centrifugal separation to obtain the clustered platinum-manganese nano fiber.
The one-dimensional clustered platinum-manganese nano-fiber prepared by the preparation method is adjusted to the molar quantity ratio of platinum to manganese of 3:1 by adjusting the ratio of platinum to manganese, the morphology of the one-dimensional clustered platinum-manganese nano-fiber is observed by a transmission electron microscope, and as shown in fig. 4, the one-dimensional clustered platinum-manganese nano-fiber is a clustered platinum-manganese alloy one-dimensional nano-fiber material.
Example 3
A preparation method of a clustered platinum-manganese alloy one-dimensional nanofiber material comprises the following steps:
(1) preparing a precursor solution: mixing 5mL of triethylene glycol and 5mL of N, N-dimethylformamide, adding 100 mu L of 0.1M triethylene glycol solution of chloroplatinic acid and 300 mu L of 0.1M triethylene glycol solution of manganese chloride into the mixed solution, uniformly stirring, adding 0.4g of potassium hydroxide, stirring and dissolving for 2 hours until the potassium hydroxide is completely dissolved and the color of the solution is changed from light yellow to red;
(2) and (2) transferring the precursor solution prepared in the step (1) into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 4 hours at 170 ℃, cooling the solution, washing with ethanol and water for three times respectively, and performing centrifugal separation to obtain the clustered platinum-manganese nano fiber.
The platinum-manganese nanofiber prepared by the preparation method is adjusted to the molar quantity ratio of platinum to manganese of 1:3 by adjusting the ratio of platinum to manganese, and the morphology of the platinum-manganese nanofiber is further observed by using a transmission electron microscope, as shown in fig. 5, the platinum-manganese nanofiber is a clustered platinum-manganese alloy one-dimensional nanofiber material.
Comparative example 1
A preparation method of a platinum-manganese alloy comprises the following steps:
(1) preparing a precursor solution: mixing 5mL of triethylene glycol and 5mL of N, N-dimethylformamide, adding 100 mu L of 0.1M of triethylene glycol solution of chloroplatinic acid and 100 mu L of 0.1M of triethylene glycol solution of manganese chloride into the mixed solution, uniformly stirring, adding 0.1g of potassium hydroxide into the mixed solution, stirring and dissolving for 2 hours until the potassium hydroxide is completely dissolved and the color of the solution is changed into red from light yellow;
(2) and (2) transferring the precursor solution prepared in the step (1) into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 4h at 170 ℃, cooling the solution, washing with ethanol and water for three times respectively, performing centrifugal separation to obtain cluster-shaped platinum-manganese nanoparticles, further observing the appearance of the cluster-shaped platinum-manganese nanoparticles by using a transmission electron microscope to obtain a cluster formed by platinum-manganese alloy nanoparticles by adjusting the amount of potassium hydroxide to be 0.1g, wherein the cluster is formed by platinum-manganese alloy nanoparticles.
Comparative example 2
A preparation method of a platinum-manganese alloy comprises the following steps:
(1) preparing a precursor solution: mixing 5mL of triethylene glycol and 5mL of N, N-dimethylformamide, adding 100 mu L of 0.1M of triethylene glycol solution of chloroplatinic acid and 100 mu L of 0.1M of triethylene glycol solution of manganese chloride into the mixed solution, uniformly stirring, adding 0.2g of potassium hydroxide into the mixed solution, stirring and dissolving for 2 hours until the potassium hydroxide is completely dissolved and the color of the solution is changed into red from light yellow;
(2) transferring the precursor solution prepared in the step (1) into a polytetrafluoroethylene high-temperature reaction kettle, reacting for 4 hours at 170 ℃, cooling the solution, washing with ethanol and water for three times respectively, performing centrifugal separation to obtain cluster-shaped platinum-manganese nano fibers, observing the appearance of the cluster-shaped platinum-manganese nano fibers by using a transmission electron microscope to obtain a graph 7, wherein the graph shows that the platinum-manganese alloy material consists of platinum-manganese nano short wires and platinum-manganese nano particles by adjusting the amount of potassium hydroxide to be 0.2 g.
Example 4
Application of clustered platinum-manganese alloy one-dimensional nanofiber material in hydrogen evolution reaction under acidic condition
The method comprises the following steps: centrifuging a certain amount of platinum and manganese sample, adding 700 microliters of water, 300 microliters of isopropanol and 10 microliters of Nafion solution (5%) into 1mg of solid sample, preparing ink, performing ultrasonic treatment for 30 minutes, dropping 30 microliters of ink on carbon paper to perform a hydrogen evolution test, adopting a three-electrode system, using a CHI760 workstation for testing, using a carbon rod as a counter electrode, a platinum electrode clamp (with the carbon paper clamped thereon) as a working electrode, a silver chloride electrode as a reference electrode, and an electrolyte solution of 0.5M sulfuric acid, and calculating an overpotential and a Tafei slope by a linear scanning voltammetry and Tafei slope theory, as shown in FIG. 8, it can be seen from the figure that Pt is under an acidic condition3Mn1，Pt1Mn1，Pt1Mn310mA cm for Pt, Mn, Pt/C-2Overpotential of current is 41.7mV, 39mV, 67mV, 49.8mV, 274mV, 63.2mV respectively, wherein Pt1Mn1The catalyst has the best hydrogen evolution performance and the highest electrochemical activity. Further proves the hydrogen evolution electrochemical catalytic activity, Pt, of the catalyst through the Tafel slope3Mn1，Pt1Mn1，Pt1Mn3The Tafel slopes of Pt, Mn, Pt/C are 48mV dec-1，38mV dec-1，56mV dec-1，43.15mV dec-1，260mV dec-1，58mV dec-1. The smallest slope of Tafel among them is still Pt1Mn1Sample, illustrating Pt under acidic conditions1Mn1The sample has the best hydrogen evolution performance.
Example 5
Application of clustered platinum-manganese alloy one-dimensional nanofiber material in hydrogen evolution reaction under alkaline condition
The method comprises the following steps: centrifuging a certain amount of platinum and manganese sample, adding 700 microliters of water, 300 microliters of isopropanol and 10 microliters of Nafion solution (5%) into 1mg of solid sample obtained, preparing ink, performing ultrasonic treatment for 30 minutes, dropping 30 microliters of ink on carbon paper to perform hydrogen evolution test, adopting a three-electrode system, using a CHI760 workstation for testing, using a carbon rod as a counter electrode, and using a platinum electrode clamp (carbon paper is clamped on the carbon paper)) As a working electrode, a silver chloride electrode as a reference electrode, and an electrolyte of 1M potassium hydroxide, the overpotential and the Tafel slope were calculated by linear sweep voltammetry and Tafel slope theory, as shown in FIG. 9, it can be seen from the graph that Pt is present under alkaline conditions3Mn1，Pt1Mn1，Pt1Mn310mA cm for Pt, Mn, Pt/C-2The overpotential of the current is 81.3mV, 67.54mV, 84mV, 104.3mV, 453.11mV and 187.89mV respectively, wherein the Pt1Mn1 catalyst has the best hydrogen evolution performance and the highest electrochemical activity. Further proves the hydrogen evolution electrochemical catalytic activity, Pt, of the catalyst through the Tafel slope3Mn1，Pt1Mn1，Pt1Mn3The Tafel slopes for Pt, Mn, Pt/C are 74mV dec-1，52mV dec-1，84mV dec-1，89mV dec-1，266mV dec-1，124mV dec-1. The least slope of Tafel is still the Pt1Mn1 sample, indicating that the P1tMn1 sample has the best hydrogen evolution performance under alkaline conditions.
The platinum-manganese alloy nanomaterials obtained by changing the addition amounts of KOH in step (1) of example 1 to 0.1g, 0.2g, and 0.7g, respectively, were prepared and then tested for their hydrogen evolution lsv diagrams under alkaline and acidic conditions, respectively, as shown in FIGS. 10 and 11, and it can be seen from FIG. 10 that 10mA cm corresponding to 0.1g of KOH, 0.2g of KOH, 0.4g of KOH, and 0.7g of KOH were obtained under alkaline conditions-2The overpotentials of the currents were 611mV, 97.1mV, 67.54mV and 99mV, respectively, and it can be seen that Pt prepared by adding 0.4g KOH was obtained1Mn1The performance of nanofibers is best under alkaline conditions. As can be seen from FIG. 11, 0.1g KOH, 0.2g KOH, 0.4g KOH and 10mA cm corresponding to 0.7g KOH were obtained under the alkaline condition-2The overpotentials of the currents were 387mV, 55mV, 39mV and 75mV, respectively, and it can be seen that Pt prepared by adding 0.4g KOH had1Mn1The performance of nanofibers is best under acidic conditions. As described above, Pt was prepared by adding 0.4g of potassium hydroxide1Mn1The hydrogen evolution performance of nanofibers is best.
The above detailed description of a clustered pt-mn alloy nanofiber material and its preparation method and its application in hydrogen evolution reaction with reference to examples is illustrative and not restrictive, and several examples can be cited within the limits of the invention, so that variations and modifications without departing from the general concept of the invention shall fall within the scope of the invention.
Claims (9)
1. A preparation method of a clustered platinum-manganese alloy one-dimensional nanofiber material is characterized by comprising the following steps:
(1) preparing a precursor solution: adding a chloroplatinic acid solution and a manganese salt solution into a mixed solution of triethylene glycol and N, N-dimethylformamide, and uniformly stirring and mixing; then adding potassium hydroxide into the solution, and stirring until the potassium hydroxide is completely dissolved and the solution is changed from light yellow to red;
(2) solvent thermal reaction: and (2) transferring the precursor solution prepared in the step (1) into a reaction kettle, reacting for 4-8 h at 160-190 ℃, cooling the solution, washing, and centrifuging to obtain the clustered platinum-manganese alloy one-dimensional nanofiber material.
2. The production method according to claim 1, wherein in the step (1), the chloroplatinic acid solution is a solution prepared by dissolving chloroplatinic acid in triethylene glycol; the manganese salt solution is prepared by dissolving manganese chloride in triethylene glycol.
3. The method according to claim 1 or 2, wherein in the step (1), the volume ratio of the triethylene glycol to the N, N-dimethylformamide to the chloroplatinic acid solution to the manganese salt solution is (5-10): (1-5): (0.05-0.15): (0.05-0.3).
4. The preparation method according to claim 1 or 2, wherein in the step (1), the concentrations of the chloroplatinic acid solution and the manganese salt solution are both 0.02-0.1M; .
5. The production method according to claim 1 or 2, wherein in the step (1), the mass ratio of the chloroplatinic acid to the manganese salt is 1 (0.3-3).
6. The method according to claim 1 or 2, wherein in the step (1), the mass-to-volume ratio of the potassium hydroxide to the chloroplatinic acid solution is (0.1-0.6) g: (0.05-0.15) mL.
7. The production method according to claim 1 or 2, wherein in the step (2), the washing is three times each with ethanol and water.
8. The clustered platinum-manganese alloy one-dimensional nanofiber material prepared by the preparation method according to any one of claims 1 to 7, wherein the clustered platinum-manganese alloy one-dimensional nanofiber material is a clustered one-dimensional nanowire.
9. The use of the clustered platinum manganese alloy one-dimensional nanofiber material as claimed in claim 8 in hydrogen evolution reactions.
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