CN114293202A - Catalyst, preparation method and application thereof - Google Patents
Catalyst, preparation method and application thereof Download PDFInfo
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- CN114293202A CN114293202A CN202111658774.XA CN202111658774A CN114293202A CN 114293202 A CN114293202 A CN 114293202A CN 202111658774 A CN202111658774 A CN 202111658774A CN 114293202 A CN114293202 A CN 114293202A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 23
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- 150000002940 palladium Chemical class 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 150000002503 iridium Chemical class 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
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- 238000009826 distribution Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- ZSKCYRQOFSOVNM-UHFFFAOYSA-K Cl.Cl[Ir](Cl)Cl Chemical compound Cl.Cl[Ir](Cl)Cl ZSKCYRQOFSOVNM-UHFFFAOYSA-K 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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Images
Classifications
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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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Abstract
The invention discloses a catalyst and a preparation method and application thereof. The catalyst comprises an Ir-Pd monatomic alloy. The monatomic alloy (SAAs) developed by the scheme of the invention has extremely high activity and ultrahigh large-current stability, the cost of the catalyst of the scheme of the invention is about 1/2 of a commercial Pt/C catalyst, the water electrolysis efficiency per unit atom of the catalyst can reach more than 2 times of that of the commercial Pt/C catalyst, and the absolute performance is about 5 times. The catalyst of the scheme of the invention has good stability, and the stability can reach more than one month under the working condition of large current; the overpotential of the catalyst in a KOH solution of 1mol/L is 16mV, which is far lower than that of other traditional catalysts in the related art.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a catalyst, and a preparation method and application thereof.
Background
Energy and environment are one of the important issues involved in the sustainable development of human society, and people are gradually moving from fossil fuels to sustainable non-fossil energy sources without pollution. Hydrogen is one of ideal clean energy sources, and hydrogen production by water electrolysis is an important means for realizing industrial and cheap hydrogen preparation. During electrolysis of water, the efficiency of an electrocatalyst Hydrogen Evolution (HER) reaction is affected by H in solution+The effect of concentration.In general, the activity of HER for acidic electrolytes, such as sulfuric acid solution, is about 2 to 3 orders of magnitude that for alkaline electrolytes. However, the electrocatalyst for the anode reaction in the acidic water electrolysis process is a high-cost Ir/Ru-based material, and the use of the material causes the cost of the whole water electrolysis hydrogen production system to be high. Therefore, the development of efficient alkaline HER catalysts is particularly critical to reduce the cost of the overall electrolytic water system.
At present, the catalyst with better efficiency in the alkaline HER process is a commercial Pt/C catalyst, but the Pt has low reserve in the earth crust and high price, so that the hydrogen production cost is high, and the large-scale industrial application is difficult to realize. The development of low cost HER catalysts is therefore imminent.
In recent years, a large number of catalysts have been developed and adapted to basic HER, and Ir-based catalysts have been developed in part of the related art, however, the cost of Ir alone as HER catalyst is still high.
On this basis, how to reduce the amount of noble metal while maintaining or even improving the catalyst efficiency is an effective way to reduce the cost of HER catalyst preparation.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a catalyst which has lower cost.
The invention also provides a preparation method of the catalyst.
The invention also provides an application of the catalyst.
According to one aspect of the present invention, a catalyst is presented, the catalyst comprising an Ir-Pd monatomic alloy.
According to a preferred embodiment of the present invention, at least the following advantages are provided: the catalyst of the scheme of the invention is a monatomic alloy catalyst, the catalytic efficiency of the catalytic site is extremely high and can reach 100 percent, the basic catalyst in the prior art is mainly Pt-based, so that the cost is higher and the catalytic efficiency is general, and the catalyst of the scheme of the invention has lower cost and better catalytic performance. Scheme of the inventionThe developed monatomic alloys (SAAs) have extremely high activity and ultrahigh large-current stability, the cost of the catalyst of the scheme of the invention is about 1/2 of that of a commercial Pt/C catalyst, the water electrolysis efficiency per unit atom can reach more than 2 times that of the commercial Pt/C catalyst, and the absolute performance is about 5 times. The catalyst of the scheme of the invention has good stability and can work under a large current working condition (1.2A/cm)2) The stability can reach more than one month; the overpotential of the catalyst in a KOH solution of 1mol/L is 16mV, which is far lower than that of other traditional catalysts in the related art.
In some embodiments of the invention, the catalyst is an Ir-Pd monatomic alloy.
In some preferred embodiments of the present invention, the Ir-Pd monatomic alloy has an Ir to Pd atomic ratio of 1:10 or less. The catalyst has higher catalytic efficiency (which is obviously higher than that of Pd/C) and lower cost (which is lower than that of Pt/C).
In some preferred embodiments of the present invention, the Ir-Pd monatomic alloy has an Ir to Pd atomic ratio of 1: between 25 and 1: 100.
In some more preferred embodiments of the present invention, the Ir-Pd monatomic alloy has an Ir to Pd atomic ratio of 1: 40 to 1: 100. Within this range of ratios, the catalytic efficiency is significantly higher than Pt/C.
In some more preferred embodiments of the present invention, the Ir-Pd monatomic alloy has an Ir to Pd atomic ratio of about 1: 50. within this range of the ratio interval, the catalytic efficiency will be further significantly improved.
According to another aspect of the present invention, there is provided a method for preparing the above catalyst, comprising the steps of:
s1, taking the Pd/C mixed solution, adding a surfactant and a reducing agent I, and reacting to obtain a mixed solution;
s2, adding an iridium salt solution into the mixed solution to enable iridium to generate zero-valent iridium through a reduction reaction according to the iridium salt solution, and preparing the catalyst;
wherein the reducing agent I is Sodium Borohydride (SB).
The preparation method according to a preferred embodiment of the present invention has at least the following advantageous effects: the method of the scheme of the invention can better control the synthesis process of the material, thereby better obtaining the monatomic alloy catalyst which has outstanding alkaline HER performance; SB in the reducing agent I cannot be replaced, and other reducing agents are adopted, so that the reduction is difficult to realize.
In some embodiments of the invention, the iridium is reduced to zero-valent iridium by addition of a reducing agent II.
In some embodiments of the present invention, the amounts and components of the reducing agents I and II may be the same or different.
In some preferred embodiments of the present invention, the amount of the reducing agent I added is greater than the amount of the reducing agent II added.
In some preferred embodiments of the present invention, the reducing agent I or II is added in the form of a solution, and the concentration of the reducing agent I or II is 0.1-1 mol/L. The addition concentration of the reducing agent mainly affects the size of the catalyst, and further affects the atom utilization rate and performance of the catalyst to a certain extent. If low-concentration sodium borohydride is adopted to directly reduce Ir, the reaction rate is slow, the high-concentration reduction is accelerated, but agglomeration is easily caused if the concentration is too high, and the cost is increased, so that the range is good.
In some preferred embodiments of the present invention, the molar ratio of the reducing agent I to Pd is 1.5 to 5: 1.
In some preferred embodiments of the invention, the molar ratio of the reducing agent II to Ir is between 5:1 and 100: 1. Too high a charge will cause agglomeration of the nanoparticles.
In some embodiments of the present invention, the preparation method further includes a step of performing post-treatment on the product after the reaction in step S2, specifically including: and (3) performing solid-liquid separation on the product after the reaction, collecting a solid phase part, adding the solid phase part into water and an ethanol solution for dispersion, centrifuging again, repeating the dispersion and centrifugation processes, and drying the collected solid phase part to obtain the catalyst.
In some embodiments of the invention, the number of times the dispersing, centrifuging process is repeated is 2 or more times; more preferably, the number of times is 3 or more.
In some embodiments of the invention, the drying temperature is from room temperature to 80 ℃; preferably, the room temperature is 15 ℃ or higher.
In some preferred embodiments of the present invention, the surfactant is a non-ionic carbon-based surfactant; more preferably a nonionic polymer compound; more preferably polyvinylpyrrolidone (PVP). The surfactant acts to limit the diffusion of Ir-Pd, so that the resulting catalyst has a small and uniform particle size, which is generally achieved with carbon-based active materials that are neutral in aqueous solution.
In some preferred embodiments of the invention, the surfactant is a bromine-containing surfactant; more preferably a bromine-containing carbon-based surfactant; still more preferably cetyltrimethylammonium bromide (CTAB).
In some preferred embodiments of the present invention, in the step S1, the concentration of the surfactant in the Pd/C solution after the surfactant is added is 0.02 to 0.1 mol/L.
In some embodiments of the present invention, the mass ratio of Pd to C in the Pd/C mixed solution is 1: 2-1: 20.
in some preferred embodiments of the present invention, the mass ratio of Pd to C in the Pd/C mixed solution is about 1: 5.
in some embodiments of the present invention, the Pd/C mixed solution is prepared by: the palladium salt is added to the carbon black dispersion.
In some preferred embodiments of the present invention, the palladium salt is added to the carbon black dispersion in the form of a solution; more preferably, the concentration of the palladium salt in the solution is 0.01mol/L to 0.1 mol/L.
In some embodiments of the invention, the palladium salt is selected from at least one of ammonium chloropalladate, sodium chloropalladate, potassium chloropalladate, or palladium chloride. Other palladium sources such as organic palladium and the like can be used, different palladium sources mainly influence the cost of the catalyst, and certain difference exists in the utilization efficiency, for example, ammonium chloropalladate is greater than sodium chloropalladate and potassium chloropalladate.
In some embodiments of the present invention, the iridium salt may be a conventional iridium salt. Since Ir is small, the extent of ionization of different Ir sources only affects their deposition rate.
According to a further aspect of the present invention, a hydrogen evolution electrode is proposed, the surface of which is provided with the above catalyst.
In some embodiments of the invention, the hydrogen evolution electrode is a hydrogen evolution electrode for the production of hydrogen from an alkaline electrolyte.
The invention also provides a preparation method of the hydrogen evolution electrode, which comprises the step of arranging the catalyst on a base material to obtain the hydrogen evolution electrode.
The preparation method of the hydrogen evolution electrode according to the embodiment of the invention has at least the following beneficial effects: the preparation method is simple and convenient to operate and low in cost, and the prepared hydrogen evolution electrode has good catalytic hydrogen evolution performance and can replace expensive noble metal-based electrodes used in the field of catalysis.
In some embodiments of the invention, the substrate is selected from copper, carbon steel, titanium, cobalt, nickel, stainless steel, or glassy carbon.
In some embodiments of the invention, the substrate is preferably vitreous carbon.
The fifth aspect of the invention provides the application of the hydrogen evolution electrode in the hydrogen production by water electrolysis.
In some embodiments of the invention, the water electrolysis to produce hydrogen is to produce hydrogen in an alkaline electrolyte.
The application of the embodiment of the invention has at least the following beneficial effects: the catalyst provided by the scheme of the invention has high catalytic activity, has a good application effect in hydrogen production by water electrolysis, and particularly has high catalytic efficiency in the hydrogen production process by alkaline electrolyte.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a scanning transmission electron microscope image at different magnifications of a catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph of the results of a distribution test of different elements of the catalyst prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of the catalyst prepared in example 1 of the present invention;
FIG. 4 is an atomic level image and corresponding line analysis plot of the catalyst prepared in example 1 of the present invention;
FIG. 5 is a graph showing the results of hydrogen evolution performance tests of the catalysts prepared in examples 1 to 3 of the present invention and the catalyst of comparative example 1, and the results of stability tests of the catalytic agent prepared in example 1;
FIG. 6 is a graph comparing the results of hydrogen evolution performance tests for the catalysts prepared in examples 1 and 4;
FIG. 7 is a graph comparing the results of hydrogen evolution performance tests of the catalysts prepared in examples 1 and 5.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the present invention, the meaning of "about" means plus or minus 2%, unless otherwise specified.
Example 1
The catalyst is prepared by the following specific process:
1) dispersing 100mg of carbon black in 100ml of water by using ultrasound (30min), and dissolving 0.2mmol of ammonium chloropalladate in the water to obtain a Pd/C mixed solution (the mass ratio of Pd/C is 20:100, and the loading capacity of a commercial Pt/C catalyst is referred);
2) 1.84g CTAB was added;
3) preparing 0.1mol/LSB solution, and adding 0.5mmol SB into the solution obtained in the step 2) in the form of solution;
4) standing the solution treated in the step 3) (for 1 hour), adding 4 mu mol of iridium chloride hydrochloride solution after the reaction is stopped, and stirring for 10min to form a uniform solution;
5) adding the SB solution containing 0.2mmol of SB prepared in the step 3);
6) and after the solution is kept stand for 1 hour, centrifuging the obtained product, collecting a sample and drying to obtain powder, namely the target product.
Example 2
This example prepared a catalyst which differed from example 1 only in that the amount of iridium chloride added was adjusted to 2. mu. mol.
Example 3
This example prepared a catalyst which differed from example 1 only in that the amount of iridium chloride added was adjusted to 8. mu. mol.
Example 4
This example prepared a catalyst which differed from example 1 only in that CTAB was replaced with 1g pvp (molecular weight 24 kDa).
Example 5
This example prepared a catalyst that differed from example 1 only in replacing ammonium chloropalladate with sodium chloropalladate.
Comparative example 1
This comparative example is a commercial Pt/C commercially available.
Comparative example 2
This comparative example prepared a Pd/C which differed from example 1 in that: only the procedure before the addition of the iridium chloride hydrochloride solution was followed by drying under the same conditions as in example 1.
Test examples
The experimental example tests the micro-morphology and the structure of the catalysts prepared in examples 1 to 5 and the catalytic hydrogen evolution performance of the catalysts prepared in examples 1 to 5 and the catalysts prepared in comparative examples 1 to 2.
Wherein: the results of Scanning Transmission Electron Microscope (STEM) tests of the catalyst prepared in example 1 are shown in FIG. 1, in which circles represent Ir atoms, FIG. a is a STEM on a scale of 5nm, FIG. b is a STEM on a scale of 5nm at another angle, and FIG. c is a STEM on a scale of 1 nm.
The results of the element distribution test of the catalyst prepared in example 1 are shown in fig. 2, in which a is a high angle annular dark field image (HAADF) diagram, b is an element distribution diagram of Ir, and C is an element distribution diagram of C; d is the element distribution diagram of Pd.
The X-ray diffractometer (XRD) test results of the catalyst prepared in example 1 are shown in fig. 3.
The STEM, element distribution and XRD patterns of the catalysts prepared in examples 2-5 are similar to those of FIGS. 1-3, and are not repeated to avoid redundancy.
An atomic scale image of the catalyst prepared in example 1 and the corresponding line analysis curves are shown in a and b of fig. 4.
The results of the hydrogen evolution performance test of the catalysts prepared in examples 1 to 3 and the catalyst of comparative example 1 are shown as a in fig. 5, and the results of the stability test of the catalyst prepared in example 1 are shown as b in fig. 5. The stability test results for the catalysts prepared in examples 2-5 are similar to b in FIG. 5 and are not repeated to avoid redundancy.
The results of the hydrogen evolution performance tests on the catalysts prepared in examples 1 and 4 are shown in fig. 6, in volts.
The results of the hydrogen evolution performance tests on the catalysts prepared in examples 1 and 5 are shown in fig. 7, in which the voltage is in volts.
The hydrogen evolution performance test is carried out by adopting a conventional method, and specifically comprises the following steps: and (3) dropping the electro-catalyst dispersion liquid (1-10mg/mL, 5mg/L is selected in the test) with a certain concentration on the surface of a glassy carbon electrode (the diameter is 3-6mm, 5mm is selected in the test), naturally drying, and then selecting a three-electrode system to test the hydrogen evolution overpotential of each catalyst in a 1mol/L KOH solution.
As can be seen from fig. 1, the particle size of the catalyst produced is around 5 nm. Ir exists in the form of a single atom on the surface of the Pd particle. The circles in the graph c mark the Ir monoatomic atoms, which have a higher brightness compared to the Pd particles.
As can be seen in FIG. 2, the Ir/Pd was uniformly dispersed, indicating that an alloy structure was formed.
In fig. 3, from left to right, the first is the characteristic envelope peak of C. The second peak (characteristic peak for Pd at 38 °) indicates the formation of Pd metal. There is no peak of Ir, indicating that Ir does not form a significant large particle, consistent with the results of fig. 1.
As can be seen from FIG. 5a, the hydrogen evolution catalytic performance of the catalyst prepared by the embodiment of the invention is significantly better than that of Pd/C, wherein the hydrogen evolution catalytic performance is significantly better than that of Pt/C when the atomic ratio of Ir to Pd is 1:50 and 1:100, and especially the performance is better when the atomic ratio is 1: 50. And the atomic ratio is 1:25, the catalyst has better catalytic performance, but the cost is obviously reduced relative to that of Pt/C. As can be seen from fig. 5b, the catalyst prepared according to the embodiment of the present invention has an ultra-long stability, and the long-term stability test result for one month is good.
As can be seen from fig. 6, the effect with CTAB is comparable to that of PVP.
As can be seen from fig. 7, the effect is similar when different palladium sources are used.
In conclusion, the IrPd monatomic alloy catalysts (SAAs) according to the present invention have outstanding basic HER performance. The IrPd SAAs designed by the invention not only can be technically prepared simply, but also has better potential in the aspects of popularization and application.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A catalyst, characterized by: the catalyst comprises an Ir-Pd monatomic alloy.
2. The catalyst of claim 1, wherein: the atomic ratio of Ir to Pd in the Ir-Pd monatomic alloy is below 1: 10; preferably, the Ir-Pd monatomic alloy has an Ir to Pd atomic ratio of 1: between 25 and 1: 100; further preferably, the Ir-Pd monoatomic alloy has an Ir to Pd atomic ratio in the range of 1: 40 to 1: 100; even more preferably, the Ir-Pd monatomic alloy has an Ir to Pd atomic ratio of about 1: 50.
3. a method of preparing the catalyst of claim 1 or 2, wherein: the method comprises the following steps:
s1, taking the Pd/C mixed solution, adding a surfactant and a reducing agent I, and reacting to obtain a mixed solution;
s2, adding an iridium salt solution into the mixed solution to enable iridium to generate zero-valent iridium through a reduction reaction according to the iridium salt solution, and preparing the catalyst;
wherein the reducing agent I is sodium borohydride.
4. The method for preparing a catalyst according to claim 3, characterized in that: the reducing agent I is added in the form of a solution, and the concentration of the reducing agent I is 0.1-1 mol/L; preferably, the molar ratio of the reducing agent I to Pd is 1.5-5: 1.
5. The method for preparing a catalyst according to claim 3, characterized in that: the preparation method further comprises a step of post-treating the product obtained after the reaction in the step S2, and specifically comprises the following steps: after solid-liquid separation of the reacted product, collecting a solid phase part, adding the solid phase part into water and ethanol solution for dispersion, centrifuging again, repeating the dispersion and centrifugation processes, and drying the collected solid phase part to obtain the catalyst; preferably, the number of times of repeating the dispersing and centrifuging process is 2 or more; more preferably, the number of times is 3 or more; preferably, the drying temperature is from room temperature to 80 ℃; more preferably, the room temperature is 15 ℃ or higher.
6. The method for preparing a catalyst according to claim 3, characterized in that: the surfactant is a nonionic carbon-based surfactant; more preferably a nonionic polymer compound; even more preferably polyvinylpyrrolidone; preferably, the surfactant is a bromine-containing surfactant; more preferably a bromine-containing carbon-based surfactant; even more preferably cetyltrimethylammonium bromide; preferably, in the step S1, the concentration of the surfactant in the Pd/C solution after the surfactant is added is 0.02-0.1 mol/L.
7. The method for preparing a catalyst according to claim 3, characterized in that: the mass ratio of Pd to C in the Pd/C mixed solution is 1: 2-1: 20; preferably, the mass ratio of Pd to C in the Pd/C mixed solution is about 1: 5; preferably, the preparation method of the Pd/C mixed solution is as follows: adding palladium salt into the carbon black dispersion liquid; preferably, the palladium salt is added to the carbon black dispersion in the form of a solution; more preferably, the concentration of the palladium salt in the solution is 0.01mol/L to 0.1 mol/L.
8. A hydrogen evolving electrode characterized by: the surface of the hydrogen evolution electrode is provided with the catalyst of claim 1 or 2; preferably, the hydrogen evolution electrode is a hydrogen evolution electrode for hydrogen production by an alkaline electrolyte.
9. A preparation method of a hydrogen evolution electrode is characterized in that: comprising disposing the catalyst of claim 1 or 2 on a substrate to obtain the hydrogen evolution electrode.
10. Use of the hydrogen evolution electrode according to claim 8 for the electrolysis of water for the production of hydrogen.
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