CN115928127A - Self-supporting catalyst and preparation method and application thereof - Google Patents
Self-supporting catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 150000002815 nickel Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 11
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 7
- 229940102253 isopropanolamine Drugs 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 5
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- -1 alcohol amine Chemical class 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910003962 NiZn Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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 provides a self-supporting catalyst and a preparation method and application thereof, belonging to the technical field of electrochemical catalytic materials. The self-supported catalyst comprises a self-supported metal carrier and a catalyst loaded on the surface of the supported metal carrier, and the catalyst is a hexagonal phase nickel nano-porous catalyst. The self-supporting catalyst can be used for alkaline electrolysis of water to generate hydrogen. The self-supporting catalyst has the advantages of high specific surface area, good catalytic activity and oxidation resistance and the like, and the preparation method is simple, low in raw material cost, low in equipment requirement and good in technical effect.
Description
Technical Field
The invention relates to the technical field of electrochemical catalytic materials, in particular to a self-supporting catalyst and a preparation method and application thereof.
Technical Field
Hydrogen is the most ideal novel clean energy in the world today and in the future, and the method for producing hydrogen by electrolyzing water in an alkaline environment is the most feasible way for producing hydrogen on a large scale so far, but the Hydrogen Evolution Reaction (HER) reaction kinetics under the condition of high pH is slow, and the efficiency of producing hydrogen by electrolyzing water is limited to a great extent. In order to reduce energy consumption and improve energy conversion efficiency, the process needs a high-efficiency, low-cost, continuous and stable catalyst to reduce energy consumption, and further realizes the practical application of hydrogen production by water electrolysis.
At present, the high-activity catalyst is still a noble metal-based catalyst such as platinum, ruthenium, iridium and the like. However, it is expensive and has poor stability, which limits its large-scale application. Therefore, the electrocatalyst with low development cost, high catalytic activity and good stability is the key of the practical application of the hydrogen production by water electrolysis.
Among numerous non-noble metal-based electrocatalysts with excellent performance, low price and good stability, the theoretical hydrogen evolution activity of metal Ni is closest to that of noble metal Pt, and the metal Ni has the characteristics of good conductivity, high catalytic activity, low price, easy obtainment, environmental friendliness and the like, so that the industrial application and the practical popularization of the metal Ni catalyst which is most likely to be cheap and efficient for electrolyzing water to prepare hydrogen are vigorously developed and deeply researched. However, the existing problem of metallic Ni is that its catalytic activity and stability are not very good.
Therefore, there is still a need for a catalyst for hydrogen evolution by electrolysis with good catalytic activity and good stability.
Disclosure of Invention
The invention provides a self-supporting catalyst, a preparation method and application thereof, aiming at the problems, wherein the self-supporting catalyst can be used for hydrogen evolution of alkaline electrolyzed water. The self-supporting catalyst has the advantages of high specific surface area, good catalytic activity and oxidation resistance and the like, and the preparation method is simple, low in raw material cost, low in equipment requirement and good in technical effect.
In a first aspect, the present invention provides a self-supported catalyst.
A self-supported catalyst comprises a self-supported metal carrier and a catalyst loaded on the surface of the supported metal carrier, wherein the catalyst is a hexagonal phase nickel nano-porous catalyst.
In some embodiments, the structure of the supporting metal carrier is a porous foam structure, a plate-like structure, or a mesh structure.
In some embodiments, the supporting metal support is at least one of nickel foam, copper foam, and nickel mesh.
In a second aspect, the present invention provides a method for preparing the self-supported catalyst of the first aspect.
A process for preparing the self-supported catalyst of the first aspect, comprising:
step (1): pretreatment of a supporting metal carrier: carrying out ultrasonic treatment on the support type metal carrier by using ethanol, washing by using water, carrying out ultrasonic treatment by using a hydrochloric acid aqueous solution, washing by using water and ethanol respectively, and drying by blowing to obtain a pretreated support type metal carrier;
step (2): preparing a precursor solution: mixing nickel salt with water and an alcamines reagent, heating and refluxing for reaction, and obtaining a precursor solution after the reaction is finished;
and (3): precursor loading by carrier: cooling the precursor solution obtained in the step (2) to room temperature, immersing the pretreated support type metal carrier obtained in the step (1) into the precursor solution obtained in the step (2), and taking out to obtain a carrier loaded with a precursor; or alternatively
Cooling the precursor solution obtained in the step (2) to room temperature, and coating the precursor solution obtained in the step (2) on the surface of the pretreated support type metal carrier obtained in the step (1) to obtain a carrier loaded with the precursor;
and (4): sintering and forming: and (4) calcining the precursor-loaded carrier obtained in the step (3) at a certain temperature under the inert gas atmosphere, then cooling to room temperature, ultrasonically cleaning with ethanol, and drying to obtain the self-supported catalyst.
In some embodiments, the nickel salt comprises nickel formate or nickel formate dihydrate.
In some embodiments, the alkanolamine agent is at least one of isopropanolamine or isobutanolamine.
In some embodiments, the concentration of hydrochloric acid in the aqueous hydrochloric acid solution is from 0.5mol/L to 1.5mol/L.
In some embodiments, the temperature of the heating reflux is from 90 ℃ to 150 ℃.
In some embodiments, the heating reflux is performed for a reaction time of 0.5h to 1.0h.
In some embodiments, the molar ratio of the nickel salt to the alkanolamine reagent charged is 1; and/or
In some embodiments, the molar ratio of water to the alkanolamine reagent charged is 1.
In some embodiments, the certain temperature is 200 ℃ to 400 ℃.
In some embodiments, the temperature rise rate of the step (4) during the temperature rise to the certain temperature is 5 ℃/min to 10 ℃/min.
In some embodiments, the calcination is for a time period of 3h to 6h.
In a third aspect, the invention provides an application of the self-supported catalyst or the self-supported catalyst obtained by the preparation method.
Use of a self-supported catalyst according to the first aspect or a self-supported catalyst obtained by the preparation method according to the second aspect for the electrolytic hydrogen evolution.
In some embodiments, the electrolytic hydrogen evolution is electrolytic water hydrogen evolution.
In some embodiments, the electrolytic hydrogen evolution is an electrolytic water hydrogen evolution reaction performed under alkaline conditions.
Advantageous effects
Compared with the prior art, one embodiment provided by the invention has at least one of the following beneficial effects:
(1) Reduced metallic Ni is a highly efficient basic hydrogen evolution catalyst, but loses catalytic activity because it is highly susceptible to surface formation of dense oxide layers in air. Therefore, the key point is to synthesize the 0-valent metal Ni catalyst which has higher activity, larger specific surface area and is more stable under the air environment and electrochemical conditions.
(2) The self-supported catalyst prepared by the preparation method provided by the invention has a hexagonal phase structure, and is different from a crystal structure of a fcc phase-loaded nickel electrode.
(3) Compared with a commercial nickel foam electrode without load and an fcc phase nickel electrode with load, the self-supported catalyst provided by the invention has higher HER activity and excellent technical effect.
(3) By adjusting alcamines reagent and Ni in precursor solution 2+ The size of the catalyst loaded on the surface of the supported metal carrier and the loading capacity of the catalyst on the supported metal carrier can be regulated and controlled by the proportion of the alcohol amine reagent, the calcination temperature and the like, wherein the alcohol amine reagent and the Ni are mixed 2+ The preferred feeding molar ratio of 3 c to 350 c is more favorable for reducing the size of the catalyst supported on the surface of the supported metal carrier and for increasing the loading of the catalyst on the supported metal carrier.
(4) The nickel formate dihydrate or nickel formate can be used as the nickel salt of the precursor solution, and the nickel formate dihydrate or the formate in the nickel formate has certain reducibility, so that the metal nickel can be self-reduced at high temperature, the operation is simplified, and the process industrialization is facilitated.
(5) Reduced metallic Ni is a highly efficient basic hydrogen evolution catalyst, but loses catalytic activity because it is highly susceptible to surface formation of dense oxide layers in air. Therefore, the key point is to synthesize the 0-valent metal Ni catalyst which has higher activity, larger specific surface area and is more stable under the air environment and electrochemical conditions, and the adopted alcamines reagents (preferably isopropanolamine and isobutanol amine) can form a ligand with nickel formate to promote the lattice transformation of nickel of the complex precursor at lower temperature; the synthesized hexagonal phase metallic nickel is oxidized in the air, an amorphous oxide/hydroxide leakage layer is spontaneously formed, and high-activity Ni exists below the leakage layer 0 The area is used as a stable and antioxidant electrocatalytic active center, namely, a synergistic effect is formed at the lattice interface of the supported hexagonal phase nickel and the face-centered cubic phase crystal form metal carrier, which is beneficial to promoting the electroreduction of protons in HER reaction to generate hydrogen and also beneficial to maintaining the stability of the active center of the catalyst.
(6) The preparation method provided by the invention adopts a simple heat treatment self-reduction method to grow the hexagonal phase metallic nickel nano-particles in situ on the self-supporting carrier, has the advantages of simple synthesis steps, low cost and controllable particle size, is suitable for industrial popularization, and has certain large-scale application prospect.
Definition of terms
In the context of the present invention, all numbers disclosed herein are approximate values, regardless of whether the word "about" or "approximately" is used. Based on the disclosed numbers, it is possible that the numerical value of each number will vary by less than 10% or reasonably as recognized by one of skill in the art, such as by 1%, 2%, 3%, 4%, or 5%.
The terms "above", "below", "within" and the like are to be understood as including the instant numbers, e.g., two or more means ≧ two.
The term "and/or" should be understood to mean any one of the options or a combination of any two or more of the options.
The term "wt%" means mass percentage.
The term "plurality" means at least two, such as 2, 3, 4 or 5, and the like.
The term "room temperature" means ambient temperature and may be from 10 ℃ to 35 ℃, alternatively from 15 ℃ to 35 ℃, alternatively from 20 ℃ to 30 ℃, alternatively 25 ℃.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to 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. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Drawings
FIG. 1 is an SEM photograph of a self-supported catalyst obtained in example 2.
Fig. 2 is an XRD pattern of the self-supported catalyst obtained in example 2.
Figure 3 is a graph of HER three-electrode test LSV of the self-supported catalysts from examples 2, 5, 6 with no commercial foam nickel supported, fcc phase nickel supported electrodes.
FIG. 4 is an SEM photograph of the self-supported catalysts obtained in examples 1 to 4.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, some non-limiting examples are further disclosed below to further explain the present invention in detail.
No load commercial nickel foam: : the purity of the special foamed nickel for the battery of Suzhou Cheng Er Nuo science and technology company is 99.8 percent, the porosity is 95 percent, and the areal density is 280g/m 2 。
Loading fcc phase nickel electrode: the preparation is carried out with reference to the following documents: solmaz R, et al, preparation and characterization of Pd-modified Raney-type NiZn coatings and the third application for alkaline water electrolysis, international Journal of Hydrogen Energy (2016), http:// dx. Doi. Org/10.1016/j. Ijhydyne. 2016.07.221.221
Example 1: preparation of self-supporting catalyst (molar ratio of alcamines reagent to nickel salt is 1
Preparing a precursor solution: the molar ratio of the raw materials is 1:1:1 Isopropanolamine (C) was weighed separately 3 H 9 NO), nickel formate dihydrate [ Ni (COOH) 2 ·2H 2 O]Mixing with deionized water, stirring, heating and refluxing at 100 deg.C for 30min, and cooling to room temperature to obtain precursor solution;
pretreatment of a supporting metal carrier: taking foamed nickel, adding absolute ethyl alcohol for ultrasonic treatment for 10min, taking out, washing with deionized water, carrying out ultrasonic treatment for 10min with 1mol/L concentrated hydrochloric acid, taking out, washing with deionized water and ethyl alcohol respectively, and finally drying with nitrogen to obtain a pretreated supported metal carrier;
sintering and forming: completely soaking the pretreated support type metal carrier in a precursor solution, fishing out, heating to 300 ℃ at the heating rate of 5 ℃/min, calcining at 300 ℃ for 6h, cooling to room temperature, sequentially and respectively ultrasonically cleaning for 5min by deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ to obtain the self-support type catalyst, wherein the self-support type catalyst is named hcp Ni/NF-1.
Example 2: preparation of self-supporting catalyst (molar ratio of alcamines reagent to nickel salt is 2
Preparing a precursor solution: the molar ratio of the components is 2:1:1 Isopropanolamine (C) was weighed separately 3 H 9 NO), nickel formate dihydrate [ Ni (COOH) 2 ·2H 2 O]Mixing with deionized water, stirring, heating and refluxing at 100 deg.C for 30min, and cooling to room temperature to obtain precursor solution;
pretreatment of a supporting metal carrier: taking foamed nickel, adding absolute ethyl alcohol for ultrasonic treatment for 10min, taking out, washing with deionized water, carrying out ultrasonic treatment for 10min with 1mol/L concentrated hydrochloric acid, taking out, washing with deionized water and ethanol respectively, and finally blowing by using nitrogen to obtain a pretreated support type metal carrier;
sintering and forming: completely soaking the pretreated support type metal carrier in a precursor solution, fishing out, heating to 300 ℃ at the heating rate of 5 ℃/min, calcining at 300 ℃ for 6h, cooling to room temperature, sequentially and respectively ultrasonically cleaning for 5min by deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ to obtain the self-support type catalyst, wherein the self-support type catalyst is named hcp Ni/NF-2.
Example 3: preparation of self-supporting catalyst (molar ratio of alcamines reagent to nickel salt is 3
Preparing a precursor solution: the molar ratio of the components is 3:1:1 separately weighing isopropanolamine (C) 3 H 9 NO), nickel formate dihydrate [ Ni (COOH) 2 ·2H 2 O]Mixing with deionized water, stirring, heating and refluxing at 100 deg.C for 30min, and cooling to room temperature to obtain precursor solution;
pretreatment of a supporting metal carrier: taking foamed nickel, adding absolute ethyl alcohol for ultrasonic treatment for 10min, taking out, washing with deionized water, carrying out ultrasonic treatment for 10min with 1mol/L concentrated hydrochloric acid, taking out, washing with deionized water and ethyl alcohol respectively, and finally drying with nitrogen to obtain a pretreated supported metal carrier;
sintering and forming: completely soaking the pretreated support type metal carrier in a precursor solution, fishing out, heating to 300 ℃ at the heating rate of 5 ℃/min, calcining at 300 ℃ for 6h, cooling to room temperature, sequentially and respectively ultrasonically cleaning for 5min by deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ to obtain the self-support type catalyst, wherein the self-support type catalyst is named hcp Ni/NF-3.
Example 4: preparation of self-supporting catalyst (molar ratio of alcamines reagent to nickel salt is 4
Preparing a precursor solution: the molar ratio of the raw materials is 4:1:1 separately weighing isopropanolamine (C) 3 H 9 NO), nickel formate dihydrate [ Ni (COOH) 2 ·2H 2 O]Mixing with deionized water, stirring, heating and refluxing at 100 deg.C for 30min, and cooling to room temperature to obtain precursor solution;
pretreatment of a supporting metal carrier: taking foamed nickel, adding absolute ethyl alcohol for ultrasonic treatment for 10min, taking out, washing with deionized water, carrying out ultrasonic treatment for 10min with 1mol/L concentrated hydrochloric acid, taking out, washing with deionized water and ethyl alcohol respectively, and finally drying with nitrogen to obtain a pretreated supported metal carrier;
sintering and forming: completely soaking the pretreated support type metal carrier in a precursor solution, fishing out, heating to 300 ℃ at the heating rate of 5 ℃/min, calcining at 300 ℃ for 6 hours, cooling to room temperature, sequentially and respectively ultrasonically cleaning for 5min by deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ to obtain the self-support type catalyst, wherein the self-support type catalyst is named hcp Ni/NF-4.
Example 5: preparation of self-supporting catalyst
Preparing a precursor solution: and (3) according to molar ratio: 1:1 Isobutanolamine (C) was weighed separately 4 H 11 NO), nickel formate dihydrate [ Ni (COOH) 2 ·2H 2 O]Mixing with deionized water, stirring, and heating and refluxing at 90 deg.C for 30minThen cooling to room temperature to obtain a precursor solution;
pretreatment of a supporting metal carrier: carrying out ultrasonic treatment on the foamy copper by using absolute ethyl alcohol for 10min, taking out the foamy copper, washing the foamy copper by using deionized water, carrying out ultrasonic treatment on the foamy copper by using 1mol/L concentrated hydrochloric acid for 10min, taking out the foamy copper, washing the foamy copper by using deionized water and ethyl alcohol respectively, and finally drying the foamy copper by using nitrogen to obtain a pretreated supported metal carrier;
sintering and forming: completely soaking the pretreated support type metal carrier in a precursor solution, fishing out, heating to 400 ℃ at the heating rate of 8 ℃/min, calcining at 400 ℃ for 6h, cooling to room temperature, sequentially and ultrasonically cleaning for 5min by deionized water and absolute ethyl alcohol respectively, and then drying in a vacuum drying oven at 60 ℃ to obtain the self-support type catalyst, wherein the self-support type catalyst is named hcp Ni/CF.
Example 6: preparation of self-supporting catalyst
Preparing a precursor solution: and (4) according to molar ratio: 1:1 Isobutanolamine (C) was weighed separately 4 H 11 NO), nickel formate dihydrate [ Ni (COOH) 2 ·2H 2 O]Mixing with deionized water, stirring, heating and refluxing at 120 deg.C for 30min, and cooling to room temperature to obtain precursor solution;
pretreatment of a supporting metal carrier: carrying out ultrasonic treatment on the nickel screen by using absolute ethyl alcohol for 10min, taking out the nickel screen, washing the nickel screen by using deionized water, carrying out ultrasonic treatment on the nickel screen by using 1mol/L concentrated hydrochloric acid for 10min, taking out the nickel screen, washing the nickel screen by using deionized water and ethanol respectively, and finally blowing the nickel screen by using nitrogen to obtain a pretreated support type metal carrier;
sintering and forming: completely soaking the pretreated support type metal carrier in a precursor solution, fishing out, heating to 350 ℃ at the heating rate of 8 ℃/min, calcining at 350 ℃ for 4h, cooling to room temperature, sequentially and respectively ultrasonically cleaning for 5min by deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ to obtain the self-support type catalyst, wherein the self-support type catalyst is named hcp Ni/NM.
Example 7: performance detection
SEM image analysis: taking the self-supported catalyst obtained in example 2, and detecting the SEM picture (scanning electron microscope picture) and the XRD picture (X-ray diffraction analysis picture); the SEM images (scanning electron microscope images) of the self-supported catalysts obtained in example 1, example 3, and example 4 were taken, and the results are shown in fig. 1 and fig. 4.
XRD pattern analysis: the XRD patterns (X-ray diffraction analysis patterns) were measured from the self-supported catalyst obtained in example 2 and the fcc phase-supported nickel electrode (face-centered cubic phase-supported nickel electrode), respectively, and the results are shown in fig. 2.
HER three-electrode test: the HER (hydrogen evolution reaction under high pH conditions) performance of the self-supported catalyst (sample 3) obtained in example 2, the self-supported catalyst (sample 1) obtained in example 5, the self-supported catalyst (sample 2) obtained in example 6, the unsupported Commercial nickel foam (Commercial NF), and the fcc phase supported nickel electrode (fcc Ni/NF) were examined in a 1M KOH solution at 25 ℃ using a standard three-electrode system using Linear Sweep Voltammetry (LSV), and the results are shown in fig. 3.
And (4) conclusion:
as can be seen from fig. 1, the self-supported catalyst provided by the present invention is in the form of spherical particles with nanometer scale, has a larger specific surface area, and can expose more catalytically active sites.
As can be seen from fig. 2, the crystal form of the self-supported catalyst provided by the present invention is different from the crystal form of the face-centered cubic phase nickel of the fcc phase nickel-supported electrode, and the crystal form of the self-supported catalyst provided by the present invention is a hexagonal phase structure.
As can be seen from fig. 3, compared with the electrode without commercial nickel foam and with fcc-phase nickel, the self-supported catalyst provided by the present invention has higher HER activity and excellent technical effect, and in addition, compared with the molar ratio of the alkanolamine reagent to the nickel salt in other proportions, the molar ratio of the alkanolamine reagent to the nickel salt is 3.
As can be seen from fig. 4, the molar ratio of the alcoholamines reagent to the nickel salt is preferably 3:1, the reduction and the loading of nickel nano particles (catalyst loaded on the surface of a supporting metal carrier) are more facilitated.
While the methods of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications of the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of the present invention within the context, spirit and scope of the invention. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is specifically noted that all such substitutions and modifications will be apparent to those skilled in the art and are intended to be included within the present invention.
Claims (10)
1. The self-supported catalyst is characterized by comprising a self-supported metal carrier and a catalyst loaded on the surface of the supported metal carrier, wherein the catalyst is a hexagonal phase nickel nano-porous catalyst.
2. The self-supported catalyst of claim 1, the structure of the supported metal support being a porous foam structure, a plate structure or a mesh structure.
3. The self-supported catalyst of any of claims 1-2, wherein the supported metal support is at least one of nickel foam, copper foam, and nickel mesh.
4. A method for preparing the self-supported catalyst of any one of claims 1 to 3, comprising:
step (1): pretreatment of a supporting metal carrier: carrying out ultrasonic treatment on the support type metal carrier by using ethanol, washing by using water, carrying out ultrasonic treatment by using a hydrochloric acid aqueous solution, washing by using water and ethanol respectively, and drying by blowing to obtain a pretreated support type metal carrier;
step (2): preparing a precursor solution: mixing nickel salt with water and an alcamines reagent, heating and refluxing for reaction, and obtaining a precursor solution after the reaction is finished;
and (3): precursor loading by carrier: cooling the precursor solution obtained in the step (2) to room temperature, immersing the pretreated support type metal carrier obtained in the step (1) into the precursor solution obtained in the step (2), and taking out to obtain a carrier loaded with a precursor; or
Cooling the precursor solution obtained in the step (2) to room temperature, and coating the precursor solution obtained in the step (2) on the surface of the pretreated support type metal carrier obtained in the step (1) to obtain a carrier loaded with the precursor;
and (4): sintering and forming: and (4) calcining the precursor-loaded carrier obtained in the step (3) at a certain temperature under the inert gas atmosphere, cooling to room temperature, ultrasonically cleaning with ethanol, and drying to obtain the self-supporting catalyst.
5. The method of claim 4, wherein the nickel salt comprises nickel formate or nickel formate dihydrate.
6. The method according to any one of claims 4 to 5, wherein the alkanolamine reagent is at least one of isopropanolamine or isobutanolamine.
7. The production method according to any one of claims 4 to 6, wherein the concentration of hydrochloric acid in the aqueous hydrochloric acid solution is from 0.5mol/L to 1.5mol/L; and/or
The temperature of the heating reflux is 90-150 ℃; and/or
The reaction time for heating reflux to carry out reaction is 0.5h-1.0h.
8. The production method according to any one of claims 4 to 7, wherein the molar ratio of the nickel salt to the alcoholamine reagent is from 1; and/or
The feeding molar ratio of the water to the alcohol amine reagent is 1.
9. The method according to any one of claims 4 to 8, wherein the certain temperature is 200 ℃ to 400 ℃; and/or
The heating rate of the step (4) in the process of heating to the certain temperature is 5-10 ℃/min; and/or
The calcining time is 3h-6h.
10. Use of a self-supported catalyst according to any one of claims 1 to 3 or a self-supported catalyst obtained by the preparation process according to any one of claims 4 to 9 for the electrolytic evolution of hydrogen; optionally, the electrolytic hydrogen evolution is electrolytic water hydrogen evolution;
optionally, the electrolytic hydrogen evolution is an electrolytic water hydrogen evolution reaction performed under alkaline conditions.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167456A (en) * | 2020-01-16 | 2020-05-19 | 厦门大学 | Catalyst, preparation method and application in hydrogen production by water electrolysis |
| WO2021143151A1 (en) * | 2020-01-16 | 2021-07-22 | 厦门大学 | Catalyst, preparation method therefor, and process for electrocatalytic decomposition of water into hydrogen |
| WO2021184563A1 (en) * | 2020-03-19 | 2021-09-23 | 苏州楚捷新材料科技有限公司 | Preparation method for foamed nickel-based catalyst for hydrogen production by water electrolysis |
| CN113846343A (en) * | 2021-07-17 | 2021-12-28 | 北京工业大学 | Preparation method of nickel-molybdenum carbide electrocatalyst |
| CN114395765A (en) * | 2022-01-20 | 2022-04-26 | 苏州大学张家港工业技术研究院 | High-stability alkaline solution hydrogen evolution electrocatalyst and preparation method and application thereof |
-
2022
- 2022-11-28 CN CN202211499941.5A patent/CN115928127A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167456A (en) * | 2020-01-16 | 2020-05-19 | 厦门大学 | Catalyst, preparation method and application in hydrogen production by water electrolysis |
| WO2021143151A1 (en) * | 2020-01-16 | 2021-07-22 | 厦门大学 | Catalyst, preparation method therefor, and process for electrocatalytic decomposition of water into hydrogen |
| WO2021143152A1 (en) * | 2020-01-16 | 2021-07-22 | 厦门大学 | Catalyst, preparation method, and use in hydrogen production by water electrolysis |
| WO2021184563A1 (en) * | 2020-03-19 | 2021-09-23 | 苏州楚捷新材料科技有限公司 | Preparation method for foamed nickel-based catalyst for hydrogen production by water electrolysis |
| CN113846343A (en) * | 2021-07-17 | 2021-12-28 | 北京工业大学 | Preparation method of nickel-molybdenum carbide electrocatalyst |
| CN114395765A (en) * | 2022-01-20 | 2022-04-26 | 苏州大学张家港工业技术研究院 | High-stability alkaline solution hydrogen evolution electrocatalyst and preparation method and application thereof |
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