CN111545218A - Novel high-dispersion transition metal doped RuO2/C composite material and preparation method thereof - Google Patents
Novel high-dispersion transition metal doped RuO2/C composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 74
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 71
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000006185 dispersion Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 105
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical class [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 74
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 53
- 238000000227 grinding Methods 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- 239000001103 potassium chloride Chemical class 0.000 claims abstract description 26
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- RFYYQFJZJJCJNT-UHFFFAOYSA-N pentane-2,4-dione;ruthenium Chemical compound [Ru].CC(=O)CC(C)=O RFYYQFJZJJCJNT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000002244 precipitate Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 42
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 23
- 238000002791 soaking Methods 0.000 claims description 22
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 4
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 238000011068 loading method Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- -1 transition metal acetylacetone complexes Chemical class 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 52
- 239000000047 product Substances 0.000 description 42
- 239000008367 deionised water Substances 0.000 description 41
- 229910021641 deionized water Inorganic materials 0.000 description 41
- 238000001816 cooling Methods 0.000 description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 38
- 238000005303 weighing Methods 0.000 description 36
- 229910052573 porcelain Inorganic materials 0.000 description 33
- 239000000243 solution Substances 0.000 description 24
- 239000012298 atmosphere Substances 0.000 description 22
- 239000007787 solid Substances 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 19
- 229910052707 ruthenium Inorganic materials 0.000 description 19
- 238000001291 vacuum drying Methods 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 16
- 229910000510 noble metal Inorganic materials 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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Abstract
The invention discloses a novel high-dispersion transition metal doped RuO2a/C composite material and a preparation method thereof. The method comprises the following steps: taking acetylacetone metal complexes (transition metal acetylacetone complexes and ruthenium acetylacetone) as metal precursors, grinding and mixing with mixed inorganic salts of potassium bromide and potassium chloride, then pyrolyzing the ground mixture at high temperature under argon atmosphere, then oxidizing at relatively low temperature, and finally performing oxidationThe mixed inorganic salt is removed by washing, and the transition metal doped RuO with high dispersion, uniform nano particle size and high loading capacity can be obtained2a/C composite material. The highly dispersed transition metal doped RuO2The transition metal doped nano particles loaded by the/C composite material have a carbon coating structure and stable properties. The method of the invention is simple and safe, and the obtained product has high purity, complete structure, good metal dispersibility and high loading capacity, and is suitable for being used as a catalyst for electrocatalytic reaction (oxygen evolution reaction).
Description
Technical Field
The invention relates to the field of preparation of metal carbon-based composite materials, in particular to novel high-dispersion transition metal doped RuO2a/C composite material and a preparation method thereof.
Background
Ruthenium is also widely used in the field of catalysis, as a noble metal, in particular as a catalyst for Oxygen Evolution Reactions (OER). In fact, ruthenium is much cheaper than iridium, which is several times as expensive as ruthenium, and it is more economical than iridium if it is used industrially as an oxygen evolution catalyst. Therefore, it is very significant to develop a ruthenium electrocatalyst having excellent catalytic activity. The noble metal is highly dispersed on the carrier, so that more active sites of the catalyst can be exposed, and the utilization rate of the noble metal is improved. In addition, cheap transition metals are adopted for doping, so that the purposes of optimizing the activity and stability of the catalyst and reducing the using amount of noble metals can be achieved (J.J.Mao, C.T.He, J.J.Pei, W.X.Chen, D.S.He, Y.Q.He, Z.B.Zhuang, C.Chen, Q.Peng, D.S.Wang, Y.D.Li.Nat.Commun.2018,9,4958.). However, although the noble metal ruthenium-based composite materials have a wide variety and show excellent performance in many practical applications, most of the noble metal ruthenium-based composite materials reported at present have disadvantages such as low loading capacity, easy sintering and the like, are not favorable for forming a large number of active sites, so that the material is used as an electrode material in an increased amount to increase the thickness of the electrode, and are not favorable for mass transfer of reactants and products (j.yu, y.n.guo, s.x.she, s.s.miao, m.ni, w.zhou, m.l.liu, z.p.sho.adv.mater.2018, 30,1800047). In addition, most of the precious metal-based composite materials reported at present have single active sites and single functions. Thus, the preparation is suitable for electrocatalysisNovel highly dispersed transition metal doped RuO2the/C composite material has the characteristics of diffusion, mass transfer and the like which are superior to those of other noble metal ruthenium-based composite materials with single active site and low loading capacity, which is a great problem faced by material workers. The demand of social development is higher requirement in the field of noble metal ruthenium-based composite materials.
At present, the noble metal ruthenium-based electrocatalyst has high oxygen evolution catalytic activity and good stability in alkalinity, but has poor stability in acidity, and cannot meet the requirement of large-scale industrial production. Many ruthenium-based electrocatalysts reported at present have poor mass transfer effect due to serious agglomeration of active components, less exposure of active sites, no access of electrolyte, and lower actual usable specific surface area than the actual specific surface area of the material, and poor conductivity of the catalyst. Furthermore, most ruthenium-based catalysts reported have a single function and yet to have improved stability (g.wu, x.s.zheng, p.x.cui, h.y.jiang, x.q.wang, y.t.qu, w.x.chen, y.lin, h.li, x.han, y.m.hu, p.g.liu, q.h.zhang, j.j.ge, y.c.yao, r.b.sun, y.e.wu, l.gu, x.hong, y.d.li, Nature commu.2019, 10,4855; m.zhao, z.t.chen, z.h.lyu, z.d.hood, m.h.xie, m.vara, m.f.chi, y.n.xia.am.am.m.em.12.2019, 7028, 7036). Aiming at the problems and limitations presented by the ruthenium-based electrocatalyst, finding the high-activity and high-stability nano ruthenium-based catalyst for OER is a research hotspot in the field of current electrocatalysis. For example, the catalytic activity can be effectively improved by adjusting and controlling the electronic structure around the active site Ru through transition metal doping, and the stability of the material can be ensured to the greatest extent by synthesizing low-price ruthenium through electron transfer. Therefore, as an alternative catalyst, the transition metal doped ruthenium-based bimetallic oxide can improve the catalytic activity through the structural design while reducing the cost, and becomes a hot spot of interest in recent years (j.wang, y.j.ji, r.g.yin, y.y.li, q.sho, x.q.huang.j.mater.chem.a,2019,7, 6411-. However, most of the methods reported so far cannot prepare a noble metal ruthenium-based composite material having a high loading and a high dispersion of active metalOr the preparation process is complex, the energy consumption is high, and the efficiency is low. Obviously, in order to further improve the application potential of the existing noble metal ruthenium-based composite material in many applications, the above bottleneck problem must be overcome, and a new highly dispersed transition metal doped RuO is provided2A new route for the/C composite material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a novel high-dispersion transition metal doped RuO2a/C composite material and a preparation method thereof.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention aims to overcome the defects of the existing noble metal ruthenium-based electrocatalyst, and provides a method for preparing transition metal-doped RuO with high dispersion, uniform nanoparticle size and high loading capacity by taking acetylacetone metal complexes (including transition metal acetylacetone complexes and ruthenium acetylacetone) as metal precursors, grinding and mixing the acetylacetone metal complexes with mixed inorganic salts of potassium bromide and potassium chloride, then pyrolyzing the ground mixture at high temperature in an argon atmosphere, oxidizing at relatively low temperature, and finally washing with water to remove the mixed inorganic salts2a/C composite material. The highly dispersed transition metal doped RuO2The transition metal doped nano particles loaded by the/C composite material have a carbon coating structure and stable properties. The method is simple and safe, and the obtained product has high purity, complete structure, good metal dispersibility and high loading capacity, and is suitable for electrocatalytic reaction.
The invention provides a novel high-dispersion transition metal doped RuO2The preparation method of the/C composite material comprises the following steps:
(1) mixing a transition metal acetylacetone complex with acetylacetone ruthenium, then adding inorganic salt, fully grinding and uniformly mixing to obtain a mixture of the inorganic metal salt and the acetylacetone complex;
(2) placing the mixture of the inorganic metal salt and the acetylacetone complex in the step (1) in an argon atmosphere, heating, and performing high-temperature pyrolysis treatment to obtain a mixture of the high-dispersion transition metal-doped Ru/C composite material and the mixed inorganic metal salt;
(3) heating the mixture of the high-dispersion transition metal doped Ru/C composite material and the mixed inorganic metal salt in the step (2) for oxidation treatment to obtain an oxidized mixture;
(4) soaking the oxidized mixture obtained in the step (3) in deionized water to fully dissolve inorganic salt therein, filtering to obtain precipitate (removing the inorganic salt by a filtering method), and drying to obtain the novel high-dispersion transition metal doped RuO2a/C composite material.
Further, the mass ratio of the transition metal acetylacetone complex in the step (1) to ruthenium acetylacetone is 1: (4-10).
Preferably, the grinding time of the step (1) is 0.5 h.
Further, the transition metal acetylacetone complex in the step (1) is one or more of cobalt acetylacetonate, copper acetylacetonate, iron acetylacetonate, nickel acetylacetonate, manganese acetylacetonate, and the like.
Further, the inorganic salt in step (1) comprises potassium bromide and potassium chloride.
Further, the mass ratio of the potassium bromide to the potassium chloride is (1-4): 1.
preferably, the mass ratio of the transition metal acetylacetone complex in the step (1) to ruthenium acetylacetone is 1: (4-10).
Further, the mass ratio of the inorganic salt to the transition metal acetylacetone complex in the step (1) is (20-80): 1.
further, the temperature of the high-temperature pyrolysis treatment in the step (2) is 600-800 ℃, and the time of the high-temperature pyrolysis treatment is 1-5 h.
Further, the temperature of the oxidation treatment in the step (3) is 150-350 ℃, and the time of the oxidation treatment is 1-4 h.
Preferably, the atmosphere of the oxidation treatment in the step (3) is an air atmosphere.
Preferably, the drying temperature in step (4) is 70 ℃.
The invention provides a preparation method of the compoundThe obtained novel high-dispersion transition metal doped RuO2a/C composite material. The material has the characteristics of carbon coating structure, stable property, high metal loading capacity and the like.
The preparation method provided by the invention is characterized in that acetylacetone metal complexes (including transition metal acetylacetone complexes and ruthenium acetylacetone) are used as metal precursors, and are ground and mixed with mixed inorganic salts of potassium bromide and potassium chloride, then the ground mixture is pyrolyzed at high temperature under argon atmosphere, then is oxidized at relatively low temperature, and finally is washed by water to remove the mixed inorganic salts, so that transition metal-doped RuO with high dispersion, uniform nano particle size and high loading capacity can be obtained2a/C composite material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the novel high-dispersion transition metal doped RuO prepared by the invention2the/C composite material has the structural advantages and the synergistic effect: the copper-doped hollow cobalt phosphide nano-particles are beneficial to forming a large number of open structures, so that more active sites are exposed, and the waste of internal atoms is avoided; the open structure can provide a larger reaction interface for OER and is beneficial to the timely diffusion of generated gas and ions; in addition, transition metal doped RuO due to synergistic effect2The active sites will exhibit more excellent electrocatalytic properties than the active sites of a single metal species;
(2) the preparation method provided by the invention has the advantages of simple preparation process, safety, controllability, less time consumption and energy consumption, and most importantly, the prepared high-dispersion transition metal doped RuO2the/C composite material has excellent catalytic performance on electrocatalytic reaction, and when the catalyst is used for oxygen evolution reaction under acidic condition, the catalytic activity and stability of the catalyst are far higher than those of ruthenium-based catalysts prepared by the traditional method.
Drawings
FIG. 1 shows a highly dispersed transition metal copper doped RuO prepared in example 15 of the present invention2A transmission electron microscope photograph of the/C composite material;
FIG. 2 shows highly dispersed transition metal cobalt doped RuO prepared in example 16 of the present invention2A transmission electron microscope photograph of the/C composite material;
FIG. 3 shows RuO doped with highly dispersed transition metal nickel prepared in example 17 of the present invention2A transmission electron microscope photograph of the/C composite material;
FIG. 4 shows highly dispersed transition metal iron doped RuO prepared in example 18 of the present invention2A transmission electron microscope photograph of the/C composite material;
FIG. 5 shows RuO doped with highly dispersed transition metal manganese prepared in example 19 of the present invention2And the transmission electron microscope photograph of the/C composite material.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Weighing 100mg of ruthenium acetylacetonate and 25mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the two, adding the weighed ruthenium acetylacetonate, continuously and fully grinding until the color of the mixture is uniform, placing the ground mixture in a cuboid small porcelain boat, and adding a cover for placing. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 2
100mg of ruthenium acetylacetonate and 10mg of copper acetylacetonate were weighed out for further use, and 3.375g of potassium bromide and chloride were weighed outAnd 1.125g of potassium, grinding and mixing the inorganic metal salts, adding weighed ruthenium acetylacetonate, continuously and fully grinding until the color of the mixture is uniform, placing the ground mixture in a cuboid small porcelain boat, and adding a cover for placing. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 3
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 2.25g of potassium bromide and 2.25g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 4
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.75g of potassium bromide and 0.75g of potassium chloride, grinding and mixing inorganic metal salts of the two for later use, adding the weighed ruthenium acetylacetonate into the mixture, wherein the mass ratio of the inorganic metal salts to the ruthenium acetylacetonate is 40:1, continuously and fully grinding the mixture until the color of the mixture is uniform, and grinding the mixtureThe ground mixture was placed in a rectangular small porcelain boat, and a lid was added. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 5
Weighing 200mg of ruthenium acetylacetonate and 30mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the two for later use, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 600 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and vacuum drying the precipitate at 70 ℃ for 12 h to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 6
Weighing 50mg of ruthenium acetylacetonate and 7.5mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the two for later use, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the cuboid small porcelain boat for placing the mixture. Subsequently, the system is heated at the heating rate of 2 ℃/min under the protection of argonKeeping the temperature at 730 ℃ for 3h, naturally cooling to 250 ℃, introducing air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution to obtain precipitate, cleaning the precipitate with deionized water for a plurality of times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 7
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 1h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 8
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 5h, naturally cooling to 250 ℃, introducing air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, and soaking the obtained product in the obtained productUltrasonically dispersing in deionized water for 5min until no colorless crystalline solid exists, filtering the solution to obtain precipitate, washing with deionized water for several times, and vacuum drying at 70 deg.C for 12 hr to obtain novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 9
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 600 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and vacuum drying the precipitate at 70 ℃ for 12 h to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 10
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, washing the precipitate with deionized water for several times, and placing the precipitate in a containerVacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 11
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 150 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 12
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 350 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 13
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 1h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 14
Weighing 100mg of ruthenium acetylacetonate and 15mg of copper acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 4h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 h to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite).
Example 15
100mg of ruthenium acetylacetonate and15mg of copper acetylacetonate is reserved, 3.375g of potassium bromide and 1.125g of potassium chloride are weighed, the two inorganic metal salts are ground and mixed, weighed ruthenium acetylacetonate is added, the mass ratio of the inorganic metal salts to the ruthenium acetylacetonate is 40:1, the mixture is continuously and fully ground until the color of the mixture is uniform, and then the ground mixture is placed in a cuboid small porcelain boat and is placed well by adding a cover. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Cu-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite). FIG. 1 shows Cu-RuO prepared in this example2The transmission electron microscope picture of the/C composite material can show that Cu-RuO2the/C composite material nano particles are closely arranged and uniform in size.
Example 16
Weighing 100mg of ruthenium acetylacetonate and 15mg of cobalt acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the ruthenium acetylacetonate and the potassium bromide, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the boat for placing: . Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Co-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite). FIG. 2 shows the Co-RuO prepared in this example2Transmission of/C composite materialPhotograph under an electron microscope, it can be seen that Co-RuO2the/C composite material nano particles are closely arranged and uniform in size.
Example 17
Weighing 100mg of ruthenium acetylacetonate and 15mg of nickel acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the two for later use, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, adding a cover to the boat, and placing the mixture: . Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Ni-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite). FIG. 3 shows Ni-RuO prepared in this example2The transmission electron microscope photograph of the/C composite material shows that Ni-RuO2the/C composite material nano particles are closely arranged and uniform in size.
Example 18
Weighing 100mg of ruthenium acetylacetonate and 20mg of iron acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the two, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the mixture is uniform in color, placing the ground mixture into a cuboid small porcelain boat, adding a cover, and placing the mixture: . Heating the system to 730 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, washing the precipitate with deionized water for several times, and placing the precipitate in a containerVacuum drying at 70 ℃ for 12 hours to obtain novel high-dispersion Fe-RuO2Composite material of/C (the novel highly dispersed transition metal doped RuO2a/C composite). FIG. 4 shows Fe-RuO prepared in this example2The transmission electron microscope picture of the/C composite material can show that Fe-RuO2the/C composite material nano particles are closely arranged and uniform in size.
Example 19
Weighing 100mg of ruthenium acetylacetonate and 15mg of manganese acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing inorganic metal salts of the two, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the color of the mixture is uniform, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the small porcelain boat for placing the mixture. Then, heating the system to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, changing the temperature to be air atmosphere, keeping the temperature for 2h, naturally cooling to room temperature, taking out the obtained product, soaking the obtained product in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, taking out the precipitate, cleaning the precipitate with deionized water for several times, and performing vacuum drying at 70 ℃ for 12 hours to obtain the novel high-dispersion Mn-RuO2Composite material/C (i.e. the novel highly dispersed transition metal doped RuO2a/C composite). FIG. 5 shows Mn-RuO prepared in this example2The transmission electron microscope photograph of the/C composite material shows that Mn-RuO2the/C composite material nano particles are closely arranged and uniform in size.
Comparative example
Weighing 100mg of ruthenium acetylacetonate for later use, weighing 3.375g of potassium bromide and 1.125g of potassium chloride, grinding and mixing the inorganic metal salts, adding the weighed ruthenium acetylacetonate into the mixture, continuously and fully grinding the mixture until the color of the mixture is uniform, placing the ground mixture into a cuboid small porcelain boat, and adding a cover to the cuboid small porcelain boat for placing the mixture. Then, the system is heated to 730 ℃ at the heating rate of 2 ℃/min under the protection of argon, is kept for 3 hours, is naturally cooled to 250 ℃, is changed into an air atmosphere, andkeeping the temperature for 120min, naturally cooling to room temperature, taking out the obtained product, soaking in deionized water, ultrasonically dispersing for 5min until no colorless crystalline solid exists, filtering the solution, washing with deionized water for several times, and vacuum drying at 70 ℃ for 12 hours to obtain a control RuO2a/C composite material.
Effect testing
Oxygen evolution reaction test in acid electrolyte: 1mg of the composite material was weighed out and ultrasonically dispersed in 500. mu.L of a mixed solution containing ethanol, water and nafion (V/V/V245: 245:10), and 15. mu.L of the dispersed solution was dropped on the surface of a glassy carbon electrode by a pipette gun and dried at room temperature. 10 μ L of the dispersed dispersion was dropped onto a glassy carbon electrode and dried at room temperature as a working electrode rotating disk test at 0.1M H saturated with oxygen2SO4In the solution, different rotating speeds of a working electrode connected with an electrode rod in the test process are controlled by rotating a disc electrode, and the electrochemical behavior of the material is researched. Electrocatalytic oxygen evolution reaction test: the sweep rate was 5mV/s and the potential interval was 1.0 to 0.8V (vs. Ag/AgCl). Table 1 shows RuO as a comparative example of the present invention2/C and highly dispersed transition Metal doped RuO prepared in examples 15-192the/C composite material is 0.5M H2SO4The current density of the oxygen evolution reaction in the solution is 10mA/cm2Overpotential data table as needed. As can be seen from Table 1 below, the transition metal doped samples have good performance for electrocatalytic oxygen evolution reaction in acidic electrolytes and compared to the control RuO without transition metal doping2The performance of the catalyst is obviously improved, and the current density reaches 10mA cm-2The required overpotential is significantly reduced. Transition Metal doped RuO prepared in other examples2The electrocatalytic performance of the/C composite is substantially similar to that of the example.
TABLE 1
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. Novel high-dispersion transition metal doped RuO2The preparation method of the/C composite material is characterized by comprising the following steps:
(1) mixing a transition metal acetylacetone complex with acetylacetone ruthenium, then adding inorganic salt, grinding and uniformly mixing to obtain a mixture of the inorganic metal salt and the acetylacetone complex;
(2) placing the mixture of the inorganic metal salt and the acetylacetone complex in the step (1) in an argon atmosphere, heating, and performing high-temperature pyrolysis treatment to obtain a mixture of the high-dispersion transition metal-doped Ru/C composite material and the mixed inorganic metal salt;
(3) heating the mixture of the high-dispersion transition metal doped Ru/C composite material and the mixed inorganic metal salt in the step (2) for oxidation treatment to obtain an oxidized mixture;
(4) soaking the oxidized mixture obtained in the step (3) in water, filtering to obtain precipitate, and drying to obtain the novel high-dispersion transition metal doped RuO2a/C composite material.
2. The novel highly dispersed transition metal doped RuO of claim 12The preparation method of the/C composite material is characterized in that the mass ratio of the transition metal acetylacetone complex in the step (1) to ruthenium acetylacetone is 1: (4-10).
3. The novel highly dispersed transition metal doped RuO of claim 12The preparation method of the/C composite material is characterized in that the transition metal acetylacetone complex in the step (1) is one of cobalt acetylacetonate, copper acetylacetonate, iron acetylacetonate, nickel acetylacetonate and manganese acetylacetonate.
4. The novel highly dispersed transition metal doped RuO of claim 12The preparation method of the/C composite material is characterized in that the inorganic salt in the step (1) comprises potassium bromide and potassium chloride.
5. The novel highly dispersed transition metal doped RuO of claim 42The preparation method of the/C composite material is characterized in that the mass ratio of the potassium bromide to the potassium chloride is (1-4): 1.
6. the novel highly dispersed transition metal doped RuO of claim 12The preparation method of the/C composite material is characterized in that the mass ratio of the inorganic salt to the transition metal acetylacetone complex in the step (1) is (20-80): 1.
7. the novel highly dispersed transition metal doped RuO of claim 12The preparation method of the/C composite material is characterized in that the temperature of the high-temperature pyrolysis treatment in the step (2) is 600-800 ℃, and the time of the high-temperature pyrolysis treatment is 1-5 h.
8. The novel highly dispersed transition metal doped RuO of claim 12The preparation method of the/C composite material is characterized in that the temperature of the oxidation treatment in the step (3) is 150-350 ℃.
9. The novel highly dispersed transition metal doped RuO of claim 12The preparation method of the/C composite material is characterized in that the time of the oxidation treatment in the step (3) is 1-4 h.
10. Novel highly dispersed transition metal doped RuO prepared by the preparation method of any one of claims 1 to 92a/C composite material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112077334A (en) * | 2020-09-03 | 2020-12-15 | 南京晓庄学院 | Preparation method and application of transition metal doped ruthenium-rhodium alloy |
| WO2023221315A1 (en) * | 2022-05-16 | 2023-11-23 | 北京化工大学 | Metal-doped ruthenium oxide nano material, preparation method therefor, and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016221471A (en) * | 2015-06-01 | 2016-12-28 | 公立大学法人大阪府立大学 | Perovskite oxide catalyst for oxygen evolution reaction |
| CN107317070A (en) * | 2017-05-16 | 2017-11-03 | 上海交通大学 | Lithium-air battery cathode spinel structure sulfide catalytic agent material and preparation method thereof |
| CN108144607A (en) * | 2017-12-26 | 2018-06-12 | 吉林大学 | Iridium acid strontium class catalyst, preparation method and its application in terms of electro-catalysis cracks acid aquatic products oxygen |
| CN109560297A (en) * | 2018-11-26 | 2019-04-02 | 新疆大学 | A kind of solvent-free method for preparing template of porous carbon coating nano metal particles |
| CN110562961A (en) * | 2019-08-26 | 2019-12-13 | 广西大学 | Method for in-situ synthesis of nitrogen and sulfur co-doped stereo graphene |
-
2020
- 2020-04-23 CN CN202010329014.3A patent/CN111545218A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016221471A (en) * | 2015-06-01 | 2016-12-28 | 公立大学法人大阪府立大学 | Perovskite oxide catalyst for oxygen evolution reaction |
| CN107317070A (en) * | 2017-05-16 | 2017-11-03 | 上海交通大学 | Lithium-air battery cathode spinel structure sulfide catalytic agent material and preparation method thereof |
| CN108144607A (en) * | 2017-12-26 | 2018-06-12 | 吉林大学 | Iridium acid strontium class catalyst, preparation method and its application in terms of electro-catalysis cracks acid aquatic products oxygen |
| CN109560297A (en) * | 2018-11-26 | 2019-04-02 | 新疆大学 | A kind of solvent-free method for preparing template of porous carbon coating nano metal particles |
| CN110562961A (en) * | 2019-08-26 | 2019-12-13 | 广西大学 | Method for in-situ synthesis of nitrogen and sulfur co-doped stereo graphene |
Non-Patent Citations (2)
| Title |
|---|
| YIYI WU: "Ni-Co Codoped RuO2 with Outstanding Oxygen Evolution Reaction Performance", 《APPLIED ENERGY MATERIALS》 * |
| 吕鹏: "柠檬酸辅助固相研磨法制备铜基催化剂及在CO2加氢合成甲醇反应中的性能研究", 《分子催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112077334A (en) * | 2020-09-03 | 2020-12-15 | 南京晓庄学院 | Preparation method and application of transition metal doped ruthenium-rhodium alloy |
| WO2023221315A1 (en) * | 2022-05-16 | 2023-11-23 | 北京化工大学 | Metal-doped ruthenium oxide nano material, preparation method therefor, and use thereof |
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